NEW ENERGY RESOURCES: HYDROGEN

1
NEW ENERGY RESOURCESHYDROGEN

• MANUFACTURING HYDROGEN
• NO NATURAL SOURCES OF ELEMENTAL H2 EXIST
• THUS, THERE IS NO NATURAL SOURCE OF HYDROGEN
  ENERGY
• COMPARE CARBON (AS COAL), HYDROCARBONS ALL HAVE
  DIRECTLY AVAILABLE ENERGY
• WE HAVE TO USE ENERGY TO PRODUCE HYDROGEN
• CAN MAKE HYDROGEN FROM WATER IN SEVERAL WAYS.
  NET RESULT IS ALWAYS
• 2H2O ? 2H2 O2.. ?H 62,050 BTU/LB H2
• IF WE GET THE HYDROGEN FROM WATER AND THEN JUST
  BURN IT, AT BEST WE GET OUR ENERGY BACK!

2
NEW ENERGY RESOURCESHYDROGEN

• MANUFACTURING HYDROGEN
• ELECTROLYSIS OF WATER
• 2H2O ? 2H2 O2 ?H 62,050 BTU/LB
• 1 BTU 251.6 CALORIES 1054.2 JOULES
• 1 kW 1.34 HP 3,415 BTU/HR 3.600 x 106
  JOULES
• STEAM REFORMING OF NATURAL GAS (METHANE)
• CH4 2H2O ? CO2 4H2 OR
• CH4 H2O ? CO 3H2 (HYDROGEN-RICH SYNGAS)
• THERE ARE OTHER VARIATIONS.
• THESE ARE ALL EXAMPLES OF WATER-SPLITTING
  REACTIONS ALTHOUGH, IN THIS CASE THE METHANE
  CONTRIBUTES A LOT OF THE HYDROGEN. THIS REDUCES
  THE ENERGY REQUIRED PER LB OF H2.

3
NEW ENERGY RESOURCESHYDROGEN

• MANUFACTURING HYDROGEN
• WATER-SPLITTING WITH CARBON
• C H2O ? CO H2 (THE WATER-GAS REACTION)
• 3C O2 H2O ? 3CO H2 (CO-RICH SYNGAS
  REACTION)
• SOME CO2 PRODUCTION IS ALSO LIKELY
• WIDELY USED COMMERCIALLY TO MAKE SYNGAS
• IN PRINCIPAL, OTHER SPLITTERS CAN BE USED
• V2O3 H2O ? V2O4 H2 (COULD ALSO USE FeO ?
  Fe2O3)
• ALSO METALS LIKE Al OR Mg.
• BUT THE SPLITTER HAS TO BE RECYCLED FOR
  RE-USE.AND THAT COSTS MONEY!
• ONLY SPLITTERS CONTAINING HYDROGEN (
  HYDRO-CARBONS) REALLY HELP THE ENERGY BALANCE

4
NEW ENERGY RESOURCESHYDROGEN

• MANUFACTURING HYDROGEN
• HYDROGEN IS A BY-PRODUCT OF SOME PROCESSES
• E.G., CHLOR-ALKALI PROCESS FOR CHLORINE AND NaOH
• GOOD ECONOMICS BUT A SMALL OF THE TOTAL
• THE LARGEST MANUFACTURER IS THE OIL INDUSTRY
• NEARLY ALL BY HYDROCARBON REFORMING
• HYDROCARBONS MAY BE CH4, REFINERY GAS (CNH2N2)
• H2 IS USED MAINLY IN HYDROCRACKING DISTILLATE ?
  GASOLINE OR IN THINNING HEAVY CRUDES
• ADJUSTING THE DEGREE OF SATURATION OF FOOD OILS
• SOME NUMBERS
• 1 KG H2 1.2 US GAL GASOLINE ( 1 UK Gallon)
  136,800 BTU
• 1 US GAL GASOLINE 0.1337 FT3, CONTAINS 122,000
  BTU
• 1 KG H2 AS GAS 427.6 FT3 VOLUME OF 3,200 GAL
  GASOLINE!
• FOR STORAGE, HYDROGEN MUST BE COMPRESSED TO
  5000-10.000 PSI OR LIQUEFIED

