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GREEN LUBRICANTS CURRENT TRENDS. INDIAN SCHOOL OF PETROLEUM SEMINAR. DR A.K.BHATNAGAR PETROTECH CHAIR PROFESSOR INDIAN INSTITUTE OF TECHNOLOGY NEW DELHI 23 RD AUGUST 2003. TOPICS COVERED. BACKGROUND GREEN LUBRICANTS DEFINED TEST METHODS TRENDS- BASE STOCKS, ADDITIVES
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GREEN LUBRICANTSCURRENT TRENDS INDIAN SCHOOL OF PETROLEUM SEMINAR DR A.K.BHATNAGAR PETROTECH CHAIR PROFESSOR INDIAN INSTITUTE OF TECHNOLOGY NEW DELHI 23RD AUGUST 2003
TOPICS COVERED • BACKGROUND • GREEN LUBRICANTS DEFINED • TEST METHODS • TRENDS- BASE STOCKS, ADDITIVES • MOTIVATIONAL EFFORTS • BIOBASED LUBRICANTS • CONCLUSIONS
iitd CLEAN ENVIRONMENT MOVEMENT • BEGAN WITH “ SILENT SPRING” NOVEL BY • RAQUEL CARSON -A HALF FICTION & HALF TRUTH • DOCUMENTARY. • CHLORINATED HYDROCARBONS,PARTICULARLY • DDT & RELATED PESTICIDES WITHDRAWN. • CHLORINATED SOLVENTS AND MANY POSSIBLE • TOXIC COMPONENTS OF HYDROCARBONS CAME • UNDER ATTACK • RIO AND KYOTO CONFERENCES AND EMERGENCE • OF SEVERAL NATIONAL ANF INTERNATIONAL NGOs • ADDED FURTHER IMPETUS • TODAY HYDROCARBON INDUSTRY IS THE • TARGET OF ATTACK BY ENVIRONMENTALISTS.
CLEAN ENVIRONMENT MOVEMENT (CONTD) • RESULT • CLEANING OPERATION AT HEAVY COST STARTED. LUBRICANT • INDUSTRY WAS ALSO NO EXCEPTION. • NEW STANDARDS,NEW REQUIREMENTS AND THEREFORE NEW • PROCESSES, NEW FEED STOCKS EMERGED FOR BASE OILS / • ADDITIVES • TOXIC COMPONENTS SUCH AS CHLORINATED PARAFFINS, • HEAVY METALS, AROMATICS,NITRITES ETC REMOVED • FROM FINISHED LUBRICANTS. • DAYS FOR ECO-FRIENDLY FUELS eg. LPG. CNG, ETHANOL, • BIODIESEL ETC HAVE ALREADY COME. • DAYS FOR ECOFRIENDLY LUBES • DONOT APPEAR FAR
LUBE OIL & POLLUTION • WORLD LUBE OIL CONSUMPTION (1995) 40.0 MMT • LUBES FOR TOTAL LOST SYSTEM @ 10% 04.0 MMT • 2 stroke oil • mould release • metal working • greases • chain lubricant • miscellaneous • USED OIL ( NONRECYCLED) 30% 12 MMT • TOTAL POLLUTING OIL 16 MMT LUBE OILS ARE OMNIPRESENT UNCONTROLLED RELEASE IN USA ALONE - 4.7 MMT Ref : S.Mohanti, envirotech India
LUBRICATING OILS: OVERVIEW • Finished lubricants account for about 1% of total crude oil consumption* Lubricating Oil Base oil(80-95%)+Additive Package(05-20%) *Source : Concawe Report No. 5/96 (Europe)
