![[BioMatNet Database - FAIR Program]](../images/Fair.gif) |
Commercial Success of ECLAIR Programme
AGRE-0010: The methyl esters of rapeseed: new industrial outlets for agriculture
|
Contacts
To find similar Items, click on a keyword below:
Bulk Chemicals
:
FAIR-CT98-4822 Commercial Success of the ECLAIR Programme
:
Paints/Coatings/Plastics
:
Pharmaceuticals/Cosmetics
:
Vegetable Oil/Fat
This Item is taken from a report produced by
CPL Scientific on the
Commercial Success of ECLAIR Programme 1999
under contract FAIR-CT98-4822. The
Project Summary, Links to Individual Project Reports
and
Preface and Overview are available in separate
items.
AGRE-0010: The methyl esters
of rapeseed: new industrial outlets for agriculture
Science Background
Various chemical reactions (oleochemistry) can be used to modify the
fatty acid constituents of vegetable oil or the glycerol that is released
as a byproduct during production of methyl esters from vegetable oils,
such as in the production of rape methyl ester ( RME). At the time this
project was being carried out, this ester was being actively developed
throughout the European Union as a substitute diesel fuel.
Objectives
This project aimed to identify other industrial uses for derivatised
fatty acids and glycerol. This included development of ingredients for use
in lubricants, paints, cosmetics and liquid waxes as well as of reagents
for use in the leather industry. Both chemical and enzymatic methods of
production were investigated, including some at pilot scale.
Significant changes and results since end of ECLAIR
The project was coordinated by ONIDOL, the French
Oilseed Interprofessional Organisation. ONIDOL is a member of PROLEA, the
French agriculture association that gathers together the oilseed
activities of FOP (represents producers of oilseed and high-protein
crops), CETIOM (the Interprofessional Technical Centre for Oilseed),
ONIDOL and Sofiproteol (the financial arm for the sector). Hispano
Quimica, Spain, who produce formulations for the leather, metal, textile
and cosmetic industries, have been reorganized and have not been involved
in further collaboration. Robbe, France, are a seed crushing factory with
interests in technical oils and chemicals for paints and coatings, as well
as in biodiesel production. Robbe carried out laboratory and pilot
synthesis, as well as identification of basic characteristics. Other
participants were INPT/CATAR, French Institute of Petroleum (IFP) and
ITRG. Two process patents have been granted to the IFP. Some results from
this project are already exploited in existing processes. Others have
been, or should soon be, taken up by commercial organisations. Further
research is required to improve processes and compound properties.
Results
At end of this ECLAIR project
A wide range of chemically derived products had been developed, while
enzymatic esterification had been shown to be impractical in this context.
Some of the chemical reactions investigated were scaled up at pilot level.
However, in general, further work was still required for use in industrial
production. The products were suitable for use in a wide range of
applications, particularly in the lubricants field where specific
properties such as biodegradability and low toxicity could give these
products an advantage over petroleum-based products. Processes developed
to valorize glycerol had 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 was anticipated.
Current position
The 10 main project areas gave the following results
that presented opportunities for commercial application in the short or
middle term, the remaining required further work. Participants from the
ECLAIR project have also participated in a number of other projects funded
under AIR or FAIR.
Applications that could be developed in the short term:
- new outlets for use of glycerin - byproduct of, for example,
hydrolysis or transesterification of vegetable oils in biofuel plants
- fatty chain chemistry – sulfitation, sulfation and sulfurisation
studies (Hispano Quimica) – with the objective of manufacturing
bases used in extraction of fat in leather production. Rapeseed oils and
methyl esters were used in such reactions and the products were
assessed. Good results were obtained for sulfation but not for
sulfitation. Application of the results enabled improvements in Hispano
Quimica's existing processes in terms of reagent stability and cost.
- Oligomerisation – analytical study of synthesis of oligomers
resulted in an innovative process patented (IPF) for synthesis of
oligomers from methyl ester. Oligomerisation (Robbe) of rapeseed oil at
255 degrees C, without catalyst, led to highly viscous products,
suitable for use as lubricants. The work led to a around 10 compounds
with commercial potential. Ester dimers prepared by the IFP process
showed to 90% biodegradability. These were tested in formulations for
steel sheet-drawing and 2 stroke engine lubrication.
- Heavy esters – esterification/transesterification with polyols
were studied at laboratory and pilot scales (Robbe/Hispano Quimica).
Oleic acid from rapeseed or sunflower were used to prepare methyl esters
as well as derivatised with polyols such as trimethylolpropane,
pentaerythritol or 2-ethylhexanol. Trimethylolpropane esters of rapeseed
oil (HQ) performed well at low temperatures
- Liquid waxes – ITERG prepared liquid waxes from partially
hydrogenated rapeseed methyl esters, and linear or branched fatty
alcohols (C12 or C14) by chemical transesterification producing 10
different compounds in yields of around 90%. Hispano Quimica
investigated their suitability for use in cosmetic formulations.
- Polyglycerol and polyglycerol esters – Crude glycerol from
biofuel process was synthesized (IPF/Robbe) and derived products tested
in several application in place of ethoxylates, at a competitive price.
