WO2008110468A1 - Procédé de production d'acide acétique et d'acide formique par oxydation en phase gazeuse d'éthanol - Google Patents

Procédé de production d'acide acétique et d'acide formique par oxydation en phase gazeuse d'éthanol Download PDF

Info

Publication number
WO2008110468A1
WO2008110468A1 PCT/EP2008/052499 EP2008052499W WO2008110468A1 WO 2008110468 A1 WO2008110468 A1 WO 2008110468A1 EP 2008052499 W EP2008052499 W EP 2008052499W WO 2008110468 A1 WO2008110468 A1 WO 2008110468A1
Authority
WO
WIPO (PCT)
Prior art keywords
mixture
solvent
formic acid
water
component
Prior art date
Application number
PCT/EP2008/052499
Other languages
German (de)
English (en)
Inventor
Christoph RÜDINGER
Hans-Jürgen EBERLE
Harald Voit
Original Assignee
Wacker Chemie Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wacker Chemie Ag filed Critical Wacker Chemie Ag
Publication of WO2008110468A1 publication Critical patent/WO2008110468A1/fr

Links

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers

Definitions

  • the invention relates to a process for the preparation of acetic and formic acid by gas phase oxidation of ethanol with oxygen using a catalyst in a cyclic process.
  • acetic acid can be prepared by gas phase oxidation of ethanol by means of catalysts.
  • Vanadium and / or molybdenum and titanium oxides So far, however, no economically and operationally fully satisfactory method could be found.
  • Acetaldehyde from ethanol by gas phase oxidation with oxygen on a vanadium oxide catalyst Acetaldehyde from ethanol by gas phase oxidation with oxygen on a vanadium oxide catalyst.
  • US 5,840,971 describes a process for the production of acetic acid by oxidation of ethanol with oxygen using VTi y O x catalysts.
  • a yield of 84% and a maximum acetic acid production of 356 g per liter of catalyst and hour is achieved.
  • the crude acid is obtained as an aqueous solution.
  • the concentration and purification of the thus obtained crude acid, the removal of acetaldehyde and especially the economic separation of formic acid is not described.
  • a disadvantage of the process is the high pressure drop in the reactor and the low acetic acid concentration in the reaction gas, which requires expensive apparatus for operation and product isolation.
  • BR 19960315 and BR 9601959 similarly describe US 5,840,971 processes for the production of acetic acid by oxidation of ethanol with oxygen using VTi y O x catalysts inter alia on a silicon carbide support.
  • VTi y O x catalysts inter alia on a silicon carbide support.
  • EP 0294846 describes a process for the catalytic
  • Oxidation of an alcohol by means of a Mo x V y Z z catalyst gives as by-products ethylene and ethane and only a low acetic acid yield. There is no information about an economical processing of the products.
  • a disadvantage of all these processes and catalysts is poor controllability of the oxidation reaction and the low cost of acetic acid production or acetic acid workup at high space-time performance.
  • acetic and formic acid by gas phase oxidation is particularly economical when catalysts and in particular shell catalysts are used, in which the active composition is applied as a thin layer on a nonporous carrier body, and ethanol-containing starting material and pure oxygen are used in a circulation process and the separated from this cycle via water absorption raw or dilute acid prepared by a special integrated process and separated into the two pure target products acetic and formic acid.
  • the invention relates to a process for the preparation of acetic acid and formic acid by gas phase oxidation of mixtures containing ethanol or ethanol in the presence of oxygen over a catalyst comprising a) a component I of one or more oxides of the
  • Alumina and b. A component II containing 0.1 to 1.5% by weight, based on the weight of component I and per m 2 / g specific surface area of component I,
  • Vanadium pentoxide wherein the process is carried out in a circulatory system, and the resulting crude acid is separated by water absorption from the circulation and this aqueous phase is then separated by an extraction and several distillation steps in pure acetic and formic acid.
  • the inventive method provides in contrast to the methods known from the prior art equally high acid yields and thus good raw material utilization, high crude acid concentrations, which are reflected in low processing costs and at the same time an increased volume-related acid productivity (high space / time performance), which in turn reflected in lower equipment costs.
  • the process according to the invention is preferably suitable for the preparation of acetic acid and formic acid.
  • a significant advantage of the procedure according to the invention is that, in the production of acetic acid, the by-products formed thereby in small amounts are obtained as valuable substances, especially in the form of formic acid.
