an overview of renewable fuels dubrovnik,croatia june 17, 2011
DESCRIPTION
Biodiesel, ETBE with wet ethanol and overview of Cellulose and Algae to ethanol and BiofuelTRANSCRIPT
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An overview of Renewable Fuels An overview of Renewable Fuels Ethanol From Cellulose and Bio-diesel Ethanol From Cellulose and Bio-diesel
from Conventional/Algae feed and from Conventional/Algae feed and economic options for ETBE economic options for ETBE
Dr. Amarjit BakshiDr. Amarjit BakshiPresidentPresident
Refining Hydrocarbon TechnologiesRefining Hydrocarbon TechnologiesTexas, USA.Texas, USA.
www.rhtgulfcoast.comwww.rhtgulfcoast.comPresented atPresented at
GREEN FORUMGREEN FORUM2 2 ndnd Green Refining & Petrochemicals Forum Green Refining & Petrochemicals Forum
17 June, 201117 June, 2011Rixos Libertas, Dubrovnik, CroatiaRixos Libertas, Dubrovnik, Croatia1 RHT
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Ethanol as a FuelEthanol as a Fuel • Ethanol has been increasing as fuel Ethanol has been increasing as fuel
around the World, 93 % by fermentation around the World, 93 % by fermentation and 7 % from synthetic hydrocarbon and 7 % from synthetic hydrocarbon feeds. feeds.
• Domestic production reduces demand of Domestic production reduces demand of other fuels.other fuels.
• Reduce oil demand, Trade deficits, create Reduce oil demand, Trade deficits, create jobs in rural area, reduce COjobs in rural area, reduce CO22, reduce , reduce pollution.pollution.
• Ethanol has 35 % oxygenates which Ethanol has 35 % oxygenates which reduces NOreduces NOxx and particulates. and particulates. RHT
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Feed used for EthanolFeed used for EthanolSugar FeedstocksSugar Feedstocks
• Fermentation of BiomassFermentation of Biomass
• Sugar Feedstocks, 6 carbon sugars, Sugar Feedstocks, 6 carbon sugars, glucose and precursors to glucose are glucose and precursors to glucose are easy to convert.easy to convert.
• Sugarcane is popular in Brazil and Sugarcane is popular in Brazil and very successfulvery successful
• Beet root, sorghum and variousBeet root, sorghum and various RHT
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Feed used for Ethanol Feed used for Ethanol Starchy Feed stocks Starchy Feed stocks
• Starchy molecules are made up of long chain of Starchy molecules are made up of long chain of glucoseglucose
• Starchy molecules can be fermented to glucose Starchy molecules can be fermented to glucose and ethanol.and ethanol.
• Cereal grain, potato, cassava Cereal grain, potato, cassava • In USA , Maize/corn and wheat is used to In USA , Maize/corn and wheat is used to
ferment to Ethanolferment to Ethanol• These feeds are hydrolyzed and go throughThese feeds are hydrolyzed and go through Sacchrification. Break the cells and specific Sacchrification. Break the cells and specific
enzymes which break the chemical bonds enzymes which break the chemical bonds multiple times.multiple times.
• RHT
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Feed used for Ethanol Feed used for Ethanol Cellulose Feed stocksCellulose Feed stocks
• Wood, woodchips, other fibrous plant Wood, woodchips, other fibrous plant waste, Paper, Cardboard.waste, Paper, Cardboard.
• Forest Comprise75 to 85 % of world’s Forest Comprise75 to 85 % of world’s fibrous waste. India farming seaweed.fibrous waste. India farming seaweed.
• It is outside the human food chain.It is outside the human food chain.
• Makes cellulose material relatively Makes cellulose material relatively inexpensive feed stocks for ethanol inexpensive feed stocks for ethanol production. production.
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Cellulose Processing to EthanolCellulose Processing to Ethanol
• Hemicellulose contains 6 carbon Hemicellulose contains 6 carbon hexose sugars and pentose which is hexose sugars and pentose which is
5 carbon sugar and to enhance the 5 carbon sugar and to enhance the efficiency pentose have to be efficiency pentose have to be converted to Ethanol. converted to Ethanol.
• The fermentation of hexose and The fermentation of hexose and pentose need different type of pentose need different type of microorganisms.microorganisms.