Process co-patented by IPF and ONIDOL. Reaction of PGs with fatty acids
gave a number of compounds of various molecular weights and
hydrophilic-lipophilic balance (HLB). Ethoxylated emulsifiers were
replaced in several formulations by polyglycerol esters and good results
obtained in formulations for spinning oils with palm kernal oil
polyglycerol monoester. Promising results were obtained when they were
used as metal working fluids (MWFs) but further work was needed due to
the complexity of the technology.
- glycerol esters – INPT investigated the valorization of glycerol
by making ether linkages between glycerol and fatty chains producing
compounds tested for various industrial applications, with the best
results obtained when they were tested for use as antistatic compounds
for the textile industry. Many of the properties relating to friction
coefficients (associated with fibre/fibre and fibre/metal interaction)
were comparable to those of current products used in this industry.
Activities and processes requiring further work:
- reactivity of carboxyl function – preparation of polyalcohol
esters and liquid waxes
- reactivity of fatty chain – selective and continuous
hydrogenation and dimerisation
- hydrogenation – fixed bed continuous hydrogenation of rapeseed
methyl esters was achieved (IFP). However, this was not found to be an
economically competitive way to produce oleic acid, since new high oleic
acid varieties of sunflower and rapeseed became available.
- sulferization of rapeseed methyl esters gave poor lubricants
- epoxydation of oils and esters (Robbe) did not lead to industrial
applications. However chemical opening of epoxydes may generate new
compounds. This possibility was followed up in an AIR project (see
below)
- original process for preparation of epibromhydrine was implemented
(INPT), but the market share for this compound is very small as it
competes with epichlorhydrine
- decarbonylation of methyl esters – catalysts tested (IFP)
display some instability
Participation in further EU funded RTD activities
include:
-
AIR3-CT94-2218:
Reactivity of fatty esters and glycerol: new methods,
coordinated by ROBBE, in which various fatty derivatives have been
prepared at the laboratory scale and a number of catalysts and processes
have been improved. Good results have been obtained for synthesis of
polyurethanes, patenting has been considered. Samples were produced for
application testing showing that some of the derivatives were effective.
However, formulation costs have to be reduced. Samples of fatty amines
have been assessed and the stability of the catalysts studied in order
to perfect the pilot process. Monoglycerides preparations were improved
and scaled-up. Samples of estolides (polyesters of fatty hydroxyacids)
have been prepared.
-
AIR1-CT92-0169:
Biodiesel: Utilization of vegetable oils and their derivatives as
diesel fuel, included the participation of Onidol –
Sofiproteol in this demonstration project, that led to the formation of
the European Economic Interest Group (EEIG) known as Eurobiodiesel. This
showed that all technical barriers had been overcome, with the main
barriers to expansion economic or customer acceptance.
-
FAIR3-CT97-1829:
Polyglycerols chemistry ecology and applications of polyglycerol
esters, is coordinated by Onidol – Sofiproteol with
the objective of generating a complete description of polyglycerol-based
surfactants in terms of structural-property relationships, as well as to
assess the market for polyglycerols.
-
FAIR5-CT97-3884:
CTVO-NET: Chemical-technical utilization of vegetable oils,
includes the participation of Onidol – Sofiproteol in this
concerted action that aims to link RTD activities in oleochemistry, as
well as the production of vegetable oils, with the needs of industry in
this sector.
Impact
Commercial
Patents:
- The dimerization of esters by an original process of the French
Institute of Petroleum: "Procédé perfectionné
pour oligomériser les acides et les esters polyinsaturés",
FR 93-005 05, 1993
- The preparation of polyglycerol and polyglycerol esters with another
original process of the French Institute of Petroleum: "Procédé
de polyglycérols et d’esters de polyglycérols",
FR 91-07 175, 1991
Hispano Quimica has exploited the results of work on
sulfitation and sulfation for its existing processes: The gains obtained
range from 20% for sulfitation process and 10% for sulfation.
Opportunities exist for the commercial development of
heavy esters, dimers and polyglycerol esters.
- heavy esters – trimethylolpropane tested by HQ for low
temperature lubrication – a range of various heavy esters has been
made up by Robbe to be submitted to industrial customers
- dimers – a pilot scale synthesis is scheduled by Robbe and IPF –
to supply potential customers with samples for plasticiser and lubricant
formulations.
- polyglycerol esters – pilot synthesis of polyglycerols was
anticipated in a 100 l reactor. This would furnish the potential
customers with the samples required for lubricant and emulsifier
formulations
Middle term developments:
- liquid waxes – ITERG – being assessed for cosmetic
formulations by Hispano Quimica
- glycerol esters – NPIT – being assessed for antistatic
coatings for yarns by HQ
Numerous industrial products with low toxicity and high
biodegradability can be made at a low cost from the biomass. In order to
promote an industrial product it may be advisable to continue reducing the
cost prices of the processes.
The key point for a heavy investment can only come, in
opinion of Sofiproteol, from a constraining European legislation for
certain applications where biodegradability or non-toxicity are more than
required. Hence, priority should be given to biodegradation assessments in
order to define the biodegradability standards concerning lipochemistry.
Associated
Research has been continued by the participants.
Contacts
Author
Onidol-Sofiproteol
