titre 1 : Biolubricants : technical and market survey - Valbiom

In the framework of the Project IBIOLAB -- 

Document « FARR-Wal » - Avec le soutien de la Région wallonne – DG Agriculture Page 1 / 24 

Réf. 2007_MHN_08 

Biolubricants: technical and market survey -- July 2007 

Marie Hélène NOVAK 

Biolubricants: technical and market survey 

SURVEY 2: July 2007 

PATENTS: an overview of patents on biolubs 23 

LEGISLATION: when regulations push the market 24 

MARKETS: from the marketplace (but nobody knows) 25-29 

BOOKS: for your gift list … 30-32 

TECHNICAL SIDE: what’s new from lab’s 33-56 

ON THE WEB: how your competitors communicate on their biolubs ! 57-64 

ECO-LABELS IN EUROPE: who get one? 65 

23 -- PATENTS (May 2007) 

This second IBIOLAB biolubricant’s Survey opens on a new chapter relative to Patenting. As a first 

approach, we searched in International and European databases to present some patents (or patent 

applications) on biolubricants, biobased products or processes that are part of the IBIOLAB project. 

At this stage, we limited our search in subclass C10M: LUBRICATING COMPOSITIONS and USE OF 

CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING 

COMPOSITION 1 of the International Patent Classification (IPC), Eighth edition 

(www.wipo.int/classifications/en/). In this subclass, "lubricant" or "lubricating composition" included 

cutting oils, hydraulic fluids, metal drawing compositions, flushing oils, slushing oils, or the like. 

The subclass is divided into “Base-material”, “Thickeners”, “Additives”, “Mixtures of base-materials, 

thickeners and additives”, “Compositions characterised by physical properties”, “Aqueous 

compositions”, “Working-up” and “Preparation or after-treatment”. 

Base-material 

The “Base-material” category is subdivided into either “Petroleum fractions” or “Fatty oil fractions” 

(C10M 101/04). This latest being more relevant for IBIOLAB, we search in the European Patent 

database, esp@cenet (www.espacenet.com) to find about 1354 Patents in the Worldwide database. In 

the WIPO (www.wipo.int) database for Patent Applications, only 28 are found within this category. It’s 

interesting to see the number of applications relative to lubricant with fatty oil fractions as base 

material during time (Figure 1), by Country (Figure 2) and by the name of the applicant (Figure 3). 

1 that excludes : 

o well drilling compositions 

o mould release, i.e. separating, agents for metals, for plastics or substances in a plastic state, in 

general, for glass; 

o textile lubricating compositions 

o immersion oils for microscopy

6 

5 

4 

3 

2 

1 

0 

1981 

1982 

1983 



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Number of Patent applications C10M-101/04 organized by Year of Publication 

1984 

1985 

1986 

1987 

1988 

1989 

1990 

1991 

1992 

1993 

Figure 3 : Number of Patent applications in C10M-101/04 category, organized by Year of 

publication (Publication year is the year of the PCT international publication). 

12 

10 

8 

6 

4 

2 

0 

Number of Patent applications C10M-101/04 

organized by Country of origin 

US JP DE EP NL IT IL FI AU 

Figure 2: Number of Patent applications in C10M-101/04 category, organized by Country 

of origin 

1994 

1995 

1996 

1997 

1998 

1999 

2000 

2001 

2002 

2003 

2004 

2005 

2006



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First Applicant / Assignee Nr of patent applications 

CARGILL, INCORPORATED 3 

HENKEL 3 

NIPPON OIL CORPORATION 3 

DORMA GMBH + CO. KG 2 

THE UNITED STATES OF AMERICA, SECRETARY OF AGRICULTURE 2 

ARIZONA CHEMICAL COMPANY 1 

BEKU ENVIRONMENTAL PRODUCTS LTD. 1 

BIORAMA 2000 S.R.L. 1 

COGNIS DEUTSCHLAND GMBH 1 

E.I. DU PONT DE NEMOURS AND COMPANY KNOWLTON, Susan 1 

FUCHS PETROLUB AG 1 

KAO CORPORATION INAYA 1 

LOCKHEED MARTIN IDAHO TECHNOLOGIES COMPANY 1 

MJ RESEARCH & DEVELOPMENT 1 

NAT CAN CORP 1 

NTN CORPORATION 1 

RAISION TEHTAAT OY AB LÄMSÄ 1 

SHELL INTERNATIONALE RESEARCH 1 

STATE OF ISRAEL MINISTRY OF AGRICULTURE 1 

WAVERLY LIGHT AND POWER 1 

Figure 3: Name of the Applicant for C10M 101/04 applications. 

Search with keywords in Class C10M 

Searching in the subclass C10M could also be done using keywords. Doing that, we selected the 

most relevant items. Patents are recorded since 1982. 

No result was found with keywords like: FINA, ELF, stearin, erucic, standoils. Only one result with 

sunflower (founded also with other keyword). 

Among the patents found, we selected those that we feel most relevant for IBIOLAB’s work. Each 

Patent is identified by its Publication number. In the attached EXCEL file, it’s easy to browse the 

196 selected Patents. A hyperlink opens the corresponding summary in the WIPO database. On 

most of the Applications/patents, the complete description, Claims and other informations are 

available (on the “thumbnail grooves”). The original and exhaustive descriptions of the Patents are 

also available in esp@cenet database (www.espacenet.com) where you can also find an idea of their 

juridical status. 

The number of Patents selected with IBIOLAB’s keywords is increasing since 1983 to 2006 (Figure 

4). 

The authors of 62 of the 196 selected patents have only one patent in the selection (Figure 5). 

HENKEL (DE) is company having applied for most patents, followed by EXXON (US), LUBRIZOL (US) 

and COGNIS (DE). In fact, 92 Patents comes from USA, 55 from Germany, 11 from Japan and 9 

from France (Figure 6). The other countries having more than two Patents are Finland, The 

Netherlands, and Great-Britain.



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Keyword Total Patent found Nr of selected Patents 

concrete 6 4 

metal working 76 23 

hydraulic 130 30 

gear 9 8 

plant 17 6 

vegeta* 33 31 

rapeseed / canola 7 6 

biodegradable 34 33 

malea* 4 3 

emulsion 17 3 

additive 451 42 

FUCHS 5 4 

CARGILL 6 6 

COGNIS 15 9 

TOTAL 7 3 

HENKEL 130 42 

20 

18 

16 

14 

12 

10 

8 

6 

4 

2 

0 

1983 

1984 

1985 

1986 

1987 

1988 

1989 

1990 

1991 

1992 

1993 

1994 

Figure 4: Number of Patents Applications out of Class C10M based on IBIOLAB’s keywords 

One must keep in mind that all patents presented in this section are not necessary running. It might 

sometimes be only Patent Applications, and these could have been rejected, or still in an 

examination phase (even if the application is published). A patent could be out of work: 

- If the fees are not paid; 

- If the geographical cover doesn’t include your country (or the country where you want to use 

the product/process); 

- If 20 years have passed since its publication. 

In fact, when a Patent protects a product or a process that can interest you, additional investigations 

are needed to check out its validity. That can be done in searching in database like 

http://www.epoline.org/portal/public/registerplus, where the extensive information can be found, but also 

in asking Competent bodies. 

1995 

1996 

1997 

1998 

1999 

2000 

2001 

2002 

2003 

2004 

2005 

2006 

2007



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ot her (1 patent each) 

SÜDZUCKER 

MONSANTO COMPANY 

IM PERIAL CHEM ICAL INDUSTRIES 

IDEM ITSU KOSAN 

GREAT LAKES CHEM ICAL 

FUCHS PETROLUB 

TOTAL FRANCE 

RAISION TEHTAAT 

NIPPON OIL CORPORATION 

INTERNATIONAL LUBRICANTS 

CHEM TURA CORPORATION 

USA SECRETARY OF AGRICULTURE 

UNICHEM A CHEM IE 

CARGILL INCORPORATED 

RENEWABLE LUBRICANTS 

COGNIS CORPORATION 

THE LUBRIZOL CORPORATION 

EXXON CHEMICAL 

HENKEL 



2 

2 

2 

2 

2 

2 

3 

3 

3 

3 

3 

4 

6 

6 

8 

9 

13 

15 

Figure 5 : Patents Applicants out of Class C10M based on IBIOLAB’s keywords 

FR; 9 

JP; 11 

FI; 7 

other; 9 

GB; 6 

NL; 7 

DE; 55 

44 

US; 92 

Figure 6 : Countries of Patents Applicants out of Class C10M based on IBIOLAB’s keywords 

70



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24 -- LEGISLATION: biodegradable hydraulic oil used in UK 

http://www.forestry.gov.uk/forestry/infd-6gukva 

UKWAS (the UK Woodland Assurance Standard ) requires that ‘biodegradable lubricants are used 

where practical’ and all chainsaws and harvesters working on Forestry Commission (the UK 

government department responsible for the protection and expansion of Britain's forests and woodlands) land 

use biodegradable oils for chain lubrication and all Forestry Commission harvesters and forwarders 

use biodegradable oil in their hydraulic systems. In financial year 2004/05, 90,000 litres or 80 

tonnes of mineral oils were replaced with biodegradable oils in the Forestry Commission’s fleet. 

