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DRAWINGS CLAIMS ALLOWED . TERMINAL 0 DlSCLAl MER

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7 The term of this patent subsequent to (date) has been disclaimed. (Assistant Examiner) (Date)

0 The term of this patent shall not extend beyond the expiration date of U S Patent. No. ISSUE FEE

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WARN I NG: The information disclosed hereln may be restricted Unauthorized disclosure may be prohibited by the United States Code Title 35, Sections 122, 181 and 368 'ossession outside the U S . Patent & Trademark Office is restricted to authorized employees and contractors only.

Form PTO-436A FILED WITH: DISK (CRF) FICHE CD-RO (Rev 6/99)

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CLASS FILING DATE

iERlAL NUMBER e 05/22/2001 .",\ , 09/863,127 208

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- COMMISSIONER FOR PATENE UNITED STATES PATENT AND TRADEMARK OFFICE

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CONFIRMATION NO. 9590 , Illlull 11111 lllU 11111 11111 111111 UII 111111 1111 lilll lllll llllll II 1111 Bib Data Sheet

ATTORNEY GROUP ART UNIT DOCKET NO.

1764 020839-0003OOUS

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'P LlCA NTS Rudolf W. Gunnerman, Reno, NV; Paul S. Moote, Park City, UT; Mark T. Cullen, Reno, NV;

TOTAL IN DE PE N DE N' CLAIMS SHEETS

DRAWING 50 3

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1380

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FEES: Authority has been given in Paper NO. to chargekredit DEPOSIT ACCOUN No. for following:

1350

TLE

eatment of crude,oil fractions, fossil fuels, and products thereof with ultrasound

p All Fees

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(19) United States (12) Patent Application Publication (10) Pub. NO.: US 2003/0051988 A1

Gunnerman et al. (43) Pub. Date: Mar. 20.2003

TREATMENT OF CRUDE OIL FRACTIONS, FOSSIL FUELS, AND PRODUCTS THEREOF WITH ULTRASOUND

Inventors: Rudolf W. Gunnerman, Reno, NV (US); Paul S. Moote, Park City, UT (US); Mark T. Cullen, Reno, NV (US)

Correspondence Address: TOWNSEND AND TOWNSEND AND CREW, LLP TWO EMBARCADERO CENTER EIGHTH FLOOR SAN FRANCISCO, CA 94111-3834 (US)

Appl. No.: 09/863,127

Filed: May 22,2001

Publication Classification

Int. Cl? .............................. CO7C 1/00; C07C 2/00; C07C 4/00; C07C 5/00

(52) U.S. C1. ........... 204/157.15; 204D57.6; 204D57.78; 441904

(57) ABSTRACT

Crude oil fractions, fossil fuels, and organic liquids in general in which it is desirable to reduce the levels of fused-ring compounds, aromatics, and olefins are combined with an aqueous phase to form an emulsion and treated with ultrasound with the effect of opening rings in the fused-ring compounds, saturating aromatics, and converting the olefins to paraffins. In fossil fuels and crude oil fractions, the process raises the API gravity, and in diesel fuels, the process raises the cetane index and thereby improves performance. In fuels and fractions with sulfur-containing and nitrogencontaining components, thc process rcduccs the level of these compounds. The process can be performed both with and without the added presence of hydrogen peroxide. The invention is performed either as a continuous process or a batch process.

US 200310051988 A1 1

Mar. 20,2003

TREATMENT OF CRUDE OIL FRACTIONS, FOSSIL FUELS, AND PRODUCTS THEREOF WITH

ULTRASOUND

BACKGROUND OF THE INVENTION

[OOOl] 1. Field of the Invention

[0002] This invention resides in the field of chemical processes for the treatment of crude oil fractions and the various types of products derived and obtained from these sources. In particular, this invention addresses reformation processes as ring-opening reactions and the saturation of double bonds, to upgrade fossil fuels and convert organic products to forms that will improve their performance and expand their utility. This invention also resides in the removal of sulfur-containing compounds, nitrogen-containing compounds, and other undesirable components from petroleum and petroleum-based fuels.

[0003] 2. Description of the Prior Art

[0004] Fossil fuels are the largest and most widely used source of power in the world, offering high efficiency, proven performance, and relatively low prices. There are many different types of fossil fuels, ranging from petroleum fractions to coal, tar sands, and shale oil, with uses ranging from consumer uses such as automotive engines and home heating to commercial uses such as boilers, furnaces, smelting units, and power plants.

[OOOS] Fossil fuels and other crude oil Eractions and products derived from natural sources contain a vast array of hydrocarbons differing widely in molecular weight, boiling and melting points, reactivity, and ease of processing. Many industrial processes have been developed to upgrade these materials by removing, diluting, or converting the heavier components or those that tend to polymerize or otherwise solidify, notably the olefins, aromatics, and fused-ring compounds such as naphthalenes, indanes and indenes, anthracenes, and phenanthracenes. A common means of eITecting the conversion of these compounds is saturation by hydrogenation across double bonds.

[OO06] For fossil fuels in particular, a growing concern is the need to remove sulfur compounds. Sulfur from sulfur compounds causes corrosion in pipeline, pumping, and refining equipment, the poisoning of catalysts used in the refining and combustion of fossil fuels, and the premature failure of combustion engines. Sulfur poisons the catalytic converters used in diesel-powered trucks and buses to control the emissions of oxides of nitrogen (NOJ. Sulfur also causes an increase in particulate (soot) emissions from trucks and buses by degrading the soot traps used on these vehicles. The burning of sulfur-containing fuel produces sulfur dioxide which enters the atmosphere as acid rain, inflicting harm on agriculture and wildlife, and causing hazards to human health.

[OO07] The Clean Air Act of 1964 and its various amendments have imposed sulfur emission standards that are difficult and expensive to meet. Pursuant to the Act, the United States Environmental Protection Agency has set an upper limit of 15 parts per million by weight (ppmw) on the sulfur content of diesel fuel, effective in mid-2006. This is a severe reduction from the standard of 500 ppmw in effect in the year 2000. For reformulated gasoline, the standard of 300 ppmw in the year 2000 has been lowered to 30 ppmw,

effective Jan. 1,2004. Similar changes have been enacted in the European Union, which will enforce a limit of 50 ppmw sulfur for both gasoline and diesel fuel in the year 2005. The treatment of fuels to achieve sulfur emissions low enough to meet these requirements is difficult and expensive, and the increase in fuel prices that this causes will have a major influence on the world economy.

[OOOS] The principal method of fossil fuel desulfurization in the prior art is hydrodesulfurization, Le., the reaction between the fossil fuel and hydrogen gas at elevated temperature and pressure in the presence of a catalyst. This causes the reduction of organic sulfur to gaseous H,S, which is then oxidized to elemental sulfur by the Claus process. A considerable amount of unreacted H,S remains however, with its attendant health hazards. A further limitation of hydrodesulfurization is that it is not equally effective in removing all sulfur-bearing compounds. Mercaptans, thioethers, and disulfides, for example, are easily broken down and removed by the process, while aromatic sulfur compounds, cyclic sulfur compounds, and condensed multicyclic sulfur compounds are less responsive to the process. Thiophene, bemthiophene, dibenzothiophene, other condensed-ring thiophenes, and substituted versions of these compounds, which account for as much as 40% of the total sulfur content of crude oils from the Middle East and 70% of the sulfur content of West Texas crude oil, are particularly refractory to hydrodesulfurization.

[0009] In addition to sulfur-bearing compounds, nitrogen- bearing compounds are also sought to be removed from fossil fuels, since these compounds tend to poison the acidic components of the hydrocracking catalysts used in the refinery. The removal of nitrogen-bearing compounds is achieved by hydrodenitrogenation, which is a hydrogen treatment performed in the presence of metal sulfide catalysts. Both hydrodesulfurization and hydrodenitrogenation require expensive catalysts as well as high temperatures (typically 400” F. to 850” F., which is equivalent to 204” C. to 254’ C.) and pressures (typically SO psi to 3,500 psi). These processes require a source of hydrogen or an on-site hydrogen production unit, which entails high capital expenditures and operating costs. In both of these processes, there is also a risk of hydrogen leaking from the reactor.

[OOlO] Of possible relevance to this invention are co- pending US. patent application Ser. No. 09/676,260. entitled “Oxidative Desulfurization of Fossil Fuels With Ultrasound,” Teh Fu Yen, et al., inventors, filed Sep. 28, 2000, and co-pending US. patent application Ser. No. 09/812,390, entitled “Continuous Process for Oxidative Desulfurization of Fossil Fuels With Ultrasound and Prod- ucts Thereof,” Rudolf W. Gunnerman, inventor, filed Mar. 29,2001. Both of these applications are incorporated herein by reference in their entirety for all legal purposes capable of being served thereby.

SUMMARY OF THE INVENTION

[OOll] It has now been discovered that fossil fuels, crude oil fractions, and many of the components that are derived from these sources can undergo a varicty of bcncficial conversions and be upgraded in a variety of ways by a process that applies ultrasound to these materials in a multiphase reaction medium. The organic material is combined with an aqueous phase to form an emulsion, placing

US 2003/0051988 A1 Mar. 20,2003 2

the phases in intimate contact during the exposure to ultrasound. Hydrogen gas is not required, nor are the high temperature and pressure that are commonly needed for hydrogenations of the prior art. In certain embodiments of the invention, the ultrasound treatment is performed in the presence of a hydroperoxide, and in certain embodiments as well, a transition metal catalyst is used. One of the surprising discoveries associated with certain embodiments of this invention, however, is that the conversions achieved by this invention can be achieved without the inclusion of a hydroperoxide in the reaction mixture.

[0012] Included among the conversions achieved by the present invention are the removal of organic sulfur compounds, the removal of organic nitrogen compounds, the saturation of double bonds and aromatic rings, and the opening of rings in fused-ring structures. The API gravities of fossil fuels and crude oil fractions are raised (Le., the densities lowered) as a result of treatments in accordance with the invention. The invention thus resides in part in the process of using ultrasound to achieve these conversions. The invention further resides in processes for converting aromatics to cycloparaffins, and opening one or more rings in a fused-ring structure, thereby for example converting naphthalenes to monocyclic aromatics, anthracenes to naphthalenes, fused heterocyclic rings such as benzothiophenes, dibenzothiophenes, benzofurans, quinolines, indoles, and the like to substituted benzenes, acenaphthalenes and acenaphthenes to indanes and indenes, and monocyclic aromatics to noncyclic structures. Further still, the invention resides in processes for converting olefins to paraffins, and in processes for breaking carbon-carbon bonds, carbon- sulfur bonds, carbon-metal bonds, and carbon-nitrogen bonds.

[0013] In addition to raising the API gravity of a petroleum-based fuel, the invention raises the cetane index of petroleum fractions and cracking products whose boiling points or ranges are in the diesel range. The term “diesel range” is used herein in the industry sense to denote the portion of crude oil that distills out after naphtha, and generally within the temperature range of approximately 200’ C. (392” F.) to 370’ C.(698’ E). Fractions and cracking products whose boiling ranges are contained in this range as well as those that overlap with this range to a majority extent are included. Examples of refinery fractions and streams within the diesel range are fluid catalytic cracking (FCC) cycle oil fractions, coker distillate fractions, straight run diesel fractions, and blends. The invention also impartsother beneficial changes such as a lowering of boiling points and a removal of components that are detrimental to the performance of the fuel and those that affect refinery processes and increase the cost of production of the fuel. Thus, for example, FCC cycle oils can be treated in accordance with the invention to sharply reduce their aromatics content.

[0014] A further group of crude oil fractions for which the invention is particularly useful are gas oils, which term is used herein as it is in the petroleum industry, to denote liquid petroleum distillates that have higher boiling points than naphtha. The initial boiling point may be as low as 400’ F. (ZOO’ C.), but the preferred boiling range is about 500’ F. to about 1100’ F. (approximately equal to 260’ C. to 595’ C.). Examples of fractions boiling within this range are FCC slurry oil, light and heavy gas oils, so termed in view of their

different boiling points, and coker gas oils. All of the terms in this and the preceding paragraph are used herein as they are in the petroleum art.

[OOlS] By virtue of the conversions that occur as a result of the process of this invention, hydrocarbon streams experience changes in their cold flow properties, including their pour points, cloud points, and freezing points. Sulfur compounds, nitrogen compounds, and metal-containing compounds are also reduced, and the use of a process in accordance with this invention significantly lessens the burden on conventional processes such as hydrodesulfurization, hydrodenitrogenation, and hydrodemetallization, which can therefore be performed with greater effectiveness and efficiency.

[0016] These and other advantages, features, applications and embodiments of the invention are made more apparent by the description that follows.

DETAILED DESCRIPTION OF THE INVENTION AND SPECIFIC EMBODIMENTS

[0017] The term “liquid fossil fuel” is used herein to denote any carbonaceous liquid that is derived from petroleum, coal, or any other naturally occurring material, as well as processed fuels such as gas oils and products of fluid catalytic cracking units, hydrocracking units, thermal cracking units, and cokers. and that is used to generate energy for any kind of use, including industrial uses, commercial uses, governmental uses, and consumer uses. Included among these fuels are automotive fuels such as gasoline, diesel fuel, jet fuel, and rocket fuel, as well as petroleum residuum- based fuel oils including bunker fuels and residual fuels. No. 6 fuel oil, for example, which is also known as “Bunker @’ fuel oil, is used in oil-fired power plants as the major fuel and is also used as a main propulsion fuel in deep draft vessels in the shipping industry. No. 4 fucl oil and No. 5 fucl oil are used to heat large buildings such as schools, apart- ment buildings, and office buildings, and large stationary marine engines. The heaviest fuel oil is the vacuum residuum from the fractional distillation, commonly referred to as “vacuum resid,” with a boiling point of 565” C. and above, which is used as asphalt and coker feed. The present invention is useful in the treatment of any of these fuels and fuel oils for purposes of reducing the sulfur content, the nitrogen content, and the aromatics content, and for general upgrading to improve performance and enhance utility. Certain embodiments of the invention involve the treatment of fractions or products in the diesel range which include, but are not limited to, straight-run diesel fuel, feed-rack diesel fuel (as commercially available to consumers at gasoline stations), light cycle oil, and blends of straight-run diesel and light cycle oil ranging in proportion from 10:90 to 9O:lO (straight-run diese1:light cycle oil).

[OOlS] The term “crude oil fraction” is used herein to denote any of the various refinery products produced from crude oil, either by atmospheric distillation or vacuum distillation, including fractions that have been treated by hydrocracking, catalytic cracking, thermal cracking, or cok- ing, and those that have been desulfurized. Exarnplcs arc light straight-run naphtha, heavy straight-run naphtha, light steam-cracked naphtha, light thermally cracked naphtha, light catalytically cracked naphtha, heavy thermally cracked naphtha, reformed naphtha, alkylate naphtha, kerosene,

US 2003/0051988 A1 3

Mar. 20,2003

hydrotreated kerosene, gasoline and light straight-run gasoline, straight-run diesel, atmospheric gas oil, light vacuum gas oil, heavy vacuum gas oil, residuum, vacuum residuum, light coker gasoline, coker distillate, FCC (fluid catalytic cracker) cycle oil, and FCC slurry oil.

[0019] The term “fused-ring aromatic compound” is used herein to denote compounds containing two or more fused rings at least one of which is a phenyl ring, with or without substituents, and including compounds in which all fused rings are phenyl or hydrocarbyl rings as well as compounds in which one or more of the fused rings are heterocyclic rings. Examples are substituted and unsubstituted naphthalenes, anthracenes, benzothiophenes, dibenzothiophenes, benzofurans, quinolines, and indoles.

[0020] The term “olefins” is used herein to denote hydrocarbons, primarily those containing two or more carbon atoms and one or more double bonds.

[0021] Fossil fuels and crude oil fractions treated by ultrasound in accordance with this invention have significantly improved properties relative to the same materials prior to treatment, these improvements rendering the products unique and improving their usefulness as fuels. One of these properties is the API gravity. The term “API gravity” is used herein as it is among those skilled in the art of petroleum and petroleum-derived fuels. In general, the term represents a scale of measurement adopted by the American Petroleum Institute, the values on the scale increasing as specific gravity values decrease. Thus, a relatively high API gravity means a relatively low density. The API gravity scale extends from -20.0 (equivalent to a specific gravity of 1.2691) to 100.0 (equivalent to a specific gravity of 0.6112).

[0022] To illustrate the range of applicability of the present invention and its effect on liquid fossil fuels and crude oil fractions, Table I below lists unit streams within the diesel boiling range and unit streams within the gas oil boiling range, with a range of values for various parameters for stream, and a range of how much each parameter can be reduced or increased by the ultrasound treatment of the present invention.

TABLE I

Refinery Unit Streams: Parameter Ranges and Effects of Invention: f+) Denotes Increase: (-) Denotes Reduction

Diesel Boiling Range Materials (Boiling Range 300-750’ E, 1 5 0 4 0 ° C.):

FCC Cycle Crude Straight- Unit Stream Oil Run Diesels Coker Distillates

API 15-30 27-45 27-45 change (+) 3-30 (+) 1-15 (+) 0-15 Cetane index 2 5 4 3 0 6 0 28-40 change (+) 1-30 (+) 1-20 (+) 1-25 Aromatics (weight %) 30-95 0-50 30-95 change (-) 14-) 50 (-) I-(-) 25 (-) I-(-) 40 Nitrogen (ppm as N) 0-10,MlO 0-10,000 0-10,000 change (as % of initial (-) 1-90 (-) 1-90 value) Bromine number 5-40 0-5 10-50 change (as %) (-) 1-95 (-) 1-95 (-) 1-95

(-) 1-90

Sulfur (weight % as S) 0.05-5 0.01-5 0.05-5 change (as % of initial (-) 5-95 value)

(-) 5-95 (-) 5-95

TABLE I-continued

Refinery Unit Streams: Parameter Ranges and Effects of Invention: (+) Denotes Increase; (-) Denotes Reduction

Pour Point (“ F.) 10-40 (-10)4 0-30

Cloud Point C F.) 10-45 (-low5 0-35 change (“ E) (-) 5-50 (-) 5-50 (-) 5-50

change (“ E) (-) 5-50 (-) 5-50 (-) 5-50

Gas Oil Boiling Range Materials (Boiling Range 500-1100° E, 260-59S0 C.):

FCC Cycle Unit Stream -+ Oil Crude Gas oils Coker Gas oils

API (-15)-25 change (+) 1-40 Aromatics (weigbt %) 30-95 change (-) 14-1 80 Nitrogen (ppm as N) 0-10.000 change (as % of initial (-) 1-90 value)

Residue (Conradson) (%) Sulfur (weight % as S) 0.05-7 change (as % of initial (-) 5-95 value) Pour Point (“ F.) 50-150

Change Carbon (-) 1-90

change (“ E) (-) 5-100

5-35 (+) 1-25 0-50 (-) 14-1 40 0-10,000 (-) 1-90

(-) 1-90

0-30 (+) 1-30 20-80 (-) I-(-) 50 0-10,000 (-) 1-90

(-) 1-90

0.01-7 (-) 5-95

(-) 5-100 50-150

0.05-7 (-) 5-95

(-) 5-100 50-150

[0023] The ultrasound process of the present invention is applicable to any liquid fossil fuels, preferably those with API gravities within the range of -10 to 50, and most preferably within the range of 0 to 45. For materials boiling in the diesel range, the process of the invention is preferably performed in such a manner that the starting materials are converted to products with MI gravities within the range of 37.5 to 45. FCC cycle oils are preferably converted to products with API gravities within the range of 30 to 50. For liquid fossil fuels in general, the process of the invention is preferably performed to achieve an increase in API gravity by an amount ranging from 2 to 30 API gravity units, and more preferably by an amount ranging from 7 to 25 units. Alternatively stated, the invention preferably increases the API gravity from below 20 to above 35.

[0024] As stated above, fossil fuels boiling within the diesel range that are treated in accordance with this invention experience an improvement in their cetane index (also referred to in the art as the “cetane number”) upon being treated in accordance with this invention. Diesel fuels to which the invention is of particular interest in this regard are those having a cetane index greater than 40, preferably within the range of 45 to 75, and most preferably within the range of 50 to 65. The improvement in cetane index can also be expressed in terms of an increase over that of the material prior to ultrasound treatment. In certain preferred embodiments, the increase is by an amount ranging from 1 to 40 cetane index units, and more preferably by an amount ranging from 4 to 20 units. As a still further means of expression, the invention preferably increases the cetane index from below 47 to about 50. This invention can be used to produce diesel fuels having a cetane index of greater than 50.0, or preferably greater than 60.0. In terms of ranges, the invention is capable of producing diesel fuels having a cetane index of from about 50.0 to about 80.0. and preferably from about 60.0 to about 70.0. The cetane index or

US 2003/0051988 A1

number has the same meaning in this specification and the appended claims that it has among those skilled in the art of automotive fuels.

[OOZS] As noted above, certain embodiments of the invention involve the inclusion of a hydroperoxide in the reaction mixture. The term “hydroperoxide” is used herein to denote a compound of the molecular structure

R-0-0-H

[0026] in which R represents either a hydrogen atom or an organic or inorganic group. Examples of hydroperoxides in which R is an organic group are water-soluble hydroperoxides such as methyl hydroperoxide, ethyl hydroperoxide, isopropyl hydroperoxide, n-butyl hydroperoxide, sec-butyl hydroperoxide, tert-butyl hydroperoxide, 2-methoxy-2-propyl hydroperoxide, tert-am yl hydroperoxide, and c yclohexyl hydroperoxide. Examples of hydroperoxides in which R is an inorganic group are peroxonitrous acid, peroxophosphoric acid, and peroxosulfuric acid. Preferred hydroperoxides are hydrogen peroxide (in which R is a hydrogen atom) and tertiary-alkyl peroxides, notably tert-butyl peroxide.

[0027] The aqueous fluid that is combined with the fossil fuel or other liquid organic starting material in the processes of this invention may be water or any aqueous solution. The relative amounts of organic and aqueous phases may vary, and although they may affect the efficiency of the process or the ease of handling the fluids, the relative amounts are not critical to this invention. In most cases, however, best results will be achieved when the volume ratio of organic phase to aqueous phase is from about 8:l to about 15, preferably from about 5: l to about 1:1, and most preferably from about 4:l to about 2 1 .

[002S] When a hydroperoxide is present, the amount of hydroperoxide relative to the organic and aqueous phases can also be vaned, and although the conversion rate and yield may vary somewhat with the proportion of hydroperoxide, the actual proportion is not critical to the invention, and any excess amounts will be eliminated by the ultrasound. When the hydroperoxide is added as a solute in the aqueous solution that is used as the aqueous phase, best results are generally achieved with a hydroperoxide concentration of from about 10 ppm to about 100 ppm by weight, and preferably from about 15 ppm to about 50 ppm by weight, of the aqueous solution, particularly when the hydroperoxide is H,O,. Alternatively, when the H,O, amount is calculated as a component of the combined organic and aqueous phases, best results will generally be achieved in most systems with an H,O, concentration within the range of from about 0.0003% to about 0.03% by volume (as H,O,), and preferably from about 0.001% to about 0.01%, of the combined phases. For hydroperoxides other than H,O,, the preferred concentrations will be those of equivalent molar amounts.

[0029] In certain embodiments of this invention as well, a surface active agent or other emulsion stabilizer is included to stabilize the emulsion as the organic and aqueous phases are being prepared for the ultrasound exposure. Certain pctrolcum fractions contain surface active agents as naturally-occurring components of the fractions, and these agents may serve by themselves to stabilize the emulsion. In other cases, synthetic or non-naturally-occurring surface active agents can be added. Any of the wide variety of

Mar. 20,2003 4

known materials that are effective as emulsion stablizers can be used. Listings of these materials are available McCutch- eon’s Volume 1: Emulsifiers & Detergents-1999 North American Edition, McCutcheon’s Division, MC Publishing Co., Glen Rock, NJ., USA, and other published literature. Cationic, anionic and nonionic surfactants can be used. Preferred cationic species are quaternary ammonium salts, quaternary phosphonium salts and crown ethers. Examples of quaternary ammonium salts are tetrabutyl ammonium bromide, tetrabutyl ammonium hydrogen sulfate, tributylmethyl ammonium chloride, benzyltrimethyl ammonium chloride, benzyltriethyl ammonium chloride, methyltricaprylyl ammonium chloride, dodecyltrimethyl ammonium bromide, tetraoctyl ammonium bromide, cetyltrimethyl ammonium chloride, and trimethyloctadecyl ammonium hydroxide. Quaternary ammonium halides are useful in many systems, and the most preferred are dodecyltrimethyl ammonium bromide and tetraoctyl ammonium bromide.