5
NEW ENERGY RESOURCESHYDROGEN

• HYDROGEN EFFICIENCY COST IN USE
• EFFICIENCY COMPROMISED BY NEED TO MAKE IT!
• MANUFACTURING COST ESTIMATES, /KG, 8/2005
  (COMPARE WHOLESALE GASOLINE CURRENTLY AT APPROX
  2.50
• 1.2MM KG/DAY, COAL GASIFICATION - 2.52 - 5.00
• 1.2MM KG/DAY, NATURAL GAS REFORMING - 2.86 -
  5.60
• 24,000 KG/DAY, NATURAL GAS REFORMING - 6.15 -
  12.00
• 24,000 KG/DAY, BIOMASS GASIFICATION - 7.80 -
  14.00
• 480 KG/DAY, NATURAL GAS REFORMING - 6.51-
  13.00)
• 480 KG/DAY, ELECTROLYSIS (GRID POWER) - 6.98 -
  14.00)
• 480 KG/DAY, WIND TURBINE ELECTROLYSIS -
  11.25- 22.00)
• 480 KG/DAY, PHOTOVOLTAIC ELECTROLYSIS -
  29.94- 60.00)
• - INCLUDE STORAGE COSTS FOR 24 HR OPERATION
• SOURCE TMG 2005 ANALYSIS FOR NYSERDA BASED ON
  NRC 2/04 ANALYSIS, UPDATED WITH CURRENT RAW
  MATERIAL COSTS
• FIRST NUMBER IS MOST OPTIMISTIC, THE SECOND IS
  MORE REALISTIC

6
NEW ENERGY RESOURCESHYDROGEN

• HYDROGEN EFFICIENCY COST IN USE
• CONCLUSION TO MAKE HYDROGEN COST-COMPETITIVE
  WITH GASOLINE, BUILD BIG PLANTS W/TRANSPORTATION
  AND DISTRIBUTION INFRASTRUCTURE AT AN ESTIMATED
  2005 COST OF gt2 BN PER 1.2MM KG HYDROGEN
• TO REPLACE GASOLINE ALONE, WE NEED MORE THAN 300
  SUCH FACILITIES MORE TO REPLACE OTHER
  HYDROCARBON FUELS. NIMBY AND PERMITTING WILL
  BE A HUGE PROBLEM!
• NO SOUND BUSINESS CASE HAS BEEN DEVELOPED
  PRIVATE INDUSTRY WILL NOT INVEST MAJOR CAPITAL -
  YET
• SMALLER FACILITIES PRODUCE HYDROGEN THAT FAR
  EXCEEDS THE CURRENT COST OF GASOLINE
• FCVs ARE MUCH LESS EFFICIENT ON THE ROAD THAN
  CLAIMED AND HAVE INADEQUATE RANGE
• CONTINUED USE OF FOSSIL FUELS WITH C CAPTURE IN,
  E.G., DIESEL OR HYBRID VEHICLES MAY BECOME
  PREFERABLE
• See, e.g., Honda FCX test, Car Driver, July
  2005

7
NEW ENERGY RESOURCESHYDROGEN

• SOURCE-TO-USE (AKA WELL-TO-WHEELS) ANALYSIS
• COAL ? STEAM ? ELECTRICITY ? TRANSMISSION ?
  AC/DC ? HYDROGEN ? PURIFICATION ? LIQUID H2 ?
  TUBE OR CRYO TRUCK ? TANK ? FUEL CELL ?
  DC/AC? ? MOTORS ? WHEELS
• COAL ? STEAM ? ELECTRICITY 35 EFFICIENCY
• ELECTRICITY ? H2 (ELECTROLYSIS) 65 EFFICIENCY
• H2 LIQUEFACTION 85 EFFICIENCY (NEGATIVE J-T)
• TRANSPORTATION 90 EFFICIENCY (DETERMINED BY
  DISTANCE)
• HANDLING 95 EFFICIENCY
• FUEL CELL TO WHEELS (CURRENT) 40-45 EFFICIENCY
  (FUEL CELL ALONE WITH NO ACCESSORIES IS ABOUT 65
  EFFICIENT)
• OVERALL EFFICIENCY, SOURCE (COAL) TO FCV WHEELS
• 100 x .35 x .65 x .85 x .90 x .95 x .40 6.6
• NOT VERY IMPRESSIVE!
• CONCLUSION HYDROGEN IS AN ENERGY HOG.