  • the intermediate formic acid portion is largely decomposed and there are CO and CO2, which must be disposed of.
  • Ethanol is a readily available, industrially produced chemical. Usually, ethanol is produced by fermentation of biological sugars and / or starch and / or cellulose-containing, generally carbohydrate-containing vegetable raw materials.
  • inventive method is equally suitable for the use of pure ethanol, ethanol-containing mixtures and / or ethanol-containing crude products as Eduktstrom and thus ethanol as a partial or sole
  • Carbon source for the gas phase oxidation Preference is given to using particularly inexpensive water-containing ethanol mixtures which can be produced with less energy expenditure and have a water content of between 4 and 96% by weight of water, preferably between 10 and 90% by weight, more preferably with a water content of between 20 and 80% by weight. , Due to the particular insensitivity of the process to impurities in the feed, it is also possible to use undistilled, only mechanically clarified, ethanol-containing aqueous solutions or fermentation broths as raw material for the process.
  • the reaction temperature of the gas-phase oxidation is generally from 100 0 C to 400 0 C, preferably 150 ° C to 300 0 C, particularly preferably 180 ° C to 250 ° C.
  • the reaction is generally carried out at pressures between 1.2 * 10 5 and 51 * 10 5 Pa, preferably between 3 * 10 5 and 21 * 10 5 Pa, more preferably between 4 * 10 5 and 12 * 10 5 Pa.
  • Suitable catalysts for the process according to the invention are all catalysts which are generally described for the partial oxidation of alcohols.
  • mixed oxide catalysts containing vanadium oxides are used.
  • Particularly preferred are mixed oxide materials which
  • component a) may also contain one or more oxides of the metals from the group boron, silicon, hafnium, niobium, tungsten, lanthanum and cerium. In the doping of component a) with the oxides mentioned, these are generally present in an amount of from 1 to 30% by weight, based on the total weight of component a).
  • component b a part of the vanadium pentoxide, preferably 10 to 90 wt .-%, be replaced by one or more oxides of molybdenum, chromium and antimony, and / or as additional component b) one or more oxides of alkali metals, Alkaline earth metals, elements of the 5th and 6th main group of the Periodic Table of the Elements (PSE) and the transition metals to be included.
  • PSE Periodic Table of the Elements
  • the amount of these dopants 0.005 to 15 wt .-%, calculated as oxides and based on the total weight of component b).
  • compositions having a high surface area of component a) of from 40 to 300 m 2 / g Preference is given to compositions having a high surface area of component a) of from 40 to 300 m 2 / g, it being possible where appropriate for tin, niobium or tungsten oxide to be present, and to a component b) which reacts with Mo, and / or Cr, and / or Sb and / or Au is doped.
  • the catalytically active mixed oxide composition may optionally contain from 10 to 50% by weight, based on the total weight of the catalytically active mixed oxide composition, of inert diluents from the group comprising silicon dioxide, silicon carbide and graphite.
  • the catalytically active composition is preferably applied as a supported shell catalyst on an unsporous support.
  • the catalytically active mixed oxide composition is preferably applied in a proportion of 1 to 40 wt .-%, preferably 5 to 25 wt .-%, each based on the total weight of carrier body and active mass, as a shell on the outer surface of the carrier body.
  • the layer thickness is preferably 10 to 2000 .mu.m, in particular 100 to 1000 microns.
  • the shell catalyst may also contain multiple layers differing in composition. It is also possible for one or more components of the active components a) and b) to be present in different concentrations in the individual layers.
  • the inner layer contains only component a) and the outer layer contains components a) and b).
  • a conceivable embodiment is a multilayer coated catalyst, wherein the inner and the outer layer each contain the components a) and b) and for the inner layer, a higher specific surface area is selected for the component a) than for the outer layer.
  • Suitable materials for the inert, non-porous carrier body are generally all inert under the operating conditions of the gas phase oxidation and on the
  • Non-porous materials include steatite, Duranit, silicon carbide, magnesium oxide, silica, silicates, aluminates, metals such as stainless steel, and optionally mixtures of these substances.
  • ceramic materials such as steatite.
  • the shape of the inert, non-porous carrier body of the shell catalyst is arbitrary.
  • suitable Shapes are spheres, cylinders, hollow cylinders, cuboids, tori, saddles, spindles, helices.