[0030] The preferred surface active agents are those that will promote the formation of an emulsion between the organic and aqueous phases upon passing the liquids through a common mixing pump, but that will spontaneously separate the product mixture into aqueous and organic phases suitable for immediate separation by decantation or other simple phase separation procedures. One class of surface active agents that will accomplish this is liquid aliphatic C,,-C,, hydrocarbons and mixtures of such hydrocarbons, preferably those having a specific gravity of at least about 0.82, and most preferably at least about 0.85. Examples of hydrocarbon mixtures that meet this description and are particularly convenient for use and readily available are mineral oils, preferably heavy or extra heavy mineral oil. The terns “mineral oi1,””heavy mineral oil,” and “extra heavy mineral oil“ are well known in the art and are used herein in the same manner as they are commonly used in the art. Such oils are readily available from commercial chemicals suppliers throughout the world.

[0031] When an added emulsifying agent is used in the practice of this invention, the appropriate amount of agent to use is any amount that will perform as described above. The amount is otherwise not critical and may vary depending on the choice of the agent, and in the case of mineral oil, the grade of mineral oil. The amount may also vary with the fuel composition, the relative amounts of aqueous and organic phases, and the operating conditions. Appropriate selection will be a matter of routine choice and adjustment to the skilled engineer. In the case of mineral oil, best and most efficient results will generally be obtained using a volume ratio of mineral oil to the organic phase 1 of from about 0.00003 to about 0.003.

[0032] In certain embodiments of the invention, a metallic catalyst is included in the reaction system to regulate the activity of the hydroxyl radical produced by the hydroperoxide. Examples of such catalysts are transition metal catalysts, and preferably metals having atomic numbers of 21 through 29, 39 through 47, and 57 through 79. Particularly preferred metals from this group are nickel, sulfur, tungsten (and tungstates), cobalt, molybdenum, and combinations thereof. In certain systems within thc scope of this invcntion, Fenton catalysts (ferrous salts) and metal ion catalysts in general such as iron (10, iron (111), copper (I), copper (10, chromium (111), chromium (VI), molybdenum, tungsten, cobalt, and vanadium ions, are useful. Of these, iron (11),

US 200310051988 A1 5

Mar. 20,2003

iron (111), copper (11), and tungsten catalysts are preferred. For some systems, such as crude oil, Fenton-type catalysts are preferred, while for others, such as diesel-containing systems, tungsten or tungstates are preferred. 'lbngstates include tungstic acid, substituted tungstic acids such as phosphotungstic acid, and metal tungstates. In certain embodiments of the invention, nickel, silver, or tungsten, or combinations of these three metals, are particularly useful. The metallic catalyst when present will be used in a catalytically effective amount, which means any amount that will enhance the progress of the reaction (Le., increase the reaction rate) toward the desired goal, particularly the ob- dation of the sulfides to sulfones. The catalyst may be present as metal particles, pellets, flakes, shavings, or other similar forms, retained in the ultrasound chamber by physical barriers such as screens or other restraining means as the reaction medium is allowed to pass through. [0033] The temperature of the combined aqueous and organic phases during ultrasound exposure may vary widely, although in most cases it is contemplated that the temperature will be within the range of from about 0" C. to about 500" C., preferably from about 20" C. to about 200" C., and most preferably from about 40" C. to about 125" C. In many cases, it will be beneficial to preheat the two phases, either individually or together, prior to their entry into the ultrasound chamber. The optimal degree of preheating will vary with the particular organic liquid to be treated and the ratio of aqueous to organic phases, provided that the temperature is not high enough to volatilize the organic liquid. With diesel fuel, for example, best results will most often be obtained by preheating the fuel to a temperature of at least about 70" C., and preferably from about 70" C. to about 100". The aqueous phase may be preheated to any temperature up to its boiling point. [0034] Ultrasound used in accordance with this invention consists of soundlike waves whose frequency is within or above the range of normal human hearing, i.e., in the range of 2 kHz (2,000 cycles per second) or above. Ultrasonic energy with liequencies as high as 10 gigahertz (10,000, 000,000 cycles per second) has been generated, but for the purposes of this invention, useful results will be achieved with frequencies within the range of from about 2 kHz to about 100 kHz, and preferably within the range of from about 10 kHz to about 50 kHz. Ultrasonic waves can be generated from mechanical, electrical, electromagnetic, or thermal energy sources. The intensity of the sonic energy may also vary widely. For the purposes of this invention, best results will generally be achieved with an intensity ranging from about 10 watts/cm2 to about 3000 watts/cm*, or preferably from about 50 watts/cm2 to about 1500 watts/ cm2. The typical electromagnetic source is a magnetostrictive transducer which converts magnetic energy into ultrasonic energy by applying a strong alternating magnetic field to certain metals, alloys and femtes. The typical electrical source is a piezoelectric transducer, which uses natural or synthetic single crystals (such as quartz) or ceramics (such a barium titanate or lead zirconate) and applies an alternating electrical voltage across opposite faces of the crystal or ceramic to cause an alternating expansion and contraction of crystal or ceramic at the impressed frequency. Ultrasound has wide applications in such areas a s cleaning for the

system, materials testing, machining, soldering and welding, electronics, agriculture, oceanography, and medical imaging. The various methods of producing and applying ultrasonic energy, and commercial suppliers of ultrasound equipment, are well known among those skilled in the use of ultrasound.

[0035] The exposure time of the multiphase reaction medium to ultrasound is not critical to the practice or to the success of the invention, and the optimal exposure time will vary according to the type of fuel being treated. An advantage of the invention however is that effective and useful results can be achieved with a relatively short exposure time. Apreferred range of exposure times is from about 1 second to about 30 minutes, and a more preferred range is from about 15 seconds to about 1 minute.

[0036] Improvements in the efficiency and effectiveness of the process can also be achieved by recycling or secondary ultrasound treatments. A fresh supply of water may for example be added to the treated and separated organic phase to form a fresh emulsion which is then exposed to further ultrasound treatment, either on a batch or continuous basis. This re-exposure to ultrasound can be repeated multiple times for even better results. This is readily achieved in a continuous process by a recycle stream or by the use of a second stage ultrasound treatment, and possibly a third stage ultrasound treatment, with a fresh supply of water at each stage.

[0037] In systems where the reaction induced by ultrasound produces undesirable byproducts in the organic phase, these byproducts can be removed by conventional methods of extraction, absorption, or filtration. When the byproducts are polar compounds, for example, the extraction process can be any process that extracts polar compounds from a non-polar liquid medium. Such processes include solid- liquid extraction, using adsorbents such as silica gel, activated alumina, polymeric resins, and zeolites. Liquid-liquid extraction can also be used, with polar solvents such as dimethyl formamide, N-methylpyrrolidone, or acetonitrile. A variety of organic solvents that are either immiscible or marginally miscible with the fossil fuel, can be used. Tolu- ene and similar solvents are examples.

[0038] The ultrasound-assisted reformation reaction generates heat, and with certain starting materials it is preferable to remove some of the generated heat to maintain control over the reaction. When gasoline is treated in accordance with this invention, for example, it is preferable to cool the reaction medium in the ultrasound chamber. Cooling is readily achievable by conventional means, such as the use of a liquid coolant jacket or a coolant circulating through a cooling coil in the interior of the ultrasound chamber. Water at atmospheric pressure is an effective coolant for these purposes. When cooling is achieved by immersing the ultrasound chamber in a coolant bath or by use of a circulating coolant, the coolant may be at a temperature of about 50" C. or less, preferably about 20" C. or less, and more preferably within the range of from about -5" C. to about 20" C. Suitable cooling methods or devices will be readily apparent to those skilled in the art. Cooling is generally unnecessary with diesel fuel, gas oils, and resids.

[0039] Operating conditions in general for the practice of this invention can vary widely, depending on the organic material being treated and the manner of treatment. The pH

_ - I

electronics, automotive, aircraft, and precision instruments industries, flow metering for closed systems such as coolants in nuclear power plants or for blood flow in the vascular

US 2003/0051988 A1 6

Mar. 20,2003

of the emulsion, for example, may range from as low as 1 to as high as 10, although best results are presently believed to be achieved within a pH range of 2 to 7. The pressure of the emulsion as it enters the ultrasound chamber can likewise vary, ranging from subatmospheric (as low as 5 psia or 0.34 atmosphere) to as high as 3,000 psia (214 atmospheres), although preferably less than about 400 psia (27 atmopheres), and more preferably less than about 50 psia (3.4 atmospheres), and most preferably from about atmospheric pressure to about 50 psia.

[0040] The operating conditions described in the preceding paragraphs that relate to ultrasound conditions, the inclusion of emulsion stabilizers and catalysts, and the general conditions of temperature and pressure apply to the process of the invention regardless of whether or not hydrogen peroxide or any other hydroperoxide is present in the reaction mixture. One of the unique and surprising discoveries of this invention is that the levels of sulfur-containing compounds and nitrogen-containing compounds are reduced substantially regardless of whether a hydroperoxide is present.

[0041] The process can be performed either in a batchwise manner or in a continuous-flow operation. Continuous-flow operations are preferred. In a currently preferred system, the ultrasound exposure is performed in a horizontal pipe reactor, 12 inches (30.5 cm) in diameter and 6 feet (1.83 m) in length, although a useful range of dimensions may be a diameter of from 4 inches to 24 inches (10.2 to 61 cm) and a length of 1 foot to 50 feet (30.5 to 1,524 cm), preferably from 6 feet to 12 feet (183 to 366 cm). The pipe is divided longitudinally into 5 sections or cells with perforated vertical walls separating the cells. A horizontal screen in each cell supports the metal catalyst particles and the perforated vertical walls serve to retain the particles in each cell. Ultrasound probes penetrate the top of the pipe and extend into the pipe interior, with one probe extending into each cell. Emulsion is passed through the pipe and thus through each cell in succession, at a rate of approximately 75 gallons/minute (4.7 liters per second, or 2,570 bbuday). The volume ratio of organic to aqueous phases is 1:OS.

[0042] The following examples are offered for purposes of illustration and are not intended to limit the scope of the invention.

EXAMPLE 1

[0043] A petroleum-derived fuel was treated in accordance with the present invention in a stainless steel ultrasound chamber having an internal volume of 3 liters. Ametal screen inside the chamber supported a bed of solid metal catalyst consisting of a mixture of tungsten flakes and nickel pellets, and positioned above the catalyst bed was an ultrasound probe whose lower end terminated approximately 5 cm above the catalyst bed. Ultrasound was supplied to the probe by an ultrasound generator as follows:

[0044] Ultrasound generator:

[0045] Supplier: Sonics & Materials, Inc., New-

[OM61 Power supply: net power output of 800

[0047] Voltage: 120 V, single phase

town, Conn., USA

watts (run at 50%)

[0048] Current: 10 amps

[0049] Frequency: 20 kHz

[OOSO] The fuel used in this test was a 70/30 (volume ratio) mixture of straight-run diesel and FCC light cycle oil. Each fuel was combined with water at a ratio of approximately 2 parts by volume of fuel to 1 part by volumc of watcr. Hydrogen peroxide was added as a 3% aqueous solution, at 0.0025 parts by volume of the solution to 1 part by volume of the water. The fuel and water were both preheated to 75' C. Extra heavy mineral oil, obtained from Mallinckrodt Baker Inc., Philipsburg, NJ., USA, was used as a surface active agent and added at a rate of approximately 1 drop of a 10% solution per 0.375 Lof the total mixture. The mixture was heated to approximately 85' C. and emulsified with a high-speed shear mixer. The resulting emulsion was passed through the ultrasound chamber as a continuous stream at a flow rate of approximately 1 gallon per minute (3.8 liters/ min). Residence time in the ultrasound chamber was approximately 1 minute.

[OOSl] The two-phase aqueous-organic mixture emerging from the ultrasound chamber passed through two cloth filters into a separation chamber. The organic phase was drawn from the top of the chamber and the aqueous phase Gom [he bottom. The organic phase emerging from a single pass through the ultrasound chamber and separator was washed with acetonitrile. In some cases, the organic phase was recycled through the ultrasound chamber with fresh water at the same ratios and conditions used in the first pass. When recycling was performed twice, the sulfur content of the organic phase with a solvent wash was substantially the same as that achieved with a single pass followed by the solvent wash. [OOS2] The fuel, both before and after treatment in the ultrasound chamber, was analyzed for concentrations of individual sulfur-containing compounds (test method: ASTM D-5623) and for total sulfur (test method: ASTM D-2622, using a sulfur analyzer Model SLFA-20, Horiha Instruments, Inc., Knoxville, Tenn., USA, with a detection limit of 20 ppm). The results, which demonstrate a sharp drop in the sulfur content, particularly among the thiophencs, are shown in Table 11.

TABLE I1

Sulfur Components After Treatment IoDm S bv weight): Before Treatment and Solvent Extraction

benzothiophene methyl benzothiophenes dimethyl benzothiophenes trimethyl benzothiophenes tetramethyl benzothiophenes dibcnzothiophene methyl dibenzothiophenes dimethyl dibenzothiophenes trimethyl dibenzothiophenes unidentified volatile sulfur hydrogen sulfide sulfur dioxide carbonyl sulfide ethyl mercaptan methyl sulfide carbonyl disulfide isopropyl mercaptan ethylene sulfide t-butyl mercaptan

10 186 486 490 464 169 395 450 21s 396 C1 C1 C1 Cl Cl Cl C1 C1 C1

Cl

Cl 1 3 14 2 10 12 9 18 C1 <I Cl C1 el Cl

cl C1 Cl

US 2003/0051988 A1

TABLE 11-continued

7 Mar. 20,2003

TABLE IIIcontinued

Sulhu Components After Treatment (ppm S by weight): Before Treatment and Solvent Extraction

n-propyl mercaptan <I c1 ethyl methyl sulfide <I <1 thiophene <I <l sec-butyl mercaptan <l <l isobutyl mercaptan c1 c1 ethyl sulfide <1 <l n-butyl mercaptan <1 <l methyl disulfide <1 <I 2-methyl thiophene <1 <l 3-metbyl thiophene <I <1 tetrahydrothiophene c1 <I ethyl methyl disulfide <1 <I 2-etbyl thiophene <I c1 2,s-dimethyl thiophene <1 <1 J-ethyl thiophene <I Cl 2.4 & 2,3-dimethyl thiophene c1 cl 3,4-dimethyl thiophene <1 <l methyl ethyl thiophenes <I <1 trimethyl thiophenes <1 <I tetramethyl thiophenes cl c1 Total Sulfur by X-Rny 0.3260 0.007 Spectroscopy (weight %)

[0053] The fuel was also given a full chemical analysis by ASTM D-5134 Mod. both before and after treatment, with results shown in Table 111.

TABLE 111

Before Treatment After Treatment (weight %) (weight %)

n-hexane cyclohexane trans-] ,2dimethylcyclopentane n-heptane methylcyclohexane traas,cis-l,2,3-trimethylcyclopentane N,N-dimethyl formamide toluene 2-methylheptane 3-mcthylheptane trans-l,2-dimethylcyclohexane n-octane cis- 1 ,2-dimethylcyclohexane 2,4-dimethylheptane eth ylcyclohexane 2,6-dimethylheptane 1,1,3-trimethylcyclohexane 2,s-dimethylheptane 3,S-dimethylheptane ethylbenzene trans,trans-I ,2,4-trimethylcyclohexane meta-x ylene para-xylene 2,3-dimethylheptane 2,3-dimethylheptane D/L 3-ethylheptane Cmethyloctanc 2-methyloctane 3-methyloctane cis,cis- 1,2,3-trimethylcyclohexane 3-ethylheptane 3-methyloctane cis,cis-1,2,4-trimethylcyclohexane orthoxylene cis-1 -ethyl-3-methylcyclohexane trans-1-ethyl-4-meth ylcyclohexane isobutylcyclopentane

0.01 0.01 0.01 0.02 0.03 0.01

0.30 0.01 0.19 0.01 0.02 0.01 0.01 0.01 0.06 0.03

0.01 0.01

0.02 0.06 0.01 0.01 0.01 0.06

0.01 0.01

0.01 0.02 0.01 0.05 0.02 0.01

0.02 0.02 0.01

0.01 0.04 0.01 0.05 0.01

0.01 0.03 0.08 0.01

0.02 0.01 0.01 0.04 0.01 0.09 0.01 0.05


1-ethyl- 1-methylcyclohexane cis,trans-1,2~-trimethylcyclohexane trans,trans-1,2,3-trimethylcyclohexane a-nonane trans-1 -ethyl-3-methylcyclohexane trans-I-ethyl-2-methylcyclohe~ne C, naphthenes 2,2-dimethyloctane isopropylcyclohexane cis-lzthyl-2-methylcyclohexane sec-butylcyclopentane 2.4-dimethyloctane Z,&dimcthyloctane 2,5-dimethyloctane n-prop ylcyclohexane n-butylcyclopentane 3,s-dimethylcctanc n-pmpylbemne 3,6-dimethyloaane I-methyl-3-cthylbenne I-methyl-4-ethylbenzene 2,3-dimethyloctane 1,3,5-trlnethylbenzene Ceth yloctane 5-methylnonane Cmethylnonane 1-methyl-2-ethylbenzene 2-metbylnonane 3-ethyloctane 3-me thylnonane 1,2,3~-tetramcthylcyclohexanc 1,2,3,4-tetramethylcyclohexane 1,4-dimethyl-2-ethylcyclohexane 1,2,4-trimethylbenzene cis-1 -methyl-3-pmpylcyclohexane cis-1.3-diethylcyclohexane trans-1-methyl-3-pmpylcyclohexane trans-l,3diethyIcyclohexane l-ethyl-2,3-dimethylcyclohexane isobutylbenzene cis-1-methyl-4-pmpylcyclohexane sec-butylbenzene n-decane 1,3,S-trimethylbenzene 1,2,3,4-tetramethylcyclohexane trans-1.3-diethylcyclohexane 1,2,3-trimethylbenzene I-methyl-3-isopropylbcnzcoe I-methyl-4-isopropylbenzcne I-methyl-2-pmpylbenzene 2J-dihydroindene sec-butylcyclohexane 1-methyl-2-isopropylbemene butylcyclohexane 1,3-diethylbenzene trans-1-methyl-4-t-butylcyclohexane I-methyl-3-n-pmpylbenzene I-methyl-4-n-pmp ylbenzene 1,4-diethylbenzene n-butylbenzene 1,3-dimethyl-S-cthylbcnzene 1,2-diethylbcnzene I-methyl-2-n-pmpylbenzene cis-1-methyl-4-t-butylcyclohexane 5-methyldecane 4methyldecane 2-methyldecane 1,4-dimethyl-2-ethylbenzene 1,3-dimethyl-4-ethylbeazene 3-methyldecane 1,2-dimethyl-4-ethylbenzene 1,3-dimethyl-2-ethylbenzene

0.12 0.01

0.01

0.02

0.02 0.01

0.02 0.02 0.02 0.01 0.01 0.02

0.01 0.01 0.03

0.01 0.02

0.01

0.06 0.02 0.01

0.01 0.01 0.01

0.03 0.01

0.01

0.01 0.04

0.01 0.01 0.01 0.02 0.01 0.01 0.02 0.01

0.02 0.06 0.03 0.02 0.02 0.03 0.03 0.02 0.02 0.01

0.01 0.01 0.01 0.48 0.07 0.02 0.35 0.07 0.04 0.02

0.05 0.18 0.03 0.17 0.05 0.01 0.04 0.10 0.04

0.08 0.06 0.01 0.05 0.13 0.07 0.05 0.05 0.17 0.01 0.04 0.01 0.03 0.08 0.12 0.02

0.04 0.04 0.02 0.01 0.75

0.02 0.02 0.01 0.02 0.02 0.01 0.03 0.04 0.03 0.12 0.04 0.08 0.01

0.03 0.02 0.02 0.06 0.04 0.09

0.09 0.01 0.06 0.01 0.02

US 2003/0051988 A1

TABLE IIIcontinued

8 Mar. 20,2003

TABLE IIIcontinued

Before Treatment After Treatment (weight %) (weight 96)

tricyclodecane I-methylindan 1,2-dimethyl-J-cthylbemenc n-undecane 1,2,4,5-tetramethylbenzene 1,2,3,5-tetramethylbenzene C,, unidentified 4-methylindan 5-methylhdan 1,2,3,4-tetramethylbenzene 2-methylindan tetralin 6-meth ylundecane 5-meth ylundecane 4-meth ylundecane 3-methylundecane 2-meth ylundccane naphthalene naphthalene3-methyludecane C,, aromatics ndodecane dodecanes 2-methylnaphthalene 1-methylnaphthalene tridecanes n-tridecane tetradecanes n-tetradeane pentadecanes n-pentadecanes hexadecanes n-hexadecane heptadecanes n-heptadccanes

0.03 0.04 0.01 0.03 0.02 0.63 0.39 0.02 0.01 0.05 0.03 0.10 0.39 0.04 0.02 0.03 0.02 0.07 0.03 0.02 0.01 0.01 0.03 0.05 0.02 0.06 0.04 0.05

0.12 0.05 0.13 0.05 0.45 0.54 0.91 0.40 0.50 0.58 1.19 0.81 3.30 2.55 2.83 1.00 6.95 5.01 4.47 1.63 9.55 6.52 5.30 2.46

10.20 7.20 3.57 2.43

10.61 8.44 3.60 3.13


pristane octadecanes n-octadecanc phytane nonadecanes a-nonadecane eicosanes n-eicosane heneicosanes docosanes tricosanes tetramsanes pentacosanes

unidentified

Molecular Weight of Sample Molecular Weight of C, Plus Density of Sample Density of C,, Plus

1.28 7.52 1.97 0.83 5.85 1.77 5.63 0.97 4.30 2.14 0.50 0.04 0.01

Total: 100.00 220.24 220.24

0.8245 0.8245

1.78 7.46 2.71 1.46 7.20 2.79 7.14 2.71 7.35 5.74 3.30 1.18 0.10

0.16

100.00 229.13 230.24

0.8680 0.8280

EXAMPLE 2

[0054] Using the same equipment and procedures as Example 1, four fuels were treated in accordance with the invention. The fuels were straight-run diesel, feed-rack diesel, light cycle oil, and a 70/30 (by volume) blend of straight-run diesel and light cycle oil. Various properties and analytical data, obtained by conventional methods widely used in the industry, are listed in Table IV below.

