Chang Am L&S Co. LTD., 1 환경친화적 윤활제의 개발 및 동향 Developments & Trends of Environmental Friendly Lubricants 조원오 *, 김영운 **, 정근우 ** * 장암엘에스㈜ 기술연구소 ** 한국화학연구원

Chang Am L&S Co. LTD., 2 Major Trends Environmental Equipment severity Quality

Chang Am L&S Co. LTD., 3 Environmental Trends Fundamental Motivations are: –Resource Conservation –Toxicological Consideration –Environmental Acceptability

Chang Am L&S Co. LTD., 4 “Environmental Friendly” Trends Lube Compatibility with Non-Lube Components –New Refrigeration Oils for CFC Replacement –Low Phosphorus Engine Oils –Alternate Fuels such as Methanol, LNG, etc New Product Opportunities –Biodegradable Hydraulic Oils, Grease, etc

Chang Am L&S Co. LTD., 5 Environmental Protection Trends Increasing Lube Component Restrictions –Pb, Hg, Cd, Cr 6+, Zn, Cl, P, NO2, others Increasing “Green” Performance –Longer Oil Drains, thereby Reducing Used Oil Volumes Used Oil Issue : Recycle or Disposal

Chang Am L&S Co. LTD., 6 Global Eco-Labelling 일본 Eco Mark 독일 Blue Angel 미국 Green Seal 한국

Chang Am L&S Co. LTD., 7 Biodegradable Lubricants

Chang Am L&S Co. LTD., 8 Degree of Biodegradation Functional Group –Ester Oils : –Hydrocarbon (HC) : –Branched HC : –PAG : –Phenyl Group : –Low Viscosity : –High Viscosity : Biodgradation High Low High Low High Low

Chang Am L&S Co. LTD., 9 Biodegradable? A chemical substance which can be broken down by the metabolic action of living organisms such as bacteria, fungi and yeasts Be different from the processes of physical or chemical degradation Take place at the same time as chemical or physical processes

Chang Am L&S Co. LTD., 10 Terminology Primary Biodegradation –The breakdown of the parent compound Ultimate Biodegradation –The conversion of materials to CO 2 and H 2 O Ready Biodegradation –The potential to degrade quickly in unadapted systems Inherent Biodegradation –The potential to degrade eventually if sufficient time is allowed

Chang Am L&S Co. LTD., 11 Biodegradation Test Methods OECD Series ISO 9439 ASTM D5864 CEC-L-33 Series Modified AFNOR ( Association Francasise de Normalization ) Modified MITI (Japanese Ministry of International Trade and Industry) Modified Sturm

Chang Am L&S Co. LTD., 12 Biodegradation Process Substance + O 2 Substance CO 2 + H 2 O + New Cell A B Primary Biodegradation Ultimate Biodegradation Inoculum Removal of Org. Comp. OECD 301A, 301E ISO 7827 CEC L-33-A-93 Determination of BOD & COD OECD 302C, 301D, 301F ISO 9408, Determination of CO 2 OECD 301B ISO 9439, ASTM D5864 Production of New Cell Nephelometer

Chang Am L&S Co. LTD., 13 CEC-L-33-A-93 TEST Comparing the primary biodegradability of lubricants in aerobic aquatic condition Using inoculum from a municipal sewage works with a bacteria level of at least 10 6 CFU/mL Test duration : 21 days at 25 o C Determining the reduction in oil content by Infrared absorption of the CH 3 - and CH 2 - bands at 2930cm -1

Chang Am L&S Co. LTD., 14 CEC-L-33-A-93 TEST Limitations –The biodegradability value only relates to soluble components –The test conditions do not relate to conditions generally experienced in the environment

Chang Am L&S Co. LTD., 15 Experimental Procedure 2 Neutral flasks 3 Test flasks 2 Poisoned flasks Extraction with solvent IR Analysis Shaking & Incubation o C) IR Analysis Extraction with solvent Inoculum & Mother solution Inoculum > 10 6 CFU/mL Sewage Solution Biodegradation % = (P-T/P) x 100 T=(T 21 -B / T 0 -B) x 100, T 21 : Tested Sample after 21 days P=(P 21 / T 0 -B) x 100, P 21 : Poisoned Sample after 21 days

Chang Am L&S Co. LTD., 16 Incubator for CEC-L-33-A-93 Reactor Mixing and Temperature Controller Shaking incubator For CEC-L-33-A-93 test Shaking incubator For CEC-L-33-A-93 test