  • the basic body can also have one or more recesses, such as depressions, grooves, holes, or protruding parts, such as pins, tips, webs.
  • Other examples are rings, ring segments, bar rings, pierced balls, spherical segments.
  • suitable as carriers are ordered packings, such as monoliths or cross-channel structures. Carrier shapes with the highest possible geometric surface area per volume, for example rings or hollow cylinders, are preferred. In a particularly preferred
  • the inert support body have the form of hollow cylinders, which have one or more notches on the upper and / or lower flat side of the hollow cylinder walls, so that the interior of the hollow cylinder is connected to the cavities surrounding the hollow spaces via openings.
  • the dimensions of the carrier bodies are generally predetermined by the reactors for gas phase oxidation.
  • the shaped bodies have a length or a diameter of 2 to 20 mm.
  • the wall thickness for example in the case of rings or hollow cylinders, is advantageously 0.1 to 4 mm.
  • reactors for carrying out the process according to the invention it is generally possible to use embodiments which are suitable for carrying out oxidation reactions in the gas phase and are capable of removing the high heat of reaction without excessively heating the reaction mixture.
  • the process according to the invention can be carried out continuously or intermittently, that is to say the feed of the reactor input mixture can be carried out with a constant feed or with a cyclically varying feed composition.
  • the gas mixture may preferably be attached to the catalyst in a Fixed bed, for example, react in a tube-bundle reactor or tray reactor, or in a fluidized bed or fluidized bed.
  • cooled tube bundle reactors with a fixed catalyst bed.
  • Particular preference is given to designs with tube bundles arranged individual tubes with an inner tube diameter of 10 mm to 50 mm and a tube length of 1 m to 6 m.
  • the flow rate in the reaction tubes is generally between 0.1 m / s and 10 m / s, preferably between 0.3 m / s and 5 m / s, more preferably 0.5 to 3 m / s.
  • the reaction tubes can be filled with catalyst of different composition, shape and dimension.
  • the filling may preferably be introduced into the reaction tubes in a homogeneous or zone-wise manner in the axial direction.
  • Each zone may preferably contain a randomly diluted or mixed catalyst.
  • the source of oxygen necessary for gas phase oxidation is generally an oxygen-containing gas.
  • oxygen-containing gas e.g. Air
  • oxygen-enriched air preferably oxygen-enriched air
  • an inert gas preferably nitrogen and / or argon, may additionally be present.
  • an inert gas of 0 to 25 vol .-% can be supplied.
  • the volume fraction of water vapor of the reactor input gas fed to the reactor is generally from 0 to 80% by volume, preferably from 1 to 40% by volume, particularly preferably from 3 to 30% by volume, of water vapor.
  • the proportion of ethanol in the reaction gas, measured at the reactor inlet, is generally 0.1 to 20% by volume, preferably 0.3 to 10% by volume, particularly preferably 0.5 to 3.0% by volume.
  • the process according to the invention is operated with gas recirculation as circulation process.
  • the proportion of carbon oxides and further reaction by-products in the reactor input gas depends on the reaction regime and acid separation and is generally from 0 to 95% by volume, preferably 10 to 95% by volume, particularly preferably 55 to 85% by volume.
  • Reactor input gases add up to 100% by volume in each case.
  • Gas passage through the reactor and circulation process can be used.
  • high boilers such as the carboxylic acids acetic and formic acid
  • the crude acid from the reaction starting gas is preferably separated off with a countercurrent wash, direct current wash, crossflow wash, quench cooling, partial condensation or a combination of these processes. Further details on preferred embodiments are described in EP 0960875 and EP 1035101, the disclosures of which are intended to be part of this application and hereby incorporated by reference.
  • the reaction gas cycle is carried out so that the reaction starting gas, either the reactor leaving or the recirculated gas mixture, a portion of the resulting in the gas phase oxidation acetic acid and formic acid, via a partial condenser or a countercurrent wash with a suitable solvent, preferably water, a portion of acids and other compounds is withdrawn.
  • a suitable solvent preferably water
  • the separation is carried out so that the partial pressure of these acids at the reactor inlet remains low, unreacted ethanol and further convertible intermediates such as acetaldehyde, ethyl acetate, methyl acetate, ethyl formate, methyl formate, etc. but mostly remain in the recycle gas and are returned to the reactor inlet.
  • one part of the reactor outlet gas generally from 60 to 99.8% by weight, preferably from 90 to 99.5% by weight, to remove the acid fraction up to the abovementioned residual acid content, and then this part the reactor outlet gas is returned to the reactor.