TABLE IV

Comparisons Before (B) and After (A) Treatment for Four Different Fuels (Treatment Includes Solvent Extraction)

70/30 Vol. Ratio

(Indus- Straight Run try Straight-Run Feed Rack DieseVLight

Specifi- Diesel Diesel Cycle Oil Light Cycle Oil

cation) B A B A B A B A

Gravity, API 30-40 32.8 40.5 33.9 38.2 33.0 38.2 21.4 42.6 Total sulfur, 15 2,500 5 228 64 228 64 5,572 8 PPm (4 Cetane Index 41 46.5 63 46 55 46 55 30.0 64.5 Copper strip 1A 1A Flash 160 172 230 124 Ramsbottom 0.35 0.15 0.29 0.07 0.29 0.07 0.38 0.05 Carbon

Middle Distillate nsts:

Pour Point (" E, Summer) Cloud Point (" E, Summer) Color Flash

Wscosity 4 2.9 3.4 2.9 3.4 3.5 3.7

10 0 25 -15 0 5 25 10 25

36 16 36 -4 12 8 34 20 34

Q.5 0.5 0.5 1.5 co.5 125 154 164 160 li2 196 180

US 2003/0051988 A1

TABLE IVcontinued

9 Mar. 20,2003

Comparisons Before (B) and After (A) Treatment for Four Different Fuels (Treatment Includes Solvent Wraction)

70/30 Vol. Ratio

(Indus- Straight Run try, Straight-Run Feed RacL DieseILight

S p e d - Diesel Diesel Cvcle Oil Light Cvcle Oil

cation) B A B A B A B A

Distillation, D-86 O E

Initial Boiling Point 5%

10% 20% 30% 40% 50% 60% 70% 80% 90% 95% End Point Recovery Residual LOSS P a r a h Monocyclo- paraffins Dicyclopam5ns Tric ycloparaffins

Para5ns Subtotal Naphthalenes Acenaphthenes Acenaphthalenes

Naphthalenes Subtotal Alkylbenzcnes IndanesfIktralins Indenes Tricyclic Aromatics

Aromatics Subtotal

Tolal

486 488 497 509 521 534 549 566 586 608 631 654 6 67 96.5 1.1 2.4

48.8 62.8 32.5 14.8 18.3 8.5

5.3 8.1 3.6 0.9 1.6 0.8

69.8 90.8 45.4 9.0 0.5 20.3 3.0 0.2 7.6 1.5 0.2 4.2

13.5 0.9 32.1 6.0 3.0 5.7 6.3 3.5 7.9 2.0 1.7 2.1 2.4 0.1 6.8

- - -

- - -

- - -

426 493 50s 517 528 540 554 5 68 584 601 625 644 653 96.5 1.8 1.7 36.1 12.6

8.2 1.5

58.4 12.1 4.7 2.6

19.4 6.2 9 3.1 3.9

-

-

- 16.7 8.3 22.5 22.2

100.0 100.0 1m.o 1m.o

[OOSS] The last 15 rows of Table IV demonstrate the effect of the invention in converting olefins to paraftins, saturating aromatics and opening rings. In particular, the increase in cycloparaffins shows saturation of aromatic rings, the lowering of the level of naphthalenes and the accompanying increase in indanes and tetralins demonstrate at least partial saturation of aromatics, the drop in acenaphthalenes and acenaphthenes and the rise in indanes and indenes demonstrates at least partial saturation and ring opening, the lowering of tricyclic aromatics (such as anthracenes and phenanthrenes) demonstrates at least partial saturation and ring opening, and the increase in alkybenzenes demonstrates ring opening. The “Total Sulfur‘‘ and “Cetane Index” data demonstrate the large reduction in sulfur level and the large improvement in cetane index.

EXAMPLE 3

[OO56] A reaction vessel was charged with 250 mL FCC light cycle oil, 125 mL of water, hydrogen peroxide at a concentration of 25 ppm to a pH of 2-4, one drop of a mixture of 90 parts straight-run diesel and 10 parts of extra

heavy mineral oil, and a mixture of tungsten flakes (17 g) and nickel pellets (17 g). The resulting mixture was heated to 180” E (82’ C.), then emulsified with a high-speed shear mixer at 2000 rpm for 5 seconds. An ultrasound probe, rated for 20 kHz and driven by a 750 W generator, was then placed in the solution and energized, operating at 40% intensity. After 30 seconds, the ultrasound probe was removed. The aqueous-organic mixture was then placed in a separatory funnel and allowed to separate for 5 minutes. Analytical results of the organic phase are shown in Table V

TABLE V

Comarisons Before and After Treatmen1 for Light Cvcle Oil

Before After Ultrasound Ultmsound

Gravity, API Cetane Index Total Sulfur, ppm

22.6 27.3 34.5 39.1

7073 3917

US 2003/005 1988 A1 10

Mar. 20,2003

TABLE V-continued

Comparisons Before and After Treatment for Light Cvde Oil

Before After Ultrasound Ultrasound

Total Nitrogen, ppm Carbon, weight % (ASTM

Hydrogen, weight % ( A m

P a r a b and Aromatics

D-5291)

D-5291)

JASTM D-2549):

Acyclic Parafis Monocycloparab Dicycloparafis Tric yc loparab Paraffins Subtotal Naphthalenes Acenaphthenes Acenaphthalenes Alkylbenzenes Indanes/l'etralins/lndenes Tricyclic Aromatics Aromatics Subtotal

721 88.24

10.57

32.1 9.8 4.3 0.8

46.2 16.1 6.8 3.6 7.5

12.6 6.4

53.0

415 87.01

12.0s

35.8 14.0 9.2 1.6

60.6 9.4 3.9 2.2 7.1

13.5 3.3

39.4

[0057] Like Table IV, Table V demonstrates the effect of the invention in converting olefins to paraffins, saturating aromatics and opening rings. The increase in cycloparfins shows saturation of aromatic rings, the reduction in naphthalenes and the accompanying increase in indanes and tetralins demonstrate at least partial saturation of aromatics, the reduction in acenaphthalenes and acenaphthenes and the increase in indanes and indenes demonstrates at least partial saturation and ring opening, the reduction in tricyclic aromatics (such as anthracenes and phenanthrenes) demonstrates at least partial saturation and ring opening, and the increase in alkybenzenes demonstrates ring opening. Also demonstrated are a reduction in nitrogen-bearing compounds and sulfur-bearing compounds, plus increases in API gravity, cetane index and hydrogen content.

EXAMPLE 4

[OOSS] A mixture was prepared by combining 5 gallons (19 L) of FCC light cycle oil, 2.5 gallons (9.5 L) of water containing 2 mL of heavy mineral oil, and hydrogen peroxide at a concentration of 25 ppm to a pH of 2-4. The mixture was passed through the continuous-flow ultrasound reactor of Example 1 under the conditions described in that example with a liquid hourly space velocity (LHSV) of 30 seconds. The separated organic phase was then desulfurized in a standard industry hydrodesulfurization (HDS) unit at the following conditions: temperature 650" F. (343' C.), pressure 500 psi (35 atmospheres), hydrogen circulation rate 1,000 SCF/bbl (standard cubic feet per barrel), and LHSV= 2. The API gravity, cetane index, total nitrogen, and total sulfur were determined for the initial untreated light cycle oil, the light cycle oil after ultrasound treatment, the light cycle oil after hydrodesulfurization but without ultrasound, and the light cycle oil having both been treated with ultrasound and undergone hydrodesulfurization. The results are listed in Table VI:

TABLE VI

Cornoarisions Before and After Treatmenl for Light Cycle Oil

After HDS Before HDS

Without With Without With Ultrasound Ultrasound Ultrasound Ultrasound

Gravity, MI 226 33.8 26.9 34.0 Cetane Index 34.5 47.5 39.7 47.6 Nitrogen, ppm 721 170 51.5 86 Sulfur, ppm 7073 1121 557 80 Hydrogen 450 100 usage SCF/bbl

[0059] The data in Table VI indicate that the ultrasound treatment increases both API gravity and cetane index, regardless of whether hydrodesulfurization has been performed, and decreases both sulfur and nitrogen in addition to the decreases in these elements that is achieved by hydrodesulfurization. Note also the reduction in hydrogen usage due to ultrasound.

EXAMPLE 5 [0060] A reaction mixture not containing hydrogen peroxide or any other hydroperoxide was prepared by combining:

[0061] 250 mL of a mixture of 50% FCC slurry oil

[0062] 125 mL of water, and

[0063] one drop of a mixture of 90 parts diesel and 10

[0064] The reaction mixture was heated to 180" F. (82" C.), then emulsified with a high-speed shear mixer at 2000 rpm for 5 seconds. An ultrasound probe was then placed in the reaction mixture, energized for 60 seconds and removed. The reaction mixture was then allowed to separated for ten minutes in a separatory funnel. The aqueous phase was removed from the bottom of the funnel and the oil phase was recovered and retreated three times with ultrasound in the same manner, each treatment followed by phase separation and combining of the oil phase with fresh water. The laboratory analyses of the starting material and the fourth- run product (exclusive of the kerosene) are listed in Table VII.

and 50% 1000-psi-hydrotreated kerosene,

parts heavy mineral oil surfactant (by volume).

TABLE VI1

Compakons Before and After Treatmenl for FCC Slurrv Oil

Starting 4th Kun Material Product

Gravity, API 4.8 31.2

Total Sulfur, ppm 11,380 2,252 Bromine Number 14 2 Paraffins and Aromatic4 (ASK4 D-2549):

Acyclic Para5ns 9.4 45.8 Monoc ycloparafis 9.9 16.9

Tric ycloparaffins 1.8 1.4

Total Nitrogen, ppm 2,048 500

Dicycloparafis 7 10.2

Akylbenzenes 15.3 7.5

US 2003/0051988 A1 11

TABLE VII-continued

Mar. 20,2003

TABLE VIII-continued

Comparisons Before and After Treatment for FCC Slum, Oil

Starting 4th Run Material Product

Comparisons Before and After Treatment for Coker Gas Oil


Indanesmtralins/Indenes 21.4 11.8 Naphthalenes 16.2 2.6 Acenap hthenes 8 1 Acenaphthalenes 4.4 0.8 Tricyclic Aromatics 15.2 2 Distillation D 2887 90% Point E) 900 739

[0065] Of particular significance in Table VI1 are the reduction in sulfur and nitrogen levels, the increase in cycloparaffins resulting from saturation of aromatic rings, the reduction in the distillation temperature of the 90% distillation point, and the increase in API gravity.

EXAMPLE 6

[0066] A reaction mixture not containing hydrogen peroxide or any other hydroperoxide was prepared by combining:

[0067] 250 mL of a mixture of 50% coker gas oil and

[0068] 125 mL of water, and

[0069] one drop of a mixture of 90 parts diesel and 10

[0070] The reaction mixture was heated to 180" E (82" C.), then emulsified with a high-speed shear mixer at 2000 rpm for 5 seconds. An ultrasound probe was then placed in the reaction mixture, energized for 60 seconds and removed. The reaction mixture was then allowed to separated for ten minutes in a separatory funnel. The aqueous phase was removed from the bottom of the funnel and the oil phase was recovered and retreated three times with ultrasound in the same manner, each treatment followed by phase separation and combining of the oil phase with fresh water. The laboratory analyses of the starting material and the fourth- run product (exclusive of the kerosene) are listed in Table VIII.

50% 1000-psi-hydrotreated kerosene,


TABLE VI11


Starting 4thRun Material Product

Gravity, API Total Nitrogen, pprn 'Ibtal Sulfur, ppm Bromine Number Pour Point (" F.) Para& and Aromatics ( A m D-2549):

Acyclic Paraflins Monocycloparaffins Dicycloparafis Tricycloparaffins Akylbenzenes Indanesmtralinsnndenes Naphthalenes Acenaphthenes Acenaphthalenes

13.0 33.1 3.514 976

36,920 10,860 10 2 97 10

23.6 46.4 8.7 16.1 5.4 9.4 1.2 1.2

15.1 9.1 20.0 12.0

9.6 2.4 4.4 0.8 4.2 1

Tricyclic Aromatics 7.8 1.6 Distillation D 2887 90% Point (" E) 899 744

[0071] Of particular significance in Table VI11 are the reduction in sulfur, nitrogen, bromine number (an indicator of the levels of olefins and diolefins), the sharp drop in pour point, the sharp increase in API gravity, and the increase in cycloparaffins resulting from saturation of aromatic rings.

EXAMPLE 7 [0072] A reaction mixture not containing hydrogen peroxide or any other hydroperoxide was prepared by combin-

[0073] 250 mL of a mixture of 50% coker distillate, [0074] 125 mL of water, and [0075] one drop of a mixture of 90 parts diesel and 10

[0076] The reaction mixture was heated to 180" F. (82" C.), then emulsified with a high-speed shear mixer at 2000 rpm for 5 seconds. An ultrasound probe was then placed in the reaction mixture, energized for 30 seconds and removed. The reaction mixture was then allowed to separated for ten minutes in a separatory funnel. The aqueous phase was removed from the bottom of the funnel and the oil phase was recovered and retreated three times with ultrasound in the same manner, each treatment followed by phase separation and combining of the oil phase with fresh water. The laboratory analyses of the starting material and the fourth- run product (exclusive of the kerosene) are listed in Table IX.

ing:


TABLE IX



Gravity, API Cetane index Total Sulfur, pprn Total Nitrogen, ppm Bromine Number Pour Point (" E) Paraffins and Aromatics ( A m D-2549):

Acyclic Para& Monocycloparaffins Dicycloparafis Tricycloparafis Alkylbenzenes Indanesmtralins/Indenes Naphthalenes Acenaphthenes Acenaphthalens Tricyclic Aromatics

30.0 42.8

26,900 1,057

28 10

36.4 13.0 9.4 1.9

11.9 12.7

6.6 2.9 2.0 3.2

32.8 44.7

8,960 440

9 -10

38.5 16.1 12.6 2.2 8.5

13.7 4.1 1.8 1.2 1.3

[0077] Of particular significance in Table IX are the reduction in sulfur, nitrogen, aromatics, and bromine number, and the increases in API gravity and cetane index.

US 2003/005 1988 A1 12

Mar. 20,2003

[0078] The foregoing is offered primarily for purposes of illustration. Further variations in the materials, additives, operating conditions, and equipment that are still within the scope of the invention will be readily apparent to those skilled in the art.

We claim: 1. A process for treating a crude oil fraction to reduce

levels therein of aromatics, olefins, sulfur-bearing compounds, and nitrogen-bearing compounds, and to raise the API gravity thereof, said process comprising:

(a) combining said crude oil fraction with an aqueous

(b) exposing said emulsion to ultrasound;

(c) separating said emulsion after said ultrasound expo-

(d) recovering said organic phase from said aqueous

2. A process in accordance with claim 1 in which no hydroperoxide is added to said crude oil fraction or incorporated into said aqueous liquid in forming said emulsion.

3. Aprocess in accordance with claim 1 in which step (a) comprises incorporating a hydroperoxide into said emulsion.

4. A process in accordance with claim 1 in which said crude oil fraction is a fraction boiling within the diesel range.

5. A process in accordance with claim 4 in which said crude oil fraction is a member selected from the group consisting of fluid catalytic cracking (FCC) cycle oil fractions, coker distillate fractions, straight run diesel fractions, and blends thereof.

6. A process in accordance with claim 1 in which said crude oil fraction is a fraction boiling within the gas oil range.

7. A process in accordance with claim 6 in which said crude oil fraction is a member selected from the group consisting of FCC cycle oil, FCC slurry oil, light gas oil, heavy gas oil, and coker gas oil.

8. A process in accordance with claim 1 in which said crude oil fraction is a member selected from the group consisting of gasoline, jet fuel, straight-run diesel, blends of straight-run diesel and FCC light cycle oil, and petroleum residuum-based fuel oils. 9. A process in accordance with claim 1 in which said

ultrasound exposure is at a sufficient intensity and time to cause an increase in API gravity by an amount ranging from 2 to 30 API units.

10. A process in accordance with claim 1 in which said ultrasound exposure is at a sufficient intensity and time to cause an increase in API gravity by an amount ranging from 7 to 25 API units.

ll. A process in accordance with claim 4 in which said ultrasound exposure is at a sufficient intensity and time to raise the cetane index of said diesel range crude oil fraction by an amount ranging from 1 to 40 units. 12. A process in accordance with claim 4 in which said

ultrasound exposure is at a sufficient intensity and time to raise the cetane index of said diesel range crude oil fraction by an amount ranging from 4 to 20 units.

13. Aprocess in accordance with claim 1 in which step (b) is perfoqned at an ultrasound intensity of from about 10 watts/cm to about 3000 watts/cm2.

liquid to form an emulsion;

sure into aqueous and organic phases; and

phase.

14. Aprocess in accordance with claim 1 in which step (b) is perfoqned at an ultrasound intensity of from about 50 watts/cm to about 1500 watts/cm2. 15. Aprocess in accordance with claim 1 in which step (b)

is performed at an ultrasound exposure time of from about 1 second to about 30 minutes. 16. Aprocess in accordance with claim 1 in which step (b)

is performed at an ultrasound exposure time of from about 15 seconds to about 1 minute.

17. A process in accordance with claim 1 further comprising contacting said emulsion with a transition metal catalyst during step (b).

18. A process in accordance with claim 17 in which said transition metal catalyst is a member selected from the group consisting of metals having atomic numbers of 21 through 29,39 through 47, and 57 through 79. 19. A process in accordance with claim 17 in which said

transition metal catalyst is a member selected from the group consisting of nickel, silver, tungsten, cobalt, molybdenum, and combinations thereof.

20. A process in accordance with claim 17 in which said transition metal catalyst is a member selected from the group consisting of nickel, silver, tungsten, and combinations thereof.

21.Aprocess in accordance with claim 1 in which step (a) comprises combining said crude oil fraction and said aqueous fluid at a (crude oil fraction):(aqueous fluid) volume ratio of from about 8:l to about 1:s.

22.Aprocess in accordance with claim 1 in which step (a) comprises combining said crude oil fraction and said aqueous fluid at a (crude oil fraction):(aqueous fluid) volume ratio of from about 5:l to about 1:l.

23.Aprocess in accordance with claim 1 in which step (a) comprises combining said crude oil fraction and said aqueous fluid at a (crude oil fraction):(aqueous fluid) volume ratio of from about 4:l to about 2:l.

24. A process in accordance with claim 3 in which said hydroperoxide constitutes from about 10 ppm to about 100 ppm by weight of said aqueous liquid.

25. A process in accordance with claim 3 in which said hydroperoxide constitutes from about 15 ppm to about 50 ppm by weight of said aqueous liquid.

26. A process in accordance with claim 1 in which said hydroperoxide is hydrogen peroxide.

27. A process in accordance with claim 1 in which said aqueous liquid is an aqueous solution of hydrogen peroxide at a concentration of from about 15 ppm to about 50 ppm by weight.

28. A process in accordance with claim 1 further comprising preheating said crude oil fraction to a temperature of from about 20' C. to about 200' C. prior to step (b).

29. A process in accordance with claim 1 further comprising preheating said crude oil fraction to a temperature of from about 40' C. to about 125' C. prior to step (b).

30. Aprocess in accordance with claim 1 in which step (b) is performed at a pressure of less than 400 psia.

31.Aprocess in accordance with claim 1 in which step (b) is performed at a pressure of less than 50 psia.

32. Aprocess in accordance with claim 1 in which step (b) is performed at a pressure within the range of from about atmospheric pressure to about 50 psia.

33. A process in accordance with claim 1 further comprising preheating said crude oil fraction to a temperature of from about 40' C. to about 125" C. prior to step (b).

US 2003/0051988 A1 13

Mar. 20,2003

34. A process in accordance with claim 1 further comprising incorporating an emulsion stabilizer in said emulsion.

35. A process in accordance with claim 34 in which said emulsion stabilizer is a mixture of aliphatic C,,-C,, hydrocarbons having a specific gravity of at least about 0.82.

36. A process in accordance with claim 35 in which said mixture of aliphatic C,,-C,, hydrocarbons has a specific gravity of at least about 0.85.

37. A process in accordance with claim 35 in which said mixture of aliphatic C,,-C,, hydrocarbons is heavy mineral oil.

38. A process for treating an organic liquid comprising fused-ring aromatic compounds and olefinic compounds to lower the density of said organic liquid, said process comprising:

42. A process in accordance with claim 41 in which said transition metal catalyst is a member selected from the group consisting of nickel, silver, tungsten, and combinations thereof.

43. Aprocess in accordance with claim 1 in which step (b) is performed in batchwise manner.

44. Aprocess in accordance with claim 1 in which step (b) is performed in continuous-flow manner.

45. Aprocess for removing organic sulfur from a crude oil fraction, said process comprising:

(a) combining said crude oil fraction with an aqueous

(b) exposing said emulsion to ultrasound; (c) separating said emulsion after said ultrasound expo-

sure into aqueous and organic phases;

liquid to form an emulsion;

(b) subjecting said emulsion to ultrasound at a sufficient intensity and for a sufficient time to open fused rings in fused-ring aromatic compounds in said organic liquid and to convert olefinic compounds in said organic liquid to paraffins;

(d) permitting said emulsion to separate into aqueous and organic phases of which said organic phase comprises said organic liquid; and

(e) isolating said organic liquid from said aqueous phase. 39. A process in accordance with claim 38 in which said

aqueous liquid is an aqueous solution of a hydroperoxide at a concentration of from about 10 ppm to about 100 ppm by weight. 40. A process in accordance with claim 38 in which said

aqueous liquid is an aqueous solution of hydrogen peroxide at a concentration of from about 15 ppm to about 50 ppm by weight.

41. A process in accordance with claim 38 further comprising contacting said emulsion with a transition metal catalyst while subjecting said emulsion to said ultrasound in step (b).

(e) contacting said organic phase with hydrogen gas under conditions causing conversion of said organic sulfur to sulfur dioxide by hydrodesulfurization.

46. A process in accordance with claim 45 in which no hydroperoxide is added to said crude oil fraction or incorporated into said aqueous liquid in forming said emulsion.

47. A process in accordance with claim 45 in which said crude oil fraction is a fraction boiling within the diesel range.

48. A process in accordance with claim 47 in which said crude oil fraction is a member selected from the group consisting of fluid catalytic cracking (FCC) cycle oil fractions, coker distillate fractions, straight run diesel fractions, and blends thereof.

49. A process in accordance with claim 45 in which said crude oil fraction is a fraction boiling within the gas oil range.

50. A process in accordance with claim 49 in which said crude oil fraction is a member selected from the group consisting of FCC cycle oil, FCC slurry oil, light gas oil, heavy gas oil, and coker gas oil.

* * * * *

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Attorney Docket No. 020839000300

First. lnvenfor Gunnerman, Rudolf W.

\

~ i t / ~ TREATMENT OF CRUDE OIL FRACTIONS, FOSSIL FUELS, AND PRODUCTS THEREOF WITH ULTRASOUND

Express Mail Label No. EL 827035994 US o j

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SUBTOTAL (1) 107101 2. EXTRA CLAIM FEES

I Attorney Docket No. I 020839000300 1

%ai Claims dependent laims

uitipie ependent

Large Fee. Code 103 102 104

109

110

-20" n I 3 I -3"

Entity Small Fee Fee ($1 Code 18 203 80 202 270 204

80 209

18 210

Extra Fee from Fee Claims Paid

= X F , = [$540

= \o] x p q = jloj mm xU=U

Entity

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4o

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.ADDITIONAL FEES

~

FEE CALCULATION (continued)

irge e )de 15 17

19

17 I2

13

15 (6

17 18

28 19 20 21

38

40 41 42 43 44 22

23

I26

581

I46

149

179

169

Entity Fee (8 130 50

130 2,520 920'

1,840'

110 390

890 1,390

1,890 310 310 . 270

1,510

110 1,240 1,240 440 600 130

50

180

40

710

710

710

900

Small Entlty Fee Fee Code (S) 205 65 Surcharge - late filing fee or oath '

227 25 Surcharge - late provisional filing fee

139 130 Non-English specification 147 2,520 For filing a request for reexamination 112 920' Requesting publication of SIR prior to

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or cover sheet.

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May 22,2001 Regular Utility

TREATMENT OF CRUDE OIL FRACTIONS, FOSSIL FUELS, AND PRODUCTS THEREOF WITH ULTRASOUND

No No No No No

020839-0003OOUS

Inventor us Full Capacity Rudolf W. Gunnerman Reno NV 6601 Lakeside Drive Reno NV 8951 1

Page 1 Initial 5/22/01

- . .. . ... -. . . ...

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!% I% i""? j;d. Correspondence Information i E.

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Attorney Docket No.: 20839-0003OOUS '7

PATENT APPLICATION

TREATMENT OF CRUDE OIL FRACTIONS, FOSSIL FUELS, AND PRODUCTS THEREOF

i WITH ULTRASOUND

Inventors: RUDOLF W. GUNNERMAN, a citizen of the United States of America, residing at: 6601 Lakeside Drive, Reno, Nevada 895 11

PAUL S. MOOTE, a citizen of the United States of America, residing at: 2440 Lower Lando Lane, Park City, Utah 84098

MARK T. CULLEN a citizen of the United States of America, residing at: 5605 Brookmeadow Lane, Reno, Nevada 895 11

Assignee; SulphCo, Inc. 1650 Meadowood Lane Reno, Nevada 89502, a corporation of the state of Nevada

Prepared by: M. Henry Heines TOWNSEND and TOWNSEND and CREW LLP Two Embarcadero Center, st" Floor San Francisco, California 941 11-3834 Tel: 415-576-0200

AS FILED IN U.S.P.T.0. -May 22,2001

.I .. , ' - " .-----

PATENT Attorney Docket No.: 20839-0003OOUS

5

20

25

TREATMENT OF CRUDE OIL FRACTIONS, FOSSIL FUELS, AND PRODUCTS THEREOF

WITH ULTRASOUND

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention resides in the field of chemical processes for the treatment of

crude oil fractions and the various types of products derived and obtained from these sources.