8
SOURCE-TO-USE EFFICIENCIESCALIBRATION DATA
9
ALTERNATIVE ENERGIES(GENERAL)

• WHAT ARE THE CHOICES?
• HYDROGEN
• AN ENERGY HOG IN MANUFACTURE BECAUSE IT MUST BE
  MADE FROM ANOTHER ENERGY RESOURCE! PRODUCT MUST
  ALSO BE VERY PURE
• VERY HIGH PROJECTED MANUFACTURED COST
• VERY POOR SOURCE-TO-USE EFFICIENCIES
• HUGE TECHNICAL BARRIERS TO ITS USE FOR EXAMPLE
• HIGH COST OF TRANSPORTATION AND STORAGE
• HIGH FUEL CELL COSTS AND LOW TANK-TO-WHEEL
  EFFICIENCIES IN REAL WORLD USE
• LOW COMBUSTION ENTHALPY PER UNIT VOLUME
• LOW EFFICIENCY IN MOST IC ENGINES
• MASSIVE DISINFORMATION PR CAMPAIGN

10
ALTERNATIVE ENERGIES(GENERAL)

• MOST OTHER ALTERNATE FUELS ARE ALSO
  THERMOCHEMICALLY CHALLENGED.
• OUR SCORES (BASED ON ALL FACTORS)
• HYDROGEN (D)
• CORN ETHANOL (C-)
• CELLULOSIC ETHANOL (B)
• METHANOL (B-)
• BIODIESEL (FROM VEGETABLE OILS OR ANIMAL FATS)
  (B)
• GREEN DIESEL (BY HYDROGENATING VEGETABLE OILS
  AND ANIMAL FATS) B
• BIOMASS-BASED FUELS (INCLUDING BTL FUELS) (B)
  DATA LESS CERTAIN AND COST HIGH
• DETAILS FOLLOW..

11
ENERGY USESTHAT ALSO SAVE PETROLEUM

• WE ALSO HAVE..
• CLEAN DIESEL ENGINES!
• NEW TURBODIESEL DEVELOPMENTS
• HCCI AND SIMILAR NEW-TECH ENGINES
• DEVELOPMENT PROVING DIFFICULT
• HYBRIDS (HEVs AND PHEVs)
• LOTS OF PROGRESS, STILL HIGH COST
• EVs (REINCARNATED)
• FUEL CELLS (BUT SHOW ME THE FUEL?)
• STIRLING ENGINES (b. 1816)
• EVEN STEAM.AND OTHER WORKING FLUIDS
• BIG CHANGES LIKELY TO COME FROM EMISSIONS
  ENERGY LEGISLATION BOTH HERE AND IN EUROPE

12
NEW DIESEL FUEL DEVELOPMENTS

• WHAT ARE THE NEW FUELS? (1)
• ULTRA-LOW SULFUR DIESEL FUEL (lt15 PPMW)
  MANDATORY (AND NOT NEW ANY MORE)
• OLD STANDARD WAS lt500 PPM! ACTUAL S WAS USUALLY
  150-350 PPM.
• LOW AROMATICS ALSO DESIRABLE FOR SMOKE CONTROL
• ULSD IS REFINED FROM ALMOST ANY CRUDE OIL
• HI-S REQUIRES AGGRESSIVE DESULFURIZATION
• WHICH USES EVEN MORE HYDROGEN
• ADDS COST
• RESULTS IN CHAIN FRAGMENTATION
• AND LOWERS THERMODYNAMIC EFFICIENCY OF CONVERSION

13
NEW DIESEL FUEL DEVELOPMENTS

• WHAT ARE THE NEW FUELS? (2)
• ULS DIESEL FUELS CAN ALSO BE MADE FROM
• NATURAL GAS VIA REFORMING OR PARTIAL OXIDATION
  AND FISCHER-TROPSCH CATALYSIS TO DISTILLATE (?
  GTL FUELS)
• COAL OR BIOMASS VIA GASIFICATION AND
  FISCHER-TROPSCH CATALYSIS (? CTL OR BTL FUELS)
• GTL CAN USE STRANDED OR ORPHANED GAS, THUS EASING
  DEMAND ON CONVENTIONAL NATURAL GAS
• ONLY BTL USES A RENEWABLE, SUSTAINABLE SOURCE
• MANUFACTURE OF ULSD DIESEL - PROBABLY 80
  EFFICIENT
• MANUFACTURE OF GTL DIESEL 60-65 EFFICIENT
• MANUFACTURE OF CTL DIESEL 55-65 EFFICIENT
• MANUFACTURE OF BTL DIESEL - NOT DOCUMENTED OR
  ESTABLISHED YET

