Document

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NEW ENERGY RESOURCES:HYDROGEN

• 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 ALWAYSALWAYS:– 2H2O 2H2 + O2…….. ΔΔH = +62,050H = +62,050 BTU/LB H2

– IF WE GET THE HYDROGEN FROM WATER AND THEN JUST BURN IT, AT BEST WE GET OUR ENERGY BACK!

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• MANUFACTURING HYDROGEN– ELECTROLYSIS OF WATER:

• 2H2O 2H2 + O2 ΔH = +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.

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• 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

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• 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 (CNH2N+2)• 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

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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 OPERATIONSOURCE: 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

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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 >$2 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

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• 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”.

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SOURCE-TO-USE EFFICIENCIES:SOURCE-TO-USE EFFICIENCIES:CALIBRATION DATACALIBRATION DATA

FUEL/POWER PLANT/VEHICLE

COMBINATION

NOTE: OLDER DATA FOR COMPARISON

FUEL PRODUCTION(source-to-tank)

%

FUEL USE(tank-to-

use)

%

OVERALL(source-to-

use)

%

Diesel/Electric Hybrid 81 35 28

Hydrogen fuel cell; on-board gasoline/hydrogen reformer (no longer considered feasible)

81 27 22

Hi-efficiency (European) turbodiesel w/latest fuel injection technology

81 35 22

Hydrogen fuel cell; distributed hydrogen from natural gas at retail ($7.50)

60 38 22

Gasoline/electric hybrid w/latest engine technology 81 23 20

Conventional gasoline engine w/latest engine technology 81 21 17

Hydrogen fuel cell; liquid hydrogen from natural gas, central station

41 38 16

Hydrogen fuel cell; hydrogen from electrolysis, power at retail

<28 38 <11

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• 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

ALTERNATIVE ENERGIESALTERNATIVE ENERGIES(GENERAL)(GENERAL)

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ALTERNATIVE ENERGIESALTERNATIVE ENERGIES(GENERAL)(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…..

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ENERGY ENERGY USESUSESTHAT ALSO SAVE PETROLEUMTHAT 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

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NEW DIESEL FUEL NEW DIESEL FUEL DEVELOPMENTSDEVELOPMENTS

• WHAT ARE THE NEW FUELS? (1) ULTRA-LOW SULFUR DIESEL FUEL (<15 PPMW) –

MANDATORY (AND NOT NEW ANY MORE) OLD STANDARD WAS <500 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

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NEW DIESEL FUEL NEW DIESEL FUEL DEVELOPMENTSDEVELOPMENTS

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

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FUEL DEVELOPMENTSFUEL 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

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FUEL DEVELOPMENTSFUEL DEVELOPMENTSEMISSIONS RESULTSEMISSIONS RESULTS

vs. Standard D-2 diesel

vs. California ULSD

RESULTS DEFY SIMPLE EXPLANATION!

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BIOFUELSBIOFUELSDEFINITIONSDEFINITIONS

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

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DEFINITIONSDEFINITIONS

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 (H2+CO) OTHER PRODUCTS

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FUEL DEVELOPMENTSFUEL 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”

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FUEL DEVELOPMENTSFUEL 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]

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ENERGIZING OUR FUTUREFUTURE

• BIODIESEL• TRIGLYCERIDE AND FATTY ACID STRUCTURE

http://en.wikipedia.org/wiki/Image:Fat_triglyceride_shorthand_formula.PNG

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“SYNTHETIC BIODIESEL”

• TRIGLYCERIDE AND FATTY ACID STRUCTURE

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BIODIESEL: BIODIESEL: PRODUCTION PROCESSPRODUCTION PROCESS

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BIODIESEL PRODUCTION

FROM RAPESEED OIL

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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

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A Comparison of Biodiesel Base Oils by Source and Type