In particular, this invention addresses reformation processes as ring-opening reactions and the

saturation of double bonds, to upgrade fossil fuels and convert organic products to forms that

will improve their performance and expand their utility. This invention also resides in the

removal of SUI fur-containing compounds, nitrogen-containing compounds, and other

undesirable components from petroleum and petroleum-based fuels.

2. Description of the Prior Art

Fossil fuels are the largest and most widely used source of power in the world,

offering high efficiency, proven performance, and relatively low prices. There are many

different types of fossil fuels, ranging from petroleum fractions to coal, tar sands, and shale

oil, with uses ranging from consumer uses such as automotive engines and home heating to

commercial uses such as boilers, furnaces, smelting units, and power plants.

Fossil fuels and other crude oil fractions and products derived from natural

sources contain a vast array of hydrocarbons differing widely in molecular weight, boiling

and melting points, reactivity, and ease of processing. Many industrial processes have been

developed to upgrade these materials by removing, diluting, or converting the heavier

components or those that tend to polymerize or otherwise solidify, notably the olefins,

aromatics, and fused-ring compounds such as naphthalenes, indanes and indenes,

anthracenes, and phenanthracenes. A common means of effecting the conversion of these

compounds is saturation by hydrogenation across double bonds.

For fossil fuels in particular, a growing concern is the need to remove sulfiir

compounds. Sulfur from sulfur compounds causes corrosion in pipeline, pumping, and

refining equipment, the poisoning of catalysts used in the refining and combustion of fossil

fuels, and the premature failure of combustion engines. Sulfur poiSons - the catalytic

converters used in diesel-powered trucks and buses to control the emissions of oxides of

nihogen (NO,). Sulfur also causes an increase in particulate (soot) emissions from trucks and

buses by degrading the soot traps used on these vehicles. The burning of sulfur-containing

file1 produces sulfur dioxide which enters the atmosphere as acid rain, inflicting harm on

agriculture and wildlife, and causing hazards to human health.

The Clean Air Act of 1964 and its various amendments have imposed sulfur

emission standards that are difficult and expensive to meet. Pursuant to the Act, the United

States Environmental Protection Agency has set an upper limit of 15 parts per million by

weight (ppmw) on the sulfur content of diesel fuel, effective in mid-2006. This is a severe

reduction from the standard of 500 ppmw in effect in the year 2000. For reformulated

gasoline, the standard of 300 ppmw in the year 2000 has been lowered to 30 ppmw, effective

January 1,2004.'- Similar changes have been enacted in the European Union, which will

enforce a limit of 50 ppmw sulfur for both gasoline and diesel fuel in the year 2005. The

treatment of fuels to achieve sulfur emissions low enough to meet these requirements is

difficult and expensive, and the increase in fuel prices that this causes will have a major

influence on the world economy.

The principal method of fossil fuel desulfurization in the prior art is

hydrodesulfurization, i.e., the reaction between the fossil fuel and hydrogen gas at elevated

temperature and pressure in the presence of a catalyst. This causes the reduction of organic

sulfur to gaseous HZS, which is then oxidized to elemental sulfur by the Claus process. A

considerable amount of unreacted H2S remains however, with its attendant health hazards. A

further limitation of hydrodesulfurization is that it is not equally effective in removing all

sulfur-bearing compounds. Mercaptans, thioethers, and disulfides, for example, are easily

broken down and removed by the process, while aromatic sulfiir compounds, cyclic sulfur

compounds, and condensed multicyclic sulfur compounds are less responsive to the process.

Thiophene, benzothiophene, dibenzothiophene, other condensed-ring thiophenes, and

substituted versions of these compounds, which account for as much as 40% of the total

\

sulfur content of crude oils from the Middle East and 70% of the sulfur content of West

Texas crude oil, are particularly refractory to hydrodesulhrization.

In addition to sulfur-bearing compounds, nitrogen-bearing compounds are also

sought to be removed from fossil fuels, since these compounds tend to poison the acidic

components of the hydrocracking catalysts used in the refinery. The removal of nitrogen-

bearing compounds is achieved by hydrodenitrogenation, which is a hydrogen treatment

2

performed in the presence of metal sulfide catalysts. Both hydrodesulfurization and

5

10

25

30

...-

hydrodenitrogenation require expensive catalysts as well as high temperatures (typically

400°F to 850”F, which is equivaleni to 204°C to 254°C) and pressures (typically 50 psi to

3,500 psi). These processes require a source of hydrogen or an on-site hydrogen production

unit, which entails high capital expenditures and operating costs. In both of these processes,

there is also a risk of hydrogen leaking from the reactor.

Of possible relevance to this invention are co-pending United States Patent

Application No. 09/676,260, entitled “Oxidative Desulfurization of Fossil Fuels With

Ultrasound,” Teh Fu Yen, et al., inventors, filed September 28,2000, and co-pending United

States Patent Application No. 09/8 12,390, entitled “Continuous Process for Oxidative

Desulfurization of Fossil Fuels With Ultrasound and Products Thereof,” Rudolf W.

Gunnerman, inventor, filed March 29,2001. Both of these applications are incorporated

herein by reference in their entirety for all legal purposes capable of being served thereby.

SUMMARY OF THE INVENTION

It has now been discovered that fossil fuels, crude oil fractions, and many of

the components that are derived from these sources can undergo a variety of beneficial

conversions and be upgraded in a variety of ways by a process that applies ultrasound to these

materials in a multiphase reaction medium. The organic material is combined with an

aqueous phase to form an emulsion, placing the phases in intimate contact during the

exposure to ultrasound. Hydrogen gas is not required, nor are the high temperature and

pressure that are commonly needed for hydrogenations of the prior art. In certain

embodiments of the invention, the ultrasound treatment is performed in the ,presence of a

hydroperoxide, and in certain embodiments as well, a transition metal catalyst is used. One

of the surprising discoveries associated with certain embodiments of this invention, however,

is that the conversions achieved by this invention can be achieved without the inclusion of a

hydroperoxide in the reaction mixture.

Included among the conversions achieved by the present invention are the

removal of organic sulfur compounds, the removal of organic nitrogen compounds, the

saturation of double bonds and aromatic rings, and the opening of rings in fused-ring

structures. The API gravities of fossil fuels and crude oil fractions are raised (Le., the

densities lowered) as a result of treatments in accordance with the invention. The invention

thus resides in part in the process of using ultrasound to achieve these conversions. The

3

. ... . . . . . -. . I . . . . . - - . . _. -. .. . . . . . . . . . .. - .- - .

invention further resides in processes for converting aromatics to cycloparaffins, and opening

one or more rings in a fused-ring structure, thereby for example converting naphthalenes to

monocyclic aromatics, anthracenes to naphthalenes, fused heterocyclic rings such as

benzothiophenes, dibenzothiophenes, benzofurans, quinolines, indoles, and the like to

substituted benzenes, acenaphthalenes and acenaphthenes to indanes and indenes, and

monocyclic aromatics to noncyclic structures. Further still, the invention resides in processes

for converting olefins to paraffins, and in processes for breaking carbon-carbon bonds,

carbon-sulfiir bonds, carbon-metal bonds, and carbon-nitrogen bonds.

In addition to raising the API gravity of a petroleum-based fuel, the invention

raises the cetane index of petroleum fractions and cracking products whose boiling points or

ranges are in the diesel range. The term "diesel range" is used herein in the industry sense to

denote the portion of crude oil that distills out after naphtha, and generally within the

temperature range of approximately 200°C (392°F) to 37OoC(698"F). Fractions and cracking

products whose boiling ranges are contained in this range as well as those that overlap with

this range to a majority extent are included. Examples of refinery fractions and streams

within the diesel range are fluid catalytic cracking (FCC) cycle oil fractions, coker distillate

fractions, straight run diemel fractions, and - ..-- blends. The invention also imparts other

beneficial changes such as a lowering of boiling points and a removal of components that are

detrimental to the performance of the fuel and those that affect refinery processes and

increase the cost of production of the fuel. Thus, for example, FCC cycle oils can be treated

in accordance with the invention to sharply reduce their aromatics content.

A further group of crude oil fractions for which the invention is particularly

useful are gas oils, which term is used herein as it is in the petroleum industry, to denote

liquid petroleum distillates that have higher boiling points than naphtha. The initial boiling

point may be as low as 400°F (2OO0C), but the preferred boiling range is about 500°F to

about 1100°F (approximately equal to 260°C to 595°C). Examples of fractions boiling

within this range are FCC slurry oil, light and heavy gas oils, so termed in view of their

different boiling points, and coker gas oils. All of the terms in this and the preceding

paragraph are used herein as they are in the petroleum art.

By virtue of the conversions that occur as a result of the process of this

invention, hydrocarbon streams experience changes in their cold flow properties, including

their pour points, cloud points, and freezing points. Sulfur compounds, nitrogen compounds,

and metal-containing compounds are also reduced, and the use of a process in accordance

4

with this invention significantly lessens the burden on conventional processes such as

hydrodesulfuization, hydrodenitrogenation, and hydrodemetallizatfon, which can therefore

be performed with greater effectiveness and efficiency. -~

These and other advantages, features, applications and embodiments of the

5 invention are made more apparent by the description that follows.

30

. . .‘2

DETAILED DESCFUPTION OF THE INVENTION AND SPECIFIC EMBODIMENTS

refinery products produced from crude oil, either by atmospheric distillation or vacuum

distillation, including fractions that have been treated by hydrocracking, catalytic cracking,

The term “liquid fossil fuel” is used herein to denote any carbonaceous liquid

that is derived from petroleum, coal, or any other naturally occurring material, as well as

processed fuels such as gas oils and products of fluid catalytic cracking units, hydrocracking

units, thermal cracking units, and cokers, and that is used to generate energy for any kind of

10

I

5

- .- . . - . - . - _ _ _ _ _ _ _ - . : a , . . x -‘Ti . . . - - . . . . - . - _-_ __i__ . . .. . . . . ._ __ . . . . .

. 5

10

25

cracked naphtha, light catalytically cracked naphtha, heavy thermally . cracked naphtha,

reformed naphtha, alkylate naphtha,’kerosene, hydrotreated kerosene, gasoline and light

straight-run gasoline, straight-run diesel, atmospheric gas oil, light vacuum gas oil, heavy

vacuum gas oil, residuum, vacuum residuum, light coker gasoline, coker distillate, FCC (fluid

catalytic cracker) cycle oil, and FCC slurry oil.

The term “fused-ring aromatic compound” is used herein to denote

compounds containing two or more fused rings at least one of whch is a phenyl ring, with or

without substituents, and including compounds in which all fused rings are phenyl or

hydrocarbyl rings as well as compounds in which one or more of the fused rings are

heterocyclic rings. Examples are substituted and unsubstituted naphthalenes, anthracenes, .

benzothiophenes, dibenzothiophenes, benzofurans, quinolines, and indoles.

The term “olefins” is used herein to denote hydrocarbons, primarily those r

containing two or more carbon atoms and one or more double bonds.

Fossil fuels and crude oil fractions treated by ultrasound in accordance with

this invention have significantly improved properties relative to the same materials prior to

treatment, these improvements rendering the products unique and improving their usefulness

as fbels. One of these properties is the API gravity. The term “API gravity” is used herein as

it is among those skilled in the art of petroleum and petroleum-derived fuels. In general, the

term represents a scale of measurement adopted by the American Petroleum Institute, the

values on the scale increasing as specific gravity values decrease. Thus, a relatively high API

gravity means a relatively low density. The API gravity scale extends from -20.0 (equivalent

to a specific gravity of 1.2691) to 100.0 (equivalent to a specific gravity of 0.61 12). b

To illustrate the range of applicability of the present invention and its effect on

liquid fossil fuels and crude oil fractions, Table I below lists unit streams within the diesel

boiling range and unit streams within the gas oil boiling range, with a range of values for

various parameters for stream, and a range of how much each parameter can be reduced or

increased by the ultrasound treatment of the present invention.

6

. .

FCC Cycle Oil 15-30

(+) 3-30 25-40

(+) 1-30 30-95

0- 10,000 (-) 1 - (-) 50

(-) 1-90

TABLE I Refinery Unit Streams: Parameter Ranges and Effects-iif Invention:

(+) Denotes-Increase; (-) Denotes Reduction

Crude Straight- Coker Distillates Run Diesels 27-45 27-45

(+) 1-15 (+) 0-15 30-60 28-40

(+) 1-20 (+) 1-25 0-50 30-95

(-) 1 - (-) 25 (-) 1 - (-) 40 0-10,000 0- 10,000

(-) 1-90 (-) 1-90

Diesel Boiling Range Materials (Boiling Range 300-750°F, 150-400°C):

(-) 1-95 0.05-5

Unit Stream

(-) 1-95 (-) 1-95 0.01-5 0.05-5

APT

(-) 5-95

10-40 (-) 5-50

10-45 (-) 5-50

change Cetane index

change Aromatics (weight %)

change Nitrogen (ppm as N)

change (as % of initial value)

(-) 5-95 (-) 5-95

(-10)-40 0-30 (-) 5-50 (-) 5-50

(-1 0)-45 0-3 5 (-) 5-50 (-) 5-50

Bromine number

Sulfur (weight % as S) chqnge (as %)

change (as % of initial

Unit Stream -+ API

value) '

change ( O F )

change ( O F )

Pour Point ("F)

Cloud Point ( O F )

Oil Crude Gas oils Coker Gas oils (-15)-25 5-35 0-30

change Aromatics (weight %)

change Nitrogen (ppm as N)

change (as % of initial value)

(Conradson) (%) Change Carbon Residue

Sulfur (weight % as S ) change (as % of initial value)

5-40 I 0-5 I 10-50 I

(+) 1-40 (+) 1-25 (+) 1-30 30-95 0-50 20-80

(-) 1 - (-) 80 (-) 1 - (-) 40 " (-) 1 - (-) 50

0-1 0,000 0-10,000 0-1 0,000 (-) 1-90 (-) 1-90 (-) 1-90

(-) 1-90 (-) 1-90 (-) 1-90

0.05-7 0.01-7 0.05-7 (-) 5-95 (-) 5-95 (-) 5-95

Pour Point ( O F ) change ( O F )

50-150 50-150 50-150 (-) 5-100 (-) 5-100 (-) 5-100

Gas Oil Boiling Range Materials (Boiling Range 500-1 10O0F, 260-595°C):

I FCCCycle I I ' I

The ultrasound process of the present invention is applicable to any liquid

5 fossil fuels, preferably those with API gravities within the range of -10 to 50, and most

preferably within the range of 0 to 45. For materials boiling in the diesel range, the process

7

of the invention is preferably performed in such a manner that the starting materials are

converted to products with API gravities within the range of 37.5 to:4.5. FCC cycle oils are

preferably converted to products with API gravities within the range of 30 to 50. For liquid

fossil fuels in general, the process’of the invention is preferably performed to achieve an

.increase in API gravity by an amount ranging from 2 to 30 MI gravity units, and more

preferably by’an amount ranging from 7 to 25 units. Alternatively stated, the invention

preferably increases the API gravity from below 20 to above 35.

- .. . -. . .

As stated above, fossil fuels boiling within the diesel range that are treated in

accordance with this invention experience an improvement in their cetane index (also referred

to in the art as the “cetane number”) upon being treated in accordance with this invention.

Diesel fuels to which the invention is of particular interest in this regard are those having a

cetane index greater than 40, preferably within the range of 45 to 75, and most preferably

within the range of 50 to 65. The improvement in cetane index can also be expressed in

terms of an increase over that of the material prior to ultrasound treatment. 1n.certain

preferred embodiments, the increase is by an amount ranging from 1 to 40 cetane index units,

and more preferably by an amount ranging from 4 to 20 units. As a still further means of ’.

expression, the.invention preferably increases the cetane index from below 47 to about 50.

This invention can be used to produce diesel fuels having a cetane index of greater than 50;0,

or preferably greater than 60.0. In terms of ranges, the invention is capable of producing

diesel fuels having a cetane index of from about 50.0 to about 80.0, and preferably from

about 60.0 to about 70.0. The cetane index or number has the same meaning in this

specification and the appended claims that it has among those skilled in the art of automotive

fuels. v

r

As noted above, certain embodiments of the inventiQn.inunl~e-the_inc!~s~on of

a hydroperoxide in the reaction mixture. The term “hydroperoxide” is used herein to denote a

compound of the molecular structure

. . . . ... .. .~ . ... .

.~ ..., -..\

(R-0-0-H //’’ ‘) . ...___ ~. . ’.-

in which R represents either a hydrogen atom or an organic or inorganic group. Examples of

hydroperoxides in which R is an organic group are water-soluble hydroperoxides such as

methyl hydroperoxide, ethyl hydroperoxide, isopropyl hydroperoxide, n-butyl hydroperoxide,

sec-butyl hydroperoxide, tert-butyl hydroperoxide, 2-methoxy-2-propyl hydroperoxide,

tert-amyl hydroperoxide, and cyclohexyl hydroperoxide. Examples of hydroperoxides in

which R is an inorganic group are peroxonitrous acid, peroxophosphoric acid, and

8

5

peroxosulfuric acid. Preferred hydroperoxides are hydrogen peroxide (in which R is a

hydrogen atom) and tertiary-alkyl peroxides, notably tert-butyl pero2de.

The aqueous fluid that is combined with the fossil fuel or other liquid organic _j .-..- .-- .... ,.-"- _..._

starting material in the processes of this invention may be-water or any aqueous soTuti?ny

The relative amounts of organicand aqueous phases may vary,'and although they may affect

the efficiency of the process or the ease of handling the fluids, the relative amounts are not

critical to this invention. In most cases, however, best results will be achieved when the

volume ratio of organic phase to aqueous phase is from about 8:l to about 1:5, preferably

.from about 5 : 1 to about 1 : 1, and most preferably from about 4: 1 to about 2: 1.

--.. ..._I_̂ __.c -_----* --.I>.

When a hydroperoxide is present, the amount of hydroperoxide relative to the

organic and aqueous phases can also be varied, and although the conversion rate and yield

may vary somewhat with the proportion of hydroperoxide, the actual proportion is not critical

to the invention,&d any excess amounts will be eliminated by the ultrasound. When the

hydroperoxide is added as a solute in the aqueous solution that is used as the aqueous phase,

best results are generally achieved with a hydroperoxide concentration of from about 10 ppm

to about 1.00 ppm by weight, and preferably from about 15 ppm to about 50 ppm by weight,

of the aqueous solution, particularly when the hydroperoxide is H202. Alternatively, when

the H202 amount is calculated as a component of the combined organic and aqueous phases,

best results will generally be achieved in most systems with an Hi02 concentration within the

range of from about 0.0003% to about 0.03% by volume (as H202), and preferably from

about 0.001% to about 0.01%, of the combined phases. For hydroperoxides other than H202,

the preferred concentrations will be those of equivalent molar amounts.

In certain embodiments of this invention as well, a surface active agent or

other emulsion stabilizer is included to stabilize the emulsion as the organic and aqueous

phases are being prepared for the ultrasound exposure. Certain petroleum fractions contain

surface active agents as naturally-occurring components of the fractions, and these agents

may serve by themselves to stabilize the emulsion. In other cases, synthetic or non-naturally-

occurring surface active agents can be added. Any of the wide variety of known materials

that are effective as emulsion stablizers can be used. Listings of these materials are available

McCutcheon's Volume 1: Emulsifiers & Detergents - 1999 North American Edition,

McCutcheon's Division, MC Publishing Co., Glen Rock, New Jersey, USA, and other

,published literature. Cationic, anionic and nonionic surfactants can be used. Preferred

cationic species are quaternary ammonium salts, quaternary phosphonium salts and crown

ethers. Examples of quaternary ammonium salts are tetrabutyl ammonium bromide,

. .

9

tetrabutyl ammonium hydrogen sulfate, tributylmethyl ammonium ’chloride, benzyltrimethyl

ammonium chloride, benzyltriethyl ammonium chloride, methyltricaprylyl ammonium

chloride, dodecyltrimethyl ammonium bromide, tetraoctyl ammonium bromide,

cetyltrimethyl ammonium chloride, and trimethyloctadecyl ammonium hydroxide.

Quaternary ammonium halides are useful in many systems, and the most preferred are

dodecyltrimethyl ammonium bromide and tetraoctyl ammonium bromide.

5

The preferred surface active agents are those that will promote the formation

of an emulsion between the organic and aqueous phases upon passing the liquids through a

common mixing pump, but that will spontaneously separate the product mixture into aqueous

and organic phases suitable for immediate separation by decantation or other simple phase

separation procedures. One class of surface active agents that will accomplish this is liquid

10

aliphatic C 5-C20 hydrocarbons and mixtures of such hydrocarbons, preferably those having a <’

25

30

specific gravity of at least about 0.82, and most preferably at least about 0.85. Examples of

hydrocarbon mixtures that meet this description and are particularly convenient for use and

readily available are mineral oils, preferably heavy or .extra heavy mineral oil. The terms

“mineral oil,” “heavy mineral oil,” and “extra heavy mineral oil” are well known in the art

and are used herein in the same manner as they are commonly used in the art. Such oils are

readily available from commercial chemicals suppliers throughout the world.

When an added emulsifying agent is used in the practice of this invention, the

appropriate amount of agent to use is any amount that will perform as described above. The

amount is otherwise not critical and may vary depending on the choice of the agent, and in

the case of mineral oil, the grade of mineral oil. The amount may also vary with the fuel

composition, the relative amounts of aqueous and organic phases, and the operating

conditions. Appropriate selection will be a matter of routine choice and adjustment to the

skilled engineer. In the case of mineral oil, best and most efficient results will generally be

obtained using a volume ratio of mineral oil to the organic phase 1 of from about 0.00003 to

about 0.003.

\

In certain embodiments of the invention, a metallic catalyst is included in the

reaction system to regulate the activity of the hydroxyl radical produced by the

hydroperoxide. Examples of such catalysts are transition metal catalysts, and preferably

metals having atomic numbers of 21 through 29,39 through 47, and 57 through 79.

Particularly preferred metals from this group are nickel, sulfur, tungsten (and tungstates),

cobalt, molybdenum, and combinations thereof. In certain systems within the scope of this

invention, Fenton catalysts (ferrous salts) and metal ion catalysts in general such as iron (11),

10

iron (111), copper (I), copper (11), chromium (111), chromium (VI), molybdenum, tungsten,

cobalt, and vanadium ions, are useful: Of these, iron (11), iron (111), copper (11), and tungsten

catalysts are preferred. For some systems, such as crude oil, Fenton-type catalysts are

preferred, while for others, such as diesel-containing systems, tungsten or tungstates are

preferred. Tungstates include tungstic acid, substituted tungstic acids such as

phosphotungstic acid, and metal tungstates. In certain embodiments of the invention, nickel,

silver, or tungsten, or combinations of these three metals, are particularly useful. The

metallic catalyst when present will be used in a catalytically effective amount, which means

-

5

any amount that will enhance the progress of the reaction (i.e., increase the reaction rate)

10 toward the desired goal, particularly the oxidation of the sulfides to sulfones. The catalyst

may be present as metal particles, pellets, flakes, shavings, or other similar forms, retained in

the ultrasound chamber by physical barriers such as screens or other restraining means as the

25

30

reaction medium is allowed to pass through.

The temperature of the combined aqueous and organic phases during

ultrasound exposure may vary widely, although in most cases it is contemplated that the

temperature will be within the range of from about 0°C to about 500"C, preferably from

about 20°C to about 200"C, and most preferably from about 40°C to about 125°C. In many

cases, it will be beneficial to preheat the two phases, either individually or together, prior to

their entry into the ultrasound chamber. The optimal degree of preheating will vary with the

particular organic liquid to be treated and the ratio of aqueous to organic phases, provided

that the temperature is not high enough to volatilize the organic liquid. With diesel fuel, for

example, best results will most often be obtained by preheating the fuel to a temperature of at

least about 70"C, and preferably from about 70°C to about 100". The aquecks phase may be

preheated to any temperature up to its boiling point.

