BIODIESEL NOTES 7

1
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

2
ALTERNATIVE ENERGIESDIESEL FUELS

• WHY DO WE ALSO NEED CLEAN DIESEL ENGINES?
• HIGH THERMAL EFFICIENCY ? FUEL SAVINGS
• MORE EFFICIENCY GAINS TO COME
• MAJOR CHANGES IN EMISSIONS REGULATIONS IN THE
  U.S., EUROPE AND JAPAN
• EFFECTIVELY REQUIRES FUELS THAT CONTRIBUTE TO
  EMISSIONS CONTROL
• EU NOW PROPOSING EVEN MORE EXTREME STANDARDS,
  ESPECIALLY FOR CO2
• STANDARDS SET (2/7/07) AT FLEET AVERAGE OF 130
  GM/KM (210 GM/MI)
• PRESENT FLEET RUNS UP TO 500 GM/KM EU AVERAGE
  IS NOW 200 GM/KM AND CLIMBING

3
ALTERNATIVE ENERGIESDIESEL FUELS

• CLEAN DIESELS.
• MAJOR DEVELOPMENTS IN CLEAN DIESEL ENGINE
  TECHNOLOGY HAVE BEEN LED BY EUROPEAN ENGINE
  MANUFACTURERS
• ALL NEED CLEAN FUELS TO BE EFFECTIVE
• PLUS DOWNSTREAM EXHAUST CLEANUP
• EUROPE HAS 1-10 PPM SULFUR DIESEL FUEL
• THE DIESELS ARE COMING (TO THE US, THAT IS)
• TECH LEADERS WHO WILL BRING PRODUCTS TO THE US
  ARE VW, MERCEDES (DCX), BMW, AUDI, HONDA
• FOLLOWERS HERE WILL BE DCX (JEEP), GM (V-8 DUE IN
  2008), FORD (IMPORTED FROM FORD EUROPE)

4
DIESEL ENGINE DEVELOPMENTS

• WHAT ARE THE TECHNOLOGIES?
• HIGH PRESSURE FUEL INJECTION (COMMON RAIL OR UNIT
  INJECTOR) CAN BE 30,000 PSI
• DIRECT INJECTION
• HIGH EXHAUST GAS RECIRCULATION (EGR)
• MULTI-STAGE FUEL INJECTION
• MULTI-ORIFICE FUEL INJECTORS
• MULTIPLE TURBOCHARGERS (VERY FEW SUPERCHARGERS).
  SMALLER BETTER RESPONSE
• TWO-STAGE TURBOCHARGING
• LIGHTER DESIGN, OFTEN ALL-ALUMINUM OR ALMG
• VARIABLE CAM TIMING COMING SLOWLY!
• HYDROGEN INJECTION IN INTAKE AIR (FOR DPs)
• HYDROGEN INJECTION IN EXHAUST (FOR NOX SCRs)

5
ALTERNATIVE ENERGIESDIESEL FUELS

• CLEAN DIESELS.
• NEAR FUTURE TECH TRENDS (ALL ENGINES)
• ULTRA-HIGH PRESSURE EFI
• DIRECT INJECTION (CONTINUED AND REFINED)
• HCCI (HOMOGENEOUS-CHARGE COMPRESSION IGNITION) -
  DIESEL
• CAI (COMPRESSION AUTO IGNITION) GASOLINE
• INCREASINGLY BLURRED LINE BETWEEN GAS DIESEL
• VARIABLE COMPRESSION RATIO (MOSTLY GASOLINE)
• ENGINE AUTO-OPTIMIZATION FOR VARIABLE FUELS
• IC ENGINES WILL BE AROUND FOR A WHILE!

6
ALTERNATIVE ENERGIESDIESEL FUELS

• OTHER DRIVERS
• INCREASING FUEL COSTS WORLD-WIDE
• CAN WE FIND LESS EXPENSIVE CLEAN DIESEL FUELS?
• CONCERN OVER FUTURE GLOBAL FUEL
  SUPPLIES.JUSTIFIED?
• CONCERN OVER U.S. ENERGY INDEPENDENCE
• CAN WE MAKE DIESEL FUEL FROM AN ALTERNATIVE
  RESOURCE THAT IS DOMESTIC, RENEWABLE, CLEAN AND
  PLENTIFUL?
• AND AT WHAT COST?
• CONCERN OVER CURRENT ALTERNATE FUEL QUALITY ALSO
  A FACTOR

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ALTERNATIVE DIESEL FUELSTHE EMISSIONS CHALLENGE
US 2008
8
ALTERNATIVE DIESEL FUELSTHE EMISSIONS CHALLENGE
US 2008
9
ALTERNATIVE DIESEL FUELSTHE EMISSIONS CHALLENGE

• THE REGULATIONS KEEP TIGHTENING
• ESPECIALLY FOR NOX AND NOW CO2
• EU CO2 GOING TO 130 GM/KM (EU) 210 GM/MI (US)
  BUT THESE ARE AVERAGES (FOR NOW!)
• UK CAR TAXES ARE BASED IN PART ON CO2
  EMISSIONS.WILL WE SEE THAT IN CA, THEN 50-STATE?
• CURRENT RANGE IS ABOUT 115 TO 500 GM/KM, SO 130
  WILL BE A MAJOR CHALLENGE
• REGULATORY BODIES SEEM TO BE COMPETING FOR MOST
  TOUGH AWARD
• EXPECT CA TO FOLLOW EU LEAD SOON
• ALL TRANSLATES INTO INCREASED DEMAND FOR CLEAN
  DIESEL AND CLEAN FUEL TECHNOLOGY.

