“investigation of low-reactivity solvents” · “investigation of low-reactivity solvents”...

“Investigation of Low-Reactivity Solvents” Investigators: Albert Censullo, Dane Jones, Max Wills

Cal Poly State University

Final Report Presented by

Albert CensulloProfessor

Department of ChemistryCal Poly State University

San Luis Obispo, CA

“Investigation of Low-Reactivity Solvents”

Project Objectives

•Produce database of physical and chemical properties for selected solvents and solvent mixtures

•Develop detailed chemical speciation for selected hydrocarbon solvents

“Investigation of Low-Reactivity Solvents”Database Solvent Parameters

Properties Basis for Selection; notesName, trade name, synonyms Allows lookup by a number of naming systemsCAS number Unique reference number; useful for links to other databasesFormula, molecular weight Provides basic chemical information; not applicable for mixtures

Structure Shows graphical structure; not applicable for mixtures

Chemical Class Allows comparison with other chemically related substances

MP, BP Provides information for storage/shipping conditions

Vapor pressure (at reference temperature) Gives an estimate of volatility

Evaporation rate (relative to butyl acetate) A practical measure of volatility

Flash point Significant for safe handlingSpecific Gravity Allows conversion between mass and volumeViscosity Provides an insight into pouring/mixing characteristics

Henry’s law constant Describes partitioning from aqueous phase into vapor

Solubility in water Important for formulation compatibility and disposalLog Kow Gives info about partitioning between aqueous environment and biomass

Kauri-butanol number Not applicable for all solvent classesHildebrand parameter Widely used to allow comparisons of solvency abilitieskOH Rate constant with hydroxyl radical, a scavenger for atmospheric VOCs

MIR A measure of photochemical reactivityToxic Air Contaminant Compliance with current regulations

“Investigation of Low-Reactivity Solvents”Database Solvent Selection

•Began with list of 383 solvents from ARB Consumer Product Survey

•Identified some duplicate names

•Obtained CAS numbers; sorted to reveal duplicate names/CAS number assignments

•Prepared ranked list of top 100 solvents, by sales volumes

•Draft list presented to ARB and RRAC for comments, additions, deletions

“Investigation of Low-Reactivity Solvents”List of Solvent Classes

•Alcohols (ALC)•Esters (EST)•Glycols (GLY)•Glycol Ethers (GLYE)•Halogenated (HAL)•Hydrocarbons (HYD)•Ketones (KET)•Nitrogen-Containing (NIT)•Propellants (PROP)•Miscellaneous (MISC)

“Investigation of Low-Reactivity Solvents”Members of Solvent Classes

Alcohols1-butanol1-propanol2-butanol2-ethyl-1-hexanol2-methyl-2-propanol2-propanolbenzyl alcoholcyclohexanolethanolisobutanolmethanol

Esters2-butoxyethyl acetate2-ethoxyethyl acetate2-methoxyethyl acetatebutyl acetatedimethyl adipatedimethyl glutaratedimethyl succinatedipropylene glycol methyl ether acetateethyl acetateethyl-3-ethoxypropionateglyceryl triacetateisobutyl acetateisobutyl isobuytrateisopentyl acetateisopropyl acetatemethyl acetaten-amyl acetaten-propyl acetatepropylene glycol ethyl ether acetatepropylene glycol methyl ether acetatet-butyl acetate

Glycols2-methyl-2,4-pentanedioldiethylene glycoldipropylene glycolethylene glycolpropylene glycol

Glycol Ethers1-methoxy-2-propanol2-butoxyethanoldiethylene glycol monoethyl etherdiethylene glycol monomethyl etherdiethylene glycol mono-n-butyl etherdipropylene glycol methyl etherdipropylene glycol mono butyl etherdipropylene glycol n-butyl etherpropylene glycol monobutyl etherpropylene glycol mono-t-butyl etherpropylene glycol n-propyl ether

Halogenated1,1,1-trichloroethane1,1,2-trichloroethylene1,4-dichlorobenzenechlorobenzenemethylene chloridemonochlorotolueneparachlorobenzotrifluoride