  • the untreated portion of the reactor exit gas is discarded and may be flared, for example.
  • the proportion of untreated reactor starting gas depends on how much carbon oxides CO x have been formed because they have to be removed via this branch stream. They can then be disposed of by incineration.
  • the recirculated gas mass flow is generally between 1 and 100 times the freshly fed Eduktmassenstroms, preferably between 10 times and 80 times, more preferably between 30 to 60 times.
  • the water vapor content of the gas stream exiting the absorber is generally determined by the temperature prevailing at the absorber outlet and the operating pressure.
  • the temperature is usually determined by the amount of heat removed from the absorber and the amount and temperature of the washing water stream and is generally from 50 0 C to 200 0 C.
  • the remaining acid content in the gas stream leaving the absorber is generally about pressure and temperature , the number of separation stages of the absorber and the amount of absorbent supplied (water supply).
  • the process is carried out so that the residual acid concentration of the recycled back into the reactor gas stream is reduced to 0.01 to 12 vol .-%, preferably 0.1 to 8 vol .-% by countercurrent washing.
  • the separated crude acid is generally removed by suitable conventional methods alone or in combination, such as
  • Membrane separation process drained and cleaned.
  • the low boilers separated off before further fractionation of the crude acid into its pure substances can likewise be recycled, in whole or in part, into the gas phase reactor, either alone or together with low boilers from the purification and concentration.
  • Cost-optimized processes such as those described in DE 19934411, DE 19934410 and German patent application DE 10065466, are particularly suitable for working up the diluted crude acid Revelations should be part of this application. These are hereby incorporated by reference.
  • a preferred method for the separation and purification of the dilute crude acid, an aqueous mixture of the main components low boilers, acetic acid, formic acid and high boilers is the extraction, by means of a solvent, preferably one or more compounds from the group consisting of ethers, esters, ketones and alcohols, especially preferably one or more compounds selected from the group comprising methyl tertiary butyl ether, diisopropyl ether, methyl secondary butyl ether, methylcyclopentyl ether, ethyl butyl ether, ethyl acetate and isopropyl acetate in a circular process, characterized in that the raffinate stream with a large part of the water
  • Solvent stripper is fed to the elimination of the water and the extract stream is passed into a solvent distillation column, from the top in a first step, a mixture (A) consisting of water and solvent, over the bottom of a mixture (B) consisting of acetic acid, formic acid and High boilers is separated, the mixture (B) after removal of the formic acid in a optionally equipped with side draw column then in a
  • Acetic acid distillation column is separated into pure acetic acid and high boilers, and the mixture (A) is fed to a phase separator, wherein the aqueous phase is recycled with residual amounts of solvent to the solvent stripping column, and the organic phase to the extractor.
  • Another preferred process is the extraction, by means of a solvent, preferably one or more compounds from the group consisting of ethers, esters, ketones and alcohols, more preferably one or more compounds from the group comprising methyl tertiary butyl ether, diisopropyl ether, ethyl butyl ether, cyclopentyl methyl ether, methyl 2- butyl ether, ethyl acetate and isopropyl acetate in a circular process, characterized in that the raffinate stream is supplied with a large part of the water to a solvent stripper column for the elimination of the water and the extract stream is passed into a solvent distillation column, from which in a first step overhead a mixture (A) with a large part of the solvent, from a side draw a mixture (B) consisting of formic acid, water and solvent and on the bottom a mixture (C) consisting of acetic acid and high boilers are separated, and for further processing, the mixture (B) in
  • Formic acid distillation column is transferred, and the mixture (C) is transferred to an acetic acid distillation column, then in the Essigklaredestillationskolonne overhead the pure acetic acid is isolated, in the formic acid distillation column at the bottom of the pure
  • Formic acid is isolated and removed overhead a mixture of solvent and water, which is recycled together with the mixture (A) after separation of the water content, in the extractor.