14
FUEL DEVELOPMENTS

• WHAT ARE THE NEW FUELS? (3)
• ULSD
• LOW SULFUR ? FEWER PARTICULATES, LESS PARTICLE
  AGGLOMERATION, LESS ACID, LESS VISIBLE SMOKE
• LOW AROMATICS ? FEWER PARTICULATES, LOWER PAHs
• CAN REDUCE SULFUR, AROMATICS BY HYDROGENATION
• GTL, CTL AND BTL
• SUPER-ULTRA LOW SULFUR ESSENTIALLY ZERO
• SIMILAR TO EUROPEAN ULSD
• VERY LOW AROMATICS
• OTHERWISE INDISTINGUISHABLE FROM REGULAR DIESEL
• IF DEMAND HIGH, WILL HAVE TO BE IMPORTED THE US
  DOES NOT HAVE ENOUGH NATURAL GAS
• IS BIODIESEL ANY BETTER THAN ULSD, GTL, BTL?
• VERY SIMILAR RESULTS, SOME ALDEHYDE EMISSIONS

15
FUEL DEVELOPMENTSEMISSIONS RESULTS
vs. Standard D-2 diesel
vs. California ULSD
RESULTS DEFY SIMPLE EXPLANATION!
16
BIOFUELSDEFINITIONS

• WHAT ARE BIOFUELS? (1)
• LIQUID FUELS (USUALLY) DERIVED FROM BIOLOGICAL
  SOURCES
• ETHANOL (FROM CORN STARCH BY HYDROLYSIS AND
  FERMENTATION)
• ETHANOL (FROM NON-CORN NATURAL STARCH SOURCES)
• POTATO, RICE, WHEAT, BARLEY, CASSAVA.
• ETHANOL (FROM NATURAL SUGARS)
• SUGAR CANE, SUGAR BEET.
• BIODIESEL (BY METHYLATING NATURAL OILS)
• NATURAL OIL SEEDS - CANOLA, PEANUT OR SOYBEAN
• MANY OTHERS

17
DEFINITIONS

• WHAT ARE BIOFUELS? (2)
• BIOMASS ? LIQUID FUELS
• WOOD WASTE, CROP RESIDUES (E.G. CORN STOVER),
  PURPOSE-GROWN CROPS
• USED FOR MAKING HYDROCARBONS, FUEL ALCOHOLS,
  ETHERS, OTHER OXY-FUELS
• BIOMASS ? FUEL GASES
• METHANE (LANDFILLS, DIGESTERS)
• SYNTHETIC NATURAL GAS (METHANE PLUS)
• SYNGAS (H2CO) ? OTHER PRODUCTS

18
FUEL DEVELOPMENTS

• WHAT ARE BIOFUELS? (3)
• BIODIESEL
• MADE FROM A WIDE VARIETY OF VEGETABLE OILS, E.G.
• SOYBEAN OIL (IN THE US)
• RAPESEED (CANOLA) OIL (IN EUROPE, CANADA)
• SUNFLOWER OIL LIKE RAPESEED, GOOD
  PRODUCTIVITY/ACRE
• PEANUT OIL (FIRST USED BY DR. DIESEL RUDOLPH
  DIESEL)
• CORN OIL
• ANIMAL FATS (TALLOW)
• ALSO YELLOW GREASE AND WHITE GREASE

19
FUEL DEVELOPMENTS

• WHAT ARE BIOFUELS? (4)
• BIODIESEL
• ALSO MADE FROM
• RECYCLED COOKING OILS (YELLOW GREASE) IN US,
  CANADA. ALSO PORK FAT (WHITE GREASE)
• OVERSEAS JATROPHA, OTHER HIGH OIL CONTENT NUT
  OILS (INDIA) VERY PRODUCTIVE OIL CROPS FOR POOR
  SOIL CONDITIONS
• ALL ARE MIXTURES OF FATTY ACID TRIGLYCERIDES
• WHILE IT IS POSSIBLE TO USE THESE DIRECTLY AS A
  FUEL, THIS IS NOT GOOD FOR DIESEL ENGINE BEARING
  WEAR
• THE RAW OR RECYCLED OILS MUST BE REFINED AND
  ALKYLATED
• IN PRACTICE, IT IS REACTED WITH METHYL OR ETHYL
  ALCOHOL AND A SIMPLE BASE CATALYST TO FORM THE
  FATTY ACID ALKYL ESTER AND BY-PRODUCT GLYCEROL
  WHICH ITSELF HAS SOME VALUE AS A FUEL

20
ENERGIZING OUR FUTURE

• BIODIESEL
• TRIGLYCERIDE AND FATTY ACID STRUCTURE

21
SYNTHETIC BIODIESEL

• TRIGLYCERIDE AND FATTY ACID STRUCTURE

22
BIODIESEL PRODUCTION PROCESS
23
BIODIESEL PRODUCTION FROM RAPESEED OIL
24
A Comparison of Biodiesel Base Oils by Source and
Type

