Slides 97-120

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

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

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

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


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)


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!


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


US 2008


• 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


• 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


• 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)


• 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


• 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


• 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.


• 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


• 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)


• 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


• 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


• 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!

Slides 97-120

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