  • Another preferred method is the extraction, by means of a solvent, preferably one or more compounds from the group consisting of ethers, esters, ketones, hydrocarbons and alcohols, particularly preferably one or more compounds from the group comprising methyl tertiary butyl ether,
  • Solvent distillation column is passed from the first step in a mixture (A) consisting of water and solvent, over the bottom of a mixture (B) consisting of acetic acid, formic acid and high boilers is separated, the mixture (B) after separation of the Formic acid in a column using an adjuvant in the manner of azeotropic distillation then in a Acetic acid distillation column is separated into pure acetic acid and high boilers, and the mixture (A) is fed to a phase separator, wherein the resulting aqueous phase with residual amounts of solvent of the solvent stripper column and the organic phase is returned to the extractor.
  • the resulting in the concentration and purification of the crude acid water is partially, optionally after a chemical and / or physical treatment, fed back into the countercurrent absorption.
  • the excess water from the feed and the small amount of total oxidation, which still contains very small amounts of acetic and formic acid, can be disposed of easily via a biological treatment plant.
  • Figures 1 and 2 describe in a schematic representation apparatus for the production of acetic and formic acid by gas phase oxidation of ethanol by the novel process with complete or partial recycling of the reaction starting gas.
  • the crude acid is separated off, preferably by a countercurrent absorption by means of a solvent.
  • the preferred solvent is water.
  • oxygen and ethanol-containing feed stream is mixed with the recirculated gas stream via a mixing zone (1) and together with this fed to the tube bundle reactor (2), which is cooled by means of circulation cooling (3).
  • the gas mixture leaving the reactor is passed in the main stream through a gas cooler (4) which is cooled by a circulation cooler (5).
  • the reaction gas is passed into an absorption column (6) which is filled with one or more
  • Catalyst The preparation of the catalyst used was carried out analogously to DE-19649426, characterized in that the active composition consists of oxides of titanium, vanadium, molybdenum and antimony of the empirical formula Ti a V b Mo c Sb d O e (a: 256; b: 27, c: 4, d: 20, e: 611) and in a proportion of 20% by weight, based on the weight of the carrier, of steatite rings of Dimension 3.8mm outside diameter * 2mm inside diameter * 2.7mm height is applied.
  • the catalyst was introduced with a filling height of 3000 mm.
  • the oxygen content at the reactor inlet was automatically controlled by the addition of pure oxygen at the reactor inlet to 8 vol .-%.
  • the reaction feed was 95.6 g of ethanol in the recycle gas flow direction directly after the column overhead condenser of the absorption column and 502 g / h of water in the recycle gas flow direction directly in front of the column overhead condenser of the absorption column, corresponding to a water / ethanol reaction.
  • the acid separation from the reaction gas was carried out by absorption in a countercurrent absorber with structured packing, an inner diameter of 43 mm and a packing height of 3240 mm at a head temperature of the absorber of 130 ° C.
  • the acetic acid selectivity with respect to the conversion was 86 mol%
  • the formic acid selectivity with respect to the conversion was 9 mol%.
  • the volume specific acetic acid productivity was 200 g / lh.
  • the crude acid contained 80 wt .-% water.
  • the low boiler content (boiling point lower than water) in the crude acid was below 0.3 wt .-%.
  • the high boiler fraction (boiling point higher than acetic acid) in the Crude acid was below 0.01 wt .-%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de production d'acide acétique et d'acide formique par oxydation en phase gazeuse d'éthanol ou de mélanges contenant de l'éthanol en présence d'oxygène sur un catalyseur, contenant a.) un constituant I composé d'au moins un oxyde du groupe comportant oxyde de titane, dioxyde de zirconium, dioxyde d'étain, oxyde d'aluminium et b.) un constituant II contenant 0,1 à 1,5 % en poids, par rapport au poids du constituant I et par surface spécifique m2/g du constituant I, pentoxyde de vanadium, le procédé étant réalisé dans un système de recyclage, et les acides bruts générés étant séparés du circuit par absorption d'eau et ces phases aqueuses étant ensuite séparées en acide acétique et acide formique purs par des étapes d'extraction et plusieurs étapes de distillation.
PCT/EP2008/052499 2007-03-12 2008-02-29 Procédé de production d'acide acétique et d'acide formique par oxydation en phase gazeuse d'éthanol WO2008110468A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007011847.5 2007-03-12
DE102007011847A DE102007011847A1 (de) 2007-03-12 2007-03-12 Verfahren zur Herstellung von Essig- und Ameisensäure durch Gasphasenoxidation von Ethanol