Ketonesacetonecyclohexanonediacetone alcoholdiisobutyl ketoneisophoronemethyl amyl ketonemethyl ethyl ketonemethyl isoamyl ketonemethyl isobutyl ketonemethyl isopropyl ketonemethyl propyl ketone

Miscellaneous2-cyano-2-propenoic acid, ethyl esteracetic acidacroleindecamethylcyclopentasiloxanedecamethyltetrasiloxanedodecamethylcyclohexasiloxanedodecamethylpentasiloxanehexamethylcyclotrisiloxanehexamethyldisiloxanemethyltrimethoxysilanemethyltris(trimethylsiloxy)silaneoctamethylcyclotetrasiloxaneoctamethyltrisiloxanepentane-1,5-dialtetrahydrofurantetrakis(trimethylsiloxy)silaneNitrogenous

2-amino-2-methyl-1-propanoldiethanolamineethanolamineN-methylpyrrolidonetriethylamine

Propellants1,1,1,2-tetrafluoroethane1,1-difluoroethanebutanedimethyl etherisobutanepropane

“Investigation of Low-Reactivity Solvents”Members of Hydrocarbon Solvent Class

aliphatic distillate 64742525C9-11 Isoparaffin 68551166diesel fuel 68334305heavy aliphatic solvent naphtha 64742967heavy alkylate solvent naphtha 64741657hydrofinished solvent refined parafinic petroleum oil 64742547hydrotreated light distillate 64742478hydrotreated light naphtha 64742490hydrotreated heavy naphtha 64742489isomeric hexanes 73513425isoparaffinic solvent 64741668kerosene 8008206lactol spirits 64741555medium aliphatic solvent naphtha 64742887methylhexanes 25495889mineral oil 8012951mineral spirits 64742887naphtha (light) 64741840odorless mineral spirits 64742478petroleum distillate 64742014severely hydrotreated middle distillate oil 64742467Stoddard solvent 8052413VM&P naphtha 64742898aromatic hydrocarbon 68410162light aromatic solvent naphtha 25551137heavy aromatic solvent naphtha 64742945xylenes 1330207

xylenes 1330207kerosene 8008206mineral oil 8012951Stoddard solvent 8052413methylhexanes 25495889light aromatic solvent naphtha 25551137lactol spirits 64741555heavy alkylate solvent naphtha 64741657isoparaffinic solvent 64741668naphtha (light) 64741840petroleum distillate 64742014severely hydrotreated middle distillate oil 64742467hydrotreated light distillate 64742478odorless mineral spirits 64742478hydrotreated heavy naphtha 64742489hydrotreated light naphtha 64742490aliphatic distillate 64742525hydrofinished solvent refined parafinic petroleum oil 64742547medium aliphatic solvent naphtha 64742887mineral spirits 64742887VM&P naphtha 64742898heavy aromatic solvent naphtha 64742945heavy aliphatic solvent naphtha 64742967diesel fuel 68334305aromatic hydrocarbon 68410162C9-11 Isoparaffin 68551166isomeric hexanes 73513425

CAS number sorted

“Investigation of Low-Reactivity Solvents”Members of Hydrocarbon Solvent Class

Aromatic 100 Mineral Spirits, Type IAAromatic 150 Mineral Spirits, Type IBcyclohexane Mineral Spirits, Type ICdiesel Fuel #2 Mineral Spirits, Type IIAd-limonene Mineral Spirits, Type IIBethylbenzene Mineral Spirits, Type IICheptane Mineral Spirits, Type IIICheptanes Mineral Spirits, Type IVAhexane Mineral Spirits, Type IVBhexanes Mineral Spirits, Type IVCkerosene ortho-Xylenelactol spirits para-Xylenemeta-xylene Pine oilmethylcyclohexane toluenemethylcyclopentane VM&P Naptha, Type Imineral oil VM&P Naptha, Type II

VM&P Naptha, Type IIIVM&P Naptha, Type IVXylenes (Mixture)

