EP2616427A1 - Verfahren zur herstellung von acrysläure aus ethanol und formaldehyd - Google Patents

Verfahren zur herstellung von acrysläure aus ethanol und formaldehyd

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Publication number
EP2616427A1
EP2616427A1 EP11758439.1A EP11758439A EP2616427A1 EP 2616427 A1 EP2616427 A1 EP 2616427A1 EP 11758439 A EP11758439 A EP 11758439A EP 2616427 A1 EP2616427 A1 EP 2616427A1
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EP
European Patent Office
Prior art keywords
mixture
reaction
reaction zone
reaction gas
stream
Prior art date
Legal status (The legal status 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 status listed.)
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EP11758439.1A
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German (de)
English (en)
French (fr)
Inventor
Stefanie Herzog
Stefan Altwasser
Markus Ottenbacher
Frank HÜTTEN
Annebart Engbert Wentink
Alexander SCHÄFER
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/373—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in doubly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/03—Monocarboxylic acids
    • C07C57/04—Acrylic acid; Methacrylic acid
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/05—Isotopically modified compounds, e.g. labelled

Definitions

  • the present invention relates to a process for the production of acrylic acid from ethanol and formaldehyde.
  • the present invention relates to the preparation of secondary products of acrylic acid thus produced.
  • An advantage of this procedure is that it has a comparatively high target product selectivity based on reacted propylene, which allows high acrylic acid yields from the propylene used in Kreisfahrweise of unreacted propylene in single pass.
  • propylene has a markedly economic backward integration to the fossil base petroleum feedstock (i.e., propylene is costly to produce from petroleum at comparatively low cost), allowing for overall low cost acrylic acid production.
  • WO 2005/093010 sees propylene itself as such a raw material. It proposes to continue to adhere to the two-stage heterogeneously catalyzed partial gas phase oxidation of propylene to acrylic acid in the future, but to recover the propylene required starting from methanol.
  • methanol both starting from fossil raw materials such as coal (for example lignite and hard coal, cf., for example, WO 2010/072424) and natural gas (cf., for example, WO 2010/067945), both have a greater temporal range
  • fossil raw materials such as coal (for example lignite and hard coal, cf., for example, WO 2010/072424) and natural gas (cf., for example, WO 2010/067945)
  • carbon dioxide each optionally with the concomitant use of water vapor or molecular hydrogen
  • Basic fossil raw materials in this document are to be understood as meaning basic raw materials, such as lignite, hard coal, natural gas and crude oil, which originated in geological past from decomposition products of dead plants and dead animals.
  • renewable raw materials should be understood to mean those raw materials which are obtained from fresh biomass, ie from new (present) and in the future grown (modern) plant and animal material. It has also been proposed (for example in WO 2008/023040) to produce acrylic acid and its secondary products starting from the renewable raw material glycerine.
  • glycerol as a renewable raw material is essentially only economically available as a coproduct of biodiesel production. This is disadvantageous in that the current energy balance of biodiesel production is not satisfactory.
  • the object of the present invention was therefore to provide an alternative process for preparing acrylic acid which does not have the described disadvantages of the processes of the prior art and, starting from the raw materials used for its preparation, in particular a satisfactory selectivity of the target product formation having.
  • ethanol is the most sustainable renewable raw material (ethanol is naturally produced by the fermentation of glucose-containing biomass, but biomass containing starch and cellulose can also be assumed by using an enzymatic or a biomass preceded by an acidic conversion process which converts the types of starch and cellulose into glucose, see eg WO 2010/092819).
  • ethanol is also industrially accessible by reaction of water with ethylene with the addition of catalysts such as sulfuric acid or starch applied phosphoric acid at temperatures of about 300 ° C and pressures of around 70 bar, with the advantage that ethylene is a dense backward integration to fossil Resources such as natural gas and coal which have a longer range than crude oil (eg Chemie Ingenieurtechnik - CIT, Volume 82, page 201-213, Issue 3, Published Online on February 9, 2010, Wiley - VCH Verlag Weinheim, "Alternative Synthetic Routes to Ethylene", A. Behr, A. Kleyentreiber and H. Hertge).
  • catalysts such as sulfuric acid or starch applied phosphoric acid
  • Another advantage of the procedure according to the invention is that formaldehyde is accessible by partial oxidation of methanol (eg Catalysis Review 47, pages 125 to 174, 2004; EP-A 2213370; WO 2010/022923; DE-A 2334981; WO2006 / 0163375; WO-A-2145851; WO 2005/063375; WO 03/053556; WO 2010/034480; WO 2007/059974; DE-A 102008059701; and Ullmann's Encyclopedia of Industrial Chemistry, Fifth, Completely Revised Edition, US Pat.
  • methanol synthesis gas gas mixtures of carbon monoxide and molecular hydrogen
  • the required molecular hydrogen can be as in the case of methane (a process for the production of methane from biogas or biomass is described, for example, in DE-A 102008060310 or EP-A 2220004) already contained in the carbon support;
  • the hydrogen source water is available from which the molecular hydrogen, e.g. can be obtained by electrolysis;
  • Oxygen source is usually air; see. e.g. WO 10-060236 and WO 10-060279).
  • a renewable carbonaceous raw material e.g. Lignocellulose for syngas production (see, for example, WO 10-062936).
  • the pyrolysis of biomass can be coupled directly with a water vapor reforming.
  • the present invention thus provides a process for the production of acrylic acid from ethanol and formaldehyde, which comprises the following measures: through a first reaction zone A, which is charged with at least one oxidation catalyst A, a stream of one of the reactants is ethanol and molecular oxygen and at least one heterogeneously catalysed to acetic acid and water vapor oxidized so that an acetic acid, water vapor, molecular oxygen and at least one different of water vapor inert diluent gas containing product gas mixture A is formed and a stream of product gas mixture A leaves the reaction zone A, wherein the reaction gas mixture A flowing through the reaction zone A on its way through the reaction zone A optionally further mol ekularer oxygen and / or further inert diluent gas can be supplied from the reaction zone A leaving stream of product gas mixture A (without previously perform a separation process on him) and at least one further stream containing at least one formaldehyde source is a stream of acetic acid, water vapor , mo
  • the reaction zone A is preferably charged with at least one oxidation catalyst A containing at least one vanadium oxide.
  • the reaction zone A is particularly preferably charged with at least one oxidation catalyst A containing at least one vanadium oxide, which in addition to the at least one vanadium oxide-containing oxidation catalyst dinoxide additionally contains at least one oxide from the group of the oxides of titanium, of aluminum, of zirconium and of tin.
  • reaction zone A with at least one oxidation catalyst A containing at least one vanadium oxide, which additionally comprises at least one oxide of titanium in addition to the at least one vanadium oxide.
  • the oxidation catalysts A advantageously contain the vanadium in the oxidation state +5. That is, according to the present invention, the at least one vanadium oxide-containing oxidation catalyst A suitably contains the unit (the vanadium oxide) V2O5 (vanadium pentoxide).
  • the aforementioned oxidation catalysts A advantageously contain the same in the oxidation state +4. That is to say that the oxidation catalysts additionally containing at least one oxide from the group consisting of titanium oxide, zirconium oxide and tin oxide suitably contain at least one unit (the element dioxide) from the group T1O2, ZrO2 and SnO2, within this group the unit ⁇ 1 ⁇ 2 for the Purpose of the invention is particularly advantageous, especially if it is present in the anatase modification.
  • At least one mixed oxide catalyst A comprising vanadium oxide is preferred according to the invention, the term "mixed oxide” indicating that the catalytically active oxide contains at least two mutually different metal elements EP-A 294846.
  • those oxidic catalysts of EP-A 294846 which, disregarding the oxygen contained, have the stoichiometry Mo x V y Z z , wherein Z be absent or for at least one particular metal element can stand.
  • At least one vanadium oxide-containing oxidation catalysts A are disclosed in US-A 5840971 mixed oxide catalysts whose active material consists of the elements vanadium, titanium and oxygen.
  • the supported catalysts containing vanadium pentoxide and titanium dioxide prepared in DE-A 1642938 for use for the partial oxidation of o-xylene to phthalic anhydride are also suitable as oxidation catalysts A according to the invention.
  • oxidation catalysts A comprising at least one vanadium oxide are those described in priority-oriented EP Appl. 09178015.5 are recommended in this regard.
