an overview of renewable fuels dubrovnik,croatia june 17, 2011

1616 ConfidentialConfidential 11

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

http://www.rhtgulfcoast.com/


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


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


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.

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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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(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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(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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(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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• 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%.

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THERMOCHEMICAL PROCESSES


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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• 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



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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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



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



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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RHT

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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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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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


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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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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3636 Confidential Confidential

3636

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 % .


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


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


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


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

http://www.rhtgulfcoast.com/

4545 ConfidentialConfidential 4545RHT

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

an overview of renewable fuels dubrovnik,croatia june 17, 2011

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