USED LUBE DISCHARGE TO ATMOSPHERE IN EUROPE FRESH OIL 5.3 MMT PROCESS OIL O.6 MMT AUTO LUBE 2.5 MMT IND. LUBE 1.7 MMT MARINE OIL 0.5 MMT TOTAL LOSS COLLECTABLE USED OIL 2.6 MMT (55%) AUTO LUBE 1.6 MMT IND.LUBE 1.O MMT MARINE OIL 1.O MMT COLLECTABLE USED OIL 1.5 MMT (32%) NOT RECORDED 1.1 MMT (23%)
RE-REFINING OF USED OILS • FIRST INTRODUCED IN 1930’S AND INCREASED • SIGNIFICANTLY DURING WORLD WAR II • IN 1980’S MANY ACID/CLAY RE-REFINING PLANTS IN US • WERE SHUT DOWN DUE TO INCREASED ENVIRONMENTAL • CONSCIOUSNESS AND ECONOMIC REASONS • WORLDWIDE AROUND 400 RE-REFINING PLANTS • TOTAL CAPACITY ~1800 KT/YEAR • MOST OF THE PLANTS LOCATED IN EAST ASIA,INDIA,CHINA • & PAKISTAN • INDIVIDUAL CAPACITY ON AN AVERAGE - 2 KT/YEAR • MOST OF THE PLANTS BASED ON ACID CLAY PR. Source : Concawe Report No. 5/96
RE-REFINING : INDIAN SCENARIO • RE-REFINING UNITS REGISTERED WITH MOPNG: 69* • NO ORGANIZED USED OIL COLLECTION SYSTEM • RE-REFINING PROCESSES • SIMPLE RECLAMATION, • ACID/CLAY PROCESS • QUESTIONABLE ENVIRONMENTALLY • QUESTIONABLE PRODUCT QUALITY • ‘IMPORT’ OF USED OIL BY INDIAN RE-REFINING INDUSTRY RAMPANT FROM COUNTRIES WHERE DUE TO STRINGENT ENVIRONMENTAL REGULATIONS WHICH –MAKE LOCAL DISPOSAL OF HAZARDOUS WASTE IN ACCEPTABLE MANNER COMMERCIALLY UNVIABLE *Source : Indian Express,October 27, 1995, NewDelhi
DRIVERS FOR SHIFTS IN LUBE OIL QUALITY • REGULATORY PUSH • CLEAN AIR ACT • CAFE • BASE OIL • LOWER • VISCOSITY • HIGHER VI • LOW PP • LOW • VOLATILITY • ECOFRIEDLY • CONSUMER DEMAND • PULL • WARRANTIES • EXTENDED DRAIN • ECOFRIENDLY • LUBRICANT DESIGN • FLUIDITY • OIL CONSUMPTION • FUEL ECONOMY • EXTENDED INTERVAL • ENGINE DESIGN • CAT CONVERTOR • LOW FRICTION ENGINE • AERODYNAMICS
ECO-FRIENDLY LUBRICANT • DESCRIBED IN MANY WAYS • - GREEN.BIODEGRADABLE,RECYCLABLE, • NONTOXIC,REUSABLE ETC • BIODERADABLE PRODUCT WITH LOW OR NO • TOXICITY HAVING MINIMUM IMPACT ON • ENVIRONMENT • THE MAIN DRIVING FORCE IN LAST DECADE, • MAXIMISING BIODEGRADABILITY AND • MINIMISING ECOTOXICITY TO REDUCE • ENVIRONMENTAL IMPACT
FULL LIFE CYCLE ANALYSIS-A MUST • BIODEGRADABILITY IS DEFINED • “AS SUSCEPTIBILITY OF A SUBSTANCE TO UNDERGO DEGRADATION • UNDER THE INFLUENCE OF BIOLOGICAL AGENTS SUCH AS BACTERIA, • FUNGI, YEAST ETC” • OTHER IMPORTANT CRITERIA ARE • ECO TOXICITY INCLUDING EFFECTS OF LUBRICANT AND • ITS PHOTO AND BIODEGRADED PRODUCTS ON LIVING • ORGANISM • BIOACCUMULATION POTENTIALS, • EFFECTS ON EMISSION QUALITY, • USE OF RENEWABLE RAW MATERIALS • A FULL LIFE CYCLE ANALYSIS – A PRACTICE TODAY