Ultrasound used in accordance with this invention consists of soundlike waves

whose frequency is within or above the range of normal human hearing, Le., in the range of

2 lcHz (2,000 cycles per second) or above. Ultrasonic energy with frequencies as high as 10

gigahertz (1 0,000,000,000 cycles per second) has been generated, but for the purposes of this

invention, useful results will be achieved with frequencies within the range of from about

2 kHz to about 100 kHz, and preferably within the range of from about 10 kHz to about

50 kHz. Ultrasonic waves can be generated from mechanical, electrical, electromagnetic, or

thermal energy sources. The intensity of the sonic energy may also vary widely. For the

purposes of this invention, best results will generally be achieved with an intensity ranging

from about 10 watts/cm2 to about 3000 watts/cm2, or preferably from about 50 watts/cm2 to

11

- . . . . - . - . . . - . _. -. _ _ , . .. . ._ . .

5

10

15

20

25

30

about 1500 watts/cm2. The typical electromagnetic source is a magnetostrictive transducer

which converts magnetic energy into ultrasonic energy by applying2strong alternating

magnetic field to certain metals, alloys and ferrites. The typical electrical source is a

piezoelectric transducer, which uses natural or synthetic single crystals (such as quartz) or

ceramics (such a barium titanate or lead zirconate) and applies an alternating electrical

voltage across opposite faces of the crystal or ceramic to cause an alternating expansion and

contraction of crystal or ceramic at the impressed frequency. Ultrasound has wide

applications in such areas as cleaning for the electronics, automotive, aircraft, and precision

instruments industries, flow metering for closed systems such as coolants in nuclear power

plants or for blood flow in the vascular system, materials testing, machining, soldering and

welding, electronics, agriculture, oceanography, and medical imaging. The various methods

of producing and applying ultrasonic energy, and commercial suppliers of ultrasound

equipment, are well known among those skilled in the use of ultrasound.

The exposure time of the multiphase reaction medium to ultrasound is not

critical to the practice or to the success of the invention, and the optimal exposure time will

vary according to the type of fhel being treated. An advantage of the invention however is

that effective and useful results can be achieved with a relatively short exposure time. A

preferred range of exposure times is from about 1 second to about 30 minutes, and a more

preferred range is from about 15 seconds to about 1 minute.

Improvements in the efficiency and effectiveness of the process can also be

achieved by recycling or secondary ultrasound treatments. A fresh supply of water may for

example be added to the treated and separated organic phase to form a fresh emulsion which

is then exposed to further ultrasound treatment, either on a batch or continuous basis. This

re-exposure to ultrasound can be repeated multiple times for even better results. This is

readily achieved in a continuous process by a recycle stream or by the use of a second stage

ultrasound treatment, and possibly a third stage ultrasound treatment, with a fresh supply of

water at each stage.

In systems where the reaction induced by ultrasound produces undesirable

byproducts in the organic phase, these byproducts can be removed by conventional methods

of extraction, absorption, or filtration. When the byproducts are polar compounds, for

example, the extraction process can be any process that extracts polar compounds from a

non-polar liquid medium. Such processes include solid-liquid extraction, using adsorbents

such as silica gel, activated alumina, polymeric resins, and zeolites. Liquid-liquid extraction

can also be used, with polar solvents such as dimethyl formamide, N-methylpyrrolidone, or

12

. . . . . . . .- .___--__I__.. . . -~~ . . . .. .. . .

5

10

15

20

25

30

acetonitrile. A variety of organic solvents that are either immiscible or marginally miscible

with the fossil fuel, can be used. Toluene and similar solvents are examples. -I_

The ultrasound-assisted reformation reaction generates heat, and with certain

starting materials it is preferable to remove some of the generated heat to maintain control

over the reaction. When gasoline is treated in accordance with this invention, for example, it

is preferable to cool the reaction medium in the ultrasound chamber. Cooling is readily

achievable by conventional means, such as the use of a liquid coolant jacket or a coolant

circulating through a cooling coil in the interior of the ultrasound chamber. Water at

atmospheric pressure is an effective coolant for these purposes. When cooling is achieved by

immersing the ultrasound chamber in a coolant bath or by use of a circulating coolant, the

coolant may be at a temperature of about 50°C or less, preferably about 20°C or less, and

more preferably within the range of from about -5°C to about 20°C. Suitable cooling methods

or devices will be readily apparent to those skilled in the art. Cooling is generally

unnecessary with diesel fuel, gas oils, and resids. r

Operating conditions in general for the practice of this invention can vary

widely, depending on the organic material being treated and the manner of treatment. The

pH of the emulsion, for example, may range from as low as 1 to as high as 10, although best

results are presently believed to be achieved within a pH range of 2 to 7. The pressure of the

emulsion as it enters the ultrasound chamber can likewise vary, ranging from subatmospheric

(as low as 5 psia or 0.34 atmosphere) to as high as 3,000 psia (214 atmospheres), although

preferably less than about 400 psia (27 atmopheres), and more preferably less than about

50 psia (3.4 atmospheres), and most preferably from about atmospheric pressure to about

50 psia.

The operating conditions described in the preceding paragraphs that relate to

ultrasound conditions, the inclusion of emulsion stabilizers and catalysts, and the general

conditions of temperature and pressure apply to the process of the invention regardless of

whether or not hydrogen peroxide or any other hydroperoxide is present in the reaction

mixture. One of the unique and surprising discoveries of this invention is that the levels of

sulfur-containing compounds and nitrogen-containing compounds are reduced substantially

regardless of whether a hydroperoxide is present.

The process can be performed either in a batchwise manner or in a continuous-

flow operation. Continuous-flow operations are preferred. In a currently preferred system,

the ultrasound exposure is performed in a horizontal pipe reactor, 12 inches (30.5 cm) in

diameter and 6 feet (1.83 m) in length, although a useful range of dimensions may be a

13

5

10

15

20

25

30

diameter of from 4 inches to 24 inches (10.2 to 61 cm) and a length of 1 foot to 50 feet (30.5

to 1,524 cm), preferably from 6 feet -~ to 12 feet (183 to 366 cm). Th2pipe is divided

longitudinally into 5 sections or cells with perforated vertical walls separating the cells. A

horizontal screen in each cell supports the metal catalyst particles and the perforated vertical

walls serve to retain the particles in each cell. Ultrasound probes penetrate the top of the pipe

and extend into the pipe interior, with one probe extending into each cell. Emulsion is passed

through the pipe and thus through each cell in succession, at a rate of approximately 75

gallons/minute (4.7 liters per second, or 2,570 bbl/day). The volume ratio of organic to

.aqueous phases is 1 : O S .

The following examples are offered for purposes of illustration and are not

intended to limit the scope of the invention.

< EXAMPLE 1

A petroleum-derived fuel was treated in accordance with the present invention

in a stainless steel ultrasound chamber having an intemal volume of 3 liters. A metal screen

inside the chamber supported a bed of solid metal catalyst consisting of a mixture of tungsten

flakes and nickel pellets, and positioned above the catalyst bed was an ultrasound probe

whose lower end terminated approximately 5 cm above the catalyst bed. Ultrasound was

supplied to the probe by an ultrasound generator as follows:

Ultrasound generator:

Supplier: Sonics & Materials, Inc., Newtown, Connecticut, USA

Power supply: net power output of 800 watts (run at'50%)

Voltage: 120 V, single phase

Current: 10 amps

Frequency: 20 kHz

The fuel used in this test was a 70/30 (volume ratio) mixture of straight-run

diesel and FCC light cycle oil. Each fuel was combined with water at a ratio of

approximately 2 parts by volume of fuel to 1 part by volume of water. Hydrogen peroxide

was added as a 3% aqueous solution, at 0.0025 parts by volume of the solution to 1 part by

volume of the water. The fuel and'water were both preheated to 75°C. Extra heavy mineral

oil, obtained from Mallinckrodt Baker Inc., Philipsburg, New Jersey, USA, was used as a

-- -

surface active agent and added at a rate of approximately 1 drop of a 10% solution per

0.375 L of the total mixture. The mixture was heated to approximately 85°C and emulsified

14

with a high-speed shear mixer. The resulting emulsion was passed through !the ultrasound

chamber as a continuous stream at a flow rate of approximately 1 gallon per minute (3.8 - _ .

literdmin). Residence time in the ultrasound chamber was approximately 1 minute.

' 5

10

The two-phase aqueous-organic mixture emerging from the ultrasound

chamber passed through two cloth filters into a separation chamber. The organic phase was

drawn from the top of the chamber and the aqueous phase from the bottom. The organic

phase emerging from a single pass through the ultrasound chamber and separator was washed

with acetonitrile. In some cases, the organic phase was recycled through the ultrasound

chamber with fresh water at the same ratios and conditions used in the first pass. When

recycling was performed twice, the sulfur content of the organic phase with a solvent wash

was substantially the same as that achieved with a single pass followed by the solvent wash.

The fuel, both before and after treatment in the ultrasound chamber, was

analyzed for concentrations of individual sulfur-containing compounds (test method: ASTM

D-5623) and for total sulfur (test method: ASTM D-2622, using a sulfur analyzer Model

SLFA-20, Horiba Instruments, Inc., Knoxville, Tennessee, USA , with a detection limit of

20 ppm). The results, which demonstrate a sharp drop in the sulfur content, particularly

among the thiophenes, are shown in Table 11.

TABLE 11

After Treatment Before Treatment and Solvent Extraction

Sulfur Components (ppm S by weight):

benzothiophene methyl benzothiophenes dimethyl benzothiophenes trimethyl benzothiophenes tetramethyl benzothiophenes dibenzothiophene methyl dibenzothiophenes dimethyl dibenzothiophenes trimethyl dibenzothiophenes unidentified volatile sulfur hydrogen sulfide sulfur dioxide carbonyl sulfide ethyl mercaptan methyl sulfide carbonyl disulfide

10 186 486 490 464 169 395 450 215 396 <1 <1 <1 <1 <1 4

<1 <1 1

. 3 14 2 10 12 9 18 <1 <1 <l <1 <1 <I

15

isopropyl mercaptan ethylene sulfide t-butyl mercaptan n-propy l mercaptan ethyl methyl sulfide thiophene sec-butyl mercaptan isobutyl mercaptan ethyl sulfide n-butyl mercaptan methyl disulfide 2-methyl thiophene 3-methyl thiophene tetrahydrothiophene ethyl methyl disulfide 2-ethyl thiophene 2,5-dimethyl thiophene 3-ethyl thiophene 2,4 & 2,3-dimethyl thiophene 3,4-dimethyl thiophene methyl ethyl thiophenes trimethyl thiophenes tetramethyl thiophenes

Total Sulfur by X-Ray Spectroscopy (weight '36)

The fuel was also given a full chemical analysis by ASTM D-5134 Mod. both

before and after treatment, with results shown in Table 111.

n-hexane cyclohexane trans- 1,2-dirnethylcyclopentane n-heptane methylcyclohexane trans,cis- 1,2,3-trirnethylcyclopentane N,N-dimethyl fonnamide toluene 2-methylheptane 3-methylheptane trans- 1,2-dimethylcyClohexane

b

Table I11

Before Treatment After .Treatment [weight %) [weight %I)

0.01 0.01 0.01 0.02 0.03 0.01

0.01 0.01 0.02 0.01

n-octane 0.06

0.30 -0.19

0.01 0.01 0.03

16

cis- 1,2-dimethylcyclohexane 2,4-dimethylhep tane ethylcyclohexane 2,6-dimethylheptane 1,1,3-trirnethylcyclohexane 2,5-dimethylheptane 3,5-dimethylheptane ethylb enzene trans,trans- 1,2,4-trirnethylcyclohexane meta-xylene para-xylene 2 , 3 -dimethylhep tane 2,3-dimethylheptane D/L 3 -ethylheptane 4-methyloctane 2 -met h ylo c t an e 3 -methyloctane cis,cis- 1,2,3-trim'kthylcyclohexane 3 -ethylheptane 3 -methyloctane cis,cis- 1,2,4-trirnethylcyclohexane orthoxylene cis- 1 -ethyl-3 -methylcyclohexane trans- 1 -ethyl-4-methylcyclohexane isobutylcyclopentane 1 -ethyl- 1 -methylcyclohexane cis,trans- 1,2,3 -trimethylcyclohexane trans,trans-l,2,3-trimethylcyclohexane n-nonane trans- 1 -ethyl-3 -methylcyclohexane trans- 1 -ethyl-2-methylcyclohexane CS naphthenes 2,2-dimethyloctane

. isopropylcyclohexane cis- 1 -ethyl-2-methylcyclohexane sec-butylcyclopentane 2,4-dimethyloctane 2,6-dimethyloctane 2,5-dimethyloctane n-prop ylcyclohexane n-butylcyclopentane 3,5-dimethyloctane n-prop ylbenzene 3,6-dimethyloctane 1 -methyl-3-ethylbenzene 1 -methyl-4-ethylbenzene 2,3-dimethyloctane 1,3,5-trimethylbenzene 4-ethyloctane 5-methylnonane

0.02 0.01 0.01

0.01 0.01 0.02 0.01

0.01 0.01 0.01

0.02 0.01 0.01 0.01

0.12 0.01

0.01

0.02

0.02 0.01

0.02 0.02 0.02 0.01 0.01 0.02

0;Ol

0.01 0.01 0.06

0.06 0.01 0.01 0.02 0.05

0.01

0.02 0.02 0.01 0.04 0.05

0.01 0.03 0.08 0.01 0.01 0.04 0.09 0.05 0.01 0.01 0.01 0.48 0.07 0.02 0.35 0.07 0.04 0.02

0.05 0.18 0.03 0.17 0.05 0.01 0.04 0.10 -0.04

0.08 0.06 0.07 0.05

17

4-methylnonane 1 -methyl-2-ethylbenzene 2-methylnonane 3-ethyloctane 3-methylnonane 1,2,3,5-tetrarnethylcyclohexane 1,2,3,4-tetramethylcyclohexane 1,4-dimethyl-2-ethylcyclohexane lY2,4-trimethylbenzene cis- 1 -methyl-3 -propylcyclohexane cis- 1,3-diethylcyclohexane trans- 1 -methyl-3-propylcyclohexane trans-l,3-diethylcyclohexane 1 -ethyl-2,3 -dimethylcyclohexane isobutylbenzene cis- 1 -methyl-4-propylcyclohexane sec-butylbenzene n-decane 1,3,5-trimethylbenzene 1,2,3,4-tetramethylcyclohexane trans- 1,3 -diethylcyclohexane 1,2,3-trimethylbenzene 1 -methyl-3-isopropylbenzene 1 -methyl-4-isopropylbenzene 1 -methyl-2-propylbenzene 2,3 -dihydroindene sec-butylc yclohexane 1 -methyl-2-isopropylbenzene butylcyclohexane 1,3-diethylbenzene trans- 1 -methyl-4-t-butylcyclohexane 1 -methyl-3 -n-propylbenzene 1 -methyl-4-n-propylbenzene lY4-diethylbenzene n-butylbenzene 1,3 -dimethyl-5 -ethylbenzene 1,2-diethylbenzene 1 -methyl-2-n-propylbenzene cis- 1 -methyl-4-t-butylcyclohexane 5 -methyl decane 4-methyldecane 2-methyldecane ly4-dimethy1-2-ethylbenzene 1,3 -dimethyl-4-ethylbenzene 3-methyldecane lY2-dimethyl-4-ethylbenzene 1,3 -dimethyl-2-ethylbenzene tricyclodecane 1 -methylindan 1,2-dimethy1-3-ethylbenzene

18

0.01 0.03 * . _

0.01 0.02

0.01

0.06 0.02 0.01

0.01 0.01 0.01

\

0.03 0.01.

0.01

o.oi 0.04

0.01 0.01 0.01 0.02' 0.01 0.01 0.02 0.01

0.02 0.06 0.03 0.02 0.02 0.03 0.03 0.02 0.02 0.01 0.03 0.01 0.03

0.13 0.07 0105 0.05 0.17 0.01 0.04 0.01 0.03 0.08 0.12 0.02

0.04 0.04 0.02 0.01 0.75

0.02 0.02 0.01 0.02 0.02 0.01 0.03 0.04 0.03 0.12 0.04 0.08 0.01

0.03 0.02 0.02 0.06 0.04 0.09

0.09 0.01 0.06 0.01 0.02 0.04

0.02

... . .. . . -. . . . . . . . . - . - . - . - . . . .

n-undecane 1,2,4,5-tetramethylbenzene 1,2,3,5-tetramethylbenzene C, 1 unidentified 4-methylindan 5-methylindan 1,2,3,4-tetramethylbenzene 2-methylindan tetralin 6-methylundecane 5-methylundecane 4-methylundecane 3-methylundecane 2-methylundecane naphthalene naphthalene3 -methylundecane C1 I aromatics n-dodecane dodecanes ,,

2-methylnaphthalene 1 -methylnaphthalene tridecanes n-tridecane tetradecanes n-tetradecane pentadecanes n-pentadecanes hexadecanes n-hexadecane heptadecanes n-heptadecanes pristane octadecanes n-octadecane phytane nonadecanes n-non adecan e eicosanes n-eicosane heneicosanes docosanes tricosanes tetracosanes pentacosanes unidentified

Molecular Weight of Sample

0.63

0.05 0.10 0.04 0.03 0.07 . 0.02 0.01 0.03 0.02 0.04

0.02 ’: ‘.

0.39 0.01 0.03 0.39 0.02 0.02 0.03

0.01 0.05 0.06 0.05 0.12

0.05 0.13 0.05 0.45 0.91 0.50 1.19 0.81 3.30 2.83 6.95 4.47 9.55 5.30 10.20 3.57 10.61 3.60 1.28 7.52 1.97 0.83 5.85 1.77 5.63 0.97 4.30 2.14 0.50 0.04 0.01

0.54 0.40 0.58

2.55 1 .oo 5.01 1.63 6.52 2.46 7.20 2.43 8.44 3.13 1.78 7.46 2.71 1.46 7.20 2.79 7.14 2.71 7.35 5.74 3.30 1.18 0.10 0.16

Total: 100.00 100.00

220.24 229.13

19

. . . . ._ - -. . . . . -___--, . .. _. . . . . . .

Molecular Weight of Cg Plus 220.24 230.24

0.8245 ' -. 0.8680 Density of Sample

0.8245 0.8280 Density of Cg Plus 7

- .

EXAMPLE 2

Using the same equipment and procedures as Example 1, four fuels were

treated in accordance with the invention. The fuels were straight-run diesel, feed-rack diesel,

light cycle oil, and a 70/30 (by volume) blend of straight-run diesel and light cycle oil.

Various properties and analytical data, obtained by conventional methods widely used in the

industry, are listed in Table IV below.

5

Table IV - Comparisons Before (B) and After (A) Treatment for Four Different Fuels (Treatment Includes Solvent Extraction)

r

70/30 Vol. (Indus- Ratio

try Straight Run Specifi- Straight-Run Feed, Rack Diesel/Light cation) Diesel Diesel Cycle Oil Light Cycle Oil

B A B A B A B A

Gravity, API 30-40 32.8 40.5 33.9 38.2 33.0 38.2 21.4 42.6

15 2,500 5 228 64 228 64 5,572 8 Total sulkr, '

Cetane Index 41 46.5 63 46 55 46 55 30.0 64.5

Flash 160 172 230 124

0.35 0.15 0.29 0.07 0.29 0.07 0.38 0.05 Ramsbottom

PPm (wt)

Copper strip 1A 1A

Carbon . Viscosity

Tests: Middle Distillate

4 2.9 3.4 2.9 3.'4 3.5 3.7

10 0 25 -15 0 5 25 10 25 Pour Point

( O F , Summer)

36 16 36 -4 12 8 34 20 34 Cloud Point (OF, Summer)

Color <OS 0.5 0.5 1.5 <o.s Flash 125 154 164 160 172 196 180

Distillation, D-86 OF Initial Boiling Point 5% 10% 20%

486 426 488 493 497 505 509 517

20

. .. .

30% 40% 50% 60% 70% 80% 90%

521 528 534 5 40

' 549 554 566 568 586 584

, 608 601 63 1 ' 625 654 . 644 667 653

95% End Point

Recovery 96.5 96.5

Residual 1.1 1.8

Loss 2.4 1.7

Paraffins 48.8 62.8 32.5 36.1

Monocyclo- 14.8 18.3 8.5 12.6

Dicycloparaffins - 5.3 8.1 3.6 ,8.2

Tric ycloparaffins 0.9 1.6 0.8 1.5

Paraffins Subtotal 69.8 90.8 45.4 58.4

paraffins ,

Naphthalenes

Acenaphthenes

Acenaphthalenes

Naphthalenes Subtotal

9.0 0.5 20.3 12.1

3.0 0.2 7.6 4.7

1.5 0.2 4.2 2.6

13.5 0.9 32.1 19.4

Alkylbenzenes 6.0 3.0 5.7 6.2

IndanedTetralins 6.3 3.5 7.9 9

Indenes 2.0 1.7 2.1 3.1

Tricyclic Aromatics 2.4 0.1 6.8 3.9

Aromatics Sub to tal 16.7 8.3 22.5 22.2

Total 100.0 100.0 100.0 100.0

The last 15 rows of Table IV demonstrate the effect of the invention in

converting olefins to paraffins, saturating aromatics and opening rings. In particular, the

increase in cycloparaffins shows sahiration of aromatic rings, the lowering of the level of

naphthalenes and the accompanying increase in indanes and tetralins demonstrate at least

partial saturation of aromatics, the drop in acenaphthalenes and acenaphthenes and the rise in 5

21

indanes and indenes demonstrates at least partial saturation and ring opening, the lowering of

tricyclic aromatics (such as anthracenes and phenanthrenes) demonstrates at least partial

saturation and ring opening, and the increase in alkybenzenes demonstrates ring opening.

The “Total Sulfur” and “Cetane Index” data demonstrate the large reduction in sulfur level

and the large improvement in cetane index, 5

EXAMPLE 3

10

A reaction vessel was charged with 250 mL FCC light cycle oil, 125 mL of

water, hydrogen peroxide at a concentration of 25 ppm to a pH of 2-4, one drop of a mixture

of 90 parts straight-run diesel and 10 parts of extra heavy mineral oil, and a mixture of

tungsten flakes (17g) and nickel pellets (17g). The resulting mixture was heated to 180°F

(82”C), then emulsified with a high-speed shear mixer at 2000 rpm for 5 seconds. An

ultrasound probe, rated for 20 kHz and driven by a 750 W generator, was then placed in the

solution and energized, operating at 40% intensity. After 30 seconds, the ultrasound probe

was removed. The aqueous-organic mixture was then placed in a separatory funnel and

allowed to separate for 5 minutes. Analytical results of the organic phase are shown in Table

V:

Table V - Comparisons Before and After Treatment for Light Cycle Oil

Before After Ultrasound Ultrasound


Cetane Index

Total Sulfur, ppm

Total Nitrogen, ppm

Carbon, weight % (ASTM D-529 1)

34.5 39.1

7073 3917

72 1 415

88.24 87.01

10.57 Hydrogen, weight % (ASTM D-5291) 12.05

Paraffins and Aromatics fASTM D-2549):

Acyclic Paraffins 32.1 35.8

22

Monoc ycloparafiiis 9.8 14.0

Dicy cloparaffins 4.3 9.2

Tri c ycl oparaffins 0.8 1,-6 --.-

Paraffins Subtotal 46.2 60.c

Naphthalenes 16.1 9.4

Acensiphthenes 6.8 3.9

Acenaphthalenes 3.6 2.2

Alkylbenzenes 7.5 7.1

Indanes/Tetralins/Indenes 12.6 13.5

Tricyclic Aromatics 6.4 3.3

Aromatics Subtotal 53.0 39.4

Like Table IVY Table V demonstrates the effect of the invention in converting

olefins to paraffins, saturating aromatics and opening rings. The increase in cycloparaffins

shows saturation of aromatic rings, the reduction in naphthalenes and the accompanying

increase in indanes and tetralins demonstrate at least partial saturation of aromatics, the

reduction in acenaphthalenes and acenaphthenes and the increase in indanes and indenes

demonstrates at least partial saturation and ring opening, the reduction in tricyclic aromatics

(such as anthracenes and phenanthrenes) demonstrates at least partial saturation and ring

opening, and the increasc in alkybenzenes demonstrates ring opening. Also demonstrated are

a reduction in ni trogen-bearing compounds and sulfur-bearing compounds, plus increases in

MI gravity, cetane index and hydrogen content.