  • At least one vanadium oxide-containing mixed oxide catalysts A suitable according to the invention are obtainable, for example, by the production process described in US Pat. No. 4,048,112.
  • at least one of the elements Ti, Al, Zr and Sn is assumed by a porous oxide. This is soaked in a solution of a vanadium compound. Subsequently, the solvent used to prepare the solution is advantageously largely removed (usually by the action of heat and / or reduced pressure) and the resulting catalyst precursor is subsequently calcined.
  • the vanadium compound usually in the molecular oxygen-containing Atmo- sphere, decomposed to vanadium oxide.
  • the porous oxide to be impregnated can have any geometric spatial form. Suitable for use in the process of the invention are, in particular, spheres, rings (hollow cylinders), extruded strands, pelletized pellets and monolithic forms.
  • the longitudinal extension of the aforementioned geometric shaped bodies is 1 or 2 to 10 mm (the longest expansion of a shaped body generally means in this document the longest direct connecting line between two points located on the surface of the former body).
  • containing at least one vanadium compound dissolved are suitable as vanadium compounds, e.g.
  • the solvent used is preferably water, to which, as solution promoters, complexing agents, such as, for example, are advantageously used. Oxalic acid are added.
  • the removal of the solvent to be carried out after impregnation and the calcination to be carried out can be seamlessly merging or overlapping processes.
  • the solvent is first removed at a temperature of 100 to 200 ° C. Subsequently, it is then calcined at a temperature of 400 to 800 ° C, or from 500 to 700 ° C. The calcination may be carried out in a molecular oxygen-containing atmosphere, e.g.
  • the calcination atmosphere may be above the precursor composition to be calcined or may flow over and through the precursor composition.
  • the Caicinationsdauer usually moves in the range of 0.5 h to 10 h. Higher calcination temperatures are usually associated with shorter calcination times. If comparatively low calcination temperatures are used, the calcination usually extends over a longer period of time.
  • the procedure of soaking-drying-calcination may also be repeated several times to achieve the desired loading of vanadium oxide.
  • mixed oxide catalysts A according to the invention comprising vanadium oxide
  • vanadium oxide and titanium oxide comprising composite oxide catalysts A according to the invention
  • Graphite or stearic acid as a lubricant and / or shaping aids and reinforcing aids such as microfibers of glass, asbestos, silicon carbide or potassium titanate can be added.
  • Full catalytic converter geometries suitable in accordance with the invention are (and quite generally in the case of oxidation catalysts A (in particular in the case of corresponding unsupported catalysts A (they consist only of active mass)), e.g. Solid cylinder and hollow cylinder with an outside diameter and a length of 1 or from 2 to 10 mm. In the case of the hollow cylinder, a wall thickness of 1 to 3 mm is suitable for use.
  • the tabletting can advantageously be carried out as described in the publications WO 2008/152079, WO 2008/0871 16, DE-A 102008040094, DE-A 102008040093 and WO 2010/000720. All the geometries listed in the abovementioned publications are also suitable for oxidation catalysts A according to the invention.
  • the treatment of the finely divided titanium dioxide with a vanadium compound may e.g. with a sparingly soluble vanadium compound such as V2O5 under hydrothermal conditions. Usually, however, it is carried out by means of a solution containing a vanadium compound (for example, in water or in an organic solvent (e.g., formamide or monohydric and polyhydric alcohols)).
  • Vanadium pentoxide, vanadyl chloride, vanadyl sulfate and ammonium metavanadate can be used as vanadium compounds.
  • complexing agents such as e.g. Oxalic acid may be added.
  • the shaping can also be carried out as a shell catalyst.
  • the surface of an inert carrier molding is coated with the powdered active composition produced or with the powdery precursor material which has not yet been calcined with the concomitant use of a liquid binder (coated with uncalcined precursor composition, the calcination takes place after the coating and, as a rule, drying).
  • Inert support molded articles differ from the catalytic active composition (a synonym which is also generally used in this document as “catalytically active material”) is usually that they have a significantly lower specific surface area, as a rule their specific surface area is less than 3 m 2 / g carrier moldings It should be noted at this point that all the information in this document relates to specific surfaces Provisions according to DIN 66131 (determination of the specific surface area of solids by gas adsorption (Is) according to Brunauer-Emmet-Teller (BET)).
  • Suitable materials for the aforementioned inert carrier moldings are, for example, quartz, pine glass, sintered silica, sintered or smelted clay, porcelain, sintered or melt silicates such as aluminum silicate, magnesium silicate, zinc silicate, zirconium silicate and in particular steatite (eg Steatite C 220 from CeramTec).
  • silicates such as aluminum silicate, magnesium silicate, zinc silicate, zirconium silicate and in particular steatite (eg Steatite C 220 from CeramTec).
  • the geometry of the inert carrier shaped bodies can in principle be shaped irregularly, wherein regularly shaped carrier shaped bodies such as e.g. Spheres or hollow cylinders are preferred according to the invention.
  • the longitudinal extension of the abovementioned inert carrier shaped bodies for the purposes according to the invention is 1 to 10 mm.
  • the coating of the inert carrier tablets with the respective finely divided powder is usually carried out in a suitable rotatable container, e.g. In a coating drum.
  • the liquid binder is expediently sprayed on the inert carrier moldings from an application point of view, and the surface of the carrier tablets moved in the coating drum is dusted with the respective powder (see, for example, EP-A 714 700).
  • the adhesive liquid is generally at least partially removed from the coated carrier tablet (for example by passing hot gas through the coated carrier tablets, as described in WO 2006/094766).
  • liquid binders e.g.
  • the coating of the shaped carrier bodies can also be carried out by spraying a suspension of the pulverulent mass to be applied in liquid binder (for example water) onto the surface of the inert carrier tablets (usually under the action of heat and a drying dragging gas).
  • the coating can also be carried out in a fluidized bed or powder coating plant.
  • the layer thickness of the applied to the surface of the inert carrier molding active material is suitably selected technically in the range of 10 to 2000 ⁇ , or 10 to 500 ⁇ , or 100 to 500 ⁇ , or 200 to 300 ⁇ lying.
  • Suitable shell catalysts of the type described for feeding the reaction zone A according to the invention include those whose inert carrier molding has a hollow cylinder with a length in the range of 3 to 6 mm, an outer diameter in the range of 4 to 8 mm and a wall thickness in the range of 1 to 2 mm is.
  • suitable for the purposes of the invention in the reaction zone A all in DE-A 102010028328 and DE-A 102010023312 and all disclosed in EP-A 714700 ring geometries for possible inert carrier moldings of annular Oxidationsschalenkatalysatoren A.
  • inert carrier shaped bodies for the shell oxidation catalysts A are preferably non-porous or poor in pores.
  • the active composition is introduced into the pore structure of the shaped support bodies.
  • the active materials of oxidation catalysts A suitable according to the invention may additionally contain (in addition to the already mentioned element oxides) one or more oxides of the metals boron, silicon, hafnium, niobium, tungsten, lanthanum, cerium, molybdenum, chromium, antimony , Alkali metal and alkaline earth metal, as well as the elements of the 5th and 6th main group of the periodic table and other transition metals.
  • the total content of the abovementioned oxides, based on the total weight of the active composition is from 1 to 15% by weight.
  • the term elemental oxide also includes metallates. These are negatively charged anions that are composed only of metal and oxygen.
  • the content of ethanol in the reaction gas input mixture A is generally from 0.3 to 20% by volume in the process according to the invention, preferably from 0.5 to 15% by volume, more preferably from 0.75 to 10% by volume, and very particularly preferably 1 to 5 vol .-% amount.
  • the molar amount n 0 of molecular oxygen contained in the reaction gas input mixture A is expediently dimensioned such that it is greater than the molar amount of n E t of ethanol contained in the reaction gas input mixture A.
  • the ratio no: n E t in the process according to the invention at least 1, 3, better at least 1, 5, preferably at least 1, 75 and especially preferred zugt at least 2 amount.
  • the ratio no: n E t will be no more than 10, and usually no more than 5.
  • the foregoing conditions are for the inventive process especially GR sentlich when they * to no: refer nEt *, where no * the reaction zone A in a period a total feed molar amount t of molecular oxygen and NET * in the reaction zone A. the same time t as a component of the reaction gas input mixture A total supplied molar amount of ethanol.