• BIODIESEL FUEL CHARACTERISTICS
• B-100 IS TYPICALLY A MIXTURE OF 5-7 (?) FATTY
  ACID ESTERS
• PROPORTIONS VARY WIDELY, EVEN AMONG SOY ESTERS
  FROM DIFFERENT SOURCES, LOCATIONS, CLIMATES
• DIFFERENT VEGETABLE OILS PRODUCE VERY DIFFERENT
  ESTER DISTRIBUTIONS AND HENCE DIFFERENT FUEL
  PROPERTIES
• NOT SURPRISING SINCE FA AND FAE PROPERTIES ALSO
  VARY!
• IN PRACTICE, IMPACT IS MITIGATED BY BLENDING WITH
  PETRO DIESEL
• VARIABILITY CAN BE REDUCED BY CAREFUL PLANT
  BREEDING AND/OR GE (DUPONT, MONSANTO)
• FUEL PROPERTIES AND PERFORMANCE ESPECIALLY
  EXHAUST EMISSIONS WILL BE CONTROLLED ONLY WHEN
  WE CAN CONTROL FUEL COMPOSITION - E.G.
• BIODIESEL FAE COMPOSITION, DISTRIBUTION, ARE
  MOST IMPORTANT
• PETROLEUM DIESEL SULFUR, AROMATICS CONTENT ARE
  MOST IMPORTANT
• FAE DISTRIBUTION MAY HAVE GREATEST EFFECT ON
  UNREGULATED EMISSIONS

25
A Comparison of Biodiesel Base Oils by Source and
Type
26
SIMPLIFIED FATTY ACID COMPOSITIONS OF KEY
VEGETABLE OILS
27
COMMON NATURAL OIL FATTY ACIDS (NOT ESTERS)

• Caprylic (C8) CH3(CH2)6COOH (COCONUT)
• Capric (C10) CH3(CH2)8COOH (COCONUT)
• Lauric (C12) CH3(CH2)10COOH (COCONUT, PALM
  KERNEL)
• Myristic (C14) CH3(CH2)12COOH (BUTTER, PALM
  KERNEL, COCONUT)
• Palmitic (C16) CH3(CH2)14COOH (TALLOW, LARD,
  BUTTER, PALM)
• Palmitoleic (C16) CH3(CH2)5CHCH(CH2)7COOH (COD
  LIVER OIL)
• Stearic (C18) CH3(CH2)16COOH (TALLOW)
• Oleic (C18) CH3(CH2)7CHCH(CH2)7COOH (ALMOST
  ALL)
• Linoleic (C18) CH3(CH2)4CHCH(CH2)CHCH(CH2)7COOH
  (MOST)
• Linolenic (C18) CH3(CH2)CHCH(CH2)CHCH(CH2)CHCH
  (CH2)7COOH (LINSEED, TUNG OILS)
• Arachidic (C20) CH2(CH2)18COOH (PEANUT, BUTTER)
• Eicosenoic (C20) CH3(CH2)7CHCH(CH2)9COOH (RAPE,
  MUSTARD)
• Erucic (C22) CH3(CH2)7CHCH(CH2)11COOH (TOXIC!
  SOME IN OLD CANOLA)

28
Properties of Individual Methyl Esters Found in
Biodiesel
29
A Comparison of Biodiesel Alkyl Esters by Source
and Type (1)
30
A Comparison of Biodiesel Base Oils by Source and
Type (2)

• Notes for Previous Slide
• ME methyl ester EE ethyl ester BE butyl
  ester C canola
• Methylation is by far the most common
  esterification method
• D-2 conventional petroleum diesel (varies
  widely in properties)
• HHV higher heating value LHV lower heating
  value (excludes unrecovered evaporation enthalpy
  in water vapor)
• 1 MJ/Kg 429.92 BTU/lb.
• Comments on Previous Slide
• HHV values are remarkably consistent about 10
  (HHV) or 15 (LHV) below that of typical D-2
  (biodiesel produces more combustion water)
• Cold weather performance varies widely it is
  unacceptable in some esters (e.g., tallow methyl
  ester, esterified frying oil) compared to D-2.
  Additives are usually required for lower cloud,
  pour points and CFPP
• Alkyl ester cetane numbers are usually
  significantly higher than for D-2, especially for
  canola esters.