Fatty Acid NE Brazil Soybean

Oil

US MidwestSoybean Oil

Canada #1 Canola Oil

Typical Palm Oil

Typical Jatropha Oil

Palmitic C16:0 9.3 10.1 3.9 39.6 14.5

Stearic C18:0 3.1 4.2 2.0 5.4 5.5

Oleic C18:1 33.8 24.3 61.5 41.1 50.0

Linoleic C18:2 48.3 51.5 19.1 12.4 29.5

Linolenic C18:3

5.5 8.3 9.9 n/a n/a

Margaric C20 n/a 0.1 n/a n/a n/a

Arachidic C20 n/a 0.35 0.7 n/a n/a

Gadoleic C20 n/a 0.2 1.4 n/a n/a

Behenic C22 n/a 0.4 0.4 n/a n/a

Lignoceric n/a 0.1 0.2 n/a n/a

Other n/a 0.2 0.9 1.5 0.5

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SIMPLIFIED FATTY ACID COMPOSITIONS OF KEY VEGETABLE OILS

OIL C8 C10 C12 C14 C16 C18 C20 C22

COCONUT 7 7 49 17 9 11 0 0

PALM KNL 3 5 49 17 8 18 0 0

PALM 0 0 0 4 40 58 0 0

TALLOW 0 0 0 3 29 68 0 0

CORN 0 0 0 1 10 89 0 0

SUNFLOWER 0 0 0 0 6 94 0 0

SOYBEAN 0 0 0 0 10 88 0 0

RAPESEED 0 0 0 0 3 97 0 0

MUSTARD 0 0 0 0 3 97 0 0

JATROPHA 0 0 0 0 16 82 2 0

ALGAL OIL 0 0 0 10 24 2 3.5 60.5

JOJOBA 0 0 0 0 0 12 17 71

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COMMON NATURAL OIL COMMON NATURAL OIL FATTY ACIDS (NOT ESTERS)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)5CH=CH(CH2)7COOH (COD LIVER OIL)• Stearic (C18) CH3(CH2)16COOH (TALLOW)• Oleic (C18) CH3(CH2)7CH=CH(CH2)7COOH (ALMOST ALL)• Linoleic (C18) CH3(CH2)4CH=CH(CH2)CH=CH(CH2)7COOH (MOST)• Linolenic (C18) CH3(CH2)CH=CH(CH2)CH=CH(CH2)CH=CH(CH2)7COOH

(LINSEED, TUNG OILS)• Arachidic (C20) CH2(CH2)18COOH (PEANUT, BUTTER)• Eicosenoic (C20) CH3(CH2)7CH=CH(CH2)9COOH (RAPE, MUSTARD)• Erucic (C22) CH3(CH2)7CH=CH(CH2)11COOH (TOXIC! SOME IN “OLD”

CANOLA)

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Properties of Individual Methyl Esters Found in Biodiesel

Fatty Acid Methyl Ester

Density, g/cc

@15OC

Viscosity: Cs

@ 40OC

Cetane No. Heating Value

MJ/kg

Melting PointOC

Palmitate 0.867 4.37 74 39.4 30.6

Stearate 0.867 5.79 75 40.1 39.1

Oleate 0.878 4.47 55 39.9 -19.8

Linoleate 0.890 3.68 33 39.7 -35.0

Source of Data

Janarthanan et al

Janarthanan et al

Bagby & Freedman

Bagby & Freedman

Teoh & Clements

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A Comparison of Biodiesel Alkyl Esters by Source and Type (1)

Ester

▼

Cetane

No.

Viscos

CS

Flash Pt.OC

HHV

MJ/Kg

LHV

MJ/Kg

Cloud Pt.OC

Pour Pt.OC

Soy ME 50.9 4.08 131 40.4 37.0 -0.5 tp 2.0 -1 to -3.8

Can ME 52.9 4.83 170 40.7 37.3 -4.0 -10.8

Soy EE 48.2 4.41 160 40.0 n/a -1.0 to 1.0 -4.0

Can EE 64.9 6.17 185 40.5 n/a -2.0 -15.0

Soy BE 51.7 5.24 n/a 40.7 n/a -3.0 -7.0

Tallow ME

58.8 4.8 117 40.2 n/a 13.9 9.0

Frying Oil EE

61.0 5.78 124 40.5 37.2 9.0 8.0

D-2

(Typical)

40-52 2.6 60-72 44.9 43.4 -25 to -15 -25 to +5

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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.

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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

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SIMPLIFIED FATTY ACID COMPOSITIONS OF KEY VEGETABLE OILS (REPEATED)

OIL C8 C10 C12 C14 C16 C18 C20 C22

COCONUT 7 7 49 17 9 11 0 0

PALM KNL 3 5 49 17 8 18 0 0

PALM 0 0 0 4 40 58 0 0

TALLOW 0 0 0 3 29 68 0 0

CORN 0 0 0 1 10 89 0 0

SUNFLOWER 0 0 0 0 6 94 0 0

SOYBEAN 0 0 0 0 10 88 0 0

RAPESEED 0 0 0 0 3 97 0 0

MUSTARD 0 0 0 0 3 97 0 0

JATROPHA 0 0 0 0 16 82 2 0

ALGAL OIL 0 0 0 10 24 2 3.5 60.5

JOJOBA 0 0 0 0 0 12 17 71

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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

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BIODIESELBIODIESEL

HOW IS IT MADE? BY REACTING VEGETABLE OIL WITH ALCOHOLS BY REACTING VEGETABLE OIL WITH ALCOHOLS

LIKE ETHANOL, METHANOL.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:BIODIESEL: HISTORY OF USE AS A FUELHISTORY OF USE AS A FUEL

BIODIESEL FIRST USED IN ENGINES IN THE 1890’s 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:DIESEL & BIODIESEL: DENSITY AND CETANE NUMBERDENSITY AND CETANE NUMBER

OKNOT OK

37

BIODIESEL:BIODIESEL: IMPACT ON HD VEHICLE EMISSIONSIMPACT ON HD VEHICLE EMISSIONS

[NOTE UNCERTAINTY OF NOX DATA]

“SPREAD”

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OTHER DIESEL BIOFUELSOTHER 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

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BIODIESEL NOTESBIODIESEL 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

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BIODIESEL NOTES (2)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.

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BIODIESEL NOTES (3)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

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• 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



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• 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

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• 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• BUT…CONCERN 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?

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• 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

http://www.cyberlipid.org/fa/acid0001.htm

http://www.cyberlipid.org/fa/acid0001.htm

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