50,000 litres of biodegradable chain oil and 40,000 litres of biodegradable hydraulic oil were used 

with an equivalent reduction in the use of mineral oil. The biodegradable hydraulic oil currently used 

by the Forestry Commission is BP Biohyd SE-S, which is a synthetic ester and it degrades at over 

85% as measured by the CEC-L-33-A-93 standard. The chain oil is BP Bioforst 2000, which is based 

on rapeseed oil, which degrades at over 99% as measured by the CEC-L-33-T-82 standard. 

25 -- MARKETS: Market Opportunity Summary : Soy-Based Lubricants 

USB (United Soybean Board, USA) 

January 2006, 3 pages available on http://www.unitedsoybean.org/FileDownload.aspx?File=pdf_25241M%20Lubricants.pdf. 

The market for soybean oil in lubricants will be driven by a 

combination of environmental concerns, economics and 

performance issues. Nine areas were investigated to 

determine the potential acceptance of soybean oil as a 

commercial alternative to mineral-based oils. Possible soybean 

market share is an estimate of the potential penetration once a 

technically and economically competitive product is developed 

and introduced. 

The technical advantages of rapeseed oil and the current 

political support and infrastructure will make it difficult to 

replace it by soybean oil in the European lubricant market, but 

soybean oil is significantly cheaper in the United States than 

rapeseed, or canola oil. Caterpillar, Inc. estimates that environmentally acceptable hydraulic fluids 

constitute 12 percent of the European hydraulic fluid market. Some manufacturers now market 

environmentally acceptable hydraulic fluids in the United States. ExxonMobil, Chevron and E.F. 

Houghton, a supplier of industrial hydraulic fluids, offer rapeseed-based products. Pennzoil offers a 

hydraulic fluid made with sunflower oil. AgroManagement Group of Colorado has developed a 

canola, sunflower and soy-based oil that is usable in air-cooled engines (lawnmowers, chain saws). 

Renewable Lubricants of Ohio has developed a crankcase oil using additives aimed at bringing 

higher-oleic vegetable oils up to mineral-oil standards. Valvoline continues to evaluate mid-oleic 

soybean oil for potential crankcase applications. Several new metalworking fluids have been 

introduced, many of which are based on methyl soyate (use by the Food and Drug Administration as 

an incidental food-contact product when used in rolling metal foils). Improved soybean oil basestock 

have been or are being investigated: 

- DuPont/Pioneer has developed a genetically modified soybean that produces high levels of 

oleic acid, 

- other high-oleic-acid soybean varieties have been developed through USB supported 

research at the University of Nebraska and elsewhere, 

- nontransgenic modification to produce more stable oil containing higher levels of oleic acid 

(18:1) and lower levels of saturates (USB-sponsored work by the USDA Agricultural 

Research Agency and multiple universities), 

- Archer Daniels Midland Company (ADM) and others try to increase the oleic content using a 

low-cost modification process to improve high-temperature stability, 

- Renewable Lubricants, AgroManagement Group and Valvoline have made strides in the uses 

of new additives.



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26 -- MARKETS: Competitive Intelligence for the Global Lubricants Industry, 

2006-2016 -- Year Five of a Continuing Analysis 

Kline Europe, S.A. 1 Avenue Gribaumont B-1150 Brussels Belgium Phone: +32-2 770-4740 Fax: +32-2 770-9440 

E-mail: consult@kline-europe.com 

Brochure on http://www.klinegroup.com/reports/brochures/y533d/brochure.pdf 

Available only by subscription, the reports will be published by the second quarter of 2007 

Standard price : 75,000 US $ 

This market research study and industry analysis is designed to provide business executives with 

reliable and timely insights that will assist them in: 

- Analyzing the leading companies that are active in the global marketplace. For raw material 

suppliers, analyzing these companies' current and future raw material needs and buying 

patterns 

- Accurately estimating the current size of the global lubricant market by geographic region 

and product, predicting demand growth and drivers for each of these geographic regions and 

products in the future 

- Identifying business opportunities 

- Identifying barriers to growth and developing strategies to overcome them 

The Technology and products section will address the following: 

- What environmental regulations are expected to affect the quantity or quality of lubricants 

chosen? 

- What technological changes are expected and how will they impact the industry? Who is 

driving these changes: OEMs or others (API, ACC, ACEA, JASO, etc.)? Will one OEM 

specification be adopted globally, or will individual specifications be adopted for each global 

region or market? Which category will benefit from these changes? 

- What product substitutes will be available? Will they pose a credible threat? 

- What type of products (e.g., conventional, synthetics, synthetic blends, 

biodegradable/environmentally friendly, recycled) will enjoy growth, and in what region and 

end use? 

27 -- MARKETS: World Lubricants to 2010 

Freedonia Group Inc 

Study #: 2182 Publication Date: 01-APR-07 Format: PDF Immediate Online Access Pages: 397 

Price: US $5,400.00 Sections: from $30.00 

http://freedonia.ecnext.com/coms2/summary_0285-404416_ITM 

Global demand for lubricants will reach 41.8 million metric tons in 2010. Gains will by driven by 

increasing motor vehicle ownership and use and growth in manufacturing activity. Engine oils will 

continue to claim over half of demand, while process oils will grow the fastest. Manufacturing 

markets will lead gains. This study analyzes the $35.7 billion world lubricant industry. It presents 

historical demand data for 1995, 2000 and 2005 and forecasts to 2010 and 2015 by lubricant 

formulation (e.g., petroleum, synthetic, re-refined, vegetable-based), by product (e.g., engine oils, 

process oils, hydraulic fluids, metalworking fluids), by market (e.g., motor vehicle aftermarket, 

manufacturing), by world region and for 31 major countries. The study also considers market 

environment factors, details industry structure, evaluates company market share and profiles 32 

major players including Shell, Exxon Mobil, BP, Chevron, PetroChina, Total, Sinopec, and Lukoil. 

28 -- MARKETS: « Improved oilseed rape cultivars for the biolubricant market », 

Annual Project Report, 2006 

HGCA (Home-Grown Cereals Authority) Research and Development, The Arable Group (UK) 

Scientific partners: Scottish Agricultural College 

Industry partners: Monsanto, Fuch’s Lubricants, NNFCC 

Start date and duration: 01 August 2004 for 44 months 

http://www-dev.hgca.com



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The project aims to evaluate the value and promote the market for winter oilseed rape cultivars that 

have been conventionally bred to meet as closely as possible the requirements for biolubricants and 

other specific uses. Preliminary results indicate that crop management has little influence on the 

fatty acid profile of oilseed rape but there is site to site variation. The winter oilseed rape variety 

Splendor is the first in a series of introductions that offer fatty acid profiles that are more suitable for 

the biolubricant market. They have an improved content of oleic acid and lower content of linoleic 

and linolenic acids than other conventional or hybrid varieties. Increasing the nitrogen application 

from 26 kg/ha to 190 kg/ha did significantly increase linolenic and linoleic acid content on some 

sites. 

29 -- MARKETS: AarhusKarlshamn (BINOL) Business Area Technical Products & 

Feed 

Magnus Jörsmo, President 

AarhusKarlshamn AB Skeppsgatan 19, SE-211 19 Malmö, SWEDEN E-mail : info@aak.com 

Capital Market Day, October 3, 2006 -- 20 slides Presentation 

http://www.aak.com/upload/Capital%20Market%20Day%20TPF.pdf 

The group is leading supplier of technical products and feed materials based on vegetable oils to the 

Nordic countries. Total fatty acid market in Europe is 1,300,000 MT, their served market is 500,000 

MT (market growth by 2-3 % per year). Their competitors are Cognis, Uniqema/Croda, Oleon and 

smaller, family owned companies in Germany. BINOL is a European leader in biolubricants, 

dominant in the Nordic area, with double digit growth. Biolubricant market in Europe is ~ 1 bn SEK 

(~ 0.110 bn €). Total lubricant market is static, but bio-segment grows by ~ 5-7% per year. The 

competitors are mineral oil companies and small, regional players. 85% of BINOL sales go to the 

Nordic area, the rest is Germany and US/Canada. The customers are Metalworking industry 

(automotive), Forestry industry, Construction industry and Sawmill industry. 

