Chang Am L&S Co. LTD., 1 환경친화적 윤활제의 개발 및 동향 Developments & Trends of...
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Transcript of Chang Am L&S Co. LTD., 1 환경친화적 윤활제의 개발 및 동향 Developments & Trends of...
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
Chang Am L&S Co. LTD., http://www.changam.co.kr
2
Major Trends
• Environmental
• Equipment severity
• Quality
Chang Am L&S Co. LTD., http://www.changam.co.kr
3
Environmental Trends
• Fundamental Motivations are:
– Resource Conservation– Toxicological Consideration– Environmental Acceptability
Chang Am L&S Co. LTD., http://www.changam.co.kr
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., http://www.changam.co.kr
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
Chang Am L&S Co. LTD., http://www.changam.co.kr
6
Global Eco-Labelling
일본Eco Mark
독일Blue Angel
미국Green Seal
한국
Chang Am L&S Co. LTD., http://www.changam.co.kr
7
Biodegradable Lubricants
0
10
20
30
40
50
60
No
. of P
aper
s
Chang Am L&S Co. LTD., http://www.changam.co.kr
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
Chang Am L&S Co. LTD., http://www.changam.co.kr
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., http://www.changam.co.kr
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
Chang Am L&S Co. LTD., http://www.changam.co.kr
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
Chang Am L&S Co. LTD., http://www.changam.co.kr
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
Chang Am L&S Co. LTD., http://www.changam.co.kr
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
Chang Am L&S Co. LTD., http://www.changam.co.kr
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., http://www.changam.co.kr
15
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
Chang Am L&S Co. LTD., http://www.changam.co.kr
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
Chang Am L&S Co. LTD., http://www.changam.co.kr
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
Chang Am L&S Co. LTD., http://www.changam.co.kr
18
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
Chang Am L&S Co. LTD., http://www.changam.co.kr
19
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
Chang Am L&S Co. LTD., http://www.changam.co.kr
20
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
Chang Am L&S Co. LTD., http://www.changam.co.kr
21
OECD 302C TEST
• Limitations
– Not suitable for insolube and volatile substa
nces
Chang Am L&S Co. LTD., http://www.changam.co.kr
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, 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
Chang Am L&S Co. LTD., http://www.changam.co.kr
23
Respirometer for OECD 302COxygen 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., http://www.changam.co.kr
24
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
Chang Am L&S Co. LTD., http://www.changam.co.kr
25
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
Chang Am L&S Co. LTD., http://www.changam.co.kr
26
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
Chang Am L&S Co. LTD., http://www.changam.co.kr
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
Chang Am L&S Co. LTD., http://www.changam.co.kr
28
New Anti-wear Additives II
CC44-DTC-Tz : R=C-DTC-Tz : R=C44HH99
CC66-DTC-Tz : R=C-DTC-Tz : R=C66HH1313
CC88-DTC-Tz : R=C-DTC-Tz : R=C88HH1717
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
Chang Am L&S Co. LTD., http://www.changam.co.kr
29
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
Chang Am L&S Co. LTD., http://www.changam.co.kr
30
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