Hydrocarbons

“Investigation of Low-Reactivity Solvents”Database Home Page

“Investigation of Low-Reactivity Solvents”Database Master List

“Investigation of Low-Reactivity Solvents”Database Search by Name Form

“Investigation of Low-Reactivity Solvents”Database Search by Class Form

“Investigation of Low-Reactivity Solvents”Database Search by CAS Number Form

“Investigation of Low-Reactivity Solvents”Database Sample Record

ASTM Designations for Hydrocarbon Solvents

•VM&P Naphthas•Type I (regular)•Type II (high flash)•Type III (odorless)•Type IV (low aromatic)

•Mineral Spirits and Stoddard Solvent

•Type IA,B,C (full range)•Type IIA,B,C (high flash point)•Type IIIC (odorless)•Type IVA,B,C (low dry point)

•High Flash Aromatic Naphtha

•Type I•Type II

“Investigation of Low-Reactivity Solvents”ASTM Designations for Hydrocarbon Solvents

VM&P Naphthas, according to ASTM Specification D 3735-96

Type I Type II Type III Type IVCommercial reference Regular High Flash Odorless Low AromaticAppearance Clear and free of suspended matter and undissolved waterBromine number, max 5 5 5 5Color Not darker than +28 (Saybolt scale), or 10 (platinum-cobalt scale)Aromatics, volume %, max 20 20 1 2Copper corrosion, max rating 1 1 1 1Distillation, 0/C: Initial boiling point, min 113 138 113 113 50% recovered, max 129 160 129 129 Dry point, max 154 177 154 154Flash point, min 4 27 4 4Kauri-butanol value: min 32 max 45 45 38 38Odor nonresidual nonresidual nonresidual nonresidualApparent specific gravity, 25/25C: min 0.709 0.726 0.709 0.709 max 0.786 0.786 0.754 0.754


Mineral Spirits & Stoddard Solvent, according to ASTM Specification D 235-95Note: Mineral Spirits are called "Stoddard Solvents" when used for dry cleaning

Type I Full Range Mineral Spirits Type II High Flash Point Type III OdorlessClass A Class B Class C Class A Class B Class C Class C

Aromatic Content, range, vol% 8-22 2-8 max 0-2 8-22 2-8 max 0-2 0-0.25Commercial reference regular rule 66 low aromatic regular rule 66 low aromatic odorlessAppearance All - clear and free of suspended matterFlash Point, 0/C, min 38 38 38 61 61 61 38Color, min All - not darker than +25 (Saybolt Scale) or 25 (Pt-Co Scale)Kauri-butanol value: min 29 29 28 29 29 28 ….. max 45 45 40 45 45 40 29Bromine number, max 5 1 0.1 5 1 0.1 0.1Odor All - characteristic, as agreed between purchaser and supplierDoctor test All - negativeDistillation, 0/C Initial boiling point, min 149 149 149 177 177 177 149 50% Recovered, max 182 182 182 199 199 199 196 Dry point, max 213 213 213 213 213 213 213Residue from distillation: Vol %, max All - 1.5 Acidity All - neutralCopper corrosion, max rating All - 2AApparent Specific Gravity, 15.6/15.6C: min 0.754 0.754 0.754 0.768 0.768 0.768 0.740 max 0.820 0.810 0.800 0.820 0.810 0.800 0.775


High Flash Aromatic Naphthas, Classified according to ASTM Specification D 3734-96

Type I Type IICommercial reference Aromatic 100 Aromatic 150Appearance All - clear of suspended matter and undissolved waterColor All - no darker than +28 (Saybolt scale) or 10 (Pt-Co scale)Aromatics, volume %, min 90 90Copper corrosion, 0.5 h at 100C All - no iridescence, discoloration, or gray or black deposit on copper stripDistillation, 0/C Initial bopiling point, min 149 177 50 % recovered, max 168 196 Dry point, max 179 216Flash point, 0/C, min 38 61Kauri-butanol value, min 87 85Mixed aniline point, max 60 65Odor All - characteristic, as agreed between purchaser and supplierApparent specific gravity, 25/25C 0.857 0.873