According to AAK’s president, the BINOL driving forces are: 

- • Strong total cost focus from automotive industry 

- • Substitution of mineral oil based products 

- • Health, Safety and environmental issues 

The success factors: 

- • Regional market coverage 

- • International alliances 

- • Product development and technical support 

New products launched: 

- Binol X/BioSafe XE range (First long life hydraulic oil based on renewable raw material and 

first to be awarded the EU Flower environmental label). 

- Binol Cut range (Oils for pressing of car body components, used for pressing of exterior body 

parts at Volvo Cars). 

30 -- BOOKS : Lubricating Grease 

NLGI (National Association of Lubricating Grease Manufacturers) 

2006 edition: $75. 

http://www.nlgi.com/ 

This guide serves as a source of basic information on lubricating grease and is a handy quick 

reference book. Contains material pertaining to a broad spectrum of grease related subjects. 

Written by technicians for the beginner or for the practitioner who wants to broaden knowledge.



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31 -- BOOKS : Lubricants: mineral, synthetic or biodegradable? 

Sylvia Aitken, Editor, Posted 19 February 2007 

http://www.processonline.com.au/feature_article/article.asp?item=1070 

An interview of Jeanette Wyatt from FUCHS Australia. She speaks about new technology available in 

lubricants and the advantages and disadvantages of moving away from a mineral oil-based product. 

She explains that there are many characteristics of a lubricant that need to be considered when 

matching it to the application at hand. 

32 -- BOOKS : Lubricants and Lubrication 

Theo Mang & Wilfried Dresel (Editors) 

2nd, Completely Revised and Extended Edition January 2007 ISBN: 978-3-527-31497-3 Hardcover 890 pages € 255.00 

http://www.wiley-vch.de/publish/en/books/bySubjectMS00/highlights/3-527-31497-0/?sID= 

The authors from FUCHS PETROLEUM take into account the interdisciplinary character of the field, 

considering aspects of engineering, materials science, chemistry, health and safety. The result is a 

volume providing chemists and engineers with an interdisciplinary introduction and guide to major 

lubricant applications, focusing not only on the various products but also on specific application 

engineering criteria. Chapter 7 written by Rolf Luther is relative to Lubricants in the Environment 

including: 

7.1 Definition of Environmentally Friendly Lubricants’. 

7.2 Current Situation. 

7.3 Tests to Evaluate Biotic Potential. 

7.4 Environmental Legislation 1: Registration, Evaluation and Authorization of Chemicals (REACh). 

7.5 Globally Harmonized System of Classification and Labeling (GHS). 

7.6 Environmental Legislation 2: Dangerous Preparations Directive (1999/45/EC). 

7.7 Environmental Legislation 3: Regular use. 

7.8 Environmental Legislation 4: Emissions. 

7.9 Standardization of Environmentally Compatible Hydraulic Fluids. 

7.10 Environmental Seal. 

7.11 Base Fluids. 

7.12 Additives. 

7.13 Products (Examples). 

7.14 Safety Aspects of Handling Lubricants (Working Materials). 

7.15 Skin Problems Caused by Lubricants. 

33 -- TECHNICAL SIDE: technical papers of NLGI 

http://www.nlgi.org/ 

All technical papers are $10 each, plus shipping/handling. 

Year PAPER # Title 

0604 Marketing Opportunities for Biobased Greases 

0605 Energy Savings Study: Lubricating Railroad Tangent Track with Soy-based 

2006 

2005 

Grease 

0615 Biodegradeable Sugar Mill Lubricant. What Makes it Suitable for a Sweet but 

Agressive Environment 

0501 Development of a Soy-biobased Solid Stick Lubricant 

0516 Rubber Interactions with Grease and Base Oil - When Performance & 

Biodegradability Converge: A Superior Product in a Demanding Environment 

0531 A Study on the Behavior of Lithium Greases using High Molecular Weight Fatty 

Acids



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34 -- TECHNICAL SIDE: Green approach for the preparation of biodegradable 

lubricant base stock from epoxidized vegetable oil 

Piyush S. Lathi and Bo Mattiasson 

Department of Biotechnology, Center for Chemistry and Chemical Engineering, Lund University, Lund, Sweden 

Applied Catalysis B: Environmental Volume 69, Issues 3-4, 15 January 2007, Pages 207-212 

Full article available on line: http://www.sciencedirect.com/ (Received 10 April 2006; Available online: 4 August 2006). 

A novel process for the production of biodegradable lubricant-based stocks from epoxidized 

vegetable oil with a lower pour point via cationic ion-exchange resins as catalysts was developed. 

This involves two steps, first, ring-opening reactions by alcoholysis followed by esterification of the 

resultant hydroxy group in the first step. The ring-opening reaction of epoxidized soybean oil with 

different alcohols such as n-butanol, iso-amyl alcohol and 2-ethylhexanol was carried out in 

presence of Amberlyst 15 (Dry) as a catalyst; identity of products was confirmed by IR and NMR. 

Pour points of the products were observed in the range of −5 to −15 °C. The hydroxy group of ringopening 

product of n-butanol was further reacted with acetic anhydride in presence of catalyst 

Amberlyst 15 (Dry), which was previously used to carry out ring-opening reaction by alcoholysis and 

identity of the resulting product was confirmed by IR. Pour point of the resulting product was 

observed to be −5 °C. 

35 -- TECHNICAL SIDE: Vegetable oil-based lubricants—A review of oxidation 

N.J. Fox and G.W. Stachowiak 

Tribology Laboratory, School of Mechanical Engineering, University of Western Australia, Crawley, WA 6009, Australia 

E-mail address: gws@mech.uwa.edu.au 

Journal of Materials Processing Technology Volume 109, Issues 1-2, 1 February 2001, Pages 181-189 

Full article available on line: http://www.sciencedirect.com/ 

Vegetable oils are being investigated as a potential source of environmentally favourable lubricants, 

due to a combination of biodegradability, renewability and excellent lubrication performance. Low 

oxidation and thermal stability, poor low-temperature properties and narrow range of available 

viscosities, however, limit their potential application as industrial lubricants. This review addresses 

oxidation as a limitation of vegetable oil-based lubricants. The basic mechanism of vegetable oil 

autoxidation is presented, along with methods used to monitor and analyse the products of 

oxidation. The potential impact of such oxidation products on lubrication performance is discussed. A 

brief discussion of methods used to assess and improve oxidation stability completes the review. 

36 -- TECHNICAL SIDE: Immobilized lipase-mediated long-chain fatty acid 

esterification in dense carbon dioxide: bench-scale packed-bed reactor 

study 

Chiara Giulia Laudani, Maja Habulin, Željko Knez, Giovanna Della Porta and Ernesto Reverchon 

University of Maribor, Faculty of Chemistry and Chemical Engineering, Laboratory for Separation Processes, Slovenia 

University of Salerno, Department of Chemical and Food Engineering, Fisciano (SA), Italy 

J. of Supercritical Fluids 41 (2007) 74–81 (Received 26 April 2006; Available online 19 October 2006). 


Long-chain fatty acid esters are useful functional molecules responding to the requirements of 

numerous fields of application in cosmetic, pharmaceutical and lubricant industry. In the present 

work, lipase-catalysed production of n-octyl oleate by esterification of oleic acid with 1-octanol in 

dense CO 2, as reaction medium, was performed in bench-scale packed-bed bioreactor, in order to 

obtain suitable reaction performance data for up-scaling. Lipase from Rhizomucor miehei (Lipozyme 

RM IM) was used as the biocatalyst. The experiments were planned to elucidate the effect of several 

process parameters, such as pressure, temperature, CO 2 and substrates flow rates. Pressure of 

10 MPa, temperature of 323.15 K, CO 2 flow rate of 210 dm 3 /h and substrates flow rate of 18 cm 3 /h 

were predicted to be the optimum conditions: a maximum yield of about 93% was attained. 

Performing the enzymatic reaction in the continuously operating bioreactor, a long-term enzyme 

lifetime was observed and a decrease of the Lipozyme activity was not registered over 50 days. A



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comparison with experimental results obtained in batch-wise was also proposed. Operating at the 

optimum reaction conditions, higher ester yield than those obtained in batch-mode was detected. 

Supercritical carbon dioxide (SC-CO 2) showed to be a potential medium for the n-octyl oleate 

biosynthesis for a large-scale production in continuous-mode. 

