Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D307/60—Two oxygen atoms, e.g. succinic anhydride
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
  • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
  • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
  • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E50/00—Technologies for the production of fuel of non-fossil origin
  • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

• the present invention relates to a process for producing maleic anhydride from renewable raw materials.
• 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.
• 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.
• 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.
• 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.
• 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 .
• 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, 2xl ⁇ ⁇ 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.
• 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.
• 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.
• 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.
• 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.
• plant materials can be used; materials of animal origin or materials from recovered materials of plant or animal origin (recycled materials).
• 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.
• low quality raw materials may be used such as frozen potatoes, cereals contaminated with mycotoxins or surplus sugar beet, or cheese whey.
• renewable raw materials are plant materials.
• 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.
• renewable materials are straw, wood, paper, which can advantageously come from recovered materials.
• microorganisms may possibly have been modified naturally by a chemical or physical constraint, or genetically mutant.
• the microorganism used is a Clostridium, advantageously it will be Clostridium acetobutylicum or one of its mutants.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• VPO catalyst which is at least a mixture of vanadium and phosphorus oxide, and optionally of silica
• 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.
• phthalic anhydride will also be advantageously synthesized.
• 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.
• 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).
• 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.
• 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.
• the present invention relates to the manufacture of the following polymers:
• 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
• polymers grafted with maleic anhydride monomers these polymers comprising maleic anhydride at least partly obtained from renewable materials ,.
• 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 ( ⁇ ) or electron ( ⁇ ) 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.
• 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 ⁇ -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.
• an alcohol comprising 1 to 5 carbon atoms, advantageously methanol or ethanol, to obtain the diester.
• methanol dimethyl maleate is obtained.
• the conversion of ⁇ -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.
• 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.
• Example 2a (Comparative): Use of Petrochemical Butanol Containing 0.0960% Isobutanol The effluent is collected and analyzed.
• 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.
• 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%.
• 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.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Preparation Of Compounds By Using Micro-Organisms (AREA)
• Catalysts (AREA)
• Polyesters Or Polycarbonates (AREA)
• Furan Compounds (AREA)
• Graft Or Block Polymers (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=40292573

Family Applications (1)

Country Status (7)

Families Citing this family (8)

Family Cites Families (11)

• 2008
  • 2008-07-18 FR FR0854896A patent/FR2933978B1/fr not_active Expired - Fee Related
• 2009
  • 2009-07-17 BR BRPI0916246-1A patent/BRPI0916246A2/pt not_active IP Right Cessation
  • 2009-07-17 JP JP2011517985A patent/JP2011528340A/ja active Pending
  • 2009-07-17 WO PCT/FR2009/051426 patent/WO2010007327A2/fr active Application Filing
  • 2009-07-17 CN CN2009801267093A patent/CN102089293A/zh active Pending
  • 2009-07-17 EP EP09737075A patent/EP2318386A2/fr not_active Ceased
  • 2009-07-17 US US13/003,083 patent/US8394973B2/en not_active Expired - Fee Related

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events