Publications (1)

Publication Number Publication Date
WO2008110468A1 true WO2008110468A1 (fr) 2008-09-18

Family

ID=39410028

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2008/052499 WO2008110468A1 (fr) 2007-03-12 2008-02-29 Procédé de production d'acide acétique et d'acide formique par oxydation en phase gazeuse d'éthanol

Country Status (2)

Country Link
DE (1) DE102007011847A1 (fr)
WO (1) WO2008110468A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120071687A1 (en) * 2010-09-16 2012-03-22 Basf Se Process for preparing acrylic acid from ethanol and formaldehyde
US8440855B2 (en) 2009-12-08 2013-05-14 Haldor Topsoe A/S Process for the production of acetic acid ethylene and vinyl acetate monomer

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2747561C1 (ru) * 2020-04-03 2021-05-06 Акционерное общество "Специальное конструкторско-технологическое бюро "Катализатор" Катализатор для получения муравьиной кислоты и способ его приготовления (варианты)
CN116003247B (zh) * 2022-12-30 2024-06-21 上海太和水科技发展股份有限公司 一种ZrO2催化氧化甲壳素制备有机酸的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19649426A1 (de) * 1996-11-28 1998-06-04 Consortium Elektrochem Ind Schalenkatalysator zur Herstellung von Essigsäure durch Gasphasenoxidation von ungesättigten C¶4¶-Kohlenwasserstoffen
US5840971A (en) * 1994-02-21 1998-11-24 Rhodia S.A. Process for the production of acetic acid by controlled oxidation of ethanol

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1636952A (en) 1922-03-13 1927-07-26 Barrett Co Process of producing acetaldehyde
IT1151210B (it) 1982-05-21 1986-12-17 Hydro System Srl Impianto a collettori solari formato da fasci tubieri continui in plastica,avvolti a spirale,con spire intercala isi
EP0294846A3 (fr) 1987-06-12 1990-06-20 Union Carbide Corporation Préparation d'acides organiques à partir d'alcools
BR9601959A (pt) 1996-07-17 1998-09-29 Rhodia Processo para obtenção de mistura de ácidos carboílicos aldeidos e ésteres através da oxidação catalítica de etanol e catalisador empregado para tal
EP0960875B1 (fr) 1998-05-22 2001-08-29 Consortium für elektrochemische Industrie GmbH Procédé pour la préparation d'acides carboxyliques saturés avec 1 à 4 atomes de carbone
DE19823052A1 (de) 1998-05-22 1999-11-25 Consortium Elektrochem Ind Schalenkatalysator zur Herstellung von Essigsäure durch Gasphasenoxidation von gesättigten und/oder ungesättigten C4-Kohlenwasserstoffen
DE19910866A1 (de) 1999-03-11 2000-09-21 Consortium Elektrochem Ind Verfahren und Vorrichtung zur Herstellung von gesättigten Carbonsäuren mit ein bis vier C-Atomen
DE19934410C1 (de) 1999-07-22 2000-12-14 Consortium Elektrochem Ind Verfahren zur Trennung und Reinigung eines wäßrigen Gemisches aus den Hauptkomponenten Essigsäure und Ameisensäure
DE19934411C1 (de) 1999-07-22 2001-03-22 Consortium Elektrochem Ind Verfahren zur Trennung und Reinigung einew wäßrigen Gemisches aus den Hauptkomponenten Essigsäure und Ameisensäure
DE19959413A1 (de) 1999-12-09 2001-06-21 Consortium Elektrochem Ind Trägerkatalysatoren und deren Verwendung bei der Gasphasenoxidation von Kohlenwasserstoffen
DE10065466A1 (de) 2000-12-28 2002-07-18 Consortium Elektrochem Ind Verfahren zur Trennung eines wässrigen Gemisches aus den Hauptkomponenten Essigsäure und Ameisensäure