EXAMPLE 4

A mixture was prepared by combining 5 gallons (1 9 L) of FCC light cycle oil,

2.5 gallons (9.5 L) of water containing 2 mL of heavy mineral oil, and hydrogen peroxide at a

concentration of 25 ppm to a pH of 2-4. The mixture was passed through the continuous-

flow ultrasound reactor of Example 1 under the conditions described in that example with a

liquid hourly space velocity (LHSV) of 30 seconds. The separated organic phase was then

desulfurized in a standard industry hydrodesulfurization ( H D S ) unit at the following

conditions: temperature 650°F (343"C), pressure 500 psi (35 atmospheres), hydrogen

circulation rate 1,000 SCF/bbl (standard cubic feet per barrel), and LHSV =2. The API

23

. - . - . . __ ... . - . . . - . _.

gravity, cetane index, total nitrogen, and total sulfur were determined for the initial untreated

light cycle oil, the light cycle oil after ultrasound treatment, the light cycle oil after

hydrodesulfurization but without ultrasound, and the light cycle oil h i n g both been treated

with ultrasound and undergone hydrodesulfurization. The results are listed in Table VI:

5 Table VI - Comparisons Before and After Treatment for Light Cycle Oil

Before HDS After HDS

Without With Without With U1 trasound Ultrasound Ultrasound Ultrasound

Gravity, AH 22.6 33.8 26.9 34.0

Cetane Jndex 34.5 47.5 39.7 47.6

Nitrogen, ppm 72 1 170 51.5 86

Sulfur, ppm ' 7073 1121 557 80

Hydrogen usage SCFhbl 450 100

The data in Table VI indicate that the ultrasound treatment increases both API

gravity and cetane index, regardless of whether hydrodesulfurization has been performed, and

decreases both sulfur and nitrogen in addition to the decreases in these elements that is

achieved by hydrodesulfurization. Note also the reduction in hydrogen usage due to

ultrasound.

EXAMPLE 5

A reaction mixture not containing hydrogen peroxide or any .other

. hydroperoxide was prepared by combining:

250 mL of a mixture of 50% FCC slurry oil and 50% 1000-psi-

15 hydrotreated kerosene,

125 mL of water, and

one drop of a mixture of 90 parts diesel and 10 parts heavy mineral oil

surfactant (by volume).

The reaction mixture was heated to 180°F (82"C), then ernulsified with a high-speed shear

mixer at 2000 rpm for 5 seconds. An ultrasound probe was then placed in the reaction

mixture, energized for 60 seconds and removed. The reaction mixture was then allowed to

separated for ten minutes in a separatory funnel. The aqueous phase was removed from the

20

24

bottom of the funnel and the oil phase was recovered and retreated three times with

ultrasound in the same manner, each treatment followed by phase separation and combining

of the oil phase with fresh water. The laboratory analyses of the starting - material and the

fourth-run product (exclusive of the kerosene) are listed in Table VII.

5 Table VI1 - Comparisons Before and After Treatment for FCC S lun j Oil


Gravity, API 4.8

Total Nitrogen, ppm 2,048

Total Sulfur, ppm 11,380

Bromine Number 14

Paraffins and Aromatics (ASTM D-2549): r

Acyclic Paraffins 9.4

Monoc ycloparaffins 9.9

Dic ycloparaffins 7 .

Tricycloparaffins 1.8

Alkyl benzenes 15.3

Indanes/Tetralins/Indenes 21.4

Naphthalenes 16.2

Acenaphthenes 8

Acenaphthalenes 4.4

Tricyclic Aromatics 15.2

900 Distillation D 2887 90% Point (OF)

31.2

500

2,252

2

45.8

16.9

10.2

1.4

7.5

11.8

2.6

1

0.8

2

739

. .

Of particular significance in Table VI1 are the reduction in sulfur and nitrogen

levels, the increase in cycloparaffins resulting from saturation of aromatic rings, the reduction

in the distillation temperature of the 90% distillation point, and the increase in API gravity.

EXAMPLE 6

10 A reaction mixture not containing hydrogen peroxide or any other

hydroperoxide was prepared by combining:

25

^. . . _.

250 mL of a mixture of 50% coker gas oil and 50% 1 OOO-psi-

5

- hydrotreated kerosene,

125 mL of water,-and

one drop of a mixture of 90 parts diesel and 10 parts heavy mineral oil !T


The reaction mixture was heated to 180°F (82"C), then emulsified with a high-speed shear


mixture, energized for 60 seconds and removed, The reaction mixture was then allowed to




of the oil phase with fresh water. The laboratory analyses of the starting material and the

fourth-run product (exclusive of the kerosene) are listed in Table VIII.

10

<

Table VI11 - Comparisons Before and After Treatment for Coker Gas Oil



Total Nitrogen, ppm 3.514 97.6

Total Sulhr, ppm 36,920

Bromine Number 10

Pour Point ( O F ) 97

Paraffins and Aromatics (ASTM D-2549):

Acyclic Paraffins

Monoc ycloparaffins

Dicycloparaffins

Tricycloparaffins

Alkylbenzenes

Indanes/Tetralins/Indenes

Naphthalenes

Acenaphthenes

Acenaphthalenes

23.6

8.7

5.4

1.2

15.1

20.0

9.6

4.4

4.2

10,860

2

10

46.4

16.1

9.4

1.2

9.1

12.0

2.4

0.8

1

26


744 - Distillation D 2887 90% Point ("F) 899

5

I" $$ .1:3

20

Of particular significance in Table VI11 are the reduction in sulfur, nitrogen,

bromine number (an indicator of the levels of olefins and diolefins), the sharp drop i n pour

point, the sharp increase in API gravity, and the increase in cycloparaffins resulting from

saturation of aromatic rings.

EXAMPLE 7

A reaction mixture not containing hydrogen peroxide or any other

hydroperoxide was prepared by combining:

250 mL of a mixture of 50% coker distillate,

125 mL of water, and

one drop of a mixture of 90 parts diesel and 10 parts heavy mineral oil


The reaction mixture was heated to 180°F (82"C), then emulsified with a high-speed shear


mixture, energized for 30 seconds and removed. The reaction mixture was then allowed to




of the oil phase with fresh water. The laboratory analyses of the starting material and the

fourth-run product (exclusive of the kerosene) are listed in Table IX. \

Table IX - Comparisons Before and After Treatment for Coker Gas Oil



Cetane index 42.8 44.7

Total Sulfur, ppm 26,900 8,960

Total Nitrogen, ppm 1,057 440

Bromine Number 28 9

27

- _-

Pour Point ( O F ) 10 -10

Paraffins and Aromatics (ASTM D-2549):

38.-5 --.. Acyclic Paraffins 36.4

Monocycloparaffins- --. 13.0 16.1

D ic y clop ar affins 9.4 12.6

Tric ycloparaffins 1.9 2.2

Alkylbenzenes 11.9 8.5

Indanes/Tetralins/Indenes 12.7 13.7

Naphthalenes 6.6 4.1

Acenaphthenes 2.9 1.8

Acenaphthalenes 2.0 1.2


Of particular significance in Table IX are the reduction in sulfur, nitrogen, : 1 i,Q

r-. i . i

('u '%;J

.am i,.. .I

i.11 Si 5 f :d ; u ism!

j&

aromatics, and bromine number, and the increases in API gravity .and cetane index.

The foregoing is offered primarily for purposes of illustration. Further 6

variations in the materials, additives, operating conditions, and equipment that are still within

the scope of the invention will be readily apparent to those skilled in the art. j l E c

.pc*

t

28

WE CLAIM:

1

2

3

1. A process for - - treating a crude oil fraction to 6 h c e levels therein of

aromatics, olefins, sulfur-bearing compounds, and nitrogen-bearing compounds, and to raise

the API gravity thereof, said process comprising:

4

5 emu1 sion;

6

7

8 organic phases; and

9 '

(a) combining said crude oil fraction with an aqueous liquid to form an


(c) separating said emulsion after said ultrasound exposure into aqueous and

(d) recovering said organic phase from said aqueous phase.

1 A process in accordance with claim 1 in which no hydroperoxide is

2

3

1

2

1

2

1

2

added to said crude oil fraction or incorporated into said aqueous liquid in forming said

emulsion.

3. A process in accordance with claim 1 in which step (a) comprises

incorporating a hydroperoxide into said emulsion.

4. A process in accordance with claim 1 in which said crude oil fraction

is a fraction boiling within the diesel range.

5 . A process in accordance with claim 4 in which said crude oil fraction

is a member selected from the group consisting of fluid catalytic cracking VCC) cycle oil

3 fractions, coker distillate fractions, straight run diesel fractions, and blends thereof. \1

1 .

2

6. A process in accordance with claim 1 in which said crude oil fi-action

is a fraction boiling within the gas oil range.

1 7. A process in accordance with claim 6 in which said crude oil fraction

2

3

is a member selected from the group consisting of FCC cycle oil, FCC slurry oil, light gas oil,

heavy gas oil, and coker gas oil.

1

2

3


is a member selected from the group consisting of gasoline, jet fuel, straight-run diesel,

blends of straight-run diesel and FCC light cycle oil, and petroleum residuum-based fuel oils.

29

. .. . . . __ .. . . . . . . . . . . . .. . ,

1

2

9. A process in accordance with claim 1 in which said ultrasound

exposure is at a sufficient intensity and time to cause an increase in'-kPI gravity by an amount .

3 ranging from 2 to 30 API units.

1

2

3


exposure is at. a sufficient intensity and time to cause an increase in API gravity by an amount

ranging from 7 to 25 API units.

1

2

3


exposure is at a sufficient intensity and time to raise the cetane index of said diesel range

crude oil fraction by an amount ranging from 1 to 40 units.

12. A process in accordance with claim 4 in which said ultrasound 7 exposure is at a sufficient intensity and time to raise the(cetane indexpf said diesel range

--.- /--

/ \----

-. .'-_.

crude oil fi-actio; by an amount ranging from 4tlt2LuS

13. A process in accordance with claim 1 in which step (b) is performed at

an ultrasound intensity of from about 10 watts/cm2 to about 3000 watts/cm2.


an ultrasound intensity of from about 50 watts/cm2 to about 1500 watts/cm*.


2 an ultrasound exposure time of from about 1 second to about 30 minutes.

1

. ' 2


an ultrasound exposure time of from about 15 seconds to about 1 minute.

1

2

17. A process in accordance with claim 1 further comprising contacting

said emulsion with a transition metal catalyst during step (b).

1

2

18. A process in accordance with claim 17 in which said transition metal

catalyst is a member selected from the group consisting of metals having atomic numbers of

3 21 through 29,39 through 47, and 57 through 79.

30

I " .

I

1

2


catalyst is a member selected from the group consisting of nickel, silver, tungsten, cobalt,

3 molybdenum, and combinations thereof. - - -

1

2

3 combinations thereof


catalyst is a member selected from the group consisting of nickel, silver, tungsten, and

1

2

3


combining said crude oil fraction and said aqueous fluid at a (crude oil fraction):(aqueous

fluid) volume ratio of from about 8:l to about 15.

. =* 1 1:CJ . . p?? 2 %.I


combining said crude oil fraction and said aqueous fluid at a (crude oil fiaction):(aqueous i:iQ !:rl 3 fluid) volume ratio of from about 5 : 1 to about 1 : 1. i,J ics 1 23. A process in accordance with claim 1 in which step (a) comprises SU ' id 2 combining said crude oil fraction and said aqueous fluid at a (crude oil fraction):(aqueous

i f r7 3 fluid) volume ratio of from about 4: 1 to about 2: 1. . icy 'rm

i'u 1 24. A process in accordance with claim 3 in which said hydroperoxide p+j !;3 2

1

constitutes from about 10 ppm to about 100 ppm by weight of said aqueous liquid.

25. A process in accordance with claim 3 in which said hydroperoxide

2 constitutes from about 15 ppm to about 50 ppm by weight of said aqueous liquid.

1

2 hydrogen peroxide.

26. A process in accordance with claim 1 in which said hydroperoxide is

1

2

3 '

27. A process in accordance with claim 1 in which said aqueous liquid is

an aqueous solution of hydrogen peroxide at a concentration of from about 15 ppm to about

50 ppm by weight.

1

2

28. A process in accordance with claim 1 further comprising preheating

said crude oil fraction to a temperature of from about 20°C to about 200°C prior to step (b).

31

- __ . . . - . . . ~ .. . .... . :

1

2


said crude oil fraction to a temperature of from about 40°C to about 125°C prior to step (b). -.-.

- _ . 1 30. A process in accordance with claim 1 in which step (b) is performed at

2 a pressure of less than 400 psia.

1 .

2

, 31.

a pressure of less than 50 psia.

A process in accordance with claim 1 in which step (b) is performed at

1 32. A process in accordance with claim 1 in which step (b) is performed at

2 a pressure within the range of from about atmospheric pressure to about 50 psia.

1

iI3 2


said crude oil fraction to a temperature of from about 40°C to about 125°C prior to step (b).

34. A process in accordance with claim 1 further comprising incorporating

i,iid 2 an emulsion stabilizer in said emulsion. 1:s i5u "51 1 35. A process in accordance with claim 34 in which said emulsion

' 2 7 s zwi 2 l i

stabilizer is a mixture of aliphatic CI&O hydrocarbons having a specific gravity of at least

about 0.82.

36. A process in accordance with claim 35 in which said mixture of i s &

2 aliphatic C15-C20 hydrocarbons has a specific gravity of at least about 0.85.

1 37. A process in accordance with claim 35 in which said mixture of

2 aliphatic C1&0 hydrocarbons is heavy mineral oil.

1 (;k)i A process for treating an comprising fused-ring aromatic

2 compounds and"'o1efinic compounds to lower organic liquid, said process

3 comprising:

4

5

(a) combining said organic liquid with an aqueous liquid to form an emulsion;

(b) subjecting said emulsion to ultrasound at a sufficient intensity and for a

6

7

8

9

sufficient time to open fused rings in fused-ring aromatic compounds in said organic

liquid and to convert olefinic compounds in said organic liquid to paraffins;

(d) permitting said emulsion to separate into aqueous and organic phases of

which said organic phase comprises said organic liquid; and .

32

10 (e) isolating said organic liquid from said aqueous phase.

1

2


an aqueous solution o i a hydroperoxide at a concentration of from about - 10 ppm to about 3 100 ppm by weight. - _ _ .

1

2

3 50 ppm by weight.


an aqueous solution of hydrogen peroxide at a concentration of from about 15 ppm to about

1

2

3 ultrasound in step (b).

41. A process in accordance with claim 38 further comprising contacting

said emulsion with a transition metal catalyst while subjecting said emulsion to said


!33 2 IZ9 1 4 d

catalyst is a member selected from the group consisting of nickel, silver, tungsten, and

3 combinations thdeof.

43. A process in accordance with claim 1 in which step (b) is performed in

44. A process in accordance with claim 1 in which step (b) is performed in . .

j P l l . 1 '$ 2 continuous-flow manner. i"u

/-, -1 i 45. 'i '" 1 A process for removing organic-from a crude oil fraction, said k. I 2 process compnsing:

3 (a) combining said crude oil fraction with an aqueous liquid to form an

4 emulsion;

5

6


(c) separating said emulsion after said ultrasound exposure into aqueous and

7 organic phases;

8

9

lo

(d) recovering said organic phase from said aqueous phase; and

(e) contacting said organic phase with hydrogen gas under conditions causing

conversion of said organic sulfur to sulfur dioxide by hydrodesulfurization. --r ------.--

33

46: A process accordance w th claim 1 5 in which no hydroperoxide is

added to said crude oil fraction or incorporated into said aqueous liquid in forming said '. \

emulsion. - .


is a fraction boiling within the diesel range.


is a member selected from the group consisting of fluid catalytic cracking (FCC) cycle oil

fractions, coker distillate fractions, straight run diesel fractions, and blends thereof.


is a fraction boiling within the gas oil range.


is a member selicted from the group consisting of FCC cycle oil, FCC slurry oil, light gas oil,

heavy gas oil, and coker gas oil.

34

. . - _ _ . . -.

PATENT Attorney .Docket No.: 20839-0003OOUS

5

TREATMENT QF CRUDE OIL FRACTIONS, FOSSIL FUELS, AND PRODUCTSTHEREOF

WITH ULTRASOUND

ABSTRACT OF THE DISCLOSURE

Crude oil fractions, fossil fuels, and organic liquids in general in which it is

desirable to reduce the levels of fixed-ring compounds, aromatics, and olefins are combined

with an aqueous phase to form an emulsion and treated with ultrasound with the effect of

opening rings in the fused-ring compounds, saturating aromatics, and converting the olefins

to paraffins. In fossil fuels and crude oil fi-actions, the process raises the MI gravity, and in

diesel fuels, the process raises the cetane index and thereby improves performance. Tn hels

and fractions with sulfur-containing and nitrogen-containing components, the process reduces

the level of these compounds. The process can be performed both with and without the

added presence of hydrogen peroxide. The invention is performed either as a continuous

process or a batch process.

SF 1219380~3

Attorney Docket No.: 020839-0003OOUS

Country Application No.

-_ DECLARATION - ..

As a below named inventor, I declare that:

Priority Claimed Under 35 USC 119 Date of Filing

My residence, post office address and citizenship are as stated below next to my name; I believe I am the original, first and sole inventor (if only one name is listed below) or an original, first and joint inventor (if plural inventors are named below) of the subject matter which is claimed.and for which a patent is sought on the invention entitled: TREATMENT OF CRUDE OIL FRACTIONS, FOSSIL FUELS, AND PRODUCTS THEREOF WITH ULTRASOUND the specification of which X is attached hereto or -was filed on as Application No. and was amended on (if applicable).

I have reviewed and understand the contents of the above identified specification, including the claims, as amended by any amendment referred to above. I acknowledge the duty to disclose information which is material to patentability as defined in Title 37, Code of Federal Regulations, Section 1.56. I claim foreign priority benefits under Title 35, United States Code, Section 119 of any foreign application(s) for patent or inventor’s certificate listed below and have also identified below any foreign application for patent or inventor’s certificate having a filing date before that of the application on which priority is claimed.

i:ri Id pl

Application No. , .Filing Date

!.A Application No. Date of Filing Status

Full Name of Last Name: First Name: . Middle Name or Initial: Inventor 1: GUNNERMAN RUDOLF W. Residence & City: StatelForeign Country: Country of Citizenship: Citizenship: Reno Nevada United States Post Office Post Office Address: City: State/Country: Postal Code: ’ .

Address: 6601 Lakeside Drive Reno Nevada 89511 Full Name of Last Name: First Name: Middle Name or Initial:

Residence & City: StatdForeign Country: Country of Citizenship: Citizenship: Park City Utah United States Post Office Post Office Address: City: State/Coutitry: Postal Code:

Inventor 2: MO’OTE PAUL S.

I Address: , 2440 Lower Lando Lane , ParkCitv I Utah , 84098

1 of2

Ahorney Docket No.: 020839-0003OOUS

Full Name of Inventor 3: Residence & Citizenship: Post Office Address:

Last Name: . FirstName: Middle Name or Initial: CULLEN MARK T. City: StatdForeign Country: Country of Citizenship: Reno Nevada United States Post Office Address: City: Slate/Country: Postal Code: 5605 Brookmeadow Lane ' Reno Nevada 89511

I further declare that all statements made herein of my own knowledge are true and that all statements made on information and belief are believed to be true; and further that these statements were made with the knowledge that willful false statements and the like so made are punishable by fine or imprisonment, or both, under Section 1001 of Title 18 of the United States Code, and that such willful false statements may jeopardize the validity of the application or any patent issuing thereon,

Signature of Inventor 1 Signature of Inventor 2

2 o f 2

u- l lC , . --. _ . . . . . . . . .._ . . _ _ _ _ _ . - . .

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.COMMISSIONER FOR PATEN6 ,UNITED STATES PATENT AND TRADEMARK OFFICE --

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15 16

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I28 119 I20 121

I38

140 141 I42 143 I44 I22

123

126

58 1

146

149'

179

169

Entity Fee (S) 130 50

130 2,520 920'

1,840'

110 400

920 1,440

1,960 320 320 280

1,510

110 1,280 1,280 460 620 130

50

180

40

740

740

740

900

Small Entity Fee Fee Code ($1 205 65 227 25

139 130 '147 2,520 112 920'

113 1,840'

215 55 216 200

217 460 218 720

228 980 219 160 220 160 221 140

1.38 1,510

240 55

241 640 242 640 243 230 244 310 122 130

123 50

126 180

581 40

246 370

249 370

279 370

169 900

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ASorney Docket No.: 020839-DOO3OOUS

Country

-DECLARATION

Priority Claimed Under Application No. Date of Filing 35 USC 119


Application No.

My residence, post office address and citizenship are as stated below next to my name; I believe I am the original, first and sole inventor (if only one name is listed below) or an original, first and joint inventor (if plural inventors are named below) of the subject matter which is claimed and for which a patent is sought on the invention entitled: TREATMENT OF CRUDE OIL FRACTIONS, FOSSIL FUELS, AND PRODUCTS THEREOF WITH ULTRASOUND the specification of which - is attached hereto or

X was filed on Mav 22.2001 as Application No. -09l863.127 and was amended on (if applicable).

Filing Date

I have reviewed and understand the contents of the above identified specification, including the claims, as'amended by any amendment referred to above. I acknowledge the duty to disclose information which is material to patentability as defined in Title 37, Code of Federal Regulations, Section 1.56. I claim foreign priority benefits under Title 35, United States Code, Section 119 of any foreign application(s) for patent or inventor's certificate listed below and have also identified below any foreign application for patent or inventor's certificate having a filing date before that of the application on which priority is claimed.

Application No. Date of Filing Status \I

I hereby claim the benefit under Title 35, United States Code Q 119(e) of any United States provisional application(s) listed below:

Citizenship: Post Office Address: Full Name of lnventnr 2:

Reno Nevada United States Post Office Address: City: State/Country: Postal Code: 6601 Lakeside Drive Reno Nevada 89511 Last Name: First Name: Middle Name or Initial: MOOTE PAUL S.

I claim the benefit under Title 35, United States Code, Section 120 of any United States application(s) listed below and, insofar as the subject matter of each of the claims of this'application is not disclosed in the prior United States application in the manner provided by the f i s t paragraph of Title 35, United States Code, Section 112, I acknowledge the duty to disclose material information as defined in Title 37, Code of Federal Regulations, Section 1.56 which occurred between the filing date of the prior application and the national or PCT international filing date of this application:

Residence & Citizenship: Post Office Address:

City: State/Foreign Country: Country of Citizenship: Park City Utah United States Post Office Address: City: I State/Country: Postal Code: 2440 Lower Lando Lane Park City Utah 84098

I Full Name of I Last Name: I First Name: I Middle Name or Initial: GUNNERMAN 1 RUDOLF I w . ,

I State/Foreign Country: I Country of Citizenship:

1 of2

. Attorney Docket No.: 020839-0003OOUS

' Full Name of Last Name: First Name: Inyentor 3: . CULLEN - 'MARK Residence & City: State/Foreign Country:

.'Middle Name or Initial: T. Country of Citizenship:

Citizenship: Post Office Address:

1 further declare that all statements made herein of my own knowledge are true and that all statements made on information and belief are believed to be true; and hrther that these statements were made with the knowledge that willful false statements and the like so made are punishable by fine or imprisonment, or both, under Section 1001 of Title 18 of the United States Code, and that such willful false statements may jeopardize the validity of the application or any patent issuing thereon.

Reno Nevada United States Post Office Address: City: StateKountry: Postal Code: 5605 Brookmeadow Lane Reno Nevada 89511

SF 1227250 VI

Signature of Inventor 2

Paul S. Moote ~ ~

Date

2 o f 2

.I . ..-


Mark T. Cullen ~ ~

Date '.

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Examiner Name Attorney Docket Number

Application Number 091863,127

Filing Date May 22,2001

First Named Inventor GUNNERMAN, RUDOLF w. TREATMENT OF CRUDE OIL

020839-000300

I FRACTIONS, FOSSIL FUELS, AND

F' irm or Individual Name

Address

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City

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1,

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as mylour attorney@) or agent(s) to prosecute the application identified aboie, and to transact all business in the United States Patent and Trademark Office connected therewith.