37 -- TECHNICAL SIDE: Ecological aspects of the cutting fluids and its influence 

on quantifiable parameters of the cutting processes 

M. Sokovic, and K. Mijanovic 

Faculty of Mechanical Engineering, University of Ljubljana, Slovenia 

Journal of Materials Processing Technology Volume 109, Issues 1-2, 1 February 2001, Pages 181-189 


This contribution gives an analysis of the ecological parameters of the cutting fluids and its influence 

on the machinability parameters. Evaluation of quality parameters of the cutting fluids is based on 

output parameters of production process considering also ecological norms. Some results of 

machinability tests, which were done in tapping threads into standard reference steel C 45 E4 and 

Al-alloy AlMgSiPbBi for free cutting show how it is possible to achieve acceptable machinability 

parameters by use of new environment-friendly cutting fluid. The cutting parameters were chosen 

from the technological database with respect to particular machined material/cutting tool 

combinations. This approach has been used to quantify the performance of the existing products, 

compare products in the marketplace, and search for novel cutting aid additives. 

38 -- TECHNICAL SIDE : An automated FTIR method for the routine quantitative 

determination of moisture in lubricants: An alternative to Karl Fischer 

titration 

Frederik R. van de Voort, Jacqueline Sedman, Robert Cocciardi and Steve Juneau 

McGill IR Group, Department of Food Science and Agricultural Chemistry, Macdonald Campus of McGill 

University, Sainte-Anne-de-Bellevue, Quebec, Canada 

Thermal-Lube Inc., Pointe-Claire, Quebec, Canada 

Naval Engineering Test Establishment, LaSalle, Quebec, Canada 

Talanta, Volume 72, Issue 1, 15 April 2007, Pages 289-295 (Received 16 August 2006; Available online 29 

November 2006. ) 


An accurate primary Fourier transform infrared (FTIR) method for the determination of moisture in 

mineral and ester based lubricants has been developed based on the extraction of moisture into dry 

acetonitrile. FTIR evaluation of acetonitrile extracts from new and used lubricants as well as common 

lubricant additives and contaminants which might co-extract indicated that phenolic constituents 

interfered significantly with moisture measurements. By measuring moisture at 3676 cm−1 on the 

shoulder of the asymmetric OH stretching band, spectral interferences from extracted phenolic 

constituents were minimized. The spectra of calibration standards (0–2100 ppm), prepared by 

gravimetric addition of water to dry acetonitrile, were recorded in a 1000-µm CaF2 transmission flow 

cell and produced linear standard curves having an S.D. of ~±20 ppm. Lubricant sample preparation 

involved the vigorous shaking (20 min) of a 1:1.5 (w/v) mixture of lubricant and dry acetonitrile, 

centrifugation to separate the phases, acquisition of the FTIR spectrum of the upper acetonitrile 

layer, and subtraction of the spectrum of the dry acetonitrile used for extraction. A Continuous Oil 

Analyzer and Treatment (COAT®) FTIR system was programmed to allow the automated analysis of 

acetonitrile extracts, and the methodology was validated by analyzing 58 new and used oils, 

independently analyzed by the Karl Fischer (KF) method. Linear regression of FTIR versus KF results 

for these oils produced a linear plot with a between-method S.D. of ±80 ppm. As implemented on 

the COAT® system, this FTIR method is capable of analyzing 72 acetonitrile extracts/h and provides 

a high-speed alternative to the KF titrimetric procedures for the determination of water in lubricants.



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39 -- TECHNICAL SIDE : Surface restoration induced by lubricant additive of 

natural minerals 

Yang Yua, Jialin Gua, Feiyu Kanga, Xianqing Kongb and Wei Mob 

Department of Materials Science and Engineering, Tsinghua University, Beijing, China 

Department of Automotive Engineering, Tsinghua University, Beijing, China 

Applied Surface Science Article in Press (Received 12 October 2006, Available online 4 April 2007). 


The effect of a new-fashioned lubricant additive is studied. The additive is prepared out of natural 

minerals containing flaky silicate, schungite and some other catalyzers. Applications of the additive 

obviously improve the surface mechanics properties of steel–steel friction pairs, and the 

nanohardness and the modulus of the friction surface are increased by 67 and 90%, respectively. 

The friction surface is especially examined with the high resolution transmission electron microscope 

(HRTEM), and an amorphous restoration film mostly made up of C with some Si or Si–O amorphous 

structure doped was found. Considering all research results about the restoration film, this study 

suggests the film is a sort of diamond-like carbon film (DLC film). 

40 -- TECHNICAL SIDE : Effect and mechanism of additives for ionic liquids as 

new lubricants 

Hideto Kamimuraa, Tomoo Kubob, Ichiro Minamib and Shigeyuki Morib 

Lubricants Research Laboratory, Idemitsu Kosan Corporation, Ichihara, Japan 

Department of Chemical Engineering, Iwate University, Morioka, Japan 

Tribology International Volume 40, Issue 4, April 2007, Pages 620-625 (Available online 25 January 2006). 


Ionic liquids are unique compounds, which exhibit low viscosity, non-flammability, low vapor 

pressure, and extremely high thermal stability. Therefore, they are expected as candidates for 

advanced lubricants. Several ionic liquids, derived from cations such as imidazolium, pridinium, 

ammonium, and anions such as BF 4 - , bis(trifluoromethylsulfonyl)imide (TFSI-) were examined under 

boundary conditions. It was found that tribological properties of ionic liquids are better than those of 

conventional lubricants such as synthetic hydrocarbons, synthetic esters, and fluorinated ethers. 

Careful analysis of worn surface revealed that tribochemical reactions of ionic liquids take place 

under these conditions. For example, organic fluoride, iron fluoride, iron sulfate derived from anionic 

moiety of the ionic liquids were detected by the instrumental surface-analysis with TOF-SIMS and 

XPS. Tricresylphosphate (TCP) and dibenzyldisulfide (DBDS) were found to improve anti-wear 

properties of ionic liquids to some extent. Interestingly, both additive-derived compounds and 

anionic moiety derived ones were detected on the worn surface. Moreover, additive response of ionic 

liquids was found to be superior to those for conventional lubricants. It was speculated that the 

unique tribochemical reactions will lead us to design tailor-made lubricants. Lubrication mechanism 

of ionic liquids is discussed from the viewpoint of tribochemistry. 

41 -- TECHNICAL SIDE : Investigation of anti-wear additives for low viscous 

synthetic esters: Hydroxyalkyl phosphonates 

Ichiro Minami, Keiji Hirao, Michimasa Memita and Shigeyuki Mori 

Department of Chemical Engineering, Iwate University, Morioka, Japan 

NOF Corporation, Amagasaki, Japan 



Various synthetic esters are widely applied as lubricating fluid to reduce friction and wear at 

tribological contact. Among them low viscous synthetic esters are expected to improve fuel efficiency 

by minimizing the fluid friction. These low viscous esters are composed of short-chain fatty acids. 

Therefore, low viscous synthetic esters are inherently polar molecules. Since efficiency of anti-wear



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additives decreases with increase of polarity of the base oil, new additive technology is requested. 

In this work, hydroxyalkyl phosphates [P(O)(OCHRCH2OH)3], and hydroxyalkyl phosphonates 

[P(OH)n(OCHRCH2OH)3−n, where n=1,2] are proposed as novel anti-wear additives for polar 

synthetic esters. The anti-wear additives are evaluated under the boundary conditions. The additives 

prevent wear in polar esters, in which conventional anti-wear additives do not work at all. 

Interestingly, effects of substituent in additive molecule on anti-wear properties are found. Alkyl and 

aryl derivatives reduce wear remarkably, whereas allyl derivatives exhibit poor results. It is 

speculated that the anti-wear inefiiciency of allylic compounds is due to auto-oxidation of the 

additives. A facile preparative method for hydroxyalkyl derivatives characterizes the present additive 

system. They are prepared in situ by simply mixing phosphonic acid and substituted epoxides. 

Flexiblity of lubricant design can be made possible by the present additive system. 

42 -- TECHNICAL SIDE : High-performance base fluids for environmentally 

adapted lubricants 

Anders Pettersson 

Division of Machine Elements, Luleå University of Technology, Luleå, Sweden 



Future lubricants have to be more environmentally adapted, have a higher level of performance, and 

lower total life cycle cost (LCC) than presently used lubricants. To be able to formulate those 

lubricants, the properties of the base fluids have to be well known. Base fluid properties that 

influence the formulated lubricant performance could be divided into three different groups. These 

groups are: physical, chemical, and film formation properties. In this study, properties from all of 

these groups are investigated to improve the understanding on thier influence on base fluid overall 

performance. There are more or less environmentally adapted base fluids available for formulation 

of lubricants. They could be divided into different groups, mineral, semi–synthetic, and synthetic 

fluids. Synthetic fluids could be of different types: polyalpha olefins (PAO), synthetic ester, 

polyglycols, and others. The most interesting group for formulation of environmentally adapted 

lubricants is the synthetic esters. In this study, the properties for a large number of environmentally 

adapted ester base fluids are studied in detail. The tested properties relate to the 

macroscopic/molecular behavior and include: viscosity–temperature—pressure effects, η(p,T), 

thermal conductivity, λ(p,T), and heat capacity per unit volume, ρcp(p,T). The film formation 

capability in elasto-hydrodynamic contacts is also studied. Different connections between the 

molecular structure and the performance of the fluids are discussed. As an example, it is found that 

a large number of carboxylate groups in the ester molecule improve the thermal properties, and 

thereby a thicker lubricating film could be maintained in highly loaded, high-slip contacts. 