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5840971A (en) * 1994-02-21 1998-11-24 Rhodia S.A. Process for the production of acetic acid by controlled oxidation of ethanol
DE19649426A1 (de) * 1996-11-28 1998-06-04 Consortium Elektrochem Ind Schalenkatalysator zur Herstellung von Essigsäure durch Gasphasenoxidation von ungesättigten C¶4¶-Kohlenwasserstoffen

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8440855B2 (en) 2009-12-08 2013-05-14 Haldor Topsoe A/S Process for the production of acetic acid ethylene and vinyl acetate monomer
US20120071687A1 (en) * 2010-09-16 2012-03-22 Basf Se Process for preparing acrylic acid from ethanol and formaldehyde
DE102010040923A1 (de) 2010-09-16 2012-03-22 Basf Se Verfahren zur Herstellung von Acrylsäure aus Ethanol und Formaldehyd
WO2012035019A1 (fr) 2010-09-16 2012-03-22 Basf Se Procédé de production d'acide acrylique à partir d'éthanol et de formaldéhyde
US8507721B2 (en) 2010-09-16 2013-08-13 Basf Se Process for preparing acrylic acid from ethanol and formaldehyde

Also Published As

Publication number Publication date
DE102007011847A1 (de) 2008-09-18

Similar Documents

Publication Publication Date Title
WO2011092228A1 (fr) Procédé de production d'acides carboxyliques comportant 1-3 atomes de carbone à partir de matières premières renouvelables
EP1163201B1 (fr) Procede de production d'acide acrylique
EP1261424A1 (fr) Catalyseur en forme de cylindre creux et procede de fabrication d'hydrure d'acide maleique
EP1966116A1 (fr) Procede d'oxydation en phase gazeuse heterogene et partiellement catalysee de propylene en acide acrylique
EP2244996B2 (fr) Procede de production d'esters d'acide 6-hydroxycapronique
EP3242870B1 (fr) Procédé de fabrication du tétrahydrofuranne, du 1,4-butanediol ou de la gamma-butyrolactone
EP1189861B1 (fr) Procede de purification et de preparation d'acide acrylique ou methacrylique
WO2006002703A1 (fr) Procede de production d'acide acrylique par oxydation partielle en phase gazeuse a catalyse heterogene de propylene
DE10240129B4 (de) Integriertes Verfahren zur Synthese von Propylenoxid
DE10251328B4 (de) Extraktionsverfahren zur Gewinnung von Acrylsäure
WO2008110468A1 (fr) Procédé de production d'acide acétique et d'acide formique par oxydation en phase gazeuse d'éthanol
DE19838795A1 (de) Verfahren zur kontinuierlichen Gewinnung von (Meth)acrylsäure
DE60109783T2 (de) Verfahren zur herstellung von oxiranen
WO2016110520A1 (fr) Procédé de production d'anhydride d'acide succinique et d'acide succinique très pur ou d'esters ou d'amides de ceux-ci
EP1035101B1 (fr) Procédé et dispositif pour la production d'acides carboxyliques à un à quatre atomes de carbone
EP0863124A1 (fr) Procédé de préparation de l'acide (méth)acrylique
EP1318136B1 (fr) Procédé de préparation d'acides saturés contenant 1 à 4 atomes carbone par oxidation en phase gaseuze de 2-butanone
EP0960875B1 (fr) Procédé pour la préparation d'acides carboxyliques saturés avec 1 à 4 atomes de carbone
DE10334582A1 (de) Verfahren zur Herstellung von Maleinsäureanhydrid
EP2467355A2 (fr) Procédé de production d'acide pentène-4-oïque
DE19823088A1 (de) Verfahren zur Herstellung von Säuren
DE19910628A1 (de) Verfahren zur Herstellung von gesättigten Carbonsäuren mit 1 bis 4 C-Atomen
WO2019238562A1 (fr) Procédé de préparation d'acétate de vinyle
DE2450392A1 (de) Verfahren zur herstellung von maleinsaeureanhydrid

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08717279

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08717279

Country of ref document: EP

Kind code of ref document: A1