chang am l&s co. ltd., 1 환경친화적 윤활제의 개발 및 동향 developments &...

Chang Am L&S Co. LTD., http://www.changam.co.kr

1

환경친화적 윤활제의 개발 및 동향

Developments & Trends of Environmental Friendly Lubricants

조원오 *, 김영운 **, 정근우 *** 장암엘에스㈜ 기술연구소

** 한국화학연구원


2

Major Trends

• Environmental

• Equipment severity

• Quality


3

Environmental Trends

• Fundamental Motivations are:

– Resource Conservation– Toxicological Consideration– Environmental Acceptability


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


5

Environmental Protection Trends

• Increasing Lube Component Restrictions– Pb, Hg, Cd, Cr6+, Zn, Cl, P, NO2, others

• Increasing “Green” Performance– Longer Oil Drains, thereby Reducing Used Oi

l Volumes

• Used Oil Issue : Recycle or Disposal


6

Global Eco-Labelling

일본Eco Mark

독일Blue Angel

미국Green Seal

한국


7

Biodegradable Lubricants

0

10

20

30

40

50

60

No

. of P

aper

s


8

Degree of Biodegradation

• Functional Group– Ester Oils :

– Hydrocarbon (HC) :– Branched HC :– PAG :– Phenyl Group :– Low Viscosity :– High Viscosity :

• BiodgradationHigh

Low

Low

High

Low

High

Low


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


10

Terminology

• Primary Biodegradation– The breakdown of the parent compound

• Ultimate Biodegradation– The conversion of materials to CO2 and H2O

• Ready Biodegradation– The potential to degrade quickly in unadapted syste

ms

• Inherent Biodegradation– The potential to degrade eventually if sufficient time

is allowed


11

Biodegradation Test Methods

• OECD Series• ISO 9439• ASTM D5864• CEC-L-33 Series• Modified AFNOR (Association Francasise de Norma

lization)• Modified MITI (Japanese Ministry of International Tra

de and Industry)

• Modified Sturm


12

Biodegradation Process

Substance + O2 Substance CO2 + H2O + New Cell A B

PrimaryBiodegradation

UltimateBiodegradation

Inoculum Inoculum

Removalof Org. Comp.

OECD 301A, 301EISO 7827

CEC L-33-A-93

Determinationof BOD & COD

OECD 302C,301D, 301F

ISO 9408, 10708

Determinationof CO2

OECD 301BISO 9439, 14593

ASTM D5864

Productionof New Cell

Nephelometer


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 106 CFU/mL

• Test duration : 21 days at 25 oC

• Determining the reduction in oil content by Infrared absorption of the CH3- and CH2- bands at

2930cm-1


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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


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Experimental Procedure

2 Neutral flasks3 Test flasks2 Poisoned flasks

Extraction with solvent IR Analysis

Shaking & Incubation

(21days, @25oC)IR AnalysisExtraction

with solvent

Inoculum &Mother solution

Inoculum > 106CFU/mL

Sewage Solution

Biodegradation % = (P-T/P) x 100

T=(T21-B / T0-B) x 100, T21: Tested Sample after 21 days

P=(P21 / T0-B) x 100, P21: Poisoned Sample after 21 days


16

Incubator for CEC-L-33-A-93Reactor Mixing and Temperature Controller

Shaking incubatorFor CEC-L-33-A-93 test

Shaking incubatorFor CEC-L-33-A-93 test


17

Result of CEC-L-33-A-93

* Biodegradation [%] = (P-T)/P ×100

Days

Sample

White Mineral Oil Sunflower Oil

Residual oil Content

Biodegra

Residual oil Content

Biodegra [%] [%]

Test Poisoned dation [%]

Test Poisoned dation [%]

Flask (T) Flask (P) Flask (T) Flask (P)

0 1 101.23 　　 101.23 　　　 2 98.71 　　 98.71 　　　 3 100.05 　　 100.05 　　　 mean 100 　　 100 　　21 1 58.81 97.23 39.13 8.47 101.05 91.67

　 2 59.22 96.01 38.71 11.02 104.54 85.17

　 3 59.46 - 38.46 6.41 - 93.70

　 mean 59.16 96.62 38.76 8.63 101.71 91.52


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FT-IR Spectrophotogra

c

a

Wavenumber (cm-1)

2900 2950 3000

Ab

sorb

ance

0.0

0.2

0.4

0.6

0.8

1.0

38.8 off

White mineral oil

3200

2900 2950 3000

0.0

0.2

0.4

0.6

0.8

91.5% off

Sunflower oil

Wavenumber (cm -1)

Ab

sorb

ance

b

d


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Biodegradability of Greases by CEC-L-33-A-93

Base Oil

생분

해도

(%

)