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Please change the correspondence address for the above-identified application to:

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Attorney Docket No. 20839-000300

STATEMENT UNDER 37 CFR 3.731b) -- plicanUPatent Owner: Rudolf W. Gunnerman, Paul8. Moote and Mark T. Cullen

ipplication No./Patent No.: 09/863,127 Filedllssue Date: May 22, 2001

intitled: TREATMENT OF CRUDE OIL FRACTIONS, FOSSIL FUELS, AND PRODUCTS THEREOF'WITH JLTRASOUND

;ulohCo. Inc. ' , a Nevada corDoration (Name of Assignee) (Type of Assignee, e.g.. corporation, partnership. university, government agency, etc.)

itates that it is:

0 . the assignee of the entire right, title, and interest: or 1.

2.

n the patent applicationlpatent identified above by virtue of either:

4. LEI An assignment from the inventor(s) of the patent applicationlpatent identified above. The assignment was recorded in the Patent and Trademark Oftice at Reel -, Frame -, or for which a copy thereof is attached.

an assignee of the undivided part interest of Rudolf W. Gunnerman

3R

3 . 0 A chain of title '$0" the inventor@), of the patent applicationlpatent identified above, to the current assignee as shown below:

I. From: - To :- The document was recorded in the United States Patent and Trademark Office at Reel -, Frame -, or for which a copy thereof is attached.

2. From: To :- The document was recorded in the United States Patent and Trademark Office at Reel -, Frame -, or for which a copy thereof is attached.

3. From: __ To :- The document was recorded in the United States Patent and Trademark Office at Reel -, Frame -, or for which a copy thereof is attached.

0 Additional documents in the chain of title are listed on a supplemental sheet.

0 Copies of assignments or other documents in the chain of title are attached. m: A separate copy (i.e., the original assignment document or a true copy of the original document) must be submitted to Assignment Division in accordance with 37 CFR Part 3;if the assignment is tozbe recorded in the records of the USPTO. See MPEP 302.81

The undersigned (whose title is supplied below) is empowered to sign

P ~ f i i B,, li~) I G (744 i

Date I si atdie

d d d ./ I fk?;, Gin,wrn7.U.cL Typed or printed name

c Li),;r - fik +. C.? E L> Title

Burden Hour Statement: This form is estimated to take 0.2 hours to complete. Time will vary depending upon the needs of the individual case. Any comments on the amount of time you are required to complete this form should be sent to the Chief Information Officer, US. Patent and Trademark Office, Washington. DC 20231. DO NOT SEND FEES OR COMPLETED FORMS TO THIS ADDRESS. SEND TO: Assistant Commissioner for Patents, Washington, DC 20231.

SF 1292557 VI

.- . . ._ . . ..

Attorney Docket No.: 020839-0003OOUS +

ASSIGNMENT OF PATENT APPLICATION SOLE’

WHEREAS, Rudolf W. Gunnerman, a citizen of the U.S.A. residing at 6601 Lakeside Drive, Reno, NV 895 11; hereinafter referred to as.“Assignor,” is one of the inventors of the invention described and set forth in the below-identified application for United States Letters Patent:

Title of Invention: TREATMENT OF CRUDE OIL FRACTIONS, FOSSIL FUELS, AND PRODUCTS THEREOF WITH ULTRASOUND

Filing Date: May 22,2001

Application No.: 091863,127; and

WHEREAS, SulphCo, Inc., a corporation of the state of Nevada, located at 1650 Meadowood Lane, Reno, NV, 89502, hereinafter referred to as “ASSIGNEE,” is desirous of acquiring an interest in the invention and application and in any U.S. Letters Patent and Registrations which may be granted on the same;

For gqod and valuable consideration, receipt of which is hereby acknowledged by Assignor, Assignor has assigned, and by these presents does assign to Assignee all right, title and interest in and to the invention and application and to all foreign counterparts (including patent, utility model and industrial designs), and in and to any Letters Patent and Registrations which may hereafter be granted on any patent application claiming priority from the same in the United States and all countries throughout the world, and to claim the priority from the application as provided by the Paris Convention. The right, title and interest is to be held and enjoyed by Assignee and Assignee’s successors and assigns as fully and exclusively as it would have been held and enjoyed by Assignor had this Assignment not been made, for the full term of any Letters Patent and Registrations which may be granted thereon, or of any division, renewal, continuation in whole or in part, substitution, conversion, reissue, prolongation or extension thereof. 9

Assignor further agrees that Assignor will, without charge to Assignee, but at Assignee’s expense, (a) cooperate with Assignee in the prosecution of US. Patent applications and foreign counterparts on the invention and any improvements, (b) execute, verify, acknowledge and deliver all such further papers, including applicatioris and instruments of transfer, and (c) perform such other acts as Assignee lawfully may request to obtain or maintain Levers Patent and Registrations for the invention and improvements in any and all countries, and to vest title thereto in Assignee, or Assignee’s successors and assigns.

I *

IN TESTIMONY WHEREOF,

1

Dated: I I - I 9 -a001

ss. COUNTYOF 0- 1

On 1 1 - Iq-2.00 1 ,beforeme, %@3’WWL dD w), personally appeared , per!donally known to me (or proved to & on the basis of satisfactory evidence) to be the person whose name is subscribed to the within instrument, and acknowledged to me that helshe executed the same in hisher authorized capacity, and that by hisher signature on the instrument the person, or the entity upon behalf of which the person acted, executed the instrument.

,WITNESS my hand and official seal.

Rudolf W. Gunnerman

I .- -

NOTARY PUBLIC ~..m.nmam..mu..mw~..................H.

My Commission Expires: 9 - 7- dOOs JOANNA L, CLONINGER i

Sent. 7. 2005 P

State of Nevada I Number 93-0533-2 I

SF 1292589 VI

I hereby certify that this con.espondet;ce is being deposited with the United Staies Postal Setvice as first class mail in an envelope addressed to: Attorney Docket No.: 0 2 0 8 3 9 - 0 0 0 3 Q ~ ~ ~ <’ Assistant Commissioner for Patents Washington, D.C. 20231

TOWNSEND and TOWNSEND and CREW l,LP - By:

I

IN THE UNITED STATES PATENT AND TRADEMARK OFFICE

Sir:

.. 5 - s - o a

In r application of:

Rudolf W. Gkm&al.

Filed: May 22, 2/

Application No.: 09/8

ULTRASOUND

Assistant Commissioner for Patents Washington, D.C. 20231

Examiner: uyL*- Art Unit:

INFORMATION DISCLOSURE STATEMENT UNDER 37 CFR $1.97 and 61.98

The references cited on attached form PTO-1449 are being called to the

attention of the Examiner. Copies of the references are enclosed. It is respectfully requested

that the cited references be expressly considered during the prosecution of this application, and

the references be made of record therein and appear among the “references cited” on any

patent to issue therefrom.

As provided for by 37 CFR 1.97(g) and (h), no inference should be made that

the information and references cited are prior art merely because they are in this statement and

. .. . . _. ...

Rudolf W. Gunnerman, et ab Application No.: 09/863,127 Page 2

PATENT

---. no representation is being made that-a search has been conductedbr that this statement

encompasses all the possible relevant information.

Applicant believes that no fee is required for submission of this statement, since

it is being submitted prior to the first Office Action. However, if a fee is required, the

Commissioner is authorized to deduct such fee from the undersigned's Deposit Account No.

20-1430. Please deduct any additional fees from, or credit any overpayment to, the above-

noted Deposit Account.

Respectfully submitted,

M. Henry Heines Reg. No. 28,219

TOWNSEND and TOWNSEND and CREW LLP Two Embarcadero Center, 8'h Floor San Francisco, California 941 11-3834 Tel: 415-576-0200 Fax : 4 1 5 - 5 7 6-03 00 MHH:mcd

SF 1258948 VI

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- .. . UNITED STATES

CONFIRMATION NO. 9590 FORMALITIES LETTER

I llllllll llllllll lllll111111111111111 lllll lllll lllll lllll11111111111111111111 IIIII lllll11111111 AND TOWNSEND AND CREW CADEROCENTER '0C000000006337274' EIGHTH FLOOR

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NOTICE TO FILE MISSING PARTS OF NONPROVISIONAL APPLICATION

FILED UNDER 37 CFR 1.53(b) <

Filing Date Granted

An application number and filing date have been accorded to this application. The item(s) indicated below, however, are missing. Applicant is given TWO MONTHS from the date of this Notice within which to file all required items and'pay any fees required below to avoid abandonment. Extensions of time may be obtained by filing a petition accompanied by the extension fee under the provisions of 37 CFR 1 .I 36(a).

The oath or declaration is missing. A properly signed oath or declaration in compliance with 37 CFR 1.63, identifying the application by the above Application Number and Filing Date, is required. To avoid abandonment, a late filing fee or oath or declaration surcharge as set forth in 37 CFR 1.16(e) of $130 for a non-small entity, must be submitted with the missing items identified in this letter. The balance due by applicant is $130.

A copy of this notice MUST be returned with the reply. ,, 8 . 7

Customer Service Center \I Initial Patent Examination I ivision (703) 308-1202 ' PART 2 - COPY TO BE RETURNED WITH RESPONSE

- . -- ..... _.

. _ -. f

. .

. .. .. _._- - .

' I

6 KELLY

TELEPHO N e ( 7 7 6 1 7se-qe4e

December 26,2001

Applicant: Mark Cullen and Paul Moote Serial No. : 091862,127

Filed: 5/22/01

Coin missioner U .S. Patent & Trademark Office Washington, D.C. 20231

For: TREA' FRACTIONS P R O D U C T S ULTRASOUND

1

Dear Sir:

Transmitted herewith is a declaration for two of the inventors, These inventors are represented by the undersigned and not the townsend firm who originally filed the case., a Certificate of Mailing, and a Blue Card. Please call if there are any questions.

Sincerely,

BRIAN C. KELLY

Reg. No. 32,249

BCK:fkh

End.

Received from < at 317102 9:06:14 PM [Eastern Standard Time]

I

Page. 1 of 1

UNITED STATES PATEM AND TRADEMARK OFFICE WASHINGTON. D.C. 20231

1 www.uspto.qov \.u

I I AlTORNEY DOCKET NUMBER F8N NUMBER FlLING/RECEIPT DATE FIRST NAMED APPLICANT

091863,127 05/22/2001 Rudolf W. Gunnerman 020839-0003OOUS

CONFIRMATION NO. 9590 20350 TOWNSEND AND TOWNSEND AND CREW, LLP TWO EMBARCADERO CENTER EIGHTH FLOOR SAN FRANCISCO, CA 941 11 -3834

FORMALITIES LETTER

'0C000000007248398'


NOTICE OF INCOMPLETE REPLY (NONPROVISIONAL)

filing Dale Granted

The U.S. Patent and Trademark Office has received your reply on 12/18/2001 to the Notice to File Missing Parts (Notice) mailed 07/25/2001 and it has been entered into the nonprovisional application. The reply, however, does not include the following items required in the Notice.

The period of reply remains as set forth in the Notice. You may, however, obtain EXTENSIONS OF TIME under the provisions of 37 CFR 1.1 36 (a) accompanied by the appropriate fee (37 CFR 1 . I 7(a)).

A complete reply must be timely filed to prevent ABANDONMENT of the above-identified application.

The required items noted below SHOULD be filed along with any items required above. The filing date of this nonprovisional application will be the date of receipt of the items required above.

0 The signature of the following inventor(s) is missing from the oath or declaration: Paul S. Moofe, Mark T. Cullen

\

A copy of this notice MUST be returned with the reply.

5 K Customer Service Center Initial Patent Examination Division (703) 308-1202

PART 3 - OFFICE COPY

--. . . . . . _ _ , . -

As a below named invantor, I declarc that:

My residence, post oEfice address and citizenship are as stated below next to my name; I believe I am the origidsl, first ~d sole inventor (If only,onc name is listed below) or an original, first and joidt inventor (if plural inventors are namcd below) of the subject matter which is claimed and far which a patent is sought on the invention entitled: T R E A m N T 08 CRUDE OIL FRACTIONS, FOSSIL FUELS, AND PRODUCTS TI[.IEREQF WITH ULTRASOUND the specification of which - is attached hereto or

Y wasfiledon M ay 22.2001 as Application No. 091863,127 and was amended on - (ifapplicablc).

I have revicwed and undcrstand thc contents of thc above identified specificatioa, including thc claims, as amended by any amen&mnt tefened to above. I acknowledge thc duty to disclosc bf'omtion which is material to patentability as d e h e d in Title 37, Code of Federal Regulations, Section 1.56. I claim foreign priotiry benefits under Tidc 35, Unitcd States Codo, Section I19 af any foreign application{s) for patent or inventor's certificate listed below and have also idcnrified below any foreign application for patcnt or inventor's certificate having a filing dah before that of the ppplication on which priority is claimed.

Country Application No. Date of Filing Priority Claimed Under

35 USC 119

I-

,Application No. FilinR Date

I claim ale benefit under Title 35, United Stat& Code, Section 120 of any United States application(s) listed below and, hsofar as thc subject m#er of each of the claims of this application is not disclosed in the prior United Slates application in the manner provided by the fust pamgraph of Title 35. United Statw &de, Section 112, I acknowledge the duty to disclose material information as defined in Title 37, Code of Federal Regulations, Section 1.56 which occurred betwccn the f&g datc of the prior application and the national or PCT intcmational. filing date of this application:

Application NO. Date of Filing status

_."I

I Full Namof I FintNam: I Middle Name or Initial:

Citizenship: ]Reno Nevads United Slatcs

Address: 6601 Lalceside Drive Reno Nevada 8951 1 Post Office P ~ t O f i c e hddwss: Ciry: SfdLcfCounrry: Poslal Codc:

Inventor 2: MOOTE PAUL S. Country of Citizenship: .. - Full Name of Last Name: Flnt Namc: Middle Nom or Initial;

Residence & City: Statckoreign Country: Citizenship; Park City Utah United Statcs Post Office

.. Pas1 Ollicc Address: Ciry: sLale/Counky: Pwul Code:

Addrcss: 2440 Lowcr Landa Lane Park City Utah 84098

I of2 Received from at 317102 9:06:14 PM [Eastern Standard Time]

... . . . . . - - - - - . . . .. . ...

M OU3 08-/15/01 a D 07:26 FAX 801 524 2878 Slhclair Oil Engineerins .I._ ,.. ..;:

State of Utah County o f Salt L a b

This insrmment was acknowledged bafate.me on August 10, 2001 by Paul S. Moot

20fZ

Received from 4 > al317102 9:06:14 PM [Eastern Standard Time]


Priority Claimed Under Country Application No. Date of FilinR 35 USC 119

My residence, post offlce address and citizenship arc as stated below next to my namc; I believe I am the original, fmt and sole hvcntor (ifonly one name is listed below) or an original, first and joint inventor (ifplural inventors are named below) of the subjcct matter which is claimed and for which a patent is sought on the invention entitled: TREATMENT OB CRUDE OIL FRACTIONS, FOSSIL FmLS, AND PRODUCTS THEREOF WITH ULTRASOUND the specification of which - is attached bpreto or

X was filed os May 22.2001 as Application No. 09B63.127 twd was amended on (if applicable).

Application No.

I have reviewed and understand Ihc contents o l the above idcntified specification, inchding the claims, as amended by any amendment reftrrcd to above. I acknowledge the duty to disclose infbrmation which is material to patcntability as defined in Title 37, Cadc of Federal Regulations, &chon 1.56. I claim foreign priority benefits under Titk 35, United States Code, Section 119 of any foreign application(s) for pateut or hvsntor's certificate listed below and have also identified bclow any foreign appIication for palcnt or inventor's certificate having a filing date bcfore that of the application on which priority is claimed.

Filing Date

Application No. Date of Filing status

I claim the benefit under Title 35, United States Code, Section 120 of any Unitcd States application(s) listed bclow and, insofar as t hc subject matter of each of the claims of this application is not disclosed in the prior United Statcs application in the manner provided by the first paragraph of Title 35; United States Code, Section 112, T acknowledgc the duty to disclose material information tu ddud in Titk 37, Code of Federal Regulations, Section 1.56 which occurred between thc mug date of he pdor application and the national or PCT intcrnatioaal filing date of this application:

Nevada Unitcd Stales post Office Post Omce Addrcss: City: Sta~Country: PMPI Code:

Full Name of Lasl Name: First Name: Middfc Nam or Initial:

Residtncc & City: Statflareign Country: Cdunby ofcitizenship: Citizenship; Park City Utah United States Post Office POSI Oficc Address: City: SudCauntry: POSUI Code;

Addrcss: 6601 Lakcside Drive Reno Nevada 8951 1

Inventor 2: MOOTE PAUL s. ..,- -

~ Addrcss: 2440 Lower Lando Lane Park City Utah 84098 1

t I I

f Full N a m of 1 FirsrNam: I Middle Namc or Initial: 1

1 of2

Received horn at 317102 8:56:12 PM [Eastern Standard Time]

Scatrc of Utah County oE Salt Lake

This i a s t m e n t was acknowledged before me an August IO, 2001 by Paul S. Moot

2 o f 2

Received from < a[ 317102 8:56:12 PM [Eastern Standard time]

. _- - ----- -___._.

.

country

I hereby claim the benefit'under Title 35. United States Code 4 1 lS(e) of any United States pravisiorlal application(s) listed below:

Priority Claimed Under Applicatioa No. Date of Filing 35 USC 119

I Application No. I Piling Date t

Application No.

I claim the benefit undct Title 35, United Stetes Code, Section 120 of any United States application(s) listed below and, insofar as the sabject matter of each of the claims of this application Is not disclosed in the prior United Statcs application in the manner provided by the first paragraph of Title 35, United States Code, Section 112, I acknowledge thc duty to disclose niatttial information as defined in Title 37, Code of Federal Regulations, Scction 1.56 which occurred between the filing date of the prior application and the national or P a international f i i date of this application:

Date of Filing Status

." FUI~ ~ n r n or h t Namc: First Namc: Middlc Nartleor Initial: lnvmlor I : GUNNJ3RMAN RUDOLF w. Residence & City: SratclFoni~1 Counby: Country of Citizenship: Citizenship: Reno Nevada Unitcd States post Ofice POI\ Officc Address: .' City: SIHWCountry: Postal Codc: Address: 6601 takwide Drive Rcno Nevada 89511 Full Name of Last N w r ~ ~ l First Nsnx: Middlc Name or Initial; lnvenior 2: MOOTE PAWL S. Residence & City: StatePoreign Country: Counuy of Citizenship: Citizenship: Park City Utah United States Post Office PoslOffKt Addngr: C i y StaieKountry: 1 postal C O ~ C : Address: 2440 Lowcr Lando Lane Park City Utah . 184098

I-

I I I J

1 of2 Received from 4 at 317102 9:06:14 PM [Eastern Standard Time]

----- - - . .- . -.. . ' -. _-

’ c. . . -.

Full Name of b s t Nnme: First N m : bventor 3: CULLEN Residence & City: SmtdFwign Caunby:

Citizenship: Reno post 0rnc.e Post O f h Addlass: Civ. Address:

MARK

Nevada

5605 Btooheadow Lane Reno

Middle NIW or Initial: T. Cwntry ofcitizenship: Unitcd States SukKoudtty: Pos~al Code: Nevada 89511

I further declare that all statements made herein of my own knowledge are true and that all statements made on information and belief are believed to be truc; and further that these statements were made with the knowledge that willfbl false statements and the like so made are punishable by fine or Imprisonment, or both. udder Section 1001 of Title 18 of the United States M e , and b t such willful false statements my jeopardize the validity of the application or any patent issuing thereon.


-.Rudolf W. Gunnerman ,.,,

-Date

I Signaturc of Invcntor 2

Faul S. Moote

Date

I

.-.7--”_--- Mark T. Cullcn Date VQ o /

I / I

SF 1227250 VI

Received from 4 at 317102 9:06:14 PM [Eastern Standard Time]

- - - ~ __- - - - - ---- . - -_


country c Priority Claimed Under

Application No. Datc of Filina 35-USC 119

i I 1 I

Application No. FilinLDatc

AppLication No.

Inventor I: Rcsidence gL

Date of Filinp ., Status \

.Citizenship: Post Office Addrcss: Full Name of

Full Name of I LaatNnmc: CUNNERMAN

Reno

6601 Lakeside Drive Last Name: MOOTE

city:

P& Ofticc Address:

Inventor 2: Residedcc & Citizenship: Post Oflice Addrcsr:

Fiat Namc: Middle N a m or Initial:

SUWbmign Country: Country of Citizenship:

City: SvirelCounlry: Yostal Codc:

RUDOLF w.

Nevada United States

Reno Nevada 89511

PAUL S.

....-

First Num: Middle N a m or Initial:

City: Park City Pos! Oftkc Address:

, 2440 Lowcr Land@ Lane

S t a f l o n i g n Country: Country of Citizenship: Utah United Statcs City: Park City Utah 84098

Staidcountry: Postal Cods:

101-2


. __- - - - - . - - . - - .

-- -. I Full Name of 1 Last Name: I FiktName: I Middle Namc or InlUal: 1

~ ~


I -. Rudolf W. Gunnerman - ._”_

I Date

Citizenship: I Reno I Nevada I United States ’

Post OfFice 1 Post Oficc Address: I City: I State(Coun9: [ ~ o t i ~ ~ d e :


- Paul S. Moote

Date Date

.”-” - Mark T. Cullen

I Address: I 5605 Brookmeadow Lane I Keno I Nevada I8951I I

I further declare that all statements made herein o f my own knowledge are we and that all starerntnts made on inf~rmation and &lief arc believed to be hue; and further that these statements were mado with the knowledge that Willful false statements and the likc so made are punishable by fme or imprisonment, or both, under Section 1001 of Titlc 18 of the United States Code, and that such willful false statements may jeopardize thc validity of thc application or any patent issuiug thcreon.

SF 1227250 v l

2 of2

Received from c at 3171028:56:12 PM [Eastern Standard Time]

PTO158197 (W(W

Certificate of Transmission under 37 CFR 1.8

I hereby cenlfythafthis correspondence is being facsimile transmitted to the Uniled States Patent and Trademark Office

,' bate

g r / . - c fi<+ 3 2 Z Y Y Typed or printed name erson signing Certificate

Note: 'Each paper must have it5 own ceniflcate of transmission. or this certificate must identify each submitted paper.

Buden Houf Slatcment' I hls lWm is cairnawl 10 lahe 0 05 hours 10 mmplnc Tim wlll vaf depmtding upon ihe nerds al h e indivldunl a i r . A mmrnana on Ine imbunl d Ume required Io compleie Ihis farm should k'e'eni 10 lhn C h f In(ormnlion Omtor. US. Palent and T t a d e m m Ozte, Washi ion, DC 20131. UO NOT SEND FEES OK COMPLETED FORMS TO THIS AODII€SS. SEND T O Aristant Commirsibhcr for Palenis. WashingtOfl. '&: 20231.


. . . . . - . . . . . - .

-.. -

PTOISWW paw) Approved foc d t thr h 10hllZW2 OM8 4651-oI131

US. Pawn1 nnd lreaembh 0 lma U.SOL%EPARTUENT OF COMMERCC Idec ltw P- R ~ I W w or 1995. M pecuns are requid (D respond UI B rrmcctm or inkmthn A n mnwm a U ~ M OM t l M b d rumba

PTOISWW paw) h 10hllZW2. OM8 4651-oI131

US. Pawn1 nnd lreaembh 0 lma U.SOL%EPARTUENT OF COMMERCE Approved foc d t thr

Idec ltw P- R ~ I W w or 1995. M pecuns are requid (D respond UI B rrmcctim or inkmthn A L mnw?ins a U ~ M OM t l M b d rumba


I hereby certify that this correspondence is being facsimile transmitted lo the United States Patent and Trademark Office

on

-

Note: Each paper must have its own certificate ofvansmissian; of this certificate must identify each submitted paper.

Received from < at~!i71028:56:12 PM [Eastern Standard Time]

- - .._ - - I_..-_ - -. .

-. . .


I hereby certify that this correspondence is being facsimile transmitted to the United States Patent and TrademarkOffice

bate

I_

Typed or printed nwne &wsm signing Ceriificate

Note: Each paper must have its own certificate of transmission, or lhis certificate must identify each submined paper.


. _ _ - __---____ _ _ - .


I hereby certify that this correspondence is being facsimile transmitted to the United States Patent and Trademark Office

6ate

Nore: Each paper must have its own certiAcam of tranmnsion, or this certificate must idenrify .each submined paper.