Chang Am L&S Co. LTD., 17 Result of CEC-L-33-A-93 * Biodegradation [%] = (P-T)/P ×100 Day s Sampl e White Mineral OilSunflower Oil Residual oil Content Biodegra Residual oil Content Biodegra [%] TestPoisoned dation [%] TestPoisoned dation [%] Flask (T)Flask (P)Flask (T)Flask (P) mean mean

Chang Am L&S Co. LTD., 18 FT-IR Spectrophotogra c a Wavenumber (cm -1 ) Absorbance off White mineral oil % off Sunflower oil Wavenumber (cm -1 ) Absorbance b d

Chang Am L&S Co. LTD., 19 Biodegradability of Greases by CEC-L-33-A-93 Base Oil 생분해도 (%) 윤활기유 베이스 그리스 EP 그리스 Vegeoil-A Synthetic Ester Mineral BO 53.8 % 88.1 % 81.0 % 85.1 % 87.8 % Vegeoil-B Vegeoil-C

Chang Am L&S Co. LTD., 20 OECD 302C TEST Comparing the primary biodegradability of lubricants in aerobic aquatic condition Using inoculum from a municipal sewage works with a bacteria level of at least 10 6 CFU/mL Test duration : 28 days at 25 o C A percentage of measuring the O 2 consumption

Chang Am L&S Co. LTD., 21 OECD 302C TEST Limitations –Not suitable for insolube and volatile substances

Chang Am L&S Co. LTD., 22 Experimental Procedure 6 bottles Bottle 1 : test substance in water Bottle 2, 3, & 4 : test substance in mineral Bottle 5 : reference compound in mineral Bottle 6 : mineral medium only Shaking & Incubation (28days, 25 o C) O 2 uptake Inoculum & Stock solution Sewage Solution BOD Curve BOD = mg O 2 * /mg test substance * mg O 2 = mg O 2 uptake by test substance – mg O 2 uptake by blank Biodegradation [%] = BOD/ThOD x O 2 uptake by blank : mg O 2 /L - biodegradation of aniline [%] > 40% after 7days > 65% after 14 days

Chang Am L&S Co. LTD., 23 Respirometer for OECD 302C Oxygen Supplyer Mixing Controller Automatic Temperature Controller Software Window Oxygen Cylinder Respirometer For OECD 302C test Respirometer For OECD 302C test

Chang Am L&S Co. LTD., 24 Biodegradability of Greases by OECD 302C 기유 종류 생분해도 (%) 65.8 % 48.9 % 41.7 % 45.5 % 62.8 % 70.1 % 88.9 % 91.5 % Vegeoil-A Synthetic Ester Vegeoil-B Vegeoil-C

Chang Am L&S Co. LTD., 25 Environmental Friendly Additives - Concept of Molecular Design - Metal-free & Ashless type Organic Sulfur System 중금속 (Pb, Zn, Sb), 유해원소 유해원소 (Cl, P etc) Corrosion inhibition Multi-functionality + Anti-oxidation AW/EP Properties Corrosion inhibition Biodegradability

Chang Am L&S Co. LTD., 26 New Anti-wear Additives I 식물유 식물유 변성 마찰저감소재

Chang Am L&S Co. LTD., 27 New Anti-wear Additives I Sample[Mo] 4-Ball WSD, mm SRV 1, N COF 2 생분해도 3 % in grease in oil 1% 100% % Soybean-Mo > Rapeseed-Mo > Castor-Mo 불용 500 > Commercial 불용 400 > Li-type Grease 2.Pendulum Coefficient of Friction, 1wt% in AP2M Solvent (COF=0.384) 3.by CEC L-33-A-93 4.Commercial Additive of R. T. Vanderbilt

Chang Am L&S Co. LTD., 28 New Anti-wear Additives II C 4 -DTC-Tz : R=C 4 H 9 C 6 -DTC-Tz : R=C 6 H 13 C 8 -DTC-Tz : R=C 8 H 17 Bz-thia-Tz Pyrro-DTC-Tz Aliphatic alkyl- Cyclic alkyl- Aromatic-

Chang Am L&S Co. LTD., 29 SRV EP test Four-Ball Wear test EP (N) ,000 1,200 C 4 -DTC- Tz C 6 -DTC- Tz C 8 -DTC Tz- Pyrro- DTC-Tz Bz-thia- Tz Mo-DTC Four-Ball WSD, mm C 4 -DTC- Tz C 6 -DTC- Tz C 8 -DTC Tz- Pyrro- DTC-Tz Bz-thia- Tz Mo-DTC Li-soap type grease 에 1wt% 첨가 New Anti-wear Additives II

Chang Am L&S Co. LTD., 30 Thank You ! Chang Am LS Co., Ltd. TEL : FAX :