  • An excess of molecular oxygen over the reactant ethanol over the reaction zone A is advantageous for the inventive method both for the service life of the catalyst charge of the reaction zone A and for the service life of the catalyst feed of the reaction zone B, as this excess molecular oxygen in the inventive method into the reaction gas input mixture B is introduced.
  • an inert diluent gas is to be understood as a reaction gas input mixture constituent which behaves as inert under the conditions in the respective two reaction zones A, B and - each inert reaction gas constituent per se - exceeds 95 mol in the respective reaction zone -%, preferably more than 97, or more than 98, or more than 99 mol% remains chemically unchanged.
  • the aforementioned definition also applies correspondingly to inert diluent gases in the reaction gas input mixture C and with reference to the reaction zone C, which will be introduced later in this document.
  • inert diluent gases for both the reaction zone A and the reaction zone B and C are H 2 0, C0 2 , N 2 and noble gases such as Ar and mixtures of the aforementioned gases.
  • One of the tasks of the inert diluent gases is to take up the heat of reaction liberated in the reaction zone A, thereby limiting the so-called hot spot temperature in the reaction zone A and to make the ignition behavior of the reaction gas mixture A favorable.
  • the highest temperature of the reaction gas mixture A on its way through the reaction zone A is understood as the hot-spot temperature.
  • Water vapor plays a special role as an inert diluent gas in the two reaction zones A and B in comparison with other possible inert diluent gases.
  • reaction gas input mixture A can therefore contain from 1 to 40% by volume of H.sub.2O.
  • water vapor contents of 1 to 20 vol .-% in the reaction gas input mixture A are preferred. It also takes into account the fact that both in the reaction zone A and in the reaction zone B H2O is formed as a by-product. According to the invention, the water vapor content in the reaction gas inlet mixture A is preferably 5 to 15% by volume or 7.5 to 12.5% by volume.
  • molecular nitrogen in both the reaction zone A and the reaction zone B in the process of the present invention. This is beneficial not least in that molecular nitrogen in air acts as a natural companion to molecular oxygen, making air a preferred source of the molecular oxygen required in reaction zone A.
  • pure molecular oxygen, or air enriched with molecular oxygen, or another gas mixture of molecular oxygen and inert diluent gas may also be used as the source of oxygen.
  • At least 80% by volume, preferably at least 90% by volume, frequently at least 95% by volume and sometimes 100% by volume of the inert diluent gas contained in the reaction gas input mixture A and based on molecular nitrogen, are advantageously eliminated according to the invention.
  • the reaction gas input mixture A additionally contains water vapor as inert diluent gas in addition to an inert diluent gas other than water vapor.
  • the content of the reaction gas input mixture A in non-steam inert diluent gases will be at least 5% by volume, but usually not more than 95% by volume.
  • Typical contents of inert diluent gas other than water vapor in reaction gas input mixture A are 10 to 90% by volume, preferably 30 to 90% by volume, more preferably 50 to 90% by volume and very particularly preferably 60 to 90% by volume, or 70 to 90 vol.%, especially 75 to 85 vol.%.
  • the content of the reaction gas input mixture A of molecular nitrogen at least 5 vol .-%, preferably at least 10 vol .-%, more preferably at least 20 or at least 30 vol .-% or at least 40 vol .-%, usually but not more than 95% by volume.
  • Typical contents of the reaction gas input mixture A over molecular nitrogen may be 10 to 90% by volume, preferably 30 to 90% by volume, particularly preferably 50 to 90% by volume and very particularly preferably 60 to 90% by volume, or 70 to 90 vol .-%, especially 75 to 85 vol .-% amount.
  • reaction gas mixture A (the term reaction gas mixture A in the present application encompasses all gas mixtures which occur in the reaction zone A and lie between the reaction gas input mixture A and the product gas mixture A.
  • reaction gas mixture B comprises all in the reaction zone B occurring gas mixtures, which are between the reaction gas input mixture B and the product gas mixture B) in the process according to the invention within the reaction zone A normally in the range of 100 ° C to 450 ° C, preferably in the range of 150 ° C to 400 ° C and particularly preferably in Range from 150 ° C to 350 ° C or 150 ° C to 300 ° C.
  • the aforementioned temperature range may also be 200 ° C to 300 ° C.
  • the term of the temperature of the reaction gas mixture A means primarily the temperature which the reaction gas mixture A from reaching a conversion of the ethanol contained in the reaction gas input mixture A of at least 5 mol% to Having reached the corresponding final conversion of the ethanol within the reaction zone A.
  • the temperature of the reaction gas mixture A advantageously lies over the entire reaction zone A in the abovementioned temperature ranges.
  • the reaction gas input mixture A is also supplied to the reaction zone A at a temperature in the range from 100.degree. C. to 350.degree. Frequently, however, at the entrance to the reaction zone A upstream of the actual catalytically active catalyst charge of the reaction zone A, there is a charge of the reaction zone A with solid inert material or with catalytically active catalyst charge highly diluted with such inert material.
  • the temperature of the reaction gas input mixture A fed to the reaction zone A can be adjusted comparatively easily to the value with which the reaction gas mixture A in FIG the actual catalytically active catalyst feed of the reaction zone A should occur.
  • the feed of reaction zone A with at least one oxidation catalyst A can be designed as a fluidized bed. In terms of application technology, however, the feed of reaction zone A with oxidation catalyst A is carried out as a fixed bed.
  • the reaction gas mixture A can both be pushed through the reaction zone A and sucked through it.
  • the working pressure in the reaction zone A will be> 10 5 Pa.
  • the working pressure in the reaction zone A in the range of 1, 2-10 5 Pa to 50-10 5 Pa, preferably in the range of 1, 5-10 5 to 20-10 5 Pa and more preferably in the range of 2 -10 5 to 10 6 Pa or in the range of 2-10 5 to 6-10 5 Pa.
  • the execution of the reaction zone A can suitably be carried out in a so-called "heat exchanger reactor.”
  • This has at least one primary space and at least one secondary space, which are separated from one another by a partition wall
  • the secondary space is flowed through by a fluid heat carrier, and heat exchange takes place between the two spaces through the dividing wall, the purpose of which is to maintain the temperature of the reaction gas mixture A in its path to control and control (to temper the reaction zone A) by way of the catalyst bed by way of example as heat exchanger reactors suitable for the realization of the reaction zone A of the tube bundle reactor (as described, for example, in EP-A 700714 and US Pat the prior art cited in those references) and the thermal plate reactor (as e.g.
  • the catalyst bed through which the reaction gas mixture A flows is preferably in its tubes (the primary chambers) and at least one heat carrier is passed through the space surrounding the reaction tubes (the secondary chamber).
  • Suitable heat transfer mediums for the heat exchanger reactors are, for example, molten salts, heat transfer oils, ionic liquids and water vapor.
  • tubular reactors used industrially contain at least three thousand to several tens of thousands of reaction tubes (reactor tubes) connected in parallel. Of course, the execution of the reaction zone A but also in a fluidized bed reactor or in a microreactor can be realized.
  • Oxidation catalysts of this type are known from the literature as catalysts for the heterogeneously catalyzed partial gas phase oxidation of acrolein to acrylic acid. Surprisingly, it has now been found that all multimetal oxide catalysts of the abovementioned type, which are known from the prior art as catalysts for the heterogeneously catalyzed partial gas phase oxidation of acrolein to acrylic acid, also advantageously as oxidation catalysts for the second step of the partial oxidation of ethanol to acetic acid, the partial oxidation of acetaldehyde to acetic acid, in the reaction zone A.
  • Such multimetal oxide active compositions containing Mo and V, including the catalysts comprising them, can be found, for example, in the specifications US Pat. No. 3,775,474, US Pat. No. 3,954,855, US Pat. No. 3,893,951, US Pat. No. 4,339,355, EP-A 614,872, EP-A 1041062, WO 03 / 055835 and WO 03/057653 are taken.
  • oxidation catalysts A whose active composition is at least one multimetal oxide which in addition to V and Mo additionally contains at least one of the elements W, Nb, Ta, Cr and Ce and at least one of the elements Elements includes Cu, Ni, Co, Fe, Mn and Zn.