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Ethanol from CelluloseEthanol from Cellulose
(EFC)(EFC)Three Basic EFC processesThree Basic EFC processes• Acid hydrolysisAcid hydrolysis
• Enzymatic hydrolysis Enzymatic hydrolysis
• ThermochemicalThermochemical
• Most commonly used processes are hydrolysis Most commonly used processes are hydrolysis by any acid, sulfuric acid is predominantly used by any acid, sulfuric acid is predominantly used either dilute or high concentration acid.either dilute or high concentration acid.
• Dilute acid 1 to 2 %, high temp and pressure Dilute acid 1 to 2 %, high temp and pressure produces 50 % glucose. 50 gallons of ethanol produces 50 % glucose. 50 gallons of ethanol from 1 ton of wood/Cellulose.from 1 ton of wood/Cellulose.
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Ethanol from CelluloseEthanol from Cellulose
(EFC)(EFC)Acid hydrolysisAcid hydrolysis• Dilute acid process efficiency is reduced, Dilute acid process efficiency is reduced, once the sugar produced by secondary once the sugar produced by secondary
reaction which are poison to further reaction which are poison to further fermentation step. But two step process fermentation step. But two step process can enhance yield to 80 gallons/ton can enhance yield to 80 gallons/ton Cellulose.Cellulose.
• The dilute acid process has high reaction The dilute acid process has high reaction rates, continuous process, low efficiency rates, continuous process, low efficiency and it needs small cellulose particles.and it needs small cellulose particles.
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Ethanol from CelluloseEthanol from Cellulose
(EFC)(EFC)Acid hydrolysisAcid hydrolysis
• The concentrated acid process uses 10%, The concentrated acid process uses 10%, acid at low temperature and moderate acid at low temperature and moderate pressures, reaction rates are low. Next it pressures, reaction rates are low. Next it is soaked in 30 to 40 % acid for additional is soaked in 30 to 40 % acid for additional time, and again soaked at 70 % time, and again soaked at 70 % concentration. Acid from each stage is concentration. Acid from each stage is recycled and sugars from Cellulose and recycled and sugars from Cellulose and hemicellulose are 90% which is 103 hemicellulose are 90% which is 103 gallons/ton.gallons/ton.
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Ethanol from CelluloseEthanol from Cellulose
(EFC)(EFC)ENZYMATIC HYDROLYSISENZYMATIC HYDROLYSIS
• Cellulose/hemicellulose areCellulose/hemicellulose are pretreated, pretreated, part is sent to grow cellulanzyme. Other part is sent to grow cellulanzyme. Other part is sent grow a yeast culture for part is sent grow a yeast culture for fermentation, sugar conversion and fermentation, sugar conversion and fermentation occurs simultaneously by fermentation occurs simultaneously by saccharification and co-fermentation. saccharification and co-fermentation.
• If less expensive enzymes are developed If less expensive enzymes are developed enzymatic processes hold several enzymatic processes hold several advantages.advantages.
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Ethanol from CelluloseEthanol from Cellulose
• Hybrid process where biomass is Hybrid process where biomass is thermochemically gasified, gas is treated in thermochemically gasified, gas is treated in fermenters/microorganism converts fermenters/microorganism converts gas(CO/COgas(CO/CO22/H/H22) to ethanol by fermentation. ) to ethanol by fermentation.
• Two stage route is where biomass is Two stage route is where biomass is thermochemically gasified, gas is thermochemically gasified, gas is catalytically converted to ethanol, yields are catalytically converted to ethanol, yields are 50%. methanol also is catalytic converted 50%. methanol also is catalytic converted to ethanol, enhancing yields to 80%. to ethanol, enhancing yields to 80%.
RHT
THERMOCHEMICAL PROCESSES
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Conventional Biodiesel Conventional Biodiesel New DevelopmentsNew Developments
• RHT provides technology based on RHT provides technology based on conventional vegetable oil/fats, with conventional vegetable oil/fats, with heterogeneous highly active catalyst, with heterogeneous highly active catalyst, with high yield, selectivity and high on stream high yield, selectivity and high on stream factor.factor.
• Makes no liquid or gaseous waste Makes no liquid or gaseous waste
• Product meets required specificationsProduct meets required specifications
• Is highly efficient and provides good Is highly efficient and provides good economics.economics.
