EP2144977A1

EP2144977A1 - Liquid biofuels containing dihydroxyfuran, propanol and its production process from polyols originated in agriculture

Info

Publication number: EP2144977A1
Application number: EP07734420A
Authority: EP
Inventors: Pedro Correia
Original assignee: Individual
Current assignee: Individual
Priority date: 2007-03-09
Filing date: 2007-04-27
Publication date: 2010-01-20
Also published as: PT103684A; WO2008053284A1

Abstract

Dihydroxyfuran pure or mixed with other products obtained by hydrogenation of hidroxymethylfurfural, obtained by dehydration of carbohydrates have good qualities as components of motor fuel and a competitive production cost according to the process claimed in this patent. Hydrocarbons may be sugar, cellulose or starch. Propanol obtained by a similar process of dehydration of glycerin, followed by hydrogenation of acrolein is also a good component for gasoline. Glycerin is a side product in the biodiesel production. The production process in both cases consists in a dehydration using as a solvent and as a catalyst an ionic liquid pure or mixed with methanol followed by hydrogenation of the intermediate obtained.

Description

Liquid Biofuels containing dihydroxyfuran propanol and its production process from poliols originated, in agriculture

Description

1. Field of the invention Biofuels, ionic liquids

2 . Background of the invention.

Biofuels used today are ethanol and biodiesel.

Ethanol is produced by fermentation of sugar, which is contained in sugar cane, sugar beet or obtained from starch or cellulose.

Only 8% of sugar cane corresponds to ethanol produced by fermentation of sugar directly.

Sugar cane and sugar beet have yields of 80 ton/hectar and year, which means 6,4 ton/hectar and year of ethanol.

Biodiesel is obtained by 3 different processes:

- direct use of vegetable or animal liquid fett as a component of gasoil

- Transesterification of glycerine of fett with methanol

- Hydrogenation of fett

In most cases the raw material is soja ox colza, which have yields of 3 ton/hectar and per year, which correspond to about 1 ton/hectar and per year of biodiesel. ϊhe idea of converting cellulose or sugar in liquid fuels always had the difficulty of getting the right solvent for sugar during dehydration and the difficulty of stabilizing the intermediate dihydroxynethyl furfural obtained in the dehydration before it is hydrogenated.

Sugars are very soluble in water, which is not the convenient solvent for dehydration. Sugars present a very low solubility in organic solvents. In recent years a big number of experiments on solubility of sugars and cellulose in ionic liquids have been published.

It was also published the possibility of dehydration of sugars in ionic liquids, but the difficulty of the separation and the instability of the hydroxymethyl furfural has been described (2) .

On the other side, the hydrogenation of hydroxymethyl furfural to dihydroxymethylfurfuran in water as a solvent has been published (1,3).

No reference to adapting both reactions of dehydration and hydrogenation to a production of a biofuel has been published. No reference to using dihydroxymethylfurfuran as biofuel was published.

The production of DHF from sugar cane or sugar beet corresponds to 30% of 80 ton/ha, far more than ethanol or b±odiesel .

3. Detailed description of the invention

Following reactions take place using glucose as an example of sugar

The solvent is an ionic liquid like methyl imidazolium chloride pure or preferably mixed with methanol in order to reduce the viscosity and make the diffusion of hydrogen possible. Methanol is also a stabiliser of the aldehyde function of hydroxymethylfurfural.

The 2 reactions of dehydration and hydrogenation may take place in the same reactor at a temperature of 90 - 200°C and a pressure of 2 - 200 bar . The reaction time depends on the temperature and pressure adopted.

In a laboratory scale it is possible to work in a batch reactor like Parr, stainless steel AISI316. In. the pilot plant or industrial scale a fixed bed reactor is recommended to work continuously.

Possible catalysts are Platin or Palladium on activated coal, Cr-Mo or Ni-Mo on alumina.

After the reaction, a destination is necessary to separate in the bottom of a first column the ionic liquid, and in successive columns the methanol, water and the furan compounds .

Methanol and ionic liquid are recycled.

Although furan itself is toxic, furan derivatives are not and are even contained in food like drops or bombons.

Example

In a 440 ml reactor type PARR, with stirrer, following reactants were loaded;

1-H-3 methyl imidazolium chloride 100 g

Glucose 36

Activated coal with 0,06 g/g palladium 1,2 g

The reactor was closed and inertised 5 times with nitrogen.

Then vacuum was made and 50 g methanol were loaded by suction. Hydrogen was introduced at 30 bar. The pressure increased during heating due to methanol vaporisation and also to the normal pressure increase at higher temperature.

The reactor was heated and kept one hour at 130°C.

After that time, the reactor was cooled, depressurised, opened and the content was filtered. The content was analysed by EPLC , with a column Biorad Aminex HPX 87H, mobile phase 0, 01% sulphuric acid, flow rate 6 ml/min, refraction index detector. The conversion of glucose was total. No hydroxymethyl furfural. (DHF) was found. About 90% was converted to dihydroxymethylfuran . Some side products appeared, which could be used as fuel mixed with DHF.

Bibliography

1 . Synthesis, Chemistry and Applications of 5- Hydroxymethyl - furfural and its derivatives, Jaroslaw Lewkowski, Arkivoc, 2001 , 17-54

2 . Dehydration of fructose and sucrose into 5 — hydroxymethylfurfural in the presence of 1-H-3-methyl imidazolium chloride acting both as solvent and catalyst, Claude Moreau, Annie Finiels, Laurent Vanoye, Journal of Molecular catalysis A, Chemical 253 , 2006, 165-169

3 . Hydrogenation catalytique du 5 hydroxymethylfurfural en milieu aqueux, V. Schiavo, G. Descotes, J. Montech, Bull Soc Chim France (1991) 128, 704-711

Claims

1 . Biofuels containing in their composition dihydroxy methyl furan (DHF) or other products obtained. by hydrogenation of hydroxymethyl furfural, or propanol obtained from glycerin , or mixtures of these compounds with each other and/or with etbanol and/or biodiesel and/or hydrocarbons .

2 . Process to produce the biofuel of claim 1 consisting of using as raw materials sugar, cellulose or starch , which are submitted to dehydration followed by hydrogenation in a solvent composed by ionic liquid pure or containing 1 — 50% methanol.

3 . In the process of claim 2 wherein the ionic liquid is 3 methyl imidazolium or 3 butyl imidazolium chloride

4 . In the process of claim 2 wherein the temperature is 50 - 200°C.

5 . In the process of claim 2 wherein the dehydration and the hydrogenation are in two separate steps, using in the hydrogenation step a pressure of hydrogen of 2 - 200 bar.

6 . In the process of claim 2 wherein the dehydration and the hydrogenation are in a single step, which may be batch or continuous, using an hydrogen pressure of 2 — 200 bar.

7 In the process of claim 2 wherein the hydrogenation uses as catalysts platinum or palladium on activated coal in a slurry, or Cromium - Molibdenium, or Nickel - Molibdenium on alumina in fixed bed.

9. In the process of claim 2 wherein the raw material is glycerin and the product is propanol obtained in similar conditions as describes in claims 3 to 8.