Received from at 317102 9:06:!4 PM (Eastern Standard Time]

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Certificate of Transmission under 37 CFR 1,8

hereby certify that this correspondence is being facsimile transmitted to the Jnited States Patent and Trademark Office

on 3/7AL 6ato

- Signature

gr;-c.fi//+. 3 2 2 4 7 Typed or prinled name d'$kon signing Certificate

Note: Each paper must have its own certificate of transmission. or this cenificale must Identify each submitted paper.

Recelved from at 317102 9:06:14 PM [Eastern Standard Tlme]

- _ - - - _ _


I hereby cettifythatthis correspondenceis being facsimile transmitted tothe United States Patent and Trademark Office

on ate

Typed or printed name fierson signlng Ceniificate

Note: Each paper must have its own ceniflcale oltransmission, or lhis ceitilicate must identify each submitted paper.


UNITED STATES PATENT AND WEMK OFFICE UNITED STA'I'ES DEPAR'lTvlENT OF COMMEHCE Uoiiud $tuius Puiunt and 'I'rudumrrk Ofliou Address COMMISYIONER OF PATENTS AND TRADEMARICB .

Woshinoton D C 20291

ART UNIT

APPLICATIONNO. I FILING DATE I FlRST NAMED INVENTOR I ATTORNEY DOCKET NO. I CONFIRMATION NO. I

PAPER NUMBER

09/863,127 05/22/2001 Rudolf W. Gunnerman 020839-0003OOUS 9590

20350 7590 12/18/2002

TOWNSEND AND TOWNSEND AND CREW, LLP TWO EMBARCADERO CENTER EIGHTH FLOOR SAN FRANCISCO, CA 941 11-3834

I EXAMINER I NGUYEN, TAM M

Please find below andor attached an Office communication concerning this application or proceeding.

PTO-90C (Rev. 07-01)

. - Application No.

091863,127 Oflice Acfion Summary Examiner

W Applicant(s) 3 GUNNERMAN ET AL.

Art Unit

1764 I ~ I TamM.Nguyen -- The MAILING DATE of this communication appears on the cover sheet with the'correspondence address --

'eriod for Reply

A SHORTENED STATUTORY PERIOD FOR REPLY WET TO EXPIRE 3 MONTH(S) ,FROM THE MAILING DATE OF THIS COMMUNICATION. - Extensions of time may be available under the provisions of 37 CFR 1.136(a). In no event, however, may a reply be timely filed . after SIX (6) MONTHS from the mailing date of this communication.

- If the period for reply specified above is less than thirty (30) days, a reply within the statutory minimum of thirty (30) days will be considered timely. - If NO period for reply is specified above, the maximum statutory period will apply and will expire SIX (6) MONTHS from the mailjng date of this communication. - Failure to reply within the set or extendea period for reply will, by statute, cause the application to become ABANDONED '(35 U.S.C. - Any reply received by the Office later than three months'after the mailing date of this communication, even if timely filed, may reduce any

earned patent term adjustment. See 37 CFR 1.704(b). '

'

133).

status

1 ) m Responsive to communication(s) filed on 22 May 2001 . 2a)O .This action is FINAL. 2 b ) B This action is non-final.

.3)0 Since this application is in condition for allowance except for formal matters, prosecution asdo the merits is closed in accordance with the practice under Ex parte Quayle, 1935 C.D. 11,453 O.G. 213.

Xsposition of Claims

4 ) m Claim(s) 1-50 islare pending in the application.

4a) Of the above claim(s) islare withdrawn from consideration.

5)O Claim(s) islare allowed.

6)m Claim(s) 1-50 islare rejected.

i ) ~ Claim(s) islare ' objected to.

8)o Claim@) are subject to restriction andlor election requirement. Application Papers

9 ) m The specification is objected to by the Examiner.

1O)o The drawing(s) filed on islare: a)C] accepted or b ) o objected to by the Examiner.

1 1 ) o The proposed drawing correction filed on . is: a ) O approved b ) O disapproved by the Examiner.

1 2 ) o The oath or declaration is objected to by the Examiner.

Applicant may not request that any objection to the drawing(s) be held in abeyance. See 37 CFR 1.85(a).

If approved, corrected drawings are required in reply to this Office action.

Priority under 35 U.S.C. 55 119 and 120

1 3 ) n Acknowledgment is made of a claim for foreign priority under 35 U.S.C. Q 119(a)-(d) or (f).

a ) n All .b)O Some * c ) n None of:

. 2 . 0 Certified copies of the priority documents have been received in Application No. .

b 1 .n Certified copies of the priority documents have been received.

3 . 0 Copies of the certified copies of the priority documents have been received in this National Stage, application from the International Bureau (PCT Rule 17.2(a)).

* See the attached detailed Office action for a list of the certified copies not received.

1 4 ) o Acknowledgment is made of a claim for domestic priority under 35 U.S.C. Q 119(e) (to a provisional application).

a) 0 The translation of the foreign language provisional application has been receivsd. 1 5 ) o Acknowledgment is made of a claim for domestic priority under 35 U.S.C. 99 120 andlor 121.

Attachment(s)

1) [XI Notice of References Cited (PTO-892) 2) 0 Notice of Draftsperson's Patent Drawing Review (PTO-948) 3) [XI Information Disclosure Statement(s) (PTO-1449) Paper No(s) 3 .

4) 0 Interview Summary (PTO-413) Paper No(s). __ . 5) 0 Notice of Informal Patent Application (PTO-152) 6) 0 Other:

S. Patent and Trademark OMce PTO-326 (Rev. 04-01) Office Action Summary Part of PaperNo. 7

. . . .

Application/Control Number: 09/863,127 Art Unit: 1764

Page 2

- DETAILED ACTION

Double Patenting

The nonstatutory double patenting rejection is based on a judicially created doctrine grounded in public policy (a policy reflected in the statute) so as to prevent the unjustified or improper timewise extension of the "right to exclude" granted by a patent and to prevent possible harassment by multiple assignees. See In re Goodman, 11 F.3d 1046,29 USPQ2d 2010 (Fed. Cir. 1993); In re Longi, 759 F.2d 887,225 USPQ 645 (Fed. Cir. 1985); In re Van Ornzim, 686 F.2d 937,214 USPQ 761 (CCPA 1982); In re Vogel, 422 F.2d 438,164 USPQ 619 (CCPA 1970);and, In re Thorington, 418 F.2d 528, 163 USPQ 644 (CCPA 1969).

overcome an actual or provisional rejection based on a nonstatutory double patenting ground provided the conflicting application or patent is shown to be commonly owned with this application. See 37 CFR 1.130(b).

disclaimer. A terminal disclaimer signed by the assignee must filly comply with 37 CFR3.73(b).

A timely filed terminal disclaimer in compliance with 37 CFR 1.321(c) may be used to

Effective January 1, 1994, a registered attorney or agent of record may sign a terminal

r

Claims 1, 3-37, and 45-50 are rejected under the judicially created doctrine of

obviousness-type double patenting as being unpatentable over claims 1-33 of U.S. Patent No.

6,402,939. Although the conflicting claims are not identical, they are not patentably distinct

from each other because the present claimed process is similar to the claimed process of the U.S.

Patent in terms of combining a hydrocarbon feed with an aqueous liquid to form an emulsion,

exposing the emulsion with ultrasound and recovering an organic phase from an aqueous phase.

The claimed process of the U.S. Patent does not specifically disclose that the hydrocarbon feed is

a crude oil fraction. However, the hydrocarbon feed of the U.S. Patent is a fossil fuel.

Therefore, it would have been obvious to one having ordinary skill in the art at the time the

invention was made to have modified the claimed process of the U.S. Patent by using a crude oil

fraction because one of ordinary skill in the art would employ any hydrocarbon feed in the

claimed process of the U.S. Patent including a crude oil fraction as claimed in the process of

claims 1,3-37, and 45-50.

.

ApplicatiodControl Number: 09/863,127 Page 3 Art Unit: 1764

SpeciJication -

The disclosure is objected to because of the following informalities: the limitation “no

hydroperoxide is added to said crude oil fraction or incorporated into said aqueous liquid in

forming said emylsion” in claims 2 and 46 was not described in the present specification

Appropriate correction is required.

Claim Rejections - 35 USC 8 112

The following is a quotation of the second paragraph of 35 U.S.C. 112:

The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.

Claims 21-23 are rejected under 35 U.S.C. 112, second paragraph, as being indefinite for r

failing to particularly point out and distinctly claim the subject;matter which applicant regards as

the invention.

Claims 21-23 recite the limitation “said aqueous fluid” in line 2 of the claims. There is

insufficient antecedent basis for this limitation in the claims.

Claim Rejections - 35 USC 8 103

The following is a quotation of 35 U.S.C. 103(a) which forms the basis for all

obviousness rejections set forth in this Office action:

(a) A patent may not be obtained though the invention is not identically disclosed or described as set forth in section 102 of this title, if the differences between the subject matter sought to be patented and the prior art are such that the subject matter as a whole would have been obvious at the time theinvention was made to a person having ordinary skill in the art to which said subject matter pertains. Patentability shall not be negatived by the manner in which the invention was made.

. .. . . . . . . . , . ,

ApplicationlControI Number: 09/863,127 Art Unit: 1764

Page 4

The factual inquiries set forth in Gtaharn v. John Deere Co., 383 U.S. 1, 148 USPQ 459

(1966), that are applied for establishing a background for determining obviousness under 35

U.S.C. 103(a) are summarized as follows: -

1. 2. 3. 4.

Determining the scope and contents of the prior art. Ascertaining the differences between the prior art and the claims at issue. Resolving the level of ordinary skill in the pertinent art. Considering objective evidence present in the application indicating obviousness or nonobviousness.

This application currently names joint inventors. In considering patentability of the

claims under 35 U.S.C. 103(a), the'examiner presumes that the subject matter of the various

claims was commonly owned at the time any inventions covered therein were made absent any

evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out

the inventor and i'invention dates of each claim that was not commonly owned at the time a later

invention was made in order for the examiner to consider the applicability of 35 U.S.C. 103(c)

and potential 35 U.S.C. 102(e), ( f ) or (g) prior art under 35 U.S.C. 103(a).

Claims 1-50 are rejected under 35 U.S.C. l03(a) as being unpatentable over Collins et al.

(EP-482841) in view of Jeanblanc (WO-00/15734).

Collins discloses a process for removing sulfur compounds from a hydrocarbon oil (e.,g.,

diesel fraction) by combining the oil with an aqueous solution of an oxidant such as hydrogen

peroxide and catalyst comprising tungsten. The volume ratio of the aqueous solution to the

.hydrocarbon oil is from 1 to 10. An organic phase which is reduced in sulfur is separated from

the aqueous phase. Collins also discloses that an oxidant such as hydrogen peroxide, oxygen, or

air can be used in the process. (See entire patent)

.

. .

Application/Control Number: 09/863,127 ~

Art Unit: 1764 Page 5

Collins does not disclose the use of ultrasound, does not disclose-the frequency and - -

intensity ranges of the ultrasound, does not disclose that the ultrasound exposure is at a sufficient

intensity and time to cause an increase in MI gravity or raise the cetane index, and does-not

disclose the amount of hydrogen peroxide in the aqueous solution.

Jeanblanc discloses an oxidation process of hydrocarbon liquid to remove sulfur

compounds by reacting the liquid at a temperature from 0 to 121' C and wherein ultrasound is

used during the oxidation step. (Seepages 5-8)

It would have been obvious to one having ordinary skill in the art at the time the

invention was made to have modified the process of Collins by utilizing ultrasound as taught by I

Jeanblanc because the removal of sulfur will be enhanced when employing ultrasound.

It would have been obvious to one having ordinary skill in the art at the'time the

invention was made to have modified the process of Collins/Jeanblanc by using the claimed

frequencies and intensities because Jeanblanc teaches that any type, intensity, and manner of

application of energy that is effective to increase the removal sulfur from the hydrocarbon can be

used in the process.


invention was made to have modified the process of Collins by exposing the hydrocarbon feed

mixture with ultrasound at a sufficient time to cause an increase in API and cetane index because

one of skill would operate the process of Collins with ultrasound at any sufficient time to cause

an increase in API and cetane index if one desires.


invention was made to have modified the process of Collins by using an aqueous solution having

Application/Control Number: 09/863,127 ArtUnit: 1764

Page 6

the claimed amount of hydrogen peroxide because one of skill would2mploy an aqueous

’ solution containing any amount of hydrogen peroxide including the claimed amount and it would

be expected any concentration of hydrogen peroxide in an aqueous solution would give similar

results in the process of Collins.

It is noted that both Collins and Jeanblanc do not disclose the limitations “the process for

desulfurizing a hydrocarbon oil is reduce levels of olefins, aromatics, sulfur-bearing compounds,

and nitrogen-bearing compounds and to raise the API gravity thereof’ and “lower the density of

the hydrocarbon oil”. However, these limitations are in the preamble of the claims that only state

a purpose of the invention, rather than any distinct definition of any of the claimed invention’s

limitations. Therefore, the preambles are not considered limitations for the invention.

Furthermore, the modified process of Collins is similar to the claimed process in terms of

feedstock, aqueous solution, catalyst, and ultrasound. Consequently, it would be expected that

the modified process of Collins would provide similar results as claimed.

Conclusion

The prior art made of record and not relied upon is considered pertinent to applicant’s

disclosure. \

The prior art made of record not relied upon discloses desulhrization process in which

utilizes ultrasonic energy.

Any inquiry concerning this communication or earlier communications from the

examiner should be directed to Tam M. Nguyen whose telephone number is (703) 305-7715.

The examiner can normally be reached on Monday through Thursday.

ApplicatiordControl Number: 09/863,127 Art Unit: 1764

Page 7

If attempts to reach the examiner by telephone are unsuccessful, the examiner’s

supervisor, Glenn Caldarola can be reached on 703-308-6824. The fax phone numbers for the -

organization where this application or proceeding is assigned are (703) 305-5408 for regular

communications and (703) 305-93 11 for After Final communications.

Any inquiry of a general nature or relating to the status of this application or proceeding

should be directed to the receptionist whose telephone number is (703) 308-0661.

Tam M. Nguyen Examiner

. Art Unit 1764

Tam Nguyed TN December 1 1,2002 d k Q . 0 4

Walter D. Griffin Prhnary Examiner

. . ... ..

Notice of References L

Examiner Art Unit Tam M. Nguyen 1764 Page 1 of 1

.~ I ApplicationlControl No. I Applicant(s)lPatent Under 1

* A

B

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E

F

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Cited

Document Nymber Date Classification -. Name Country Code-Number-Kind Code MM-YYYY

US-4,391,608 07-1983 Dondelewski, Michael A. 441624

US-6,402,939 06-2002 Yen et al. 20811 96

us- US-

US-

US-

US-

US-

us- US-

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FOREIGN PATENT DOCUMENTS

1 091863,127

Date Document Number

* N EP-0482841 04-1 992

* Country Code-Number-Kind Code MM-YYYY

0

P

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Reexamination GUNNERMAN ET AL.

Classification Name Country

Europe Collins et al.

I I I I U.S. PATENT DOCUMENTS

* Include as applicable Author, Title Date, Publisher, Edition or Volume, Pertinent Pages)

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US. Palen! and Trademark Office PTO-892 (Rev. 01-2001) Notice of References Cited Part of Paper No. 7

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'EXAMINER: Initial if reference considered, whether or not citation is in conformance with MPEP 609. Draw line through citation if not in conformance and not considered. Include copy of this form with next communication to applicant.

" Unique citation designation number. ' See attached Kinds of US. Patent Documents. Enter Office that issued the document, by the two-letter code (WIPO Standard ST.3). .I For Japanese patent documents, the indication of the year of the reign of the Emperor must precede the serial number of the patent document. Kind of document by the appropriate symbols as indicated on the document under WlPO Standard ST. 16 if possible. e Applicant is to place a check mark here if English language Translation is attached. Burden Hour Statement: This form is estimated to take Z.O,hours to complete. Time will vary depending upon the needs of the individual case. Any comments on the amount of time you are required to complete this form should be sent to the Chief Information Officer, US. Patent and Trademark Office. Washington. DC 20231. DO NOT SEND FEES OR COMPLETED FORMS TO THIS ADDRESS. SEND TO: Assistant Commissioner for Patents, Washington, DC 20231

'

+

/A 16 0.2- Date Considered

. . ~ . . . . . . . . . . _ _ . _

UNITED STATES PATENT AND TRADEMARK OFTICE UNITED STATES DEPARmfENT OF COMMERCE United Stutea Patent and Trudemurk Offiuu Address COMMISSIONER FOR PATENTS

PO Baxl450 Abxnndnn.Vnpma 22313-14JO rvmvwpto gov -

I APPLICATIONNO. I FILING DATE I FIRST NAMED INVENTOR 1 ATTORNEY DOCKET NO. I CONFIRMATION NO. I ~~

09/863,127 05/22/2001 ~~

Rudolf W. Gunnerman

20350 7590 07/28/2003

TOWNSEND AND TOWNSEND AND CREW, LLP TWO EMBARCADERO CENTER EIGHTH FLOOR SAN FRANCISCO, CA 941 11-3834

~~

020839-0003OOUS

I EXAMINER I ~

NGUYEN, TAM M

1 ART UNIT PAPERNUMBER

1764

DATE MAILED: 07/28/2003

Please find below andor attached an Office communication concerning this application or proceeding.

PTO-9OC (Rev. 07-01)

- ' .: -..

Application No. .

- -091863,127 Examiner

Tam M. Nguyen

Notice of Abandonment

. IxI Applicant's failure to timely file a proper reply to the Office letter mailed on 18 December 2002. (a) 0 A reply was received on (with a Certificate of Mailing or Transmission dated ), which is after the expiration of the

(b) 0 A proposed reply was received on , but it does not constitute a proper reply under 37 CFR 1 .I 13 (a) to the final rejection. period for reply (including a total extension of time of month(s)) which expired on .

Applicant(s)

GUNNERMAN ET AL. Art Unit

1764 .

Y

.

I

(A proper reply under 37 CFR 1 .I 13 to a final rejection consists only of: (1) a timely filed amendment which places the application in condition for allowance; (2) a timely filed Notice of Appeal (with appeal fee); or (3) a timely filed Request for Continued Examination (RCE) in compliance with 37 CFR 1 .I 14).

final rejection. See 37 CFR 1.85(a) and 1 .I 11. (See explanation in box 7 below). (c) 0 A.reply was received on but it does not constitute a proper reply, or a bona fide'attempt at a proper reply, tcj the non-

(d) No reply has been received. I

2. 0 Applicant's failure to timely pay the required issue fee'and publication fee, if applicable, within the statutory period of three months from the mailing date of the Notice of Allowance (PTOL-85).

(a) 0 The issue fee and publication fee, if applicable, was received on (with, a Certificate of Mailing or Transmission dated ), which is after the expiration of the statutory period for payment of the issue fee (and publication fee) set in the Notice oi

Allowance (PTOL-85).

(b) 0 The submitted fee of $ is insufficient. A balance of $ is due.

(c) 0 The issue fee and publication fee, if applicable, has not been received.

The issue fee required by 37 CFR 1 . I 8 is $ . The publication fee, if required by 37 CFR 1.18(d), is $ .

3 . 0 Applicant's failure to timely file corrected drawings as required by, and within the three-month period set in, the Notice of Allowability (PTO-37).

(a) Proposed corrected drawings were received on (with a Certificate of Mailing or Transmission dated ), which is after the expiration of the period for reply.

(b) 0 No corrected drawings have been received.

4. 0 The letter of express abandonment which is signed by the attorney or agent of record, the assignee of the entire interest, or all of the applicants.

5. The letter of express abandonment which is signed by an attorney or agent (acting in a representative capacity under 37 CFR 1.34(a)) upon the filing of a continuing application.

6 . 0 The decision by the Board of Patent Appeals and Interference rendered on and because the period for seeking court review of the decision has expired and there are no allowed claims.

7. 0 The reason@) below:

Walter D. Griffin Primary Examiner

Petitions to revive under 37 CFR 1.137(a) or (b), or requests to withdraw the holding of abandonment under 37 CFR 1.181. should be promptly filed to minimize any negative effects on patent term. .S. Patent and Trademark Office

PTO-1432 (Rev. 04-01) Notice of Abandonment Part of Paper No. 8

WlPO Pub. Nc. , p2ga , line <

I11111 1ll111ll I1 lllllS1111111111111ll Ill11 11111 MI 11111 111ll Ill11 11111 111111 1111 1111 1111 US 20030051988A1,

(19) United States (12) Patent Application Publication (10) rub. NO.: US 2003/0051988 AI

Gunnerman et al. (43) Pub. Date: Mar. 20,2003

TREATMENT OF CRUDE OIL FRACTIONS, FOSSIL' FUELS, AND PRODUCTS THEREOF WITH ULTRASOUND

Inventors: Rudolf W. Gunnerman, Reno, NV (US); Paul S. Moote, Park City, UT (US); Mark T. Cullen, Reno, NV (US)

Correspondence Address: TOWNSEND AND TOWNSEND AND CREW, LIT TWO EMBARCADERO CENTER EIGHTH FLOOR SAN FRANCISCO, CA 94111-3834 (US)

Appl. No.: 09/863,127

Piled: May,22, 2001

Publication Classification

Int. Cl? .............................. C07C 1/00; C07C 2/00; C07C 4/00; C07C 5/00

(52) U.S. CI. ........... 204L57.15; 204/157.6; 204/157.78; 44t904

(57) ABSTRACT

Crude oil fractions, fossil fuels, and organic liquids i n general in which it is desirable to reduce the levels of fused-ring compounds, aromatics, and olefins are combined with an aqueous phase to form an emulsion and treated with ultrasound with the effect of opening rings in the fused-ring compounds, saturating aromatics, and converting the olefins to paraffins. I n fossil fuels and crude oil fractions, the process raises the API gravity, and in diesel fuels, the process raises the cetane index and thereby improves performance. In fuels and tiactions with sillfur-containing and nitrogen-containing components, the process reduces the level of these compounds. The process can be performed both with and without the added presence of hydrogen peroxide. The invention is performed either as a continuous process or a batch process.

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PATENT APPLICATION SERIAL NO. *(yzK5k97 US. DEPARTMENT OF COMMERCE PATENT &D TRADEMARK OFFICE

FEE RECORD SHEET

65/25/2001 UUANli 00000014 201430 09863127 01 FC:i01 710,00 CII 02 FC:103 540.00 CII

PTO-1556 (5/87)

'U.S. GPO: 2000468-987/39595

, Application or Docket Number

PATENT APPLICATION FEE DETERMINATION RECORD I '->oq g6 2 /'2 7 ' Effective October 1,2000 *J

CLAIMS AS FILED - PART I SMALL ENTITY OTHER THAN TYPE 0 OR SMALL ENTITY -

FEE

71 0.00 FOR NUMBER FILED NUMBER EXTRA

TOTAL CHARGEABLE CLAIMS minus 20= *

BASIC FEE

X40=

+135=

TOTAL

I INDEPENDENT CLAIMS 5 minus3= I 3 , *

MULTIPLE DEPENDENT CLAIM PRESENT

* If the difference in column 1 is less than zero, enter " 0 in column 2

CLAIMS AS AMENDED - PART II OTHER THAN SMALL ENTITY OR SMALL ENTITY

OR

OR

OR

- ADDI- rlONAL FEE

RATE ADDI-

TIONAL ' FEE

X$18=

X80= - Independent * Minus *** -

FIRST PRESENTATION OF MULTIPLE DEPENDENT CLAIM n X40=

+135= +270= TOTAI

I- TOTAL 1 I --

ADDIT. FEE1 Iun ADDIT. FEf

- ADDI-

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FIRST PRESENTATION OF MULTIPLE DEPENDENT CLAIM

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CLAIMS ONLY

CLAIMS

1 . * * *

SERIAL NO.

Dq,g-ig'$ /2,1 APPLICAWS)

*MAYBE USED FORADDITIONAL CLAIMS ORADMENDMENTS

U.S.DEPARTMENT OF COMMERCE Patent and Trademark Office FORM PTO-2022 (1-98)

'US GPO 1998-443-593/89152

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I FORMALITY REVIEW I

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. idDEX OF CLAIMS N ................................. Non-elected , ,

A ......................... : ...... Appeal 0 ................................. Objected

. . ................................... d Rejected .......... ..: .................... .Allowed I ................................. Interference - -

- (Through numeral) ... Canceled .- : ................................. Restricted

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