0

20

40

60

80

100

120 윤활기유베이스 그리스EP 그리스

Vegeoil-ASynthetic

Ester

MineralBO

53.8 %

88.1 %81.0 %

85.1 %87.8 %

Vegeoil-BVegeoil-C


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OECD 302C TEST

• Comparing the primary biodegradability of lubr

icants in aerobic aquatic condition

• Using inoculum from a municipal sewage works with a bacteria level of at least 106 CFU/mL

• Test duration : 28 days at 25 oC

• A percentage of measuring the O2 consumptio

n


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OECD 302C TEST

• Limitations

– Not suitable for insolube and volatile substa

nces


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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, 25oC)O2 uptake

Inoculum &Stock solution

Sewage Solution

BOD CurveBOD = mg O2

*/mg test substance * mg O2 = mg O2 uptake by test substance – mg O2 uptake by blank

Biodegradation [%] = BOD/ThOD x 100- O2 uptake by blank : 20-30 mg O2/L- biodegradation of aniline [%] > 40% after 7days

> 65% after 14 days


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Respirometer for OECD 302COxygen Supplyer

Mixing Controller

Automatic Temperature Controller

Software Window

Oxygen Cylinder

Respirometer For OECD 302C test

Respirometer For OECD 302C test


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Biodegradability of Greases by OECD 302C

0

20

40

60

80

100

120

윤활기유베이스 그리스EP 그리스

기유 종류

생분

해도

(%

)

65.8 %

48.9 %41.7 %

45.5 %

62.8 %70.1 %

88.9 % 91.5 %

Vegeoil-ASynthetic

EsterVegeoil-B

Vegeoil-C


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Environmental Friendly Additives- Concept of Molecular Design -

Metal-free & Ashless type Organic Sulfur SystemOrganic Sulfur System

중금속중금속

(Pb, Zn, Sb),

유해원소유해원소

(Cl, P etc)

Corrosioninhibition

Multi-functionality

+

Anti-oxidationAW/EP Properties

CorrosioninhibitionSS LinkerC

S

N C

S

N

Biodegradability


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CH2

CH

CH2

O

O

O

C

C

C

R

R

O

O

O

R

2HN(CH2CH2OH)2

R C

O

O CH2 CH OH

CH2 OH

R C

O

NCH2

CH2

CH2

CH2

OH

OH

R C

O

NCH2

CH2

CH2

CH2

O

OMo

O

O

R C

O

O CH2 CH O

CH2 OMo

O

O

+1st Step

¡â [125-150¡É]

[Mo]coordination

2nd Step ¡â [125-150¡É]

- H2O

&

New Anti-wear Additives I

식물유

식물유 변성 마찰저감소재


27

New Anti-wear Additives I

Sample [Mo] 4-Ball WSD, mm SRV1, N COF2 생분해도 3

% in grease in oil 1% 100% %

Soybean-Mo 2.5 0.63 0.45 200 >2000 0.122 97

Rapeseed-Mo 2.5 0.92 0.47 300 >2000 0.122 98

Castor-Mo 7.0 1.02 불용 500 >2000 - 99

Commercial4 7.6 0.90 불용 400 >2000 - 86

1. Li-type Grease2. Pendulum Coefficient of Friction, 1wt% in AP2M Solvent (COF=0.384)3. by CEC L-33-A-934. Commercial Additive of R. T. Vanderbilt


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New Anti-wear Additives II

CC44-DTC-Tz : R=C-DTC-Tz : R=C44HH99



Bz-thia-TzBz-thia-Tz

Pyrro-DTC-TzPyrro-DTC-Tz

Aliphatic alkyl-

Cyclic alkyl-

Aromatic-

NN

NN

CH2

C O

O

SSN

S S

N

NN

NN

CH2

C O

O

SS N

S

N

S

R

R

R

R

NN

NN

CH2

C O

O

SS N

S

N

S


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SRV EP testFour-Ball Wear test EP (N)

0

200

400

600

800

1,000

1,200

C4-DTC- Tz

C6-DTC-Tz

C8-DTCTz-

Pyrro-DTC-Tz

Bz-thia- Tz

Mo-DTC

Fou

r-B

all W

SD

, mm

0.3

0.4

0.5

0.6

0.65

C4-DTC- Tz

C6-DTC-Tz

C8-DTCTz-

Pyrro-DTC-Tz

Bz-thia- Tz

Mo-DTC

0.55

0.50

0.47

0.59 0.58

0.54

1000 1000

600

400

900

300

Li-soap type grease 에 1wt%

첨가

New Anti-wear Additives II


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Thank You !Thank You !Chang Am LS Co., Ltd.Chang Am LS Co., Ltd.

TEL : +82-2-2632-9441FAX : +82-2-2632-6151

http://www.changam.co.kr

chang am l&s co. ltd., 1 환경친화적 윤활제의 개발 및 동향 developments &...

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