31
A Comparison of Biodiesel Base Oils by Source and
Type (3)

• There are many other important natural oilseed
  crops
• Oil FA constitution varies very widely
• Some extreme examples not listed in table
• Castor Oil - 90 ricinoleic acid used as a
  engine lubricant
• Tung Oil - 82 eleostearic acid used in
  furniture care products also as a diesel fuel in
  rural China!
• Ucuuba Oil (Brazil) - 73 myristic acid used to
  make candles
• Neem Oil 42 oleic acid, 21 stearic acid, 19
  palmitic acid. Unusual in that it contains
  organic sulfur compounds that make it effective
  as an insect repellent
• Tallow (animal fat) - 43 oleic acid, 24
  palmitic acid, 19 stearic acid used for
  candles and for biodiesel manufacture
• All are potential base oils for biodiesel
  manufacture
• Some (e.g., tallow, peanut, olive, sunflower)
  have been methylated and used with limited success

32
SIMPLIFIED FATTY ACID COMPOSITIONS OF KEY
VEGETABLE OILS (REPEATED)
33
COMPOSITION AND PROPERTIES

• HOW TO OPTIMISE COMPOSITION?
• OBTAIN MUCH MORE DATA ON FUNCTIONAL PROPERTIES
  VS. COMPOSITION
• BLEND FROM MULTIPLE SOURCES TO ACHIEVE SELECTED
  COMPOSITION
• E.G., COCONUT OIL RAPESEED OIL
• TALLOW ??
• NEED TO BALANCE SATURATES VS UNSATURATES NOT
  JUST CHAIN LENGTH
• WITH ENOUGH COMPOSITIONAL INFO, NO DIFFERENT THAN
  BLENDING GASOLINE OR LUBRICANTS
• NEED TO TAKE THE BASE STOCK (ULSD) INTO ACCOUNT
  IN TARGETING THE FINAL RESULT

34
BIODIESEL

• HOW IS IT MADE?
• BY REACTING VEGETABLE OIL WITH ALCOHOLS LIKE
  ETHANOL, METHANOL.
• VEGETABLE OILS (AND ANIMAL FATS) ARE A MIXTURE OF
  TRIGLYCERIDES OF MOSTLY C18 FATTY ACIDS (OLEIC,
  LINOLEIC, ETC.)
• REACTION WITH 12 WT OF AN ALKYL ALCOHOL SUCH AS
  METHANOL, ETHANOL FORMS A MIXTURE OF FATTY ACID
  ALKYL ESTERS PLUS CO-PRODUCT GLYCEROL. THE
  PRODUCTS ARE THEN SEPARATED (IF NECESSARY)
  REFINED
• HIGHER ALKYL ALCOHOLS (PROPYL, BUTYL) CAN ALSO BE
  USED CHOICE DETERMINED BY FUEL PROPERTIES SOUGHT

35
BIODIESEL HISTORY OF USE AS A FUEL

• BIODIESEL FIRST USED IN ENGINES IN THE 1890s
• BY RUDOLPH DIESEL (UNMODIFIED PEANUT OIL!)
• METHYLATED SOYBEAN OIL IN COMMON USE UNTIL ABOUT
  1920 - REPLACED BY MUCH CHEAPER PETROLEUM DIESEL
• SOME USE BY GERMANY IN WW2 BUT SYNTHETIC DIESEL
  AND SYNTHETIC AVIATION GASOLINE WERE MORE
  SUCCESSFUL
• NO REAL INTEREST UNTIL THE FOREIGN OIL SUPPLY
  CRISIS OF THE 1970s. THEN BIODIESEL WAS SEEN AS
  A DIESEL EXTENDER
• INTEREST IN BIODIESEL AS A GREEN FUEL IS MORE
  RECENT.
• NOW USED FOR HIGH LUBRICITY, CONTRIBUTION TO
  ENERGY INDEPENDENCE, EMISSIONS REDUCTIONS (PM,
  HC, CO BUT NOT NOx), CO2 RECYCLING
• HISTORY POOR QUALITY IMPROVING, BUT A LONG WAY
  TO GO.
• STILL NOT WELL UNDERSTOOD COMPARED TO PETROLEUM
  DIESEL

36
DIESEL BIODIESEL DENSITY AND CETANE NUMBER
OK
NOT OK
37
BIODIESEL IMPACT ON HD VEHICLE EMISSIONS
SPREAD
NOTE UNCERTAINTY OF NOX DATA
38
OTHER DIESEL BIOFUELS