0.874 0.903


VM&P Naphthas, according to ASTM Specification D 3735-96

Type I Type II Type III Type IVCommercial reference Regular High Flash Odorless Low AromaticAppearance Clear and free of suspended matter and undissolved waterBromine number, max 5 5 5 5Color Not darker than +28 (Saybolt scale), or 10 (platinum-cobalt scale)Aromatics, volume %, max 20 20 1 2Copper corrosion, max rating 1 1 1 1Distillation, 0/C: Initial boiling point, min 113 138 113 113 50% recovered, max 129 160 129 129 Dry point, max 154 177 154 154Flash point, min 4 27 4 4Kauri-butanol value: min 32 max 45 45 38 38Odor nonresidual nonresidual nonresidual nonresidualApparent specific gravity, 25/25C: min 0.709 0.726 0.709 0.709 max 0.786 0.786 0.754 0.754


Mineral Spirits & Stoddard Solvent, according to ASTM Specification D 235-95Note: Mineral Spirits are called "Stoddard Solvents" when used for dry cleaning

Class A Class B Class CAromatic Content, range, vol% 8-22 2-8 max 0-2Commercial reference regular rule 66 low aromaticAppearance All - clear and free of suspended matterFlash Point, 0/C, min 38 38 38Color, min All - not darker than +25 (Saybolt Scale) or 25 (Pt-Co Scale)Kauri-butanol value: min 29 29 28 max 45 45 40Bromine number, max 5 1 0.1Odor All - characteristic, as agreed between purchaser and supplierDoctor test All - negativeDistillation, 0/C Initial boiling point, min 149 149 149 50% Recovered, max 182 182 182 Dry point, max 213 213 213Residue from distillation: Vol %, max All - 1.5 Acidity All - neutralCopper corrosion, max rating All - 2AApparent Specific Gravity, 15.6/15.6C: min 0.754 0.754 0.754 max 0.820 0.810 0.800

Type I Full Range Mineral Spirits


Mineral Spirits Type III OdorlessClass A Class B Class C Class C

Aromatic Content, range, vol% 8-22 2-8 max 0-2 0-0.25Commercial reference regular rule 66 low aromatic odorlessAppearanceFlash Point, 0/C, min 61 61 61 38Color, minKauri-butanol value: min 29 29 28 ….. max 45 45 40 29Bromine number, max 5 1 0.1 0.1OdorDoctor testDistillation, 0/C Initial boiling point, min 177 177 177 149 50% Recovered, max 199 199 199 196 Dry point, max 213 213 213 213Residue from distillation: Vol %, max AcidityCopper corrosion, max ratingApparent Specific Gravity, 15.6/15.6C: min 0.768 0.768 0.768 0.740 max 0.820 0.810 0.800 0.775

Type II High Flash Point


Mineral SpiritsClass A Class B Class C

Aromatic Content, range, vol% 8-22 2-8 max 0-2Commercial reference regular rule 66 low aromaticAppearanceFlash Point, 0/C, min 38 38 38Color, minKauri-butanol value: min 29 29 28 max 45 45 40Bromine number, max 5 1 0.1OdorDoctor testDistillation, 0/C Initial boiling point, min 149 149 149 50% Recovered, max 174 174 174 Dry point, max 185 185 185Residue from distillation: Vol %, max AcidityCopper corrosion, max ratingApparent Specific Gravity, 15.6/15.6C: min 0.754 0.754 0.754 max 0.810 0.800 0.790

Type IV Low Dry Point


High Flash Aromatic Naphthas, according to ASTM Specification D 3734-96

Type I Type IICommercial reference Aromatic 100 Aromatic 150Appearance All - clear of suspended matter and undissolved waterColor All - no darker than +28 (Saybolt scale) or 10 (Pt-Co scale)Aromatics, volume %, min 90 90Copper corrosion, 0.5 h at 100C All - no iridescence, discoloration, or gray or black deposit on coppDistillation, 0/C Initial bopiling point, min 149 177 50 % recovered, max 168 196 Dry point, max 179 216Flash point, 0/C, min 38 61Kauri-butanol value, min 87 85Mixed aniline point, max 60 65Odor All - characteristic, as agreed between purchaser and supplierApparent specific gravity, 25/25C 0.857 0.873