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Conventional Biodiesel Conventional Biodiesel New DevelopmentsNew Developments
• Simple Reaction chemistrySimple Reaction chemistry
CC33HH55RR33+3CH+3CH33OH COH C33HH55(OH)(OH)33+3CH+3CH33RR
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Vegetable oil Methanol Glycerine Methyl Ester
CC33HH55RR33+3C+3C22HH55OH COH C33HH55(OH)(OH)33+3C+3C22HH55RRVegetable oil Ethanol Glycerine Ethyl Ester
Transesterification Reaction
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Conventional Biodiesel Conventional Biodiesel New DevelopmentsNew Developments
Biodiesel PropertiesBiodiesel PropertiesFuel PropertyFuel Property ASTM 6751 ASTM 6751Sulfated ash w% 0.02Sulfated ash w% 0.02Na+K mg/kg 5Na+K mg/kg 5Ca+Mg mg/mg 5Ca+Mg mg/mg 5Acid number mgKOH/g 0.5Acid number mgKOH/g 0.5Free / Total Glycerol w% 0.02/0.24Free / Total Glycerol w% 0.02/0.24Carbon residue w% 0.05Carbon residue w% 0.05Cetane number 47Cetane number 47Distillation 90% C 360 Distillation 90% C 360 Flash Pt C 130Flash Pt C 130Water and sediment v% 0.05Water and sediment v% 0.05Sulfur content mg/mg 15/500Sulfur content mg/mg 15/500
*ASTM 6751 above specs are not comprehensive. *ASTM 6751 above specs are not comprehensive. For EU spec please see For EU spec please see EN 14214 EN 14214
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Figure 1RHT- Biodiesel Process
Esterification Reactor Transesterification Reactor
LP
Gravity Separator
Methanol
Triglycerides
Biodiesel Biodiesel Product
water wash
Water
Meoh/water for recovery
Meoh for recoveryPurification
Purification
Glycerine Product
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Figure 2RHT- Biodiesel Process
Esterification Reactor Transesterification Reactors
LP
Gravity Separator
Methanol
Triglycerides
BiodieselBiodiesel Product
water wash
Water Meoh/water for recovery
Glycerine Product
Meoh for recovery
Gravity Separator
Wash Solvent
Residual Glycerine / wash solvent
Purification
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Conventional Biodiesel Conventional Biodiesel RHT- BiodieselRHT- Biodiesel
• WHY USE RHT PROCESS:WHY USE RHT PROCESS:
• Highly active heterogeneous catalyst, with Highly active heterogeneous catalyst, with high yield, selectivity and high on stream high yield, selectivity and high on stream factor.factor.
• Makes no liquid or gaseous waste Makes no liquid or gaseous waste
• Product meets required specificationsProduct meets required specifications
• Is highly efficient, simple to operate and Is highly efficient, simple to operate and provides good economics, low Capex and provides good economics, low Capex and Opex. Provides glycerol at ~99.0 %.Opex. Provides glycerol at ~99.0 %.
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Biodiesel from Algae Biodiesel from Algae New DevelopmentsNew Developments
Drivers of BiofuelsDrivers of Biofuels• High Crude oil/fossil fuel prices make it High Crude oil/fossil fuel prices make it
viable for industrialist/Governments to viable for industrialist/Governments to seek alternative fuels.seek alternative fuels.
• Energy IndependenceEnergy Independence• Tax incentives and Government mandatesTax incentives and Government mandates• Environmental securityEnvironmental security• Economic security Economic security • National securityNational security
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Biodiesel from Algae Biodiesel from Algae New DevelopmentsNew Developments
Algae PotentialAlgae Potential• Biodiesel, Aviation fuels,Ethanol, Biodiesel, Aviation fuels,Ethanol, Bio-Crude, Bio-gasolineBio-Crude, Bio-gasoline Production MethodsProduction Methods• Open ponds, bioreactor in dark, CO2 Open ponds, bioreactor in dark, CO2
Enhanced growthEnhanced growth• Extraction/dewatering/magnetic/quantum Extraction/dewatering/magnetic/quantum
fracturing systems and developmentsfracturing systems and developments• Bio-refining technologies developmentsBio-refining technologies developments
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Bodiesel from Algae Bodiesel from Algae New DevelopmentsNew Developments
• Fastest growing biomass with COFastest growing biomass with CO22 from from
power plants or other sources into the power plants or other sources into the waste land, needs nitrogen rejection.waste land, needs nitrogen rejection.
• Growth of Algae can be increased Growth of Algae can be increased thousand fold with COthousand fold with CO22 in water, cost in water, cost
effective near COeffective near CO22 sources. sources.