• BIODIESEL HAS STRONG COMPETITION!
• ETHANOL (E-DIESEL - FROM CORN, NOW BIOMASS)
• USED AS AN OXYGENATED ADDITIVE (10-15)
• SUPPOSEDLY IMPROVES EMISSIONS, COLD STARTS
• NOT APPROVED BY THE ENGINE MANUFACTURERS
• BTL FUELS (GTL-D OR FT-D WITH A BIOMASS TWIST)
• BIOMASS ? SYNGAS ? FT SYNTHESIS ? REFINED LIQUIDS
• PRODUCT S-FREE, AROMATICS-FREE DIESEL LOOK-ALIKE
• COST DEPENDS ON NG COST
• NET ENERGY RECOVERED STILL UNCERTAIN
• OXYFUELS E.G., FUEL ALCOHOLS (IF FROM BIOMASS)
• SAME BTL PROCESS, BUT DIFFERENT CATALYSTS AND
  CONDITIONS
• COST IS LOW
• PRODUCTS INCLUDE ALKYL ALCOHOLS, ETHERS, KETONES

39
BIODIESEL NOTES

• BIODIESEL FUEL NOTES
• PRIMARY USE IS AS 5-20 ADDITIVE TO PETROLEUM
  DIESEL AS AN EMISSIONS CONTROL ADDITIVE (VERY
  EFFECTIVE). B5 AND B10 ARE COMMON. B20 OFFERS
  LITTLE ADDITIONAL ADVANTAGE PLUS SOME FUEL
  INSTABILITY MATERIALS COMPATIBILITY PROBLEMS.
  BUT THE INDUSTRY WANTS TO GO THERE.
• BIODIESEL ALSO ADDS LUBRICITY TO LOW-SULFUR
  PETROLEUM DIESELS, A CHARACTERISTIC THAT MAY
  PROVE VALUABLE AS ULSD FUELS ARE INTRODUCED
  (STARTED IN OCTOBER 2006)
• THE LOW NET ENERGY RECOVERY IN BIODIESEL
  MANUFACTURE MEANS THAT USE AS A DIESEL
  SUBSTITUTE OR EXTENDER IS NOT NORMALLY VIABLE,
  EVEN WITH THE NEW SUBSIDIES

40
BIODIESEL NOTES (2)

• BIODIESEL FUEL NOTES
• FOR OPTIMUM ENERGY CONSERVATION IT IS BETTER TO
  BURN SOYBEANS AS FURNACE FUEL! (SAME PROBLEM AS
  CORN ETHANOL)
• BIODIESEL WILL EXPERIENCE MAJOR COMPETITION FROM
  SYNTHETIC FUELS THAT OFFER MANY OF THE SAME
  PROPERTIES
• SOME OF THESE SYNTHETICS MAY BE DERIVED FROM
  BIOMASS BUT THEY ARE NOT HERE YET.
• BIODIESEL IS LESS COMPRESSIBLE THAN STANDARD
  DIESEL, SYNTHETIC DIESEL IS MORE COMPRESSIBLE
  THIS CAN AFFECT INJECTOR PERFORMANCE AND TIMING.

41
BIODIESEL NOTES (3)

• ARE THERE BETTER ROUTES TO BIODIESEL? THE RIGHT
  CHOICE WOULD
• AVOID USE OF METHANOL (FOSSIL-BASED)
• AVOID GLYCEROL FORMATION
• PRODUCE A PRODUCT OF HIGHER QUALITY AND
  FUNCTIONAL PERFORMANCE
• PRODUCE MORE OF THE DESIRED END-PRODUCT (FATTY
  ACID ALKYL ESTERS OR A WHOLE NEW CONCEPT FOR
  BIODIESEL)
• PRODUCE A PRODUCT OF HIGHER ENERGY CONTENT (NOT A
  CRITICAL ISSUE)
• PRODUCE MORE BIODIESEL PER UNIT OF NATURAL OIL
  CONSUMED

42
BIODIESEL NOTES (4)

• BETTER ROUTES TO BIODIESEL?
• PROGRESS MADE IN SEVERAL AREAS, EG
• AVOID HEXANE EXTRACTION OF SOYBEAN OIL BY
  PROCESSING BEAN FLAKE WITH MeOH AND CAT
• CONTINUOUS PROCESSING USING NON-ALKALINE
  HETEROGENEOUS CATALYST
• REPLACEMENT OF METHANOL WITH BIOETHANOL
• NExBTL FORTUM OIL GAS (FORMERLY NESTE OY)
  PROCESS PRODUCES HIGH-QUALITY HYDROGENATED
  PRODUCT OTHERS FOLLOWING
• NUMEROUS OTHER PROJECTS ONGOING
• FOR MORE BACKUP INFO (MUCH DETAIL HERE)
  http//www.castoroil.in/reference/plant_oils/uses/
  fuel/bio_fuels.html