FULL LIFE CYCLE ANALYSIS IS NECESSARY TODAY • ECO TOXICITY INCLUDES EFFECTS OF LUBRICANTS • AND ITS DEGRADED PRODUCTS ON LIVING ORGANISMS • A FULL LIFE CYCLE ANALYSIS - A PRACTICE TODAY • RESEARCH&DEVELOPMENT • MANUFACTURING • BLENDING, STORAGE,DISTRIBUTION • PACKAGING • MSDS • IMPACTS DURING USE • COLLECTION OF USED OILAND PACKAGING • RECYCLING OR DISPOSAL
MOTIVATIONAL EFFORTS • MASS AWARENESS • CHANGING PERCEPTIONS • POLITICAL COMPULSIONS • IMPROVED LIVING STANDARDS • PACKAGES OF • INCENTIVES AND DISINCENTIVES
GOVERNMENT INITIATIVES • IN GERMANY ANY MATERIAL CAPABLE OF SEEPING AWAY • IS CONSIDERED UNFRIENDLY TO ENVIRONMENT • MEASURES UNDERTAKEN IN DEVELOPED NATIONS TO • PROMOTE ECOFRIENDLY PRODUCTS • LEGAL PROHIBITIONS • QUASI LEGAL ORDERS • HUGE SUBSIDIES • PRESSURE GROUPS • MANUFACTURER’S OWN INITIATIVES
GERMAN ENVIRONMENTAL REGULATIONS • THE GERMAN WATER LAW • THE DRINKING WATER DIRECTIVE • THE GERMAN GROUND LAW( IN DRAFT) • THE FEDERAL EMISSION LAW • THE RECYCLING AND WASTE LAW • THE CHEMICAL LAW • THE ENVIRONMENTAL LIABILITY LAW • GERMAN PARLIA,EMT INITIATIVES • THE “BLUE ANGEL” ECOSEAL
ENVIRONMENTAL SEAL • GLOBAL ECO NETWORK “GEN” • EUROPEAN “ECO-LABELS” • GERMAN “BLUE ANGEL” • NORDIC COUNTRIES “WHITE SWAN” • CANADIAN “MAPLE LEAF” • FRANCE “NF ECOMARK” • JAPAN “FRIENDLY TO EARTH” • USA “GREEN SEAL” • INDIA “EARTHEN PITCHER”
DETERMINATION OF WATER HAZARD WEN IS AN AVERAGE VALUE OF ACUTE ORAL MAMMALIAN, FISH AND BACTERIAL TOXICITY VALUES
EU’s LABELLING CRITERIA R511 R50- VERY TOXIC R51- TOXIC R52- HARMFUL R53- LONG TERM EFFECT
RELATIVE BIODEGRADABILITY OF BASE FLUIDS REF- MOHANTI S, ENVIROTCH 2001
VIRGIN BASE OILS (0-100%) PETROLEUM BASED SYNTHETICS SEMISYNTHETICS WATER BASED MIXED BASE OILS RECYCLED ADDITIVES (0=20%) NATURE DERIVED CHEMICALY MODIFIED SYNTHETIC SOLVENTS CHORINATED NON- CHLORINATED FINISHED LUBRICANTS
EFFECT OF CATALYTIC HYDROPROCESSING ON VI • CHEMICAL REACTION • POLYAROMATICS (VI –60 ) TO POLYNAPHTHENE (VI 20 ) • POLYNAPHTHENES (VI 20) • POLYALKYLMONOCYCLICS (VI 110) • PARAFFINS WAXES (VI 150 ) TO ISOPARAFFINS (VI 140 )
PROCESSES FOR BASE STOCK – CURRENT TRENDS • IMPROVED SOLVENT REFINING • HYDROPROCESSING/HYDROCRACKING • MAX DEWAX • SELECTIVE CATALYTIC DEWAXING • WAX HYDROISOMERISATION • LOW PRESSURE HYDROFINISHING • GTL TO BASE OIL (GROUP III)
SOME SPECIAL PROPERTIES OF GR. III BASE OILS PAO AND GR III ARE COMING CLOSE