  • X 2 Cu, Ni, Co, Fe, Mn and / or Zn,
  • X 3 Sb and / or Bi
  • X 4 one or more alkali metals
  • X 5 one or more alkaline earth metals
  • X 6 Si, Al, Ti and / or Zr
  • n the stoichiometric coefficient of the element oxygen, which is given by the
  • variables of general formula I have the following meaning:
  • X 2 Cu, Ni, Co, Fe, Mn and / or Fe,
  • X 5 Ca, Sr and / or Ba
  • X 6 Si, Al and / or Ti
  • n the stoichiometric coefficient of the element oxygen, which is given by the
  • V and Mo-containing multimetal oxide active compositions in particular those of the general formula I, can be used both in powder form and shaped to specific catalyst geometries as full catalysts for catalyzing the partial oxidation of acetaldehyde to acetic acid.
  • catalyst geometries which are suitable according to the invention, the statements already made in relation to the possible geometries of full catalyst oxidation catalysts A in this document apply correspondingly.
  • the described multimetal oxide active compounds containing V and Mo are used in the form of coated catalysts (i.e., applied to the outer surface of preformed inert catalyst supports (support moldings)) in the catalysis of the relevant second reaction step.
  • coated catalysts i.e., applied to the outer surface of preformed inert catalyst supports (support moldings)
  • support moldings support moldings
  • the statements already made in connection with shell catalyst oxidation catalysts A in this document apply correspondingly.
  • Preferred geometries of the carrier molded bodies are also spheres and rings whose longitudinal extension can be 1 to 10 mm, often 2 to 8 mm or 3 to 6 mm.
  • ring geometries according to the invention are hollow-cylindrical carrier shaped bodies with a length of 2 to 10 mm, an outer diameter of 4 to 10 mm and a wall thickness of 1 to 4 mm.
  • the hollow cylindrical carrier moldings have a length of 3 to 6 mm, an outer diameter of 4 to 8 mm and a wall thickness of 1 to 2 mm.
  • the ring geometry is called 7 mm ⁇ 3 mm ⁇ 4 mm (outer diameter ⁇ length ⁇ inner diameter).
  • the thickness of the shell of catalytically active oxide mass applied to the carrier shaped bodies in the case of the abovementioned coated catalysts is expediently from 10 to 1000 ⁇ in terms of application technology.
  • this shell thickness is 10 to 500 ⁇ , more preferably 100 to 500 ⁇ and most preferably 200 to 300 ⁇ .
  • the shell thickness over a single shell catalyst considered as uniform as possible.
  • the shell thickness is considered as uniform as possible over several coated catalyst molding.
  • Suitable materials for the inert carrier moldings are the inert materials already mentioned in this document.
  • inert materials are again mentioned alumina, silica, silicates such as clay, kaolin, steatite, pumice, aluminum silicate and magnesium silicate, silicon carbide, zirconium dioxide and thorium dioxide (a particularly preferred inert material for carrier tablets according to the invention is Steatite C 220 from CeramTec)
  • Carrier moldings having a well-formed surface roughness e.g., chop-brushed hollow cylinders as described in Research Disclosure Database Number 532036 (August 2008 published) are preferred for preparing the coated catalyst moldings.
  • the carrier shaped bodies are preferably as nonporous as possible.
  • the catalytically active oxide composition of the general formula I can be prepared as such. This is usually done by producing, from sources of the elemental constituents of the catalytically active oxide composition, a preferably intimate, preferably finely divided, dry mixture (a precursor composition) which is composed according to its stoichiometry and this at temperatures of 350 to 600 ° C calcined (thermally treated).
  • a precursor composition preferably intimate, preferably finely divided, dry mixture which is composed according to its stoichiometry and this at temperatures of 350 to 600 ° C calcined (thermally treated).
  • the calcination can be carried out both under inert gas and under an oxidative atmosphere such as air (or another mixture of inert gas and oxygen) as well as under reducing atmosphere (eg mixtures of inert gas and reducing gases such as H, N H3, CO, methane and / or Acrolein or the said reducing acting gases in each case).
  • the calcination time can be a few minutes to a few hours and usually decreases with the height of the Calcinati- onstemperatur.
  • WO 95/1 1081 describes a calcination process which is well suited according to the invention.
  • Suitable sources of the elemental constituents of the catalytically active oxide composition of the general formula I are (in general, in the case of oxidation catalysts A) those compounds which are already oxides and / or those compounds which are convertible into oxides by heating, at least in the presence of oxygen.
  • the intimate mixing of the starting compounds (sources) can be carried out in dry or wet form. If it takes place in dry form, the starting compounds are expediently used as finely divided powders and subjected to the calcination after mixing and optionally compacting. Preferably, however, the intimate mixing takes place in wet form. Usually, the starting compounds are mixed together in the form of an aqueous solution and / or suspension.
  • Particularly intimate dry mixtures are obtained in the described mixing process when starting exclusively from sources of the elementary constituents present in dissolved form.
  • the solvent used is preferably water.
  • the obtained liquid (e.g., aqueous) mass is dried, the drying process being preferably by spray-drying the liquid (e.g., aqueous) mixture at exit temperatures of 100 to 150 ° C.
  • the drying gas stream is useful in terms of application air or molecular nitrogen.
  • the catalytically active oxide composition obtained after calcination is then subsequently added to e.g. transferred by grinding in a finely divided powder, which can then be applied normally with the aid of a liquid binder on the outer surface of the carrier molded body.
  • the fineness of the catalytically active oxide mass to be applied to the surface of the carrier molding is of course adapted to the desired shell thickness as described in the prior art (cf., for example, EP-A 714700).
  • the shaped carrier bodies are moistened in a controlled manner with the liquid binder, for example by spraying, and the moistened carrier tablets are dusted with the finely divided, catalytically active oxide mass (cf., for example, EP-A 714 700 and DE-A102010023312).
  • the adhesive liquid is at least partially removed from the moistened carrier shaped body coated with active oxide material (for example, passing hot gas through, see WO 2006/094766).
  • active oxide material for example, passing hot gas through, see WO 2006/094766.
  • Suitable liquid binders include, for example, water and aqueous solutions.
  • shell-type catalysts according to the invention by initially applying finely divided precursor material to the surface of the support body, and only subsequently to calcination of the precursor material to the catalytically active oxide composition of general formula I, ie, already on the surface of the support molding located, performs.
  • Ammonium heptamolybdate tetrahydrate is advantageously used as the Mo source.
  • Preferred vanadium source is ammonium metavanadate, and in the case where element W is co-used, ammonium paratungstate heptahydrate is the preferred element source.
  • the process according to the invention in the reaction zone A for the second step of the heterogeneously catalyzed partial oxidation of ethanol to acetic acid at least one oxidation catalyst A is used whose active material is a multimetal (eg, one of the general formula I), which in addition to oxygen at least the elements Mo and V contains, is advantageously used according to the invention for the first step of the partial oxidation of ethanol to acetic acid at least one oxidation catalyst A whose active composition is a mixed oxide, in addition to oxygen and V at least one of the elements Ti (preferred), Zr and AI (and usually no Mo) (ie, at least one oxidation catalyst A which, in addition to a vanadium oxide (preferably V2O5), also comprises at least one oxide of Ti (preferably, preferably T1O2), Zr and Al).
  • a multimetal eg, one of the general formula I
  • Mo and V contains is advantageously used according to the invention for the first step of the partial oxidation of ethanol to ace
  • Such a charge of the reaction zone A with oxidation catalyst A is advantageous according to the invention in that it ensures particularly high target product selectivities of acetic acid at high conversions of the ethanol, which are related to a single pass of the reaction gas mixture A through the reaction zone A.
  • according to the invention advantageously comprises the feed of the reaction zone A with at least one oxidation catalyst A two spatially consecutive in the flow direction of the reaction gas mixture A (in said numerical order) sections 1 and 2 (between both can optionally be a loaded only with inert moldings section, which however, less preferred according to the invention).
  • the active material of the at least one oxidation catalyst A of section 1 (in section 1) which is also referred to herein as catalytically active material 1
  • the active material of the at least one oxidation catalyst A of section 2 (in section 2) which is also referred to herein as catalytically active material 2 (and different from the catalytically active material 1), at least one mixed oxide containing the elements V and Mo is (preferably one of the general formula I).
  • the at least one oxidation catalyst A of the section 1 contains, in addition to a vanadium oxide (preferably V2O5), at least one oxide of Ti (preferably, preferably T1O2), Zr and Al (and in the Usually no oxide of Mo), while the at least one oxidation catalyst A of section 2 contains, in addition to a vanadium oxide, at least one molybdenum oxide.