43
BIODIESEL NOTES (5)

• BETTER ALTERNATIVES TO BIODIESEL?
• MULTIPLE CHOICES, EG
• A VARIETY OF BIOMASS ? BIODIESEL TECH
• FERMENTATION OF BIOMASS ? MIXED ALCOHOLS
• BIOMASS GASIFICATION ? SYNGAS ? ALCOHOLS
• BIOMASS GASIFICATION ? SYNGAS ? SYNTHETIC
  HYDROCARBONS
• CAN ALSO CONVERT DIRECTLY TO A MIXTURE OF
  HYDROCARBON AND ALCOHOL (DIFFICULT!)
• MANY BTL FUELS, WHETHER OXYGENATES OR
  HYDROCARBONS, PERFORM AS WELL AS BIODIESEL OR (IN
  GASOLINE) ETHANOL

44
BIODIESEL NOTES (6)

• CAN WE MODIFY BIODIESEL FOR BETTER PERFORMANCE ?
  
• THE OLEOCHEMISTS HAVE BEEN DOING THIS FOR YEARS
  FOR FOOD OR INDUSTRIAL USES
• INTEREST IN SWITCHING AWAY FROM PETROLEUM
• FISH AND ANIMAL OILS AND FATS OUT OF PUBLIC
  FAVOR, ESPECIALLY IN EUROPE (NOT IN SE ASIA!)
• USE OF PLANT BREEDING TO ADJUST OIL CHEMISTRY
• EG, GM RAPESEED FOR LAURIC ACID PRODUCTION
• BUTCONCERN OVER USE OF GM, SO MAY BE BETTER TO
  CHEMICALLY MODIFY THE NATURAL OIL
• SURFACTANTS ARE A MAJOR DERIVATIVE OF OILS
• SO ARE A WIDE RANGE OF PAINTS AND COATINGS (ONE
  OF THE OLDEST USES OF NATURAL OILS)
• PLENTY OF UNIQUE CHEMISTRY CAN WE USE IT FOR
  BIODIESEL IMPROVEMENT?

45
BIODIESEL NOTES (7)

• CAN WE MODIFY BIODIESEL FOR BETTER PERFORMANCE ?
  
• HYDROPROCESSING OR FUNCTIONALIZATION? EXAMPLES
• CONTROLLED UNSATURATION FOR CURABLE APPLICATIONS
• WHAT IS GAINED BY INTRODUCING CHAIN-BRANCHING?
• USE FOR BIO-BASED AND BIODEGRADABLE LUBRICANTS
  CONFLICTING OBJECTIVES
• AMINE AND OTHER FUNCTIONALIZATION METHODS
• CAN EPOXIDIZE OR MALEINATE NATURAL OILS TO
  ACHIEVE POLYESTER-LIKE POLYMERS
• AGAIN, PLENTY OF UNIQUE CHEMISTRY CAN WE USE IT
  FOR BIODIESEL IMPROVEMENT?
• READ http//www.cyberlipid.org/fa/acid0001.htm
• CAN FRACTIONATE, HYDROGENATE, INTERESTERIFY
• LITTLE FUELS WORK TO DATE THE JURY IS STILL OUT

• CAN WE MODIFY BIODIESEL FOR BETTER PERFORMANCE ?
  
• HYDROPROCESSING OR FUNCTIONALIZATION? EXAMPLES
• CONTROLLED UNSATURATION FOR CURABLE APPLICATIONS
• WHAT IS GAINED BY INTRODUCING CHAIN-BRANCHING?
• USE FOR BIO-BASED AND BIODEGRADABLE LUBRICANTS
  CONFLICTING OBJECTIVES
• AMINE AND OTHER FUNCTIONALIZATION METHODS
• CAN EPOXIDIZE OR MALEINATE NATURAL OILS TO
  ACHIEVE POLYESTER-LIKE POLYMERS
• AGAIN, PLENTY OF UNIQUE CHEMISTRY CAN WE USE IT
  FOR BIODIESEL IMPROVEMENT?
• READ http//www.cyberlipid.org/fa/acid0001.htm
• CAN FRACTIONATE, HYDROGENATE, INTERESTERIFY
• LITTLE FUELS WORK TO DATE THE JURY IS STILL OUT