TRENDS IN BASE OIL USE • LIGHT VISCOSITY - EASY START,FUEL EFFICIENCY • LOW VOLATILITY – OIL CONSERVATION • & REDUCED EMISSIONS • HIGH VISCOSITY INDEX –BETTER TEMP-VISCOSITY • RELATIONSHIP • IMPROVED STABILITY – LONG DRAIN INTERVAL • REDUCED POUR POINT – LOW TEMP FLUIDITY • BETTER LUBRICITY – FUEL ECONOMY • ECOFRIENDLY - SAFE MEETING REGULATIONS
VIRGIN BASE OILS (0-100%) PETROLEUM BASED SYNTHETICS SEMISYNTHETICS WATER BASED MIXED BASE OILS RECYCLED/USED OIL ADDITIVES (0=20%) NATURE DERIVED CHEMICALY MODIFIED SYNTHETIC SOLVENTS CHORINATED NON= CHLORINATED FINISHED LUBRICANTS
USED OIL RE-REFINING IN INDIA: ISSUES • Infrastructure for Environment Friendly re-refining technology • Import of waste oil – dumping ground • Base oil quality • Record of recognized producers and users of re-refined oils in the country and curb on malpractices
USED OILS: CHARACTERISTICS USED OILS PRESENT A VARIED AND POORLY DEFINED COCKTAIL OF COMPOUNDS • IN USE, A LUBRICANT MAY BECOME CONTAMINATED, OR MAY UNDERGO DEGRADATION SO THAT ITS HAZARD TO HEALTH IS INCREASED OR NEW ONES INTRODUCED. TYPICAL PROBLEMS ARE: • CONTAMINATION WITH ENGINE COMBUSTION PRODUCTS, PARTICULARLY PCAS • CONTAMINATION WITH BACTERIA AND DECOMPOSING DEAD BACTERIA Source : Concawe Report No. 5/87
USED OILS: CHARACTERISTICS TYPICAL CONTAMINANTS AND SOURCES • PCA/PAHS OF MINERAL BASE LUBES MAY INCREASE DURING USE • UPTO TEN- FOLD INCREASE FOR CUTTING OILS AND DIESEL ENGINE OILS • HUNDRED- FOLD OR MORE FOR GASOLINE ENGINE OILS AND QUENCHING OILS Source : Concawe Report No. 5/87
OILY SLUDGE/WASTE DISPOSAL Oily sludge • Classified as hazardous waste (cat. 10 & 12 of IHWR 1989) • Significant environment risk • Contamination of ground water through leaching • Release of VOCs, odour • Health hazard due to direct/indirect exposure. • Pollutants include phenols, HCs, heavy metals like chromium, nickel, cadmium, lead, manganese, zinc, copper etc Source : Bhattacharya, NEERI, Petrotech-2001
IMPORT OF USED OIL IN INDIA : REGULATORY SCENARIO • WASTE OIL CLASSIFIED AS HAZARDOUS WASTE AS PER HW RULES 1989/2000 • ‘BASEL CONVENTION’ 1992 • ON CONTROL OF TRANSBOUNDARY MOVEMENT OF HW,PROHIBITS IMPORT OF WASTE OIL (LISTED IN ‘LIST A’, ANNEX VIII) • INDIA IS SIGNATORY TO THIS CONVENTION • HW RULES 1989/2000:PERMISSION TO IMPORT GRANTED BY MOEF UNDER RULES 13(3) AND 14 (3) RULE 13(3):MOEF MUST SATISFY ITSELF THAT IMPORTER HAS ENVIRONMENT FRIENDLY/APPROPRIATE TECHNOLOGY FOR REPROCESSING...
