EP2318386A2

EP2318386A2 - Manufacture of maleic anhydride from renewable materials, maleic anhydride obtained and uses thereof

Info

Publication number: EP2318386A2
Application number: EP09737075A
Authority: EP
Inventors: Jean-Luc Dubois
Original assignee: Arkema France SA
Current assignee: Arkema France SA
Priority date: 2008-07-18
Filing date: 2009-07-17
Publication date: 2011-05-11
Also published as: US20120015411A1; BRPI0916246A2; FR2933978B1; WO2010007327A2; WO2010007327A3; JP2011528340A; US8394973B2; CN102089293A; FR2933978A1

Abstract

The present application relates to a process for manufacturing maleic anhydride that comprises the following steps: a) fermentation of renewable raw materials and optionally purification to produce a mixture comprising at least butanol; b) oxidation of the butanol to maleic anhydride at a temperature generally between 300 and 600°C, using a catalyst based on oxides of vanadium and/or of molybdenum; c) isolation of the maleic anhydride obtained at the end of step b). It also relates to the maleic anhydride obtained from renewable raw materials, to the copolymers and the compositions comprising said maleic anhydride and also to the uses of this maleic anhydride.

Description

MANUFACTURE OF MALEIC ANHYDRIDE FROM RENEWABLE MATERIALS, MALEIC ANHYDRIDE OBTAINED AND

USES

The present invention relates to a process for producing maleic anhydride from renewable raw materials.

In particular, the invention relates to a process for the manufacture of maleic anhydride from alcohols derived from the fermentation of renewable raw materials, preferably the renewable raw materials are vegetable materials. Maleic anhydride is generally obtained by oxidation of aromatic compounds, especially benzene or by oxidation of alkanes and especially n-butane.

In recent years, mainly because of the awareness of the toxicity of benzene and the increase in its cost of production, routes have been sought for the synthesis of maleic anhydride from other raw materials. Benzene is indeed obtained from non-renewable fossil (petroleum) raw materials. But oil resources are limited, oil extraction requires digging deeper and deeper and under increasingly difficult technical conditions requiring sophisticated equipment and the implementation of ever more energy-intensive processes. These constraints have a direct consequence on the manufacturing cost of maleic anhydride.

Another synthetic route is nowadays more commonly used: oxidation of butane, but butane is also obtained from petroleum fractions and / or natural gas.

Advantageously and surprisingly, the inventors of the present application have implemented a process for the industrial manufacture of maleic anhydride from renewable raw materials.

The process according to the invention makes it possible to overcome at least part of the raw materials of fossil origin and to replace them with renewable raw materials. The maleic anhydride obtained according to the process according to the invention is of such quality that it can be used in all applications in which it is known to use maleic anhydride. In particular, the inventors have shown that it is possible to produce a maleic anhydride of higher purity by implementing the process of the invention, using renewable raw materials, rather than raw materials of origin. fossil.

The invention relates to a process for the manufacture of maleic anhydride comprising the following steps: a) fermentation of renewable raw materials and optionally purification to produce a mixture comprising at least butanol; b) oxidation of butanol to maleic anhydride at a temperature generally of between 300 and 600 ^° C., by means of a catalyst based on vanadium and / or molybdenum oxides; c) isolating the maleic anhydride obtained at the end of step b). The invention also relates to the maleic anhydride obtainable by the process according to the invention, or more generally maleic anhydride obtained from renewable raw materials.

The subject of the invention is also the uses of maleic anhydride.

Other objects, aspects and features of the invention will become apparent on reading the following description.

Stage a) of the process for producing maleic anhydride according to the invention comprises the fermentation of renewable raw materials to produce a mixture comprising at least butanol.

A renewable raw material is a natural resource, for example animal or vegetable, whose stock can be reconstituted over a short period on a human scale. In particular, this stock must be renewed as quickly as it is consumed. For example, vegetable matter has the advantage of being able to be cultivated without their consumption leading to an apparent decrease in natural resources. Unlike materials from fossil materials, renewable raw materials contain ^14C . All carbon samples from living organisms (animals or plants) are actually a mixture of 3 isotopes: ¹² C (representing about 98.892% ), ¹³ C (approximately 1.108%) and ¹⁴ C (traces: 1.2 × ^{10 -10} %) The ¹⁴ C ¹² C ratio of living tissues is identical to that of the atmosphere ¹⁴ C exists in the environment in two main forms: in the form of carbon dioxide (CO ₂ ), and in organic form, that is to say of carbon integrated in organic molecules.

