AGRE-0010 The Methyl Esters of Rapeseed: New Industrial Outlets for Agriculture

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Agriculture : Bulk Chemicals : ECLAIR Cluster I - Oils : Paints/Coatings/Plastics : Pharmaceuticals/Cosmetics : Vegetable Oil/Fat



Optimization and development of a synthesis of polyglycerols esters (PGE)

SUMMARY

This reports summarises the final results from an ECLAIR project (AGRE-0010) which investigated the opportunities for finding new uses for vegetable oils (from rapeseed in particular) and their methyl esters. The approach was based on a broad investigation of various of chemical reactions (lipochemistry) which can be used to modify the various fatty acid constituents of vegetable oil or the glycerol that is released as a by-product during production of the methyl ester (rape methyl ester or RME). This ester is now quite widely produced throughout the European Union as a substitute for diesel fuel. However, this project looked for other industrial uses, such as lubricants, paints, cosmetics, liquid waxes and reagents for the leather industry. Both chemical and enzymatic methods of production were investigated, some at pilot scale, and some procedures patented. At the time the final report was submitted to the Commission the launch of a number of products was anticipated.

INTRODUCTION

Vegetable oils, as with fats, consist of fatty acids of varying numbers of carbon atoms (chain length) and varying degree of saturation (number of double bonds), esterified with glycerol. The objective of this project was to develop new methods of lipochemistry which would facilitate the use of rapeseed oil, or the methyl ester, as a basic industrial raw material. The investigation covered the reactivity of the carboxylic group (synthesis of polyalcohols, esters and waxes) and reactions concerning the fatty part (selective hydrogenation, sulphation and dimerisation). Further, since a significant amount of glycerol is obtained as a secondary product following transesterification of triglycerids with methanol, the project also included research aimed at finding new outlets for the use of glycerin. As a result a number of processes have been developed, several of which have been patented.

TECHNICAL ACHIEVEMENTS

1. Sulphation and sulphitation of vegetable oils can lead to products which may be used in leather treatment. When methyl esters were used as raw materials for this type of product results for the sulphation reaction were satisfactory, but poor for the sulphitation reaction.

2. For sulphurisation, the properties of the rapeseed methyl esters were inadequate for such materials to be used effectively as an extreme pressure lubricant.

3. The basic reactions of transesterification and esterification with polyols have been studied in laboratories and pilot reactors. High molecular weight esters have been formed and characterised. These formulations have been tested for various uses and satisfactory and interesting results have been obtained, especially in the field of fire resistant lubricants.

4. Dimerisation has been studied at several levels. This includes a comprehensive analytical study as well as investigation of synthesis routes starting with either vegetable oil or methyl esters. An innovative process based on methyl esters has been patented. The performance of various compounds as lubricants has been investigated with variable results reflecting the nature of the trials.

5. Continuous hydrogenation of rapeseed methyl esters in order to produce methyl oleate has been demonstrated with a good yield and good selectivity. However, from an economic viewpoint, the challenge is to compete against new sunflower varieties with high oleic content.

6. The production of liquid waxes from rapeseed methyl esters and commercial fatty alcohols, using both chemical and enzymatic synthesis, has been investigated. The former route has led to a pilot production facility from which samples have been evaluated successfully as raw materials for cosmetics. Extensive toxicological studies have been carried out with acceptable results enabling a formulation strategy to be initiated.

7. Decarbonylation of methyl esters, based on various raw materials, has enabled olefins of different carbon lengths to be prepared. In addition, by modifying the catalyst, selectivity towards paraffins has been demonstrated.

8. Epoxidation of rapeseed methyl esters has been shown following optimisation of reagent quantities, nature, temperature and amount of catalytic agent. Further epoxidation reactions have been studied using substrates such as sunflower oil ethyl esters or castor oil methyl esters.

9. Work on isoacid has also been completed. Unfortunately, no circumstances could be found under which acceptable yields were obtained.

10. An innovative process for the production of polyglycerols and polyglycerol-esters, starting from raw glycerol, has been developed and patented. Samples from a pilot reactor have been introduced systematically in a wide-range of formulations, replacing ethoxylates. Good performances have been shown for products used in applications such as textile and metal working lubricants. The products also have the advantage of being biodegradable.

11. Etherification of glycerol and glycerol derivatives has been studied with the objective of preparing a wide range of products with different carbon chain lengths. These products have been evaluated in lubricant formulations; some have been demonstrated to have antistatic properties and to be biodegradable.

12. Starting from glycerol, epibromhydrin synthesis has been optimised through glycerol dibromation followed by dehydrohalogenation of resulting dibromhydrins.

PRODUCTS

Some of the reactions investigated have been scaled up at pilot level. However, in general further work, adjustments and optimisation are still required for industrial production. The products may be used in a wide range of applications, particularly in the lubricants field where specific properties such as biodegradability and low toxicity give these products an advantage over petroleum-based products. Processes developed to valorise glycerol have been optimised, especially for polyglycerol esters and ether derivatives of glycerin. These products are able to replace ethoxylated emulsifiers in formulations for coning and spinning oils or metal working fluids.

The launch of commercial product lines based on the esters and dimers is anticipated.

PARTICIPANTS

Contractors were Hispano Quimica (Barcelona), a company involved in formulations for the leather, metal, textile and cosmetic industries; Robbe (Compiègne), a seed crushing factory with interests in technical oils and chemicals for paints and coatings as well as in biodiesel production; INPT/ENSCT (the Laboratoire des Agro-Resources CATAR of the Ecole Nationale Supérieure de Chimie de Toulouse) which specialises in the industrial valorisation of products from agriculture. The following subcontractors were also involved in the project: IFP, the French Institute of Petroleum, with competence in petroleum, fuels, lubricants, and petrochemical products, as well as natural fats and oils; ITERG (Institut des Corps Gras), the French Institute for Fat and Oil, near Bordeaux.