43 -- TECHNICAL SIDE : Study of alternative lubricants to the cold extrusion of 

steel shafts 

Celio Caminaga, Frederico Ozanan Neves, Fernando César Gentile and Sérgio Tonini Button 

Department of Materials Engineering, State University of Campinas, Brazil 

Federal University of Sao Joao del Rei, Brazil 

Journal of Materials Processing Technology Volume 182, Issues 1-3, 2 February 2007, Pages 432-439 (Received 

23 February 2004; Available online 16 October 2006). 


The proposal of this work is to develop an alternative lubrication process to the cold extrusion 

associated to lubricants which are less pollutant and present similar results in terms of extrusion 

load and product quality. Four lubricants were analyzed (a mineral oil, a semi-synthetic oil, powder 

soap and wheat flour) and two lubrication methods were applied (immersion and hydrostatic). 

Statistical methods applied to the results of the experimental tests indicated that some processes 

and lubricants could be used as substitutes for common lubricants used in industry, since they 

presented results of extrusion load and product quality similar to those obtained in the industry with



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the conventional lubrication. It was found that for just one deformation stage, wheat flour was the 

best lubricant, and that for two deformation stages, the mineral oil was the best lubricant for the 

second extrusion stage. 

44 -- TECHNICAL SIDE : A Sustainability Assessment of a Biolubricant 

Bryony Cunningham, Nigel Battersby, Walter Wehrmeyer & Catriona Fothergill 

University of Surrey (UK) 

Shell Global Solutions 

Journal of Industrial Ecology Summer/Fall 2003, Vol. 7, No. 3-4, Pages 179-192 

Available on line http://www.mitpressjournals.org/doi/abs/10.1162/108819803323059460 (Posted Online March 

13, 2006). 

A sustainability matrix has been developed at Shell Global Solutions to show the environmental, 

social, and economic impacts of a product. The approach aims to be quicker and more cost-effective 

than a conventional life-cycle assessment by focusing on specific areas of concern through the 

product life cycle and then comparing products by scaling their impacts relative to one another. It 

provides a way of making qualitative and quantitative assessment that gives a depth to the 

assessment beyond data analysis. The tool includes subjective judgment, which tends to reflect 

current thinking in the company. Once the tool has been fully tested on all product types, the 

indicators that are central to the process will be assessed by external stakeholders. This article 

describes the development of the sustainability assessment tool and presents an example that 

compares the sustainability of a biolubricant (an "environ-mentally acceptable" hydraulic fluid 

meeting Swedish Standard SS 15 54 34) with that of a conventional mineral-oil-based product. The 

tool provides a quick decision-making instrument to help Shell decide which products should be 

marketed for the business to continue on a sustainable path. The tool also provides a more detailed 

level of information if a more thorough assessment is necessary. 

45 -- TECHNICAL SIDE : Superior Biolubricant from a Species of Red Microalga 

Shoshana (Malis) Arad, Lev Rapoport, Alex Moshkovich, Dorit van Moppes, Mark Karpasas, Roxana Golan, 

and Yuval Golan 

Department of Biotechnology Engineering, Ben-Gurion University of the Negev, Beer-Sheva, Israel 

E-mail Addresse: arad@ bgu.ac.il 

Langmuir, 22 (17), 7313 -7317, 2006. American Chemical Society Publications. 

Abstract on http://pubs.acs.org/cgi-bin/abstract.cgi/langd5/2006/22/i17/abs/la060600x.html (Received March 5, 

2006- Web Release Date: July 13, 2006) 

The rheological properties of the sulfated polysaccharide of the red microalga Porphyridium sp., a 

heteropolymer with a molecular weight of 3-5 × 106 Da, indicated that this material might be an 

excellent candidate for lubrication applications: the viscosity of the polysaccharide is stable over a 

range of temperatures, pH values, and salinities. In this study, various rheological and lubricant 

properties of the polysaccharide were evaluated in comparison with those of a widely used 

biolubricant, hyaluronic acid. The viscosity of the Porphyridium sp. polysaccharide remained 

essentially unchanged in a temperature range of 25-70 °C. In tribology tests on a ball-on-flat 

ceramic pair, the values for the friction coefficient and wear rate for the pair lubricated with 

polysaccharide were remarkably lower than those for hyaluronic acid, especially at high loads. In a 

test on a steel ring/ultrahigh-molecular-weight polyethylene (UHMWPE) block pair, the wear tracks 

on the surface of the UHMWPE were more pronounced for hyaluronic acid than for the 

polysaccharide. Atomic force microscopy showed that the polysaccharide was effectively adsorbed 

onto mica surfaces, forming ultrathin coating layers in the nanometer range. As is required for 

biolubricant applications, the polysaccharide was not degraded by hyaluronidase. The stability of the 

Porphyridium sp. polysaccharide to heat and to hyaluronidase combined with its ability to reduce 

friction and wear indicate its potential as an advantageous biolubricant.



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46 -- TECHNICAL SIDE : Lubricity characteristics of selected vegetable oils, 

animal fats, and their derivatives 

Fernando, S., Hanna, M., Adhikari, S. 

Mississippi State Univ, Dept Agr & Biol Engn, Dept Biol Syst Engn, Lincoln, NE USA 

E-mail Addresse: sf99@abe.msstate.edu 

Applied Engineering In Agriculture 23 (1): 5-11 Jan 2007. Publ. Amer Soc Agricultural & Biological 

Engineers, 2950 Niles Rd, St Joseph, MI 49085-9659 USA ISSN: 0883-8542 Abstract on : 

http://portal.isiknowledge.com/portal.cgi?DestApp=WOS&Func=Frame&Init=Yes&SID=S2fe3pCIdbFL54OnbAn 

Although viscosity is the most commonly used parameter to assess the effectiveness of a lubricant, 

it alone does not predict functionality sufficiently, especially in field conditions. Inherent differences 

of the chemical composition of biobased oils greatly affect how they perform. Lubricity is another 

important parameter to consider in the determination of a lubricant's effectiveness. This article 

reports lubricity characteristics of selected vegetable oils, animal fats, and their derivatives, along 

with petroleum- and mineral-oil based lubricants for comparison purposes. The article also gives a 

compilation of fatty acid profiles of selected biobased oils, fats, and their derivatives. It was found 

that all of the biobased fats, oils, and their derivatives had better lubricities than diesel fuel. All 

biobased oils and fats had a better lubricity than a turbine drip mineral oil (control). Crude vegetable 

oils had significantly better lubricities than their refined or transesterified (methylated or ethylated) 

forms. It also was found that the type of fatty acid (saturated or unsaturated) or its concentrations 

did not correlate with the lubricity value of a particular oil, fat or their derivatives. 

47 -- TECHNICAL SIDE : The performance and oxidation stability of sustainable 

metalworking fluid derived from vegetable extracts 

Abdalla, H. S., Patel, S. 

De Montfort Univ, Dept Prod & Spatial Design, Gateway, Leicester, England 

E-mail: ha@dmu.ac.uk 

Proceedings Of The Institution Of Mechanical Engineers Part B-Journal Of Engineering Manufacture 220 (12): 2027-2040 

Dec 2006 Publisher: Professional Engineering Publishing Ltd, Westminister SW1H 9Jj, England ISSN: 0954-4054 

Abstract on 


Throughout the world, the production, application, and disposal of metalworking fluid (MWF) must 

adhere to the requirements of nature and the environment. Plant-derived oils have been researched 

as the alternative to mineral-based cutting fluids as they are deemed to be more environmentally 

friendly and sustainable. This paper investigates different vegetable- and plant-derived oils in their 

pure state, as blends or as commercially available products within the industry, and measures their 

relative oxidation stability levels and their ability to perform as a lubricant. A set of standard 

techniques, such as pressure differential scanning calorimetry (PDSC), which measures the oxidation 

onset temperature and the oxidation induction time, four-ball tester, sliding resistance value (SRV), 

and micro tap methods, were utilized to analyse the tribological properties of the fluid. The results 

determined that the oxidation stability varies and is dependent on the chemical structure of the oil 

and its origins, and physiochemical processing during extraction and storage. In relation to oxidation 

stability being the sole limiting factor, the tribological performance of the oils was affected by their 

physical and chemical properties. It was apparent from the findings that the physical properties of 

the oil are also responsible for the low performance of the oil as a metal cutting fluid.