In a living organism, the ¹⁴ C / ¹² C ratio is kept constant by the metabolism because the carbon is continuously exchanged with the external environment. The proportion of ¹⁴ C being constant in the atmosphere, it is the same in the body, as long as it is alive, since it absorbs this ¹⁴ C in the same way as the ¹² C ambient. The average ratio of ¹⁴ C / ¹² C is equal to 1, 2xlθ ^{~ 12} .

¹² C is stable, that is to say that the number of atoms of ¹² C in a given sample is constant over time. ¹⁴ C is radioactive, the number of ¹⁴ C atoms in a sample decreases over time (t), its half-life being equal to 5730 years.

The ¹⁴ C content is substantially constant from the extraction of renewable raw materials, to the manufacture of the maleic anhydride according to the invention and even until the end of the use of said maleic anhydride according to the invention.

Therefore, the presence of ¹⁴ C in a material, and this, whatever the quantity, gives an indication of the origin of the molecules constituting it, namely that they come from renewable raw materials and not from fossil materials .

The amount of ¹⁴ C in a material can be determined by one of the methods described in ASTM D6866-06 (Standard Test Methods for Determining the Biobased Content of Natural Range Materials Using Radiocarbon and Isotope Ratio Mass Spectrometry Analysis).

This standard contains three methods for measuring organic carbon derived from renewable raw materials, referred to in English as "biobased carbon". The proportions indicated for the maleic anhydride of the invention are preferably measured according to the mass spectrometry method or the spectrometric method. liquid scintillation described in this standard and most preferably by mass spectrometry.

These measurement methods estimate the ratio of ¹⁴ C / ¹² C isotopes in the sample and compare it to a ratio of ¹⁴ C / ¹² C isotopes in a material of biological origin giving the 100% standard, in order to measure the percentage of organic carbon of the sample.

Preferably, the maleic anhydride obtained from materials of renewable origin according to the invention comprises a quantity of carbon derived from renewable raw materials greater than 20%, preferably greater than 50% by weight relative to the total mass of carbon of maleic anhydride.

In other words, maleic anhydride can comprise at least 0.24 × 10 ^"10% by weight of ¹⁴ C, and preferably at least 0.6 ^{10" 10} ^14% by weight C.

Advantageously, the amount of carbon derived from renewable raw materials is greater than 60%, preferably greater than 70%, even more preferably 80%.

Such a content may for example be obtained by mixing butanol of petroleum origin and butanol from renewable raw materials.

Butanol of petroleum origin can be obtained for example by hydroformylation of propylene to n-butyraldehyde, followed by hydrogenation to n-butanol. As renewable raw materials, plant materials can be used; materials of animal origin or materials from recovered materials of plant or animal origin (recycled materials).

As plant materials, there are especially sugars, starches and any plant material containing sugars, cellulose, hemicellulose and / or starches. Vegetable materials containing sugars are mainly sugar cane and sugar beet, and maple, date palm, sugar palm, sorghum, American agave; the materials containing cellulose and / or hemicellulose are, for example, wood, straw, maize cobs, grain or fruit cakes, vegetable matter containing starches are essentially cereals and legumes such as maize, wheat, barley, sorghum, rye, wheat, rice, potatoes, cassava, sweet potatoes and seaweeds.

Among the materials from recovered materials, mention may be made of vegetable or organic waste comprising sugars and / or starches and also any fermentable waste.

Advantageously, low quality raw materials may be used such as frozen potatoes, cereals contaminated with mycotoxins or surplus sugar beet, or cheese whey. Preferably renewable raw materials are plant materials.

As renewable raw materials, it is also possible to use cellulose and / or hemicellulose which, in the presence of the appropriate microorganisms, can be converted into materials comprising sugar in particular at 5 and 6 carbon atoms.

Among these renewable materials are straw, wood, paper, which can advantageously come from recovered materials.

The fermentation of renewable materials is carried out in the presence of one or more suitable microorganisms, this microorganism may possibly have been modified naturally by a chemical or physical constraint, or genetically mutant. Conventionally the microorganism used is a Clostridium, advantageously it will be Clostridium acetobutylicum or one of its mutants. The lists presented above are not exhaustive.

The fermentation step may also be preceded by a step of hydrolysis of the raw materials by means of a cellulase enzyme or a complex of several cellulase enzyme. Fermentation usually leads to the production of a mixture of products, typically the production of butanol is accompanied by an acetone production.