10
DIESEL EXHAUST SYSTEM DEVELOPMENTS

• WHAT ARE THEY?
• MOST ARE DESIGNED TO IMPROVE CONTROL OF
  PARTICULATES AND NOX - AND COMPENSATE FOR ENGINE
  CHANGES.
• SIMPLE OXIDATION CATALYST FOR HC, CO
• DIESEL PARTICULATE FILTERS (DPF)
• MONOLITH TYPE (70 OF MARKET) OR FIBER TYPE (25)
• A FEW METAL FLEECE, WOOL, SINTERED SHEET (5)
• SELECTIVE CATALYTIC REDUCTION (SCR) FOR NOX
• MOST REQUIRE AMMONIA OR UREA INJECTION
• CONTROLS FOR DPF REGENERATION DEPENDS ON TYPE
• CONTINUOUS VS. BATCH REGEN CATALYTIC.

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DIESEL FUEL ADDITIVES

• THE ISSUE
• CAN WE LEARN ANYTHING ABOUT THE EFFECT OF
  IMPURITIES FROM THE BEHAVIOR OF INTENTIONAL
  ADDITIVES?
• FOUR MAIN CATEGORIES
• ENGINE PERFORMANCE
• FUEL HANDLING
• FUEL STABILITY
• CONTAMINANT CONTROL
• AND A FEW SPECIALS MOSTLY AFTERMARKET!

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DIESEL FUEL ADDITIVES

• THREE ADDITION LOCATIONS
• REFINERY
• DISTRIBUTION SYSTEM (E.G., PIPELINE)
• AFTERMARKET (BUYER BEWARE!!)
• ENGINE PERFORMANCE ADDITIVES
• CETANE (IGNITION DELAY) IMPROVERS
• DETERGENTS (INJECTOR CLEANLINESS)
• LUBRICITY IMPROVERS
• SMOKE SUPPRESSANTS
• COMBUSTION CATALYSTS

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DIESEL FUEL ADDITIVES

• CETANE IMPROVERS
• NITRATES 2-ETHYLHEXYL (OCTYL) NITRATE
• ALSO OTHER ALKYL NITRATES
• PEROXIDES DI-TERTIARY BUTYL PEROXIDE
• PERFORMANCE OF ALL DEPENDS ON
• BASE FUEL COMPOSITION
• BASE FUEL CETANE NUMBER
• MAY HAVE NEGATIVE IMPACT ON LUBRICITY
• SO MAY ALSO NEED TO USE LUBRICITY ADDITIVE
• TYPICAL DOSAGE RATE 500-2000 PPM
• RESULTS IN 3-8 CN IMPROVEMENT

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DIESEL FUEL ADDITIVES

• DETERGENT ADDITIVES
• ASHLESS POLYMERIC POLAR/NON-POLAR TYPE
• CLEANS INJECTORS
• DOSAGE 50-300 PPM
• LUBRICITY ADDITIVES (OFTEN IN A PACKAGE)
• POLAR GROUP WITH LONG OLEOPHILIC TAIL
• ACT AS BOUNDARY LUBRICANTS
• TYPES
• MONOCARBOXYLIC FATTY ACIDS ( BIODIESEL!)
• AMIDES (FA PLUS AMINE)
• SYNTHETIC ESTERS (ESTER GROUP POLYOLEFIN)
• NATURAL DIMER ACID ESTERS (C36 DICARBOXYLIC
  ACIDS)

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DIESEL FUEL ADDITIVES

• LUBRICITY ADDITIVES (OFTEN IN A PACKAGE)
• OFTEN SHOW SHARP THRESHOLD EFFECT
• LITTLE EFFECT BELOW 100 PPM, LITTLE IMPROVEMENT
  ABOVE 200 PPM
• MECHANISM THOUGHT TO BE FILM FORMATION 100
  COVERAGE NEEDED, HENCE THE THRESHOLD
• SOME PROBLEMS REPORTED WITH LUBRICATING OIL
  INTERACTIONS
• PROBLEMS REPORTED WITH FUEL FILTER PLUGGING DUE
  TO REACTION WITH OTHER ADDITIVES PRESENT
• SOME PROBLEMS WITH PIPELINE CONTAMINATION OF JET
  FUEL ADDITION AT FUEL TERMINALS NOW COMMON
• MIXING BECOMES A PROBLEM