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48 -- TECHNICAL SIDE : Microwave irradiation effects on the structure, viscosity, 

thermal properties and lubricity of soybean oil 

Atanu Biswas, Atanu Adhvaryu, David G. Stevenson, Brajendra K. Sharma, J.L. Willet and Sevim Z. Erhan 

Plant Polymers Research Unit, USDA/ARS/NCAUR, 1815 N. University Street, Peoria, USA 

Department of Chemical Engineering, Pennsylvania State University, University Park, USA 

Industrial Crops and Products Volume 25, Issue 1, January 2007, Pages 1-7 

Full article available on line: http://www.sciencedirect.com/ (Received 20 December 2005; Available online 23 June 2006) 

Soybean oil is a highly valuable agricultural commodity for the United States. To further add value to 

soybean oil, chemical and physical modifications, as well as additives, have been extensively used to 

change the oil characteristics and properties, broadening the potential industrial applications. Heat 

treatments such as heat-bodying have been implemented to change soybean oil properties, but no 

research has studied the effects of microwave-irradiation on soybean oil structure and properties. 

Soybean oil (SBO) was heat-bodied (HB) or microwave-irradiated (MI). HB and MI (200–250 °C for 

20–60 min) oil had similar Gardner bubble viscosity (B–C range). SBO that was HB or MI had 

increased viscosity compared with untreated SBO. 1H NMR analysis showed no oxidation occurred 

for all treatments. However, HB and MI oil formed a cyclic ring structure with polymerization that 

most likely contributed to the increased viscosity. Pour point decreased from −9 °C for the untreated 

SBO, −15 °C for the HB, and −18 °C for the MI despite viscosity increases. Pour point anomaly is 

likely due to triacylglyceride cyclic ring formation. Pressurized DSC analysis showed higher oxidative 

stability for HB oil with even higher stability for MI oil. Compared with untreated SBO, HB and MI oil 

increased friction coefficient and decreased film percentage, whereas MI oil tended to leave larger 

wear scratches on the ball and disk during friction measurements. MI oil improved SBO cold-flow 

behavior, but reduced its potential as a lubricant. 

49 -- TECHNICAL SIDE : Biolubricants for the textile and tannery industries as an 

alternative to conventional mineral oils: An application experience in the 

Tuscany province 

Lazzeri, Luca, Mazzoncini, Marco, Rossi, Adanella, Balducci, Elena, Bartolini, Giuseppe, Giovannelli, Luciano, Pedriali, 

Riccardo, Petroselli, Remo, Patalano, Giampiero, Agnoletti, Giacomo, Borgioli, Andrea, Croce, Beppe, D'Avino, Lorenzo 

CRA Res Inst Ind Crops, Via Corticella 133, I-40129 Bologna, Italy 

Univ Pisa, Dipartimento Agron & Gest Agroecosistema, CON CER TEX Consorzio, Agenzia Reg Protez Ambientale Toscana, 

Houghton Italia, Chimont Int SpA, Cerealtoscana SpA, Draplane SpA, Italcol SpA, Legambiente Toscana Onlus 

Industrial Crops And Products 24 (3): 280-291 Sp. Iss. SI, NOV 2006 Publisher: Elsevier Science ISSN: 0926-6690 


In this paper, some pre-industrial studies on the potential of substituting some mineral lubricants 

(mainly alkylbenzene) widely used in textile (spinning phase of wool) and tannery (both in dry and 

damp phase) processing with formulations based on High Oleic Sunflower Oil (HOSO) will be 

discussed. This research was carried out by private companies that depend on seed production 

(farmers and their main associations, Seed Company), oil extraction, refining, and formulation. The 

new, low environmental impact formulations were tested at an industrial level to verify their 

application potential from technical, environmental, and economical viewpoints. 

The results confirmed that HOSO could substitute mineral oils in textile and tannery applications 

without any technical problem and without any facility modifications. In some cases such as crust 

leather production, the HOSO-based lubricant (BIOVIT) improved the softness of the finished 

product. The environmental impact evaluation of environmental pressure indicators confirmed how a 

higher sustainability could be obtained by the utilisation of new oils characterised by a higher 

biodegradability. Finally, the economic analysis showed a higher production cost and price of 

vegetable oils, but, at the same time, indicated the possibility of reducing the required amount due 

to a lower utilisation rate. Anyway, the price difference between the mineral and vegetable-based 

oils has to be limited to arrive at a commercial application. Based on these results, HOSO could 

represent an efficient alternative to mineral oils and so new commercial lubricant called BIOVIT 

based on HOSO began to be commercialised both for textile and tannery industries.



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50 -- TECHNICAL SIDE : Bio-based ester oils for use as lubricants in metal 

working 

Wichmann, Hubertus, Bahadir, Muefit 

Braunschweig Univ Technol, Inst Ecol Chem & Waste Anal, Braunschweig, Germany 

E-mail Addresses: hu.wichmann@tu-bs.de 

CLEAN-SOIL AIR WATER 35 (1): 49-51 FEB 2007 Publisher: WILEY-V C H VERLAG GMBH ISSN: 1863-0650 

Abstract on http://portal.isiknowledge.com/portal.cgi?DestApp=CCC&Func=Frame 

The potential application of bio-based ester oils for use as lubricants in metal working has been 

investigated for sustainable production processes in the future. When waste edible and animal fats 

came into focus as starting materials, it was already proven, that ester oils produced from plant fats 

performed very well as cooling lubricants. Waste fats were first characterized by analyzing and 

monitoring samples for one complete year. Inorganic and organic contaminations were found to be 

low and without seasonal variations. Fatty acid methyl esters (FAME) were produced by 

transesterification of the waste fats and they were separated into fractions with saturated FAME or 

unsaturated FAME by fractional crystallisation (winterisation). Further transesterification with 2ethylhexanol 

led to products that could be successfully tested as lubricants. The development of an 

extraction process aimed at the recycling of oil containing grinding mud by enabling the recirculation 

of lubricating oil and reutilization of oil-free metal chips. 

51 -- TECHNICAL SIDE : Synthesis of hydroxy thio-ether derivatives of vegetable 

oil 

Sharma, Brajendra K., Adhvaryu, A., Erhan, S. Z. 

USDA ARS, NCAUR, Food & Ind Oil Res, 1815 N Univ St, Peoria, IL 61604 USA 

Penn State Univ, Dept Chem Engn, University Pk, PA 16802 USA 

E-mail Addresse : erhansz@ncaur.usda.gov 

Journal Of Agricultural And Food Chemistry 54 (26): 9866-9872 Dec 27 2006 Publisher: Amer Chemical Soc, Washington, 

DC USA ISSN: 0021-8561. Abstract on 


Bio-based additives are desirable commodities due to their eco-friendly nature. These additives can 

demonstrate physical and chemical properties comparable to those of conventional mineral oil-based 

products. Sulfur incorporated triacylglycerol can function as an antiwear/antifriction additive for 

lubricants. The synthesis of four useful hydroxy thio-ether derivatives of vegetable oils, from 

commercially available epoxidized soybean oil and common organic thiols, is reported in this paper. 

The common thiols used herein were 1-butanethiol, 1-decanethiol, 1-octadecanethiol, and cyclohexyl 

mercaptan. Currently, there is no reported literature describing the synthesis of hydroxy thio-ether 

derivatives of vegetable oil. The reaction was monitored, and products were confirmed by NMR and 

FTIR spectroscopies. Experimental conditions involving various thiols, solvent, catalyst amount, 

time, and temperature were optimized for research quantity and laboratory scale-up. The synthetic 

process retains the vegetable oil structure, eliminates polyunsaturation in the molecule, and adds 

polar functional groups on triacylglycerol. These products can be used as agriculturally-based 

antiwear additives for lubricant applications.



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52 -- TECHNICAL SIDE : The study of epoxidized rapeseed oil used as a potential 

biodegradable lubricant 

Xuedong Wu1, Xingang Zhang, Shengrong Yang, Haigang Chen and Dapu Wang 

E-mail Addresse : wuxd-c@online.sh.cn 

School of Chemistry and Chemical Engineering, Shanghai Jiaotong University, Shanghai, People's Republic of China 

Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Science, Lanzhou, China 

Journal of the American Oil Chemists' Society Volume 77, Number 5 / May, 2000. On line Thursday, November 23, 2006 

Abstract on http://www.springerlink.com/content/t1l3271053651637/ 

The application of epoxidized rapeseed oil as a biodegradable lubricant is described. The epoxidation 

treatment has no adverse effect on the biodegradability of the base stock. Epoxidized rapeseed oil 

has superior oxidative stability compared to rapeseed oil based on the results of both oven tests and 

rotary oxygen bomb tests. Moreover, the oxidative stability can be dramatically promoted by the 

addition of a package of antioxidants. The epoxidized rapeseed oil has better friction-reducing and 

extreme pressure abilities according to tribological investigations. Formation of a tribopolymerization 

film is proposed as explanation of the tribological performance of epoxidized rapeseed oil. 