• No adverse effect on food, positive impact No adverse effect on food, positive impact on environment by reducing green houses on environment by reducing green houses gases in atmosphere.gases in atmosphere. RHT
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Bodiesel from Algae Bodiesel from Algae New DevelopmentsNew Developments
EU Bio-fuels TargetsEU Bio-fuels Targets• ~6.0 % by 2010 and ~10 % by 2020~6.0 % by 2010 and ~10 % by 2020• EU can not produce enough vegetable oilEU can not produce enough vegetable oil• Algae and Cellulose have the opportunity to Algae and Cellulose have the opportunity to
serve as feed stocks to meet the targetsserve as feed stocks to meet the targets USA Bio-fuels TargetsUSA Bio-fuels Targets • Federal RFS require ~36 billion gallons by 2022Federal RFS require ~36 billion gallons by 2022• Over 22 billion by Algae/CelluloseOver 22 billion by Algae/Cellulose• USA cannot produce enough oil/CornUSA cannot produce enough oil/Corn• Algae and Cellulose have the opportunity to Algae and Cellulose have the opportunity to
meet the difference meet the difference RHT
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Bodiesel from Algae Bodiesel from Algae New DevelopmentsNew Developments
Yields of BiodieselYields of Biodiesel• Most vegetable oil yields 50 to 110 US Most vegetable oil yields 50 to 110 US
gallon/acre, except palm which is 650 US gallon/acre, except palm which is 650 US gallon/acregallon/acre
• Algae potential >10,000 US gallon/acreAlgae potential >10,000 US gallon/acre• Trend towards large scale commercial Trend towards large scale commercial plants. As the technologies are plants. As the technologies are commercialized together with enhancing commercialized together with enhancing
the economics. Race is on with more than the economics. Race is on with more than 20 major players in field. 20 major players in field.
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Bodiesel from Algae Bodiesel from Algae New DevelopmentsNew Developments
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Grow Algae
Split in fat/ sugars
Solvent to separate Fat and Sugars
Fat /Lipids Bodiesel
Bodiesel
Sugars to Ethanol
Ethanol
ALGAE TO BIODIESEL & ETHANOL
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Bodiesel from Algae Bodiesel from Algae New DevelopmentsNew Developments
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Grow Algae in Ponds/Bio-reactor
Convert to Biomass
Convert to Bio-crude
Biocrude to
Refinery
CO2
Nutrients From Sludge
ALGAE TO BIO-CRUDE
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Bodiesel from Algae Bodiesel from Algae New DevelopmentsNew Developments
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Grow Algae in Bioreactor
DewateringAlgae Biomass
Bodiesel
Biodiesel
Ethanol
Methanol
ALGAE TO BIODIESEL & ETHANOL/Methanol
CO2
Recyclewater
EthanolMethanol
Animal Food etc
Animal food
O2/N2
separation
Light deliveryGrowth layersLow energyphotosynthesis
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Biodiesel from Algae Biodiesel from Algae • Algae dewateringAlgae dewatering FilterationFilteration CentrifugingCentrifuging Drying by unique techniqueDrying by unique techniqueSpray dryingSpray drying• Lipid ExtractionLipid Extraction Mechanical/thermal Mechanical/thermal Solvent extractionSolvent extraction Originoil claims, no dewatering before Lipid Originoil claims, no dewatering before Lipid
Extraction by ultrasonic frac, recycle nutrients Extraction by ultrasonic frac, recycle nutrients and water, less energy consumed. and water, less energy consumed.
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Biodiesel from Algae Biodiesel from Algae New DevelopmentsNew Developments
Originoil ProcessOriginoil Process• Originoil process claims reduced steps, algae is Originoil process claims reduced steps, algae is
broken into lipid and sugars by ultrasonic broken into lipid and sugars by ultrasonic fracturing and phases are separated and sent fracturing and phases are separated and sent for purification enhancing economics. Please for purification enhancing economics. Please see there website. see there website.
• More R &D is required to enhance the More R &D is required to enhance the economics, major R&D effort with industry and economics, major R&D effort with industry and government sponsorship is in progress.government sponsorship is in progress.
• RHT LLC is talking to universities for allianceRHT LLC is talking to universities for alliance and hope to start R&D work soon.and hope to start R&D work soon.
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ETBE from Wet EthanolETBE from Wet EthanolEnhancing the economicsEnhancing the economics
• Smart Configuration provides Smart Configuration provides highest conversion > 99 % above highest conversion > 99 % above
equilibrium limit.equilibrium limit.• Reduce the production costs by using wet Reduce the production costs by using wet
ethanol, easy revamp of MTBE to ETBE.ethanol, easy revamp of MTBE to ETBE.• Makes higher TBA, decompose TBA to Makes higher TBA, decompose TBA to
IB= and water, IB= is recycled and water IB= and water, IB= is recycled and water is rejected, producing ETBE to Spec.is rejected, producing ETBE to Spec.