OILY SLUDGE/WASTE DISPOSAL SLUDGE MANAGEMENT • STRINGENT REGULATORY MEASURES FOR: • ZERO HAZARDOUS WASTE REFINERY OPERATIONS • RECYCLING – THROUGH RE-USE AND/OR AS RAW MATERIALS FOR NEW VALUE ADDED PRODUCTS USING ENVIRONMENTALLY BENIGN PROCESSES • BIO-REMEDIATION ETC • BIO-REMEDIATION TECHNOLOGY IMPLEMENTATION INITIATIVES • TERI – DBT OILZAPPER TECHNOLOGY – LICENSED TO BPCL AND SHRI RAM BIOTECH • TERI – IOC (R&D) JOINT TECHNOLOGY CALLED OILI VOROUS – S – TRIAL RUNS ORGANIZED IN MATHURA AND BARAUNI REFINERY
BIOBASED LUBRICANTS • PETROCROPS AS A SOURCE OF FUEL • -A WELL STUDIED SUBJECT • BIOBASED PRODUCTS COMMON IN GREASE • BIOBASED LUBRICANTS • - A RECENT PHENEMENON • BEGINNING WITH JOJOBA, A SERIES OF • VEGETABLE OILS AS POTENTIAL LUBRICANTS • OR ADDITIVES UNDER STUDY TODAY • EG. SOYBEAN, PALM. • COCONUT, SUN FLOWER ETC
MOTIVATIONAL EFFORTS (CONTD) • GOVERNMENT INITIATIVES – • COUNTRY SPECIFIC • USA- SOY OIL • EUROPE- RAPE SEED OIL • MALAYASIA - PALM • INDIA JATROPA CURCUS ?? • SOY BEAN PRODUCTIN IN USA 2.7 BILLION BUSHELS • -HALF OF WORLDS TOTAL PRODUCTION • SOYOIL POTENTIALS - 3.6 BILLION GALLONS /YEAR • AVAILABLE AT COMPETETIVE COST 0.15 / LBS • GMO TECHNOLOGY IS FURTHER ENCOURAGING • ITS USE AS INDUSTRIAL LUBRICANT
MOTIVATIONAL EFFORTS (CONTD) • MANDATES • FEDERAL EXECUTIVE ORDER13134 ,1999 • “DEVELOPING & PROMOTING BIOBASED • PRODUCTS & BIOENERGY” TO • TRIPLE THE USE BY 2010 • IOWA STATE SENATE FILE 2185 GIVING • PURCHASE PREFERENCE TO ALL • BIOBASED LUBES & GREASE • “LEAD BY EXAMPLE”
GERMAN GOVERNMENT INITIATIVES • RESOLUTION (JUNE 16, 19940 • PROMOTE USE OF BIOLUBRICANTS AND • HYDTAULIC FLUID • RESOLUTION (28TH NOV.1995 • REVISED 1999) • REPORT ON USE OF RAPIDLY • BIODEGRADABLE LUBES • REGULATION(JUNE 2000) • PROGRAMME TO SUPPORT SUBSTITUTION • OF MINERAL OIL WITH BIOBASED OILS
MOTIVATIONAL EFFORTS(CONTD) • DUE TO PUBLIC CRAZE FOR GREEN • PRODUCTS, MANY COMPANIES NOW OFFER • BIOBASED LUBES • SOLD AS THE TOP OF SHELF, PRESTIGE • PRODUCTS FOR A NISCHE BUT GROWING • MARKET • USE ECOSEALS FOR PRODUCT • DIFFERENTIATION
SOME BIOBASED COMMERCIAL PRODUCTS REF BHATIA VK IIP(D) JUNE 2000
COMPOSITION OF COMMON VEGETABLE OILS SOURCE :SAE 941758
OXIDATIVE STABILITY V/S PERCENT OLEIC IN VEGETABLE OILS SOURCE : EUROGREASE, P 21, JULY 2000
CHANGES IN VEGETABLE OIL VISCOSITIES IN ASTM D-2271 (1000HRS @1000 PSI @78OC
CHANGES IN VISCOSITIES AS PER ASTM D-2271 OF FORMULATED FLUIDS (1000HRS @1000 PSI @78OC) * Measured @ 40oC
BIOBASED LUBRICANTS • POSITIVE SIDE • BETTER VISCOSITY-TEMP RELATIONSHIP • BETTER LUBRICITY • ECO FRIENDLY • BETTER VOLATILITY CHARACTERSTICS • SURPLUS AVAILABILITY IN SOME COUNTRIES • NEGATIVE SIDE • OXIATION,HYDROLYTIC AND THERMAL • STABILITY • HIGH PERFORMANCE ADDITIVES GMO MAY PROVIDE THE ANSWER
VIRGIN BASE OILS (0-100%) PETROLEUM BASED SYNTHETICS SEMISYNTHETICS WATER BASED MIXED BASE OILS RECYCLED ADDITIVES (0=20%) NATURE DERIVED CHEMICALY MODIFIED SYNTHETIC SOLVENTS CHORINATED NON-CHLORINATED FINISHED LUBRICANTS