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DIESEL FUEL ADDITIVES

• SMOKE SUPPRESSANTS
• CATALYSTS
• ORGANOMETALLIC BARIUM NO LONGER USED
• OTHERS ORGANOMETALLICS USED WERE
• CALCIUM
• IRON
• CERIUM
• PLATINUM
• MANY PROPRIETARY FORMULATIONS, FUEL-SOLUBLE
  ORGANOMETALLICS E.G., FAs, FAEs
• NOW LITTLE USED - FORM ENGINE DEPOSITS,
  PARTICULATES

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DIESEL FUEL ADDITIVES

• IN-CYLINDER COMBUSTION CATALYSTS
• AIM TO REDUCE FUEL CONSUMPTION, IMPROVE ENGINE
  EFFICIENCY
• BUT MODERN ENGINES ARE VERY EFFICIENT ALREADY
• SOMETIMES USEFUL FOR OLDER ENGINES AND
  LOW-QUALITY FUELS. BUT BUYER BEWARE!
• USUALLY ORGANOMETALLICS
• VERY PROPRIETARY BUT OFTEN PT-BASED
• SOME APPEAR TO REQUIRE FORMATION OF DEPOSITS
• A LOT OF OLD HISTORY RE PERFORMANCE AND EFFECTS
• HIT-AND-MISS SUCCESS
• GENERALLY NOT RECOMMENDED AND NOT APPROVED BY
  ENGINE MANUFACTURERS OR THE EPA.

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DIESEL FUEL ADDITIVES

• FUEL HANDLING ADDITIVES
• LOW-TEMPERATURE OPERABILITY ADDITIVES
• USUALLY POLYMERS THAT SOLUBILIZE WAXES
• ADDITIVE FORMULATION MAY BE FUEL-SPECIFIC
• RESULTS FOR CLOUD POINT, POUR POINT (US) AND CFPP
  (EU) ARE OFTEN VERY DIFFERENT.

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DIESEL FUEL ADDITIVES

• TYPES OF FUEL HANDLING ADDITIVES
• FLOW IMPROVERS
• AIM TO KEEP WAX CRYSTALS SMALL
• TYPICALLY ARE POLYMERS SUCH AS POLY(ETHYLENE-CO-VI
  NYL) ACETATE OR EVA
• ACT AS WAX CRYSTAL NUCLEANTS
• EFFECTIVENESS DEPENDS ON WAX DISTRIBUTION
• WAX ANTI-SETTLING ADDITIVES (WASA)
• REDUCE CRYSTAL SIZE
• KEEP THE SMALL WAX CRYSTALS IN SUSPENSION
• AVOIDS FORMATION OF THICK TANK-BOTTOM LAYER
• MAY BE AMINO-MODIFIED ACID AMIDES AND POLYMERS
  (INCLUDING MODIFIED EVA)

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DIESEL FUEL ADDITIVES

• TYPES OF FUEL HANDLING ADDITIVES
• CLOUD POINT DEPRESSANTS
• SIMPLEST CHOICE IS KEROSENE!
• BUT REFINERS PREFER CPDs TO MEET PIPELINE SPECS
• DESIGNED TO ENCAPSULATE LONG-CHAIN WAXES IN
  POLYMER SHEATH
• NOT VERY EFFECTIVE (SEE TABLE)
• MAY CONFLICT WITH FLOW IMPROVERS
• DE-ICING ADDITIVES
• WATER ALMOST ALWAYS PRESENT, MAY FORM ICE
• SOLUBILITY OF WATER IN DIESEL IS ABOUT 100 PPM
• CAN USE (A) SURFACTANTS OR (B) FP DEPRESSANTS
• (A) 10-50PPM AMINES (B) 0.02-2.0 ISOPROPANOL

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DIESEL FUEL ADDITIVES

• OTHER FUEL HANDLING ADDITIVES
• ANTIFOAM AGENTS
• DRAG REDUCING ADDITIVES (IMPROVE PIPELINE FLOW)
• ANTISTATIC ADDITIVES
• ANTIOXIDANTS
• STABILIZERS
• METAL DEACTIVATORS TYPICALLY Cu AND Fe
  CHELATORS
• DISPERSANTS
• BIOCIDES (WARNING MAY BE TOXIC!)
• DEMULSIFIERS
• CORROSION INHIBITORS
• ETC., ETC..
• SOME OR ALL MAY BE PRESENT

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DIESEL FUEL ADDITIVES

• WHAT CAN WE LEARN?
• TANK SOLID CORROSION PRODUCTS PROBABLY MOSTLY
  HYDRATED Fe3 OXIDES OR HYDROXIDES
• POSSIBILITY OF INJECTOR FOULING
• SLIGHT POSSIBILITY OF Fe ORGANOMETALLICS
  INCLUDING Fe FATTY ACID, OTHER COMPOUNDS
• THESE ARE KNOWN TO BE CATALYTICALLY ACTIVE,
  ESPECIALLY RE SMOKE FORMATION
• ADDITIONALLY, EXTRA CARE SHOULD BE TAKEN TO
  ENSURE THAT ONLY DESIRED ADDITIVES ARE PRESENT IN
  ALL RESEARCH FUELS.
• THEY CAN HAVE A MAJOR IMPACT ON RESULTS!