• 20- 25 % savings in production costs. 20- 25 % savings in production costs.
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RHT-ETBE PROCESSRHT-ETBE PROCESSEquilibrium Limits Equilibrium Limits EtherificationEtherification
CH3 - C = CH3 + C2H5OH CH3 - C - CH3
CH3CH3
OC2H5
< 88% *
Isobutylene Ethanol ETBE
RHT
* RHT overcomes equilibrium constraints. Provides IB= conversion over 99 % .
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ETBE VS MTBE PropertiesETBE VS MTBE Properties ETBE MTBE• C4/ROH Azeotrope, w% 1.5 - 1.7 3.5 - 4.0
• Boiling Point (F) 161 131
• RVP (PSI) 4 8
• Blending Octane, 112 110
• Oxygen Content, w% 15.7 18.2• 1 BBL IB= + 0.6 BBL EtOH 1.5 BBL ETBE
• 1 BBL IB= + 0.4 BBL MeOH 1.3 BBL MTBE
@ same IB= conversion 15 % more flow @ same IB= conversion 15 % more flow RHT
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FIGURE 1FIGURE 1RHT-ETBE PROCESSRHT-ETBE PROCESS
C4
4
Raffinate
ETBE
4
Fixed BedReactor
Debutanizer ETHANOLExtraction
ETHANOLRecoveryETHANOL
C 4
Water
WaterEffluent
Water
FEED
C4 Feed
C4 Feed
Side Reactor
CW
C4/ETOH
RHT
ETOHRecycle
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RHT-WET ETBE/TAEE ProcessWater Wash Column
1st Reactor
Debutanizer/Depentanizer
Condenser
Finishing Reactor
Water
Alcohol/ ETOH
Alcohol Recycle
WashWater
C4/C5
feed
C4
/C
LPS
CW
ETBE/TAEE Product
CW
MPS
CW
C4/C5 Raffinate
2 3
4
9
FIGURE 2
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RHT-ETBE/TAEE Wet Ethanol Process
DebutanizerDepentanizerBottom (from figure 2)
CW
LPS CW
Isobutylene/AmylenesTo Water WashColumn
LPS
ETBE/TAEE to OSBL
TBA/TAA and Lights
ETBE /TAEE Column
FLOW SHEET 3
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TBA decomposition
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Why RHT ETBE PROCESSWhy RHT ETBE PROCESS• Smart configuration provides 99.0 % IB=Smart configuration provides 99.0 % IB= conversion, above equilibrium limit. conversion, above equilibrium limit. • LOW COST, HIGH YIELD PROCESSLOW COST, HIGH YIELD PROCESS• For ETBE, no ethanol dehydration Unit For ETBE, no ethanol dehydration Unit
required, reducing cost by a factorrequired, reducing cost by a factor• Costs of dehydration is 20 to 30% of the Costs of dehydration is 20 to 30% of the
ETBE unit, wet ethanol cheaper than dry ETBE unit, wet ethanol cheaper than dry ethanol.ethanol.
• No Proprietary single source catalyst No Proprietary single source catalyst and loading required. RHT USP and loading required. RHT USP 7,732,6487,732,648
• Catalyst can be changed on the Catalyst can be changed on the run/during operationrun/during operation
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RHT PortfolioRHT Portfolio• Please see website Please see website www.rhtgulfcoast.comwww.rhtgulfcoast.com
and linkedin for other details and and linkedin for other details and presentations attached to profile. presentations attached to profile.
• RHT LLC provides technology for ETBE with RHT LLC provides technology for ETBE with wet ethanol, Biodiesel from vegetable oils wet ethanol, Biodiesel from vegetable oils and looking for alliances, research at and looking for alliances, research at universities on renewable fuel technologies universities on renewable fuel technologies Cellulose to Ethanol and Biodiesel from Cellulose to Ethanol and Biodiesel from Algae. Algae.
• Please contact us and look up the Patents/IP.Please contact us and look up the Patents/IP.
RHT
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Thank You Refining Hydrocarbon Technologies LLC
20130 Chateau Bend DriveKaty ( Houston Suburb),
Texas 77450USA
Dr. Amarjit BakshiPhone 281-398-8408/281-235-7780E-mail:[email protected]
www.rhtgulfcoast.com