  • the active composition of the at least one oxidation catalyst A of Section 1 or contains this active composition of 1 to 50 wt .-% V2O5 and 50 to 99 wt% Ti0 2 , preferably 3 to 40 wt .-% V 2 0 5 and 60 to 97 wt .-% Ti0 2, and most preferably 5 to 30 wt .-% V 2 0 5 and 70 to 95 wt .-% Ti0 2 .
  • the Ti0 2 is present in the aforementioned cases in the anatase modification.
  • the temperature of section 1 is advantageously independent of the temperature control of section 2.
  • the temperature of sections 1 and 2 is advantageously such that the temperature of reaction gas mixture A arithmetically averaged over the length of (catalytically active) section 1 (that is Temperature 1 , which in this document is also referred to as the arithmetically averaged reaction temperature in section 1 over the length of section 1) is 150 to 250 ° C and preferably 170 to 220 ° C, while the length of the (catalytically active) section 2 Arithmetically averaged temperature of the reaction gas mixture A (this is the temperature 2 , which is also referred to in this document as the length of section 2 averaged reaction temperature of section 2) in terms of application suitably 180 to 260 ° C, preferably 200 to 240 ° C and particularly advantageous 210-230 ° C.
  • T 2 is at least 5 ° C, preferably at least 10 ° C, more preferably at least 15 ° C or at least 20 ° C and most preferably at least 25 ° C or at least 30 ° C greater than T 1 .
  • T 2 is not more than 80 ° C and often not more than 60 ° C greater than 1 .
  • the length of the two feed sections 1 and 2 is normally dimensioned such that the conversion of ethanol to the section 1 at a single pass of the reaction gas mixture A reaches at least 90 mol%, regularly even at least 95 mol% and that achieved in section 2 Sales of acetaldehyde is also at least 90 mol% and regularly even at least 95 mol%.
  • the conversion to ethanol achieved on a single pass of the reaction gas mixture A through the sections 1 and 2 is regularly> 97 mol%, often> 98 mol% and frequently> 99 mol%.
  • the selectivity of the concomitant formation of acetic acid is usually> 85 mol%, often> 86 mol% or> 87 mol% and often even> 88 mol% or> 90 mol%.
  • the realization of the two sections 1 and 2 of the reaction zone A is in a simple manner e.g. in two series-connected heat exchanger reactors (for example two tube bundle reactors), whose respective secondary chambers are respectively flowed through by a separate fluid heat carrier.
  • the at least one primary space of the first of the two reactors in the flow direction accommodates the section 1, while the at least one primary space of the second of the two reactors in the flow direction accommodates the section 2.
  • the realization of the two sections 1 and 2 of the reaction zone A can e.g. but also in a so-called two-zone reactor, as disclosed by way of example in DE-A 2830765.
  • the two sections 1 and 2 are spatially successively housed in the same primary space and adjacent to the primary space secondary space is divided into two subspaces, one of which extends over the section 1 and the other over the section 2 and the two independently of different Flowing through inlet heat transfer fluids are flowed through.
  • Two-zone reactors also relate to the specifications DE-A 10313210, DE-A 10313209, DE-A 19948523, DE-A 19948523, DE-A 19948241, DE-A
  • Two-zone tube bundle reactors are preferably used according to the invention.
  • reaction gas input mixture A must already have all components required for the partial oxidation of ethanol to acetic acid in the extent required for the reaction. If the implementation takes place in two heat exchanger reactors connected in series, the reaction gas mixture A between the two reactors can still be e.g. molecular oxygen and / or inert gas are metered.
  • oxidation catalysts A whose active composition contains at least one vanadium oxide (also those of the general formula I), when used for the heterogeneously catalyzed partial oxidation of ethanol to acetic acid even then a fully satisfactory service life, if used to produce the reaction gas input mixture A bioethanol, ie, ethanol, which is obtained from the renewable raw biomass.
  • bioethanol usually contains, as an impurity, at least one chemical compound which has the element sulfur chemically bound.
  • the content of bioethanol in such sulfur-containing compounds is usually> 1 ppm by weight, frequently> 2 ppm by weight or> 3% by weight. ppm.
  • the abovementioned sulfur content of bioethanol is ⁇ 200 ppm by weight, or ⁇ 150 ppm by weight or in some cases ⁇ 100 ppm by weight.
  • oxidation catalysts A whose active composition contains at least one vanadium oxide are obviously largely resistant to such sulfur compounds as constituent of the reaction gas input mixture A, so that corresponding contents of sulfur compounds in the reaction gas input mixture A relating to the ethanol content of the reaction gas input gas mixture A can be tolerated in the process according to the invention.
  • the process of the invention as an ethanol source but also bioethanol into consideration, the appropriately sized content of sulfur compounds has been lowered to values ⁇ 1 ppm by weight.
  • bioethanol which satisfies the following specification can be used for the process according to the invention:
  • Chlorine-containing compounds as Cl ⁇ 0.5 ppm ASTM 4929 B
  • the sulfur contained in the reaction gas input mixture A and chemically bound in corresponding impurities in the process according to the invention as a constituent of the reaction gas input mixture B into the reaction zone B is essential is carried in it. It is surprising that the aldol condensation catalysts to be used according to the invention in reaction zone B, in particular those which are preferred according to the invention, have a completely satisfactory tolerance to sulfur-chemically bound compounds.
  • bioethanol used as raw material is transferred as such into the vapor phase and introduced into the reaction gas input mixture A.
  • aqueous bioethanol solutions can also be used in the process according to the invention in this way.
  • the aqueous ethanol obtained as a source of ethanol can also be used in bioethanol production and dissolved in the bioethanol.
  • the same is subjected to filtration and solids contained therein are filtered off.
  • the filtrate is transferred to the vapor phase and fed to the generation of the reaction gas input mixture A.
  • the loading of the catalyst fixed bed comprising at least one oxidation catalyst A contained in the reaction zone A with ethanol contained in the reaction gas input mixture A in the method according to the invention can e.g. 20 to 500, preferably 30 to 100 and particularly preferably 50 to 100 Nl / l-h.
  • the term load is used as defined in DE-A 19927624.
  • formaldehyde As a source of the required in the reaction gas input mixture B formaldehyde come for the inventive method, various raw materials into consideration.
  • One possible source is aqueous solutions of formaldehyde (see, for example, DE-A 102008059701), which are e.g. having a formaldehyde content of 35 to 50% by weight as formalin can be commercially obtained (e.g., formaldehyde 49-2015 from BASF SE).
  • formalin as a stabilizer still contains small amounts of methanol. These may, based on the weight of formalin, 0.5 to 20 wt .-%, preferably 0.5 to 5 wt .-% and preferably 0.5 to 2 wt .-% amount.
  • the formalin When converted to the vapor phase, the formalin can be used directly to produce the reaction gas input mixture B.
  • a disadvantage of the formaldehyde source formalin is that it also contains water in addition to formaldehyde, which adversely affects the position of the reaction equilibrium in the reaction zone B.
  • Trioxane is a heterocyclic compound from the acetal group that results from trimerization of formaldehyde. It is solid at atmospheric pressure (10 5 Pa) and 25 ° C, melts at 62 ° C and boils at
  • trioxane is thus a formaldehyde source which is suitable according to the invention for producing reaction gas input mixture B. Since trioxane also dissolves comparatively well in water and in alcohols such as methanol, corresponding processes can also be used for the process according to the invention Trioxane solutions are used as inventively suitable formaldehyde source. The presence of 0.25 to 0.50% by weight of sulfuric acid in trioxane solutions favors the re-dissociation of tion to formaldehyde.
  • the trioxane can also be dissolved in a liquid stream Y consisting mainly of acetic acid and the resulting solution evaporated for the purpose of generating the reaction gas input mixture B, and the trioxane contained therein are back-split at the elevated temperature into formaldehyde.
  • paraformaldehyde can be used as the formaldehyde source for the process according to the invention.
  • Paraformaldehyde is the short chain polymer of formaldehyde, the degree of polymerization of which is typically 8 to 100%. It is a white powder that is split back into formaldehyde at low pH or with heating.
  • paraformaldehyde When paraformaldehyde is heated in water, it decomposes and an aqueous formaldehyde solution is obtained, which is likewise a source which is suitable according to the invention. Sometimes it is referred to as an aqueous "paraformaldehyde solution" to delineate it from aqueous formaldehyde solutions produced by diluting formalin, but in fact paraformaldehyde as such is substantially insoluble in water.