0.874 0.903

“Investigation of Low-Reactivity Solvents”Task: Chemical Speciation of Hydrocarbon Solvents

Sample Selection

•Hydrocarbon mixtures targeted•42 samples selected and analyzed


product name CalPolyID product name CalPolyIVM&P naphtha CP1 VM&P Naphtha CP23300-66 solvent, Mineral Spirits 66 CP2 VM&P Naphtha CP24Light HC solvent CP3 Mineral Spirits CP25VM&P naphtha HT CP4 Mineral Spirits CP26Lactol Spirits CP5 xylene CP27Mineral Spirits CP6 light naphtha solvent CP28Aromatic 100 CP7 aliphatic petroleum distillates CP29Aromatic 150 CP8 VM&P naphtha CP30Mineral Spirits CP10 Aromatic 100 CP31Mineral Spirits CP11 Aromatic 150 CP32Mineral Spirits CP12 Mineral Spirits CP33Aromatic 100 CP13 xylene CP34VM&P Naphtha CP14 VM&P naphtha CP35aliphatic petroleum distillates CP15 Aromatic 100 CP36aliphatic petroleum distillates CP16 Aromatic 150 CP37Aromatic 150 CP17 isoparaffinic hydrocarbon CP38aliphatic petroleum distillates CP18 paraffinic petroleum distillate CP39xylene CP19 Xylene CP40Stoddard Solvent CP20 Xylene CP41Aromatic 100 CP21 Aromatic 100 CP42Aromatic 150 CP22 Mineral spirits CP43

Sample Types


Analytical Methodologies

•All samples run on 100 m capillary PDMS column, using GC-FID

•All samples run on 100 m capillary PDMS column, using GC-MS

•All samples run on 60 m capillary Carbowax, using GC-FID

•Many samples used SPME for verification of aromatic peaks


Comparison of PDMS and Carbowax Columns

10000

20000

30000

40000

50000

60000

70000

10 15 20 25

VM&P Naphtha 60 m columnaliphatic region

aromatic region

xylenes

5000

10000

15000

20000

25000

30000

35000

40000

35 40 45 50

retention time/minutes

VM&P Naphtha 100 m column

octane

nonane

1,3-dimethyl benzene

1,2,4-trimethylcyclohexane

retention time/minutes


Sampling With SPME

• Silica fiber tip coated withCarbowax-divinylbenzene (or otheradsorbing material) is placed incontact with solvent headspace

• Solvent molecules in headspace areadsorbed and concentrated on fiber

• Fiber is withdrawn into protectivemetal sheath and inserted into hotGC injection port where solventmolecules are thermally desorbedonto column

Fiber Tip

Metal Sheath

SPME Sampling ofSolvent Headspace

SPME Injector

PTFE Septum Cap

Coated Silica Fiber

40 mL Vial

5 mL Dioctyl Phthalate,Solvent, Internal Standards

“Investigation of Low-Reactivity Solvents”SPME vs. Direct Injection for Hydrocarbons


Selectivity of SPME for Aromatics, Carbowax Column

20000

40000

60000

80000

100000

120000

5 10 15 20 25 30

Counts / Minutes Paged Z-Zoom CURSORFile # 2 = FID1A 10/28/00 1:16 PM Res=None7-14/aromat/SPME \max

