BIODIESEL NOTES (7)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
ALTERNATIVE ENERGIESALTERNATIVE ENERGIESDIESEL FUELSDIESEL 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
ALTERNATIVE ENERGIESALTERNATIVE ENERGIESDIESEL FUELSDIESEL 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)
DIESEL ENGINE DIESEL ENGINE DEVELOPMENTSDEVELOPMENTS
• 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
AL+MG VARIABLE CAM TIMING COMING – SLOWLY! HYDROGEN INJECTION IN INTAKE AIR (FOR
DPs) HYDROGEN INJECTION IN EXHAUST (FOR NOX
SCRs)
ALTERNATIVE ENERGIESALTERNATIVE ENERGIESDIESEL FUELSDIESEL 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!
ALTERNATIVE ENERGIESALTERNATIVE ENERGIESDIESEL FUELSDIESEL 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
ALTERNATIVE DIESEL FUELSALTERNATIVE DIESEL FUELSTHE EMISSIONS CHALLENGETHE EMISSIONS CHALLENGE
US 2008
ALTERNATIVE DIESEL FUELSALTERNATIVE DIESEL FUELSTHE EMISSIONS CHALLENGETHE EMISSIONS CHALLENGE
US 2008
ALTERNATIVE DIESEL FUELSALTERNATIVE DIESEL FUELSTHE EMISSIONS CHALLENGETHE 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.
DIESEL EXHAUST SYSTEM DIESEL EXHAUST SYSTEM DEVELOPMENTSDEVELOPMENTS
• 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….
DIESEL FUEL ADDITIVESDIESEL FUEL ADDITIVES• THE ISSUE:
CAN WE LEARN ANYTHING ABOUT THE EFFECT OF IMPURITIES FROM THE BEHAVIOR OF INTENTIONAL ADDITIVES?
• FOUR MAIN CATEGORIES:ENGINE PERFORMANCEFUEL HANDLINGFUEL STABILITYCONTAMINANT CONTROL
• AND A FEW “SPECIALS” – MOSTLY AFTERMARKET!
DIESEL FUEL ADDITIVESDIESEL FUEL ADDITIVES
• THREE ADDITION LOCATIONS:REFINERYDISTRIBUTION SYSTEM (E.G., PIPELINE)AFTERMARKET (BUYER BEWARE!!)
• ENGINE PERFORMANCE ADDITIVES:CETANE (IGNITION DELAY) IMPROVERSDETERGENTS (INJECTOR CLEANLINESS)LUBRICITY IMPROVERSSMOKE SUPPRESSANTSCOMBUSTION CATALYSTS
DIESEL FUEL ADDITIVESDIESEL 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
DIESEL FUEL ADDITIVESDIESEL 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)
DIESEL FUEL ADDITIVESDIESEL 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
DIESEL FUEL ADDITIVESDIESEL 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
DIESEL FUEL ADDITIVESDIESEL 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.
DIESEL FUEL ADDITIVESDIESEL 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.
50-7030-40100-3000
PP
25-3515-20100-2000
CFPP
15-258-1250-2000
LTFT
(filterability
Test)
5-73-4200-2000
CLOUD POINT
RESULT
OF
TYPICAL
OC
TYPICAL
TREAT RATE
PPM
ADDITIVE TYPE
DIESEL FUEL ADDITIVESDIESEL FUEL ADDITIVES
• TYPES OF FUEL HANDLING ADDITIVESFLOW IMPROVERS
AIM TO KEEP WAX CRYSTALS SMALL TYPICALLY ARE POLYMERS SUCH AS POLY(ETHYLENE-
CO-VINYL) 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)
DIESEL FUEL ADDITIVESDIESEL 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
DIESEL FUEL ADDITIVESDIESEL 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
DIESEL FUEL ADDITIVESDIESEL 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!