Thus, advantageously, the fermentation step a) is followed by an isolation step of butanol. This isolation of butanol generally consists of a separation of the different products of the reaction for example by heteroazeotropic distillation. This separation can also be followed by distillation to obtain butanol in more concentrated form. Another advantage of the process according to the invention is its energy saving: the fermentation step and the possible hydrolysis step of the process according to the invention are carried out at low temperatures. Their energy cost is also low compared to the cost of extracting butane or benzene.

This energy saving is also accompanied by a decrease in the amount of CO ₂ emitted into the atmosphere.

Advantageously, step b) is carried out from n-butanol.

A step for separating n-butanol from other isomers can also be provided. Nevertheless, an advantage of the process is that the fermentation leads to a smaller number of isomers of butanol than the chemical pathway of hydroformylation of propylene. Butanol obtained by fermentation of renewable raw materials is particularly suitable for carrying out the process according to the present invention. In particular, the inventors have shown in Example 1 that n-butanol resulting from a fermentation of renewable raw materials according to step a) has a lower isobutanol / n-butanol ratio to purified butanol from raw materials. fossils, even before the possible step of isolation of n-butanol. Isobutanol and n-butanol, have very close physicochemical properties, so that a separation of these products is expensive. The provision of n-butanol, low in isobutanol at the end of step a) therefore constitutes a major economic advantage for the process that is the subject of the invention, since it makes it possible to produce maleic anhydride of excellent quality at lower cost. (Examples 2 and 3)

In addition, the impurities contained in the mixture obtained after step a), such as butanal, butan-2-ol, n-butylacetate, but-2-en-1-ol and the 1,1 dibutoxybutane lead, at least partially to obtain maleic anhydride, when subjected to the oxidation step b). This is therefore still a major economic advantage for the process object of the invention, since it allows to produce a maleic anhydride of excellent quality at a lower cost by avoiding steps of purification of these impurities.

In step b) is carried out the oxidation of the butanol obtained to produce a gas mixture comprising maleic anhydride.

Oxidation of butanol is carried out in a suitable reactor by passing the gas comprising said butanol over an oxidation catalyst at a temperature generally of between 300 and 600 ^° C. Preferably, this reaction is carried out in the presence of air or another gas comprising molecular oxygen, more preferably, the air or other gas comprising molecular oxygen is present in a large excess.

The catalysts used are generally catalysts based on vanadium and / or molybdenum oxides. These catalysts can be activated by addition of chromium oxides, cerium and / or phosphorus or by other conventional activators. The catalyst may be solid or deposited or coated on a suitable support shaped by atomization or directly deposited on at least one wall of the reactor.

The reaction can be carried out in a fixed bed, in a fluidized bed, or in a circulating fluidized bed.

According to a first variant, use will be made of a catalyst which is a mixture of molybdenum trioxide, of substantially amorphous titanium dioxide and optionally of tungsten trioxide, said oxides being present in proportions ranging from 1 to 8 moles of titanium dioxide for 3 moles of molybdenum trioxide and for 0 to 1 moles of tungsten trioxide. Preferably, the specific surface area of the titanium dioxide is greater than 150 m ² / g, preferably between 150 and 250 m ² / g. This first variant is generally carried out at a temperature between 450 ⁰ C and 600 ⁰ C, it has the further advantage of leading to an adiabatic vapor phase reaction.

According to a second variant, use will be made of a VPO catalyst which is at least a mixture of vanadium and phosphorus oxide, and optionally of silica, and the reaction will be carried out at a temperature of between 300 ^° C. and 600 ^° C., preferably between 350 ⁰ C and 500 ⁰ C. The process according to the second variant can also be carried out at a temperature of between 280 ^° C. and 300 ^° C. In this case, phthalic anhydride will also be advantageously synthesized.

According to a third variant, use will be made of a bismuth molybdate catalyst which is a mixture comprising oxides of molybdenum and of bismuth and the reaction will be carried out at a temperature of between 300 ^° C. and 600 ^° C., preferably between 350 ^° C. and 500 ^° C.

According to a fourth variant, use will be made of a catalyst containing at least molybdenum or vanadium which is a mixture comprising oxides of molybdenum and vanadium and the reaction will be carried out at a temperature of between 250 ^° C. and 600 ^° C., preferably between 350 ⁰ C and 500 ⁰ C.