53 -- TECHNICAL SIDE : TECHNICAL SIDE : Biolubricants: the green way to make 

the earth move: concern over the impact of petroleum-based lubricants on 

the planet has opened the door to environmentally acceptable alternatives. 

N. Dörmő, K. Bélafi-Bakó, L. Bartha, U. Ehrenstein and L. Gubicza 

Research Institute for Chemical and Process Engineering, University of Veszprém Hungary 

Department of Hydrocarbon and Coal Processing, University of Veszprém, Hungary 

Fraunhofer Institute for Environmental, Safety and Energy Technology, Oberhausen, Germany 

Biochemical Engineering Journal Volume 21, Issue 3, November 2004, Pages 229-234 

Available online 20 August 2004 on http://www.sciencedirect.com/ 

Biolubricant was prepared in integrated system by an esterification reaction of fusel oil and oleic 

acid, where immobilised Novozym 435 lipase enzyme was used as a biocatalyst. Firstly shaken flasks 

experiments were carried out, and the effects of water content, temperature, substrate 

concentration and the molar ratio of oleic acid and alcohols on the ester yield were investigated in 

solvent-free system. To eliminate the negative effect of the water produced in the reaction, 

integrated system was constructed, and pervaporation was used for water removal. The method was 

suitable to achieve 99.8% conversion under optimal conditions. The oleochemical ester produced 

doesn’t have aquatic toxicity and the determined tribologycal, physico-chemical properties of the 

lubricant proved that it is an environmental friendly product. 

54 -- TECHNICAL SIDE : NEW METHOD PROPOSED FOR THE ASSESSMENT OF 

LUBRICANT BIODEGRADABILITY DURING ITS USE 

E. Aranzabe 

FUNDACIÓN TEKNIKER, Spain 

The 13th International Conference on Near Infrared Spectroscopy (13th ICNIRS) in Umeå-Vasa, Sweden & Finland 15-21 

June 2007. Abstract on http://nir2007.com/ 

The OECD301 "Manometric Respirometry test" measuring the biodegradability is one of the most 

time-consuming tests. There exists another method to measure the potential biodegradability which 

is based on qualitative structure-activity relationships ("read-across") but it can't become an on-line 

technique because it consists in the study of the effect of the functional groups on the 

biodegradation of structurally similar substances. During a biodegradable oil aging, the chemical 

structure of the biolubricant changes, and its biodegradability tends to decrease. There is no method 

to control the biodegradability during use. In this work the NIR (Near Infrared) technique (off-line) is 

used to predict the biodegradability of a lubricant, and it is proposed to an online sensor 

development. One of the goals of this study has been the prediction of Biodegradability (%), with a 

quite good quality and reliability, by means of cost- effective, less time consuming and cheaper 

parameters.



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55 -- TECHNICAL SIDE : Valorisation non alimentaire des huiles de friture 

usagées en tant que lubrifiants biodégradables 

Anne-Virginie Avellan, Carine Alfos 

Institut des corps gras (Iterg), Pessac, France 

Oléagineux, Corps Gras, Lipides. Volume 12, Number 4, 290-4, Juillet-Août 2005, Biolubrifiants 

Available on line on http://www.jle.com/en/revues/agro_biotech/ocl/e-docs/00/04/15/8B/article.md?fichier=images.htm 

The market of used frying oils (UFO’s) collection in Europe is estimated to about 350,000 tons a 

year. Since the dioxin crisis in 1999, the main recycling ways of this raw material, considered as a 

waste, concern the oleochemical applications namely the production of biodiesel and fatty acids. In 

this context, the European Craft Valuil project led to a new application of UFO’s as environmentally 

friendly biodegradable lubricants in applications such as demoulding agents, industrial gear boxes 

oils and hydraulic fluids. The synthesis of biolubricant bases is carried out according to an integrated 

catalytic transesterification process: methanolysis of UFO’s followed by a transesterification in 

presence of trimethylolpropan. The lubricant performances synthesised at laboratory and pilot scales 

as well as a first process cost assessment have strongly encouraged the industrial partners to go on 

this project towards an industrial development which is in progress. 

56 -- TECHNICAL SIDE : H3PO4/Al2O3 catalysts: characterization and catalytic 

evaluation of oleic acid conversion to biofuels and biolubricant 

Lucia Regina Raddi de Araujo; Cynthia Fraga Scofield; Nídia Maria Ribeiro Pastura ; Wilma de Araujo Gonzalez 

Universidade do Estado do Rio de Janeiro, Brazil 

Instituto Militar de Engenharia, Dep. Engenharia Química, Rio de Janeiro, Brazil 

Materials Research vol.9 no.2 São Carlos Apr./June 2006 Available on line on 

http://www.scielo.br/scielo.php?script=sci_arttext&pid=S1516-14392006000200013&lng=en&nrm=iso&tlng=en 

Al2O 3 and H 3PO 4/Al 2O 3 catalysts were investigated in the conversion of oleic acid to biofuels and 

biolubricant at 1 atm and at 623 K. The catalytic tests were performed in a fixed bed and continuous 

flow reactor, using an oleic acid-catalyst ratio of 4 and N2 as the carrier gas. The reaction products 

were analyzed by gas chromatography and acidity measurements. N2 adsorption-desorption, X ray 

diffraction, 31P nuclear magnetic resonance and FT-IR spectroscopy were also employed to evaluate 

the textural, structural and acidic properties of the catalysts. The results showed that phosphoric 

acid impregnation improved the alumina decarboxylation activities, generating hydrocarbons in the 

range of gasoline, diesel oil and lubricant oil. The best catalytic performance was achieved with the 

highest surface area alumina impregnated with H 3PO 4, which was the solid that allied high total 

acidity with a large quantity of mesopores. 

57 -- ON THE WEB : Renewable Lubricants, Inc., OHIO, USA 

Website: http://www.renewablelube.com/ 

« Biobased » and « Buybio » are the new buzz words in the US Government and economic security 

is a main driving force for lubricant products coming from soy, corn, canola, sunflower and other biomaterials. 

RLI’s patented biobased technology transforms these oils into « high performance 

vegetable lubricants that can endure the harshest, hottest engines and the cruelest, coldest winters 

at a cost competitive to conventional petroleum-based products and substantially lower than 

synthetic alternatives ». STABILIZED TM is their trademark. The patented anti-oxidant, anti-wear, 

and cold flow technology is based on High Oleic Base Stock. 

A Powerpoint presentation of some applications: 

http://www.canamglass.org/reports/reportHigh%20Performance%20Energy%20Conserving%20Biobased%20Lubricants.pdf



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58 -- ON THE WEB : TERRESOLVE Envirologic ® Products, OHIO, USA 

Website: http://www.terresolve.com/product.html 

Formulated from unique base oil technologies, the Terresolve products are non-toxic, biodegradable 

and offer an environmentally preferable alternative solution to petrol-based oils in industrial and 

consumer applications. Biodegradable/Non-Toxic Products are : Hydraulic Fluids, Gear Oils, Bar and 

Chain, General Purpose, Two Cycle Engine Oil, Dust Suppressant, Universal Tractor Fluid, Grease, 

Shock Absorber, BioFlush, Diesel Fuel, Asphalt Release Agent, Streamer Fluids and Specialty 

Products (supplements). An article is available on this Website: 

The Care and Feeding of Biodegradable Lubricants : Lessons Learned in the Real World 

Fred Sullivan, Transocean, Inc and Mark Miller, Terresolve Technologies, Ltd. 

This paper will review the definitions of environmentally preferable products and strengths and 

limitations of each type. It will also review the various definitions of .biodegradable, and the 

maintenance practices required to prolong the life of the fluid and the equipment. Finally, the paper 

will present the data gathered and observations made by Transocean Inc, and Terresolve 

Technologies, Ltd during a successful nine-month (6000 hour) field demonstration in the central 

hydraulic system of the Deepwater Nautilus and utilized Terresolve.s EnviroLogic 146H vegetablebased 

hydraulic fluid. 

59 -- ON THE WEB : NanOil, Seaford, Delaware, USA 

Website: http://www.nanochemicalsystems.com 

With the current state of the world, green products are highly sought after, yet there are few green 

products available. If given a choice, more than 10% (and growing) of American consumers would 

choose a comparable environmentally-friendly product over their favorite brand. Nano-enhanced 

environmentally friendly motor oils that are non-hazardous waste disposal, biodegradable and 

smokeless in 2-cycle. Nano-sized molybdenum metal ball bearings are immersed to support the oil 

made from the byproducts of the palm bio-diesel production process. 