C7

C8

C9C10

C11C12

C13 C14

Toluene

Ethylbenzenep-Xylene

1,2,4-Trimethylbenzene

Equal masses of each component, 250C


SPME vs. Direct Injection for Hydrocarbons

-50000

0

50000

5 10 15 20 25

SPM E

D irect

A liphatic Arom atic

22% 78%

40% 60% Int S td

VM&P Naphtha and xylenes on Carbowax Column

“Investigation of Low-Reactivity Solvents”Representative Chromatograms

10000

20000

30000

40000

50000

60000

45 50 55 60 65 70 75 retention time/minutes

1-ethyl-3-methylbenzene

1,2,4-trimethylbenzeneAromatic 100 100 m column

5000

10000

15000

20000

25000

30000

35000

55 60 65 70 75 80 85 retention time/minutes

1,2-dimethyl-4-ethylbenzene

1,2,3,5-tetramethylbenzeneAromatic 150 100 m column


Format for Results

•Summary sheets by carbon number•Normal paraffins•Isoparaffins •Cyclic paraffins•Unidentified paraffins•Aromatics

•Detailed species profiles


Summary sheets by carbon number

Carbon Number Distribution, Wt%

DistillationRange

Composition,Wt%

Product C5

C6

C7

C8

C9

C10

C11

C12

C13

C14

C15

C16

C17

C18

C19 Total

n-PAR

i-PAR

c-PAR

u-PAR

AROM

“Investigation of Low-Reactivity Solvents”Species Profile Format

CP5, Lactol Spirits CAS# fractionHexane, 2,2-dimethyl 590738 0.1687Cyclopentane, 1,2- 822504 0.0987Cyclopentane, 1,2,3- 19374460 0.0799Heptane 142825 0.0723Toluene 108883 0.0654Cyclopentane, 1,3- 1759586 0.0617Cyclopentane, 1,3- 2532583 0.0566Cyclopentane, 1,2,4- 18679306 0.0529c-Paraffin, C7 0.0421Cyclopentane, ethyl 1640897 0.0386Cyclopentane, methyl 96377 0.0379Hexane, 3-methyl 589344 0.0348Cyclopentane, 1,1,3- 4516692 0.0342Cyclohexane, methyl 108872 0.0242Hexane, 2-methyl 591764 0.0217Pentane, 2,3-dimethyl 565593 0.0182Cyclopentane, 1,1- 1638262 0.0147Hexane, 2,3-dimethyl 584941 0.0095Hexane 110543 0.009Hexane, 2,4-dimethyl 116502444 0.0088Heptane, 2-methyl 592278 0.0062Cyclohexane, 1,4- 2207047 0.0049Hexane, 3-ethyl 619998 0.0044Pentane, 2,4-dimethyl 108087 0.0035Pentane, 2,3,4-trimethyl 565753 0.0032Benzene 71432 0.0031Hexane, 2,3-dimethyl 584941 0.003Cyclohexane, 1,1- 590669 0.0024Hexane, 3,4-dimethyl 583482 0.002Hexane, 3,3-dimethyl 563166 0.002Cyclopentane, 1-ethyl-2- 930892 0.0016Cyclopentane, 1,1,2- 4259001 0.0015Pentane, 2,2-dimethyl 590352 0.0014Pentane, 3,3-dimethyl 562492 0.0013Pentane, 3-methyl 96140 0.0013Cyclopentane, 1-ethyl-1- 16747505 0.001i-Paraffin, C7 0.001Pentane, 2-methyl 107835 0.001Heptane, 3-methyl 589811 0.0009Cyclopentane, 1-ethyl-1- 16747505 0.0009Octane 111659 0.0008Cyclohexane, 1,3- 638040 0.0007c-Paraffin, C8 0.0006Butane, 2,2,3-trimethyl 464062 0.0005Cyclohexane, 1,4- 624293 0.0004u-Paraffin, C8 0.0003Cyclohexane, 1,2- 6876239 0.0001Total 1.0000

“Investigation of Low-Reactivity Solvents” Investigators: Albert Censullo, Dane Jones, Max Wills

Cal Poly State University

Final Report Presented by

Albert CensulloProfessor

Department of ChemistryCal Poly State University

San Luis Obispo, CA

“investigation of low-reactivity solvents” · “investigation of low-reactivity solvents”...

Documents