  • Another formaldehyde source suitable for the process according to the invention is methylal (dimethoxymethane). It is a reaction product of formaldehyde with methanol, which forms a colorless liquid at normal pressure to 25 ° C. It is hydrolyzed in aqueous acids and forms again formaldehyde and methanol. Converted into the vapor phase, it is suitable for the preparation of reaction gas input mixture B.
  • formaldehyde is produced by heterogeneously catalyzed partial gas phase oxidation of methanol.
  • the particularly preferred formaldehyde source for forming the reaction gas input mixture B according to the invention is therefore the product gas mixture of a heterogeneously catalyzed partial gas phase oxidation of methanol to formaldehyde, optionally after a partial or total amount of possibly unreacted methanol contained therein has been separated off.
  • the temperature of the reaction gas mixture B in the process according to the invention within the reaction zone B is normally in the range from 260 to 400 ° C., preferably in the range from rich from 270 to 390 ° C, more preferably in the range 280 to 380 ° C, with advantage in the range 300 to 370 ° C and with particular advantage in the range of 300 to 340 ° C.
  • the term of the temperature of the reaction gas mixture B means in the first place that temperature which the reaction gas mixture B from reaching a conversion of the formaldehyde contained in the Christsgaseingangs- B of at least 5 mol -% has reached until the corresponding final conversion of formaldehyde within the reaction zone B.
  • the temperature of the reaction gas mixture B is advantageously over the entire reaction zone B in the abovementioned temperature ranges.
  • the reaction gas inlet mixture B is already supplied to the reaction zone B with a temperature lying in the range from 260 to 400 ° C.
  • reaction zone B upstream of the actual catalytically active catalyst charge of reaction zone B, at the entrance to reaction zone B, there is a charge of reaction zone B with solid inert material or with catalytically active catalyst charge highly diluted with such inert material.
  • the temperature of the reaction gas inlet mixture B supplied to the reaction zone B can be adjusted comparatively easily to the value at which the reaction gas mixture B is to enter the actual catalytically active catalyst feed of the reaction zone B.
  • the temperature of the reaction zone A leaving product gas mixture A is different from this temperature.
  • the stream of the product gas mixture A on its way out of the reaction zone A in the reaction zone B flow through an indirect heat exchanger in order to approach its temperature to the reaction gas input mixture B intended inlet temperature in the reaction zone B, or to bring it to this temperature.
  • the feed of reaction zone B with at least one aldol condensation catalyst B can be carried out as a fluidized bed. In terms of application technology, however, the feed of reaction zone B with aldol condensation catalyst B is carried out as a fixed bed.
  • the working pressure in the reaction zone B is lower than the working pressure in the reaction zone A due to the pressure loss entering the reaction zone A when the reaction mixture A flows through the reaction mixture A.
  • the reaction zone B can also be carried out in corresponding heat exchanger reactors such as the reaction zone A, the same preferential rules are valid.
  • the content of formaldehyde in the reaction gas input mixture B in the process according to the invention is generally 0.5 to 10% by volume, preferably 0.5 to 7% by volume and more preferably 1 to 5% by volume.
  • the ratio of nHac: nFd from in the reaction gas input mixture B contained molar amount of acetic acid ( ⁇ ) TO contained in it molar amount of formaldehyde (nFd) in the inventive method is greater than 1 and can be up to 10 (under nFd is the sum of im Reaction gas input mixture B monomer (preferred) and oligomeric and polymeric present Formaldehydizien understood, since a further lightsspal- tion to monomeric formaldehyde can only be set when flowing the reaction gas mixture B through the catalyst feed of the reaction zone B).
  • the ratio n H A C : n F d in the reaction gas input mixture B is preferably 1, 1 to 5 and more preferably 1, 5 to 3.5.
  • the acetic acid content of the reaction gas input mixture B will be in the range of 1 or from 1.5 to 20% by volume, advantageously in the range of from 2 to 15% by volume and more preferably in the range of from 3 to 10% by volume. % move.
  • the content of the reaction gas input mixture B of molecular oxygen in the process according to the invention expediently ranges from 0.5 to 5% by volume, preferably in the range from 1 to 5% by volume and more preferably in the range from 2 to 5% by volume 3 to 5% by volume.
  • the presence of molecular oxygen in the reaction gas input mixture B has an advantageous effect on the service life of the catalyst feed of the reaction zone B. However, if the oxygen content of the reaction gas mixture B is too high, unwanted carbon oxide formation occurs in the reaction zone B.
  • the water vapor content of the reaction gas input mixture B should not exceed 30% by volume in the process according to the invention, since the presence of water vapor in the reaction gas mixture B has an unfavorable effect on the equilibrium position of the aldol condensation.
  • the water vapor content of the reaction gas input mixture B will therefore generally not exceed 25% by volume and preferably 20% by volume.
  • the water vapor content of the reaction gas input mixture B will be at least 1, 5 or at least 2% by volume.
  • the water vapor content of the reaction gas input mixture B is 5 to 15% by volume and, taking into account its action and formation in the reaction zone A, above all 10 to 15% by volume.
  • the volume fraction of inert diluent gases different from water vapor in the reaction gas input mixture B will normally be at least 30% by volume.
  • the aforementioned inert gas content is at least 40% by volume or at least 50% by volume.
  • the proportion of inert diluent gas other than water vapor in the reaction gas input mixture B will not exceed 95% by volume or usually 90% by volume.
  • the reaction gas input mixture B contains 60 to 90% by volume, more preferably 70 to 80% by volume, of inert diluent gas other than water vapor.
  • preferred inert diluent gas other than water vapor is also molecular nitrogen (N 2 ) in the reaction gas input mixture B.
  • the content of the reaction gas input mixture B of molecular nitrogen may be at least 30% by volume, preferably at least 40% by volume or at least 50% by volume.
  • the reaction gas input mixture B contains not more than 95 vol .-% and usually not more than 90% by volume of molecular nitrogen.
  • the Christsgaseingangs- mixture B contains 60 to 90 vol .-%, more preferably 70 to 80 vol .-% of molecular nitrogen.
  • Suitable catalysts for feeding the reaction zone B are, for example, those listed in I & EC PRODUCT RESEARCH AND DEVELOPMENT, Vol. 1, March 1966, pages 50 to 53 are disclosed.
  • This group of basic catalysts comprises on the one hand zeolites (aluminosilicate) with anionic skeleton charge, on the inner and outer surface of which at least one cation species from the group of alkali and alkaline earth ions is (preferably Na + , K + , Ca 2+ and / or Mg 2+ ) to balance (neutralize) the negative framework charge.
  • inert hydroxide applied to inert supports eg amorphous silica (silica gel) from the group consisting of the alkali hydroxides, alkaline earth hydroxides and aluminum hydroxide (preferably KOH, NaOH, Ca (OH) 2 and Mg (OH) 2 ).
  • As component b) at least one oxide selected from boron oxide and phosphorus oxide, and optionally
  • B2O3 is preferred as boron oxide and P2O5 as phosphorus oxide.
  • Catalysts whose boron oxide content (calculated as B2O3 (based on the amount of B contained)) is from 1 to 50% by weight are preferred.
  • catalysts which are favorable according to the invention are also those whose phosphorus oxide content (calculated as P2O5 (based on the amount of P contained)) is from 1 to 50% by weight.
  • suitable aldol condensation catalysts B for the process according to the invention are also those of the abovementioned catalysts whose total content of phosphorus oxide (calculated as P2O5) and boron oxide (calculated as B2O3) is 1 to 50% by weight.
  • the abovementioned contents of phosphorus oxide and / or boron oxide are preferably from 5 to 30% by weight.
  • constituent a) is preferably at least one oxide of at least one of the elements Si, Al, Ti and Zr.
  • the combinations of titanium oxide as constituent a) and boron and phosphorus oxide as constituent b) or silica-alumina as constituent a) and boron oxide as constituent b) or aluminum oxide as constituent a) and boron oxide or phosphorus oxide as constituent are particularly favorable b).
  • the above catalysts additionally comprise a heteropolyacid, it preferably contains at least one of the elements P, B and Si as the heteroatom. If the abovementioned catalysts comprise a component c), the amount thereof normally amounts to 0.01 to 10 mmol per gram of catalyst and in many cases to 0.03 to 5 mmol per gram of catalyst.