60 -- ON THE WEB : CARL BECHEM 

Website: http://www.bechem.de 

A German lubricant manufacturer since 1834, producing Heavy-duty gear greases and oils, 

Metalworking lubricants for metal removal and metal forming, Specialized hydraulic fluids, Lubricants 

For Open Cast Mining and Biodegradable lubricants. Two brochures to Download: « GREEN 

LUBRICANTS : High Performance Lubricants and Environmental Protection » and « Biodegradable 

switchplate lubricants ». 

61 -- ON THE WEB : TOTAL lubricants 

A 12 pages brochure “Les Biolubrifiants pour le respect de l'environnement”. To be downloaded on 

http://www.lubricants.elf.com/lub/content/NT0008879A.pdf 

62 -- ON THE WEB : United Soybean Board, USA 

Website: http://www.soynewuses.org 

Provide a list of American companies selling soy-based products (e.g. Industrial Lubricants and 

Metalworking fluids). See also Market study (25--), a 3 pages article « Soy Lubricants Technical 

Background » and their Newsletter with short technical articles (downloadable), e.g.: 

Reduce Wear on Metal with Soy-Based Lubricants 

Biobased solutions March 2007 Volume 8, Issue 2



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63 -- ON THE WEB : Malaysian Palm Oil Board, Ministry of Plantation Industries 

and Commodities, Malaysia 

Website: http://mpob.gov.my 

FOOD-GRADE PALM-BASED LUBRICANT BASE FLUIDS 

LOH SOH KHEANG and CHOO YUEN MAY 

MPOB INFORMATION SERIES Nr 325 • ISSN 1511-7871 • JUNE 2006 

Although palm oil contains equal amounts of saturated and unsaturated fatty acids, its moderate 

thermal oxidative stability and cold-temperature fluidity make it potentially suitable for use as a 

biolubricant. Biodegradable food-grade palm-derived base fluids are designed for formulation of a 

wide range of lubricants for different applications in hydraulic systems, anti-wear hydraulic systems, 

air compressors, penetrating lubrication systems, reciprocating systems, as general circulating oil, 

and spindle or telemotor, bar, chain and sprocket oil. The series of palmbased fluids can also be 

used in general purpose lubricants for motors and bearings (Malaysian patent application No. PI 

20055209). 

64 -- ON THE WEB : Society of Tribologists & Lubrication Engineers (STLE) : 

2008 Annual Meeting Call for Presentations -- May 18-22, 2008 Cleveland, 

Ohio, USA 

Website: http://www.stle.org/annual_meeting/pdf/call_for_presentations2008.pdf 

STLE’s Annual Meeting & Exhibition brings together research scientists and engineers from all over 

the world to exchange information and ideas on developing energy-efficient, environmentally 

friendly, reliable, high-performance, and affordable products that enhance the global economy and 

the well-being of people worldwide. The deadline for submitting a presentation abstract is 

Oct. 1, 2007



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65 -- Eco-labels in Europe: lists of lubricants suppliers that got licenses (updated 23 July 2007) 

Swedish Standard Swedish Standard Nordic Swan (Finland) BLUE ANGEL 

BLUE ANGEL 

EUROPEAN GERMAN POSITIVE 

Hydraulic oils SS 15 Lubricating greases 

Hydraulic Fluids RAL- Lub. and Form. Oils ECO-Label 

LIST 

54 34 - 

SS 15 54 70 

UZ 79 

RAL-UZ 64 

(country) 

1 

Addinol Lube Oil 

Addinol Lube Oil 

2 Agro Oil 

Agro Oil 

3 

Agip Schmiertech. Agip Schmiertechnik 

4 

Agravis Agravis 

5 

Aral . Aral 

6 

Avia Mineralöl Avia Mineralöl 

7 

BayWa BayWa BayWa 

8 Bechem (Carl) 

Bechem (Carl) Bechem (Carl) 

9 Binol Binol Binol Biosafe Binol Biosafe (FIN) 

10 Blaser 

Swisslube 

11 BP Smörjmedel BP Smörjmedel BP & Deutsche BP 

Deutsche BP 

12 

Bremer & Leguil Bremer & Leguil 

13 

Burrenkopf Schmier. 

14 Canadian Oil A B 

15 

Calpam Mineralöl Calpam 

16 Cargill 

17 Castrol Castrol 

18 

19 

Cargo Oil Cargo Oil 

20 Car Oil (Gulf) 

21 Caterpillar Caterpillar Overs. 

22 Cognis Deutsch. Cognis Deutsch. 

23 Chemisch. Werke Klu. 

24 Deere & Company 

25 Eliassons Maskin 

26 ELASKON SACHSEN 

27 EMKA Schmiertechnik 

28 

Esso Deutschland ESSO Deutschland 

29 Exxon Mobil Lub. 

30 

FINKE Mineralölw. Finke Mineralölwerk



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31 F L Nordic (Ambra) 

32 

Fragol Schmierstoff Fragol Schmierstoff Fragol Schmierstoff 

33 

Fuchs Fuchs 

34 G. A. Lindber g 

35 Georg Oest 

Mineralöl. 

36 Green Oils 

Greenoils 

37 

Handelsges. für Kr. Handelsges. für Kr. 

38 Hebro Chem ie Hebro 

Chemie 

39 Hunold Schmierstoffe 

40 Hydroscand 

41 Kajo-Chemie Kajo-Chemie Kajo-Chemie Kajo-Chemie (DE) Kajo Chemie 

42 Kaste 

43 Kettlitz Chemie 

44 Kleenoil Panolin 

45 Kock Zerspanungste. 

46 

47 

Kompressol-Oel Verk. 

48 Lubricating Dutchman 

49 Matrix Lubricants 

50 MCB Larsson Mill. 

51 Midland 

Midland 

52 Mobil Oil 

53 

Motorex 

54 

Müller (H. Math) 

55 Natoil 

56 Neste Oil AB Neste Oil AB 

57 Nordisk Däc k.(Agip) 

58 Norsk Hydro Olje 

59 

Novance (FR) 

60 NYCO. 

61 Oelheld 

62 Oemeta Chemische 

W 

63 OMV Deutschland 

64 OK-Q8 

OK-Q8 Kuwait Petroleum 

65 

OMV Aktiengesells. 

66 Panolin Scandinav. Panolin Panolin AG Panolin (CH) 

67 

Pap Star, Vertrieb. 

68 Partek For (Valmet)



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69 Polychemie 

Limbach 

70 Preem Pet (Texaco) Preem Pet (Texaco) 

71 

Raiff. Haupt-Gen. N 

72 

Ramby Oljor& Verk. 

73 Rhenus 

Lub 

74 Röhrl 

75 Skand. Oljecen tr. 

76 SKF Maint. Prod. 

77 Shell AB Svenska Shell Shell Deutsch.Oil Shell & DEA Oil 

78 

Sips-Dieter Döcker 

79 

SRS Schmierstoffvert. 

80 

Starke & Sohn 

81 Statoil Lubricants Statoil Lubricants 

82 Sunoco 

83 Swd Lubricants 

84 

Technolub Schmier 

85 Total Lub.Sweden 

Total Deutschland 

86 

Unitech Kühlschmier. 

87 Valvoline Intern. 

88 

Veba Oel Vertrieb 

89 Voitel. Tont. Comet 

90 Voitländer 

91 Volvo CE Volvo CE Intern. 

92 WASCUT Industrieöle 

93 

Willi Schüler e. K. Min 

94 Wunsch Öle 

95 Zeller 

& Gmelin 

Status 

July 2007 

36 companies 

NO CHANGE 

76 products 

13 companies 

NO CHANGE 

19 products 

1 companie 

NO CHANGE 

9 products 

20 companies 

+2 - 1 

70 products 

12 companies 

NO CHANGE 

27 products 

2 companies 

+ 2 

13 products 

53 companies 

493 products 

http://www-v2.sp.se/km/en/tech_ser/kmo/grease.htm (greases) 

http://www-v2.sp.se/km/en/tech_ser/kmo/hydraul.htm (hydraulic) 

http://www.ymparistomerkki.fi/www/tuotteet?jta=search&pg=2 (in Finnish: voiteluöljyt) 

http://www.blauer-engel.de/englisch/navigation/body_blauer_engel.htm (hydraulic fluids) 

http://www.eco-label.com/default.htm 

http://www.fnr.de/ [Startseite > Förderprogramm > Positivliste]

titre 1 : Biolubricants : technical and market survey - Valbiom

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