Step c) of the process concerns the isolation of the maleic anhydride obtained at the end of step b). In particular when step b) is carried out according to the second variant above at a temperature of between 280 ^° C. and 300 ^° C., step c) will comprise a step of separating the maleic anhydride and the phthalic anhydride.

The present invention relates to compositions comprising maleic anhydride obtained from materials of renewable origin and uses of maleic anhydride obtained from renewable materials. In particular, the present invention relates to the use of maleic anhydride obtained from renewable source materials for the manufacture of polymers and for the manufacture of structure comprising at least one layer of these polymers.

In particular, the present invention relates to the manufacture of the following polymers:

random copolymers of maleic anhydride with olefins preferably with ethylene and / or propylene, random terpolymers of maleic anhydride, of olefins, preferably ethylene and / or propylene, and of a comonomer chosen from alkyl acrylate, alkyl methacrylate or vinyl ester,

"copolymers of styrene and maleic anhydride (in solution, in the form of resins or flakes),

polyolefins, preferably polyethylene and / or polypropylene, grafted with maleic anhydride monomers,

"fluoropolymers grafted with maleic anhydride monomers,

"polyesters grafted with maleic anhydride monomers, these polymers comprising maleic anhydride at least partly obtained from renewable materials ,.

In particular, the fluoropolymers grafted with maleic anhydride monomers are obtained by the process described in application EP 1 484 346, this patent application does not mention the use of maleic anhydride obtained from source materials. renewable. The fluoropolymers grafted with maleic anhydride monomers are obtained by the following method: a) a melt fluoropolymer is mixed with maleic anhydride, b) the mixture obtained in a) is formed into films (c) the products of step b) are exposed, in the absence of air, to photon (γ) or electron (β) irradiation at a dose of between 1 and 15 Mrad, d) the product obtained in c) is optionally treated to remove all or part of the maleic anhydride which has not been grafted onto the fluoropolymer.

In particular, the polyesters grafted with maleic anhydride monomers are obtained by the method described in application WO 97/47670, this patent application does not mention the use of maleic anhydride obtained from renewable source materials. . Polyesters grafted with maleic anhydride monomers are obtained by an addition or substitution reaction of maleic anhydride on a polyester. Maleic anhydride obtained from materials of renewable origin is also advantageously used to prepare 1,4-butanediol and / or γ-butyrolactone and / or tetrahydrofuran.

A process for the preparation of these compounds comprises the esterification of maleic anhydride obtained from materials of renewable origin with an alcohol comprising 1 to 5 carbon atoms, advantageously methanol or ethanol, to obtain the diester. For example with methanol, dimethyl maleate is obtained.

Generally distillation is used to isolate the diester.

Hydrogenation of dimethyl maleate by an excess of hydrogen at 140 ^° C. and 14 bar on a palladium / alumina catalyst leads to the formation of dimethyl succinate.

The selective hydrogenation of dimethylsuccinate on a copper / zinc oxide catalyst at about 225 ° C leads to the formation of γ-butyrolactone.

The conversion of γ-butyrolactone to tetrahydrofuran is carried out by catalytic dehydration on a silica-alumina catalyst with a high specific surface area in the presence of hydrogen at approximately 200 ^° C.

The hydrogenation of γ-butyrolactone in the presence of an excess of hydrogen over a copper / zinc oxide catalyst at an elevated temperature above 200 ^° C. leads to the formation of 1,4-butanediol.

Example 1 Analysis of Butanol Resulting from Fermentation and Butanol Resulting from Fossil Raw Materials

The analysis of butanol from fermenting renewable raw materials and butanol from fossil raw materials is illustrated in Table 1 below. Table 1

Example 2

Preparation of the Catalyst A. The VPO type catalyst A was prepared as described in the patent application US4769477 (DuPont). Vanadium oxide is reacted with 100% orthophosphoric acid, with a P / V ratio of 1.16, in a mixture of benzyl alcohol and isobutanol at reflux for 16 hours. The blue solid obtained is isolated by filtration, washed with isobutanol and acetone, dried in air at 110 ^° C. overnight.