  • the catalysts as component c) have at least one of the oxides as well as at least one of the heteropolyacids.
  • the reaction zone B is charged with aldol condensation catalysts B whose active composition is a vanadium phosphorus oxide and / or a vanadium phosphorus oxide doped with elements other than vanadium and phosphorus (also referred to in the literature as VPO catalysts) ).
  • Such catalysts are described in the literature and are particularly recommended there as catalysts for the heterogeneously catalyzed partial gas phase oxidation of hydrocarbons having at least four carbon atoms (especially n-butane, n-butenes and / or benzene) to maleic anhydride.
  • these catalysts known from the prior art for the abovementioned partial alkoxides are generally suitable as aldol condensation catalysts B for charging the reaction zone B. They are distinguished by particularly high selectivities of target product formation (the formation of acrylic acid) (with high formaldehyde conversions) Accordingly, aldol condensation catalysts can be used In the process according to the invention, for example, all those used in the documents US Pat. No. 5,275,996, US Pat. No. 5,641,722, US Pat. No. 5,137,860, US Pat. No. 5,095,125, DE-69702728 T2, WO 2007/012620, WO
  • the phosphorus / vanadium atomic ratio in the undoped or doped vanadium phosphorous oxides is advantageously 0.9 to 2.0, preferably 0.9 to 1.5, particularly preferably 0.9 to 1.2, and very particularly preferably 1.0 to 1, 1.
  • the arithmetic mean oxidation state of the vanadium in them is preferably +3.9 to +4.4 and more preferably 4.0 to 4.3.
  • these active compositions advantageously have a BET specific surface area of> 15 m 2 / g, preferably of> 15 to 50 m 2 / g and very particularly preferably of> 15 to 40 m 2 / g.
  • the vanadium-phosphorus oxide active compositions can be doped with vanadium and phosphorus-different promoter elements. Suitable promoter elements of this type are the elements of Groups 1 to 15 of the Periodic Table which are different from P and V.
  • Doped vanadium phosphorous oxides for example, disclose WO 97/12674, WO 95/26817, US-A 5,137,860, US-A 5,296,436, US-A 5,158,923, US-A 4,795,818 and WO 2007/012620.
  • Preferred promoters according to the invention are the elements lithium, potassium, sodium, rubidium, cesium, thallium, molybdenum, zinc, hafnium, zirconium, titanium, chromium, manganese, nickel, copper, iron, boron, silicon, tin, niobium, cobalt and bismuth. among which, in addition to iron, in particular niobium, molybdenum, zinc and bismuth are preferred.
  • the vanadium-phosphorus oxide active compositions may contain one or more promoter elements.
  • the total content of promoters in the catalytic active composition is, based on their weight, usually not more than 5 wt .-% (the individual promoter element each counted as electrically neutral oxide in which the promoter element has the same charge number (oxidation number) as in Active mass has).
  • X 1 Mo, Bi, Co, Ni, Si, Zn, Hf, Zr, Ti, Cr, Mn, Cu, B, Sn and / or Nb, preferably Nb,
  • X 2 Li, K, Na, Rb, Cs and / or TI
  • b 0.9 to 2.0, preferably 0.9 to 1, 5, particularly preferably 0.9 to 1, 2 and very particularly preferably 1, 0 to 1, 1, 1, c> 0 to 0, 1,
  • n is the stoichiometric coefficient of the element oxygen, which is due to the
  • the stoichiometric coefficient c is advantageously 0.005 to 0.1, preferably 0.005 to 0.05 and particularly advantageously 0.005 to 0.02, in active compounds of the general formula II.
  • the aldol condensation catalysts B may comprise the multimetal oxide active compounds of the general formula II, for example, in pure, undiluted form or diluted with an oxidic, essentially inert, dilution material as so-called unsupported catalysts.
  • Inert diluent materials suitable according to the invention are e.g. finely divided alumina, silica, aluminosilicates, zirconia, titania or mixtures thereof.
  • Undiluted unsupported catalysts are preferred according to the invention.
  • the unsupported catalysts can basically have any form.
  • Preferred unsupported catalyst bodies are spheres, solid cylinders, hollow cylinders and trilobes, the longitudinal extent of which is advantageously 1 to 10 mm in all cases.
  • the shaping is advantageously carried out with precursor powder, which is calcined only after molding.
  • the shaping is usually carried out with the addition of shaping aids such as graphite (lubricant) or mineral fibers (reinforcing aids).
  • Suitable forming methods are tableting, extrusion and extrusion.
  • the outer diameter of cylindrical unsupported catalysts is suitably 3 to 10 mm, preferably 4 to 8 mm and especially 5 to 7 mm.
  • Their height is advantageously 1 to 10 mm, preferably 2 to 6 mm and especially 3 to 5 mm. In the case of hollow cylinders the same applies.
  • the inner diameter of the opening running from top to bottom is advantageously 1 to 8 mm, preferably 2 to 6 mm and most preferably 2 to 4 mm.
  • a wall thickness of 1 to 3 mm is useful for hollow cylinders in terms of application.
  • the doped or undoped vanadium-phosphorus oxide active materials can also be used in powder form or as shell catalysts with an active mass shell applied to the surface of inert shaped support bodies as aldol condensation catalysts B in the reaction zone B.
  • the preparation of the coated catalysts, the shell thickness and the geometry of the inert shaped support bodies can be selected as described for the reaction zone A in the case of the shell catalysts.
  • a pentavalent vanadium compound eg V2O5
  • an organic, reducing solvent eg isobutanol
  • a pentavalent phosphorus compound eg ortho and / or pyrophosphoric acid
  • heating to 75 to 205 ° C, preferably at 100 to 120 ° C
  • cooling the reaction mixture to advantageously 40 to 90 ° C
  • doping element-containing compounds e.g. Iron (III) phosphate
  • Fe-containing precursor composition e.g., by filtration
  • f) drying and / or thermal pretreatment of the precursor composition optionally until incipient preformation by dehydration from the precursor composition
  • g) addition of shaping aid e.g. finely divided graphite or mineral fibers and then shaping the Vollkatalysatorvor Wunschrform stresses by e.g. Tabletting
  • the temperature of the thermal treatment usually exceeds 250 ° C, often 300 ° C or 350 ° C, but usually not 600 ° C, preferably not 550 ° C and most preferably not 500 ° C.
  • the loading of the catalyst charge of the reaction zone B with formaldehyde contained in the reaction gas mixture B can according to the invention, for example 1 to 100, preferably 2 to 50 and more preferably 3 to 30 or 4 to 10 Nl / lh.
  • the term load is used as defined in DE-A 19927624.
  • formaldehyde is produced industrially by heterogeneously catalyzed partial gas phase oxidation of methanol.
  • An inventively particularly preferred formaldehyde source for forming the reaction gas input mixture B is therefore the product gas mixture of a heterogeneously catalyzed partial gas phase oxidation of methanol to formaldehyde.
  • the process according to the invention therefore comprises a further, a third reaction zone C which is charged with at least one oxidation catalyst C and advantageously comprises the following additional measures: a third reaction zone C which is charged with at least one oxidation catalyst C becomes Stream of one containing the reactants methanol and molecular oxygen and at least one other than water vapor inert diluent gas
  • Reaction gas input mixture C passed through and heterogeneously catalyzed during the flow through the reaction zone C contained in the reaction gas mixture C methanol to formaldehyde and steam so that a formaldehyde, water vapor and at least one of water vapor different inert diluent gas containing product gas mixture C is formed and a stream of product gas mixture C the reaction zone C. leaves, wherein the reaction gas C flowing through the reaction zone C on its way through the reaction zone C optionally further molecular oxygen and / or further inert diluent gas can be supplied.
  • the formaldehyde-containing stream of product gas mixture C leaving the reaction zone C can then be used as such (ie, without first carrying out a separation process on it) to produce the reaction gas input mixture B.
  • the product gas mixture C on leaving the reaction zone C first cool (quench) to reduce undesirable subsequent reactions in the product gas mixture C before its introduction into the reaction gas input mixture B.
  • it is cooled as quickly as possible to temperatures of 150 to 350 ° C, or 200 to 250 ° C.
  • the separation zone T * from the product gas mixture C but also in a separation zone T * first a portion or the total amount of optionally contained therein, unreacted in the reaction zone C, separated methanol, and then the remaining formaldehyde-containing product gas mixture C * (in the As a result of the separation, it is possible to use the liquid state of matter) to generate the reaction gas input mixture B. From an application point of view, the separation will be carried out rectifi- catively.
