NEW ENERGY RESOURCES: HYDROGEN - PowerPoint PPT Presentation


Title: 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
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NEW ENERGY RESOURCES: HYDROGEN

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... AC/DC HYDROGEN PURIFICATION LIQUID H2 TUBE OR CRYO TRUCK TANK FUEL CELL DC/AC? ... 40-45% EFFICIENCY (FUEL CELL ALONE WITH NO ACCESSORIES IS ABOUT 65% EFFICIENT) ... – PowerPoint PPT presentation

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Title: 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
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