1 gram of precursor with a particle size of 200 to 360 microns is placed in a microreactor, and activated in situ at 435 ^° C., in a flow of 1.2% of n-butane in air. The gas flow rate is 40 ml / minute and the effluents are collected periodically, to ensure the stability of the catalyst. After 2 weeks, the catalyst reaches a state of equilibrium. The temperature is then reduced to 360 ^° C., and the butanol is injected into the air stream via a high-precision pump. Example 2a (Comparative): Use of Petrochemical Butanol Containing 0.0960% Isobutanol The effluent is collected and analyzed. The yield of maleic anhydride is 45%, and the content of methacrolein + methacrylic acid relative to maleic anhydride is 180 ppm. Example 2b (Invention): Use of Fermentation Butanol Containing 0.0660

% isobutanol. The effluent is collected and analyzed. The yield of maleic anhydride is 45%, and the content of methacrolein + methacrylic acid relative to maleic anhydride is 100 ppm.

Example 3

Preparation of catalyst B. Catalyst B is prepared as in the preceding example, but with a P / V ratio of 1.15, and by adding Bismuth nitrate together with vanadium oxide, in a ratio of V of 0.1. In this case, the precursor in addition to the VOHPO ₄ -O ₅ SH ₂ O phase, contains a BiPO ₄ phase. The catalyst is activated in a flow of 1.7% butane in air. After activation, the catalyst contains the (VO) ₂ P ₂ Oy and BiPO ₄ phases. Butanol is fed into the air stream to have a butanol partial pressure of 1%. At about 360 ⁰ C the yield of maleic anhydride is between 50 and 60%. By progressively increasing the temperature, it is possible to note intermediately between 250 and 350 ^° C., phthalic anhydride yields of between 10 and 20%.

Example 3a (Comparative): In this example a partially purified petrochemical n-butanol containing about 1.5% isobutanol is used. The yield of maleic anhydride is 55%, and the ratio between the content of methacrolein + methacrylic acid and maleic anhydride is 2630 ppm. Example 3b (Invention) In this example, butanol obtained from the fermentation is used as in Example 2b. The yield of maleic anhydride is 57% and the ratio between the content of methacrolein + methacrylic acid and maleic anhydride is 90 ppm.

Claims

13REVENDICATIONS

A process for the manufacture of maleic anhydride comprising the following steps: a) fermentation of renewable raw materials and optionally purification to produce a mixture comprising at least butanol; b) oxidation of butanol to maleic anhydride at a temperature generally of between 300 and 600 ^° C., by means of a catalyst based on vanadium and / or molybdenum oxides; c) isolating the maleic anhydride obtained at the end of step b).

2. A method of manufacturing maleic anhydride according to claim 1, characterized in that the renewable raw materials are vegetable materials selected from sugar cane and sugar beet, maple, date palm, sugar palm , sorghum, American agave, maize, wheat, barley, sorghum, rye, wheat, rice, potato, cassava, sweet potato, straw, wood, paper, seaweed.

3. A method of manufacturing maleic anhydride according to claim 1 or 2 characterized in that the fermentation step a) is followed by an isolation step of butanol.

4. Maleic anhydride obtained from renewable materials characterized in that it comprises a quantity of carbon derived from renewable raw materials greater than 20%, preferably greater than 50% by weight relative to the total mass of carbon maleic anhydride.

5. A composition comprising maleic anhydride according to claim 4 or prepared according to the method according to one of claims 1 to 3.

6. Use of maleic anhydride according to claim 4 or prepared according to the process according to one of claims 1 to 3, for the manufacture of polymers. 14

7. Use of maleic anhydride according to claim 6 characterized in that the polymers are random copolymers of maleic anhydride with olefins preferably with ethylene and / or propylene.

8. Use of maleic anhydride according to claim 6 characterized in that the polymers are random terpolymers of maleic anhydride, olefins preferably ethylene and / or propylene and a comonomer selected from alkyl acrylate , alkyl methacrylate or vinyl ester.

9. Use of maleic anhydride according to claim 6 characterized in that the polymers are copolymers of styrene and maleic anhydride.

10. Use of maleic anhydride according to claim 6 characterized in that the polymers are polyolefins, preferably polyethylene and / or polypropylene, grafted with maleic anhydride monomers.

11. Use of maleic anhydride according to claim 6 characterized in that the polymers are fluoropolymers grafted with maleic anhydride monomers.

12. Use of maleic anhydride according to claim 6 characterized in that the polymers are polyesters grafted with maleic anhydride monomers.

13. Use of a polymer according to any one of claims 6 to 12 for the manufacture of a structure comprising at least one layer of one of these polymers.

14. Use of maleic anhydride according to claim 4 or prepared according to the process according to one of claims 1 to 3, to prepare 1,4-butanediol and / or γ-butyrolactone and / or tetrahydrofuran.