  • the product gas mixture C optionally after previous direct or indirect cooling, the corresponding provided with cooling rectification column can be supplied in gaseous form.
  • the rectification column can be withdrawn from its bottom region and optionally additionally cooled by indirect heat exchange.
  • the liquid phase is sprayed via corresponding nozzles into finely divided droplets which provide the required large heat exchanger surface for the hot product gas mixture C.
  • the separated methanol is expediently recycled to the reaction zone C and used to produce the reaction gas input mixture C (compare DE-A 1618413).
  • a separation of methanol from the product gas mixture C prior to its use for generating the reaction gas input mixture B is usually carried out when the reaction zone C is designed so that the resulting conversion of methanol in the reaction zone C, based on a single passage of the product gas mixture C. through the reaction zone C is not more than 90 mol%.
  • such a methanol separation but also with corresponding methanol conversions of not more than 95 mol% can be applied.
  • such a methanol separation can be carried out as described in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A1 1, 5th Ed., VCH Weinheim on page 626 ff.
  • the oxidation catalysts C which are particularly suitable for charging the reaction zone C can be subdivided essentially into two groups.
  • the first of the two groups comprises the so-called silver contacts (silver catalysts) which have elemental silver as the active composition, whose purity is preferably> 99.7% by weight, advantageously> 99.8% by weight, preferably> 99.9% by weight. and very particularly preferably> 99.99% by weight.
  • silver contacts These have elemental silver as the active composition, whose purity is preferably> 99.7% by weight, advantageously> 99.8% by weight, preferably> 99.9% by weight. and very particularly preferably> 99.99% by weight.
  • the associated processes of heterogeneously catalyzed partial gas Phase oxidation of methanol to formaldehyde on these "silver contacts” are referred to in the art as silver processes (see, for example, "A. Nagy, G. Mestl: High-Temperature Partial Oxidation Reactions over Silver Catalysts, Appl. Catal., 188 (1999). 337-353 "," H. Schubert, U.
  • Silver oxidation catalysts C which are advantageous according to the invention for charging the reaction zone C are known, for example. in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A1 1, 5th Ed., VCH, Weinheim, p. 619-652, or in Encyclopedia of Chemical Technology, Vol. 11, 4th Ed., Wiley & Sons, New York 929-949, DE-AS 1231229, DE-AS 1294360, DE-A 1903197 and BE-patent 683130.
  • aqueous silver salt solutions whose shape may also be round
  • elemental silver preferably of the aforementioned purity
  • a perforated support eg a perforated plate, a sieve or a mesh network (preferably also of silver manufactured)
  • the total content of elemental metals present in the catalytically active silver of Ag is preferably ⁇ 2,000 ppm by weight, better ⁇ 1,000 ppm by weight, preferably ⁇ 100
  • the silver fixed bed is made as a two-layer bed, the lower layer e.g. 15 to 40 mm, preferably 20 to 30 mm thick and consists of at least 50 wt .-% of silver crystals of grain size 1 to 4 mm, preferably 1 to 2.5 mm.
  • the upper layer may e.g.
  • the flow with reaction gas input mixture C takes place in this case from top to bottom.
  • WO 2010/022923 recommends covering the silver crystals with a thin porous layer of oxidic material of at least one of the elements Al, Si, Zr and Ti (The layer thickness may be 0.3 to 10 ⁇ , preferably 1, 0 to 5.0 ⁇ , more preferably 2.0 to 4.0 ⁇ and most preferably about 3 ⁇ ), and in this way an extension of the service life of the fixed catalyst bed to reach.
  • the content of the reaction gas input mixture C to methanol in the silver process is normally at least 5 vol .-%, usually at least 10 vol .-% and can be up to 60 Vol .-% extend.
  • the aforementioned methanol content in the silver process is preferably from 15 to 50% by volume and more preferably from 20 to 40 or 30% by volume.
  • the ratio of the molar amount present in the reaction gas input mixture C is molecular oxygen (no) for the reaction gas input mixture C contained molar amount of methanol (NMe), no: ⁇ ⁇
  • the silver process is normally less than 1 ( ⁇ 1), preferably ⁇ 0 ,8th. It is more preferably from 0.2 to 0.6 and most preferably from 0.3 to 0.5 or from 0.4 to 0.5. As a rule, no: n Me in the silver process will not be less than 0.1.
  • inert diluent gases for reaction zone A also apply to reaction zone C in the silver process.
  • inert diluent gases usable in the reaction gas input mixture C in the silver process are H 2 O, CO 2, N 2 and noble gases such as Ar and mixtures of the abovementioned gases.
  • molecular nitrogen is also preferable for the reaction gas input mixture C. Its advantageousness is based not least on the fact that molecular nitrogen in air acts as a natural companion to molecular oxygen, making air a preferred source of the molecular oxygen required in reaction zone C. Of course, in the silver method according to the invention but also pure molecular oxygen, or enriched with molecular oxygen air, or other mixture of molecular oxygen and inert diluent gas can be used as the source of oxygen.
  • the reaction gas input mixture C in the silver process contains 20 to 80 vol.%, Or 30 to 70 vol.%, Or 40 to 60 vol.% Of inert diluent gas.
  • the reaction gas input mixture C in the silver method may contain 20 to 80 vol.%, Or 30 to 70 vol.%, Or 40 to 60 vol.% Of molecular nitrogen.
  • water vapor is also co-used as inert diluent gas in the reaction mixture input mixture C in the silver process.
  • the reaction gas input mixture C in the silver process may contain> 0 to 50% by volume of H2O.
  • the reaction gas input mixture C in the silver process preferably contains> 5 to 45% by volume of H 2 O, advantageously> 10 to 40% by volume and more preferably 15 to 35% by volume, or 20 to 30% by volume to H 2 0.
  • the inert gas source can be used in the silver process also for the reaction gas input mixture C of the resulting in the separation zone T stream Z. In terms of application technology, therefore, a partial flow of the material is used in the silver process. Stream Z is recycled to generate the reaction gas input mixture C in the reaction zone C.
  • reaction gas input mixtures C which are suitable according to the invention can, for example, contain 10 to 50% by volume H 2 O and 20 to 60% by volume of inert diluent gas other than water vapor (for example N 2 , or N 2 + CO 2 , or N 2 + Noble gas (eg Ar), or N 2 + CO 2 + noble gas (eg Ar).
  • inert diluent gas other than water vapor for example N 2 , or N 2 + CO 2 , or N 2 + Noble gas (eg Ar), or N 2 + CO 2 + noble gas (eg Ar).
  • reaction gas input mixtures C in the silver process may also contain from 10 to 40% by volume H2O and from 30 to 60% by volume of non-steam inert diluent gases (e.g., the foregoing).
  • reaction gas input mixture C in the silver process may also contain 20 to 40% by volume of H 2 O and 30 to 50% by volume of non-steam inert diluent gases (for example the abovementioned ones).
  • the reaction gas mixture C can both be pushed through the reaction zone C and sucked through it. Accordingly, the working pressure in the silver process within the reaction zone C can be both> 10 5 Pa and ⁇ 10 5 Pa.
  • the working pressure in the silver process in the reaction zone C 10 3 to 10 6 Pa, preferably 10 4 to 5-10 5 Pa, particularly preferably 10 4 to 2-10 5 Pa and particularly preferably 0.5-10 5 Pa to 1 is suitably from an application point of view , 8-10 5 Pa.
  • the temperature of the reaction gas mixture C (the term of the reaction gas mixture C in the present application comprises all gas mixtures occurring in the reaction zone C, which are between the reaction gas input mixture C and the product gas mixture C) in the silver process within the reaction zone C normally in the range of 400 to 800 ° C, preferably in the range of 450 to 800 ° C and more preferably in the range of 500 to 800 ° C.
  • the term of the temperature of the reaction gas mixture C (in this document also referred to as the reaction temperature in the reaction zone C) means in the first place that temperature which the reaction gas mixture C from reaching a conversion of the methanol contained in the reaction gas input mixture C of at least 5 mol% to Having reached the corresponding final conversion of the methanol within the reaction zone C.
  • the temperature of the reaction gas input mixture C in the silver process over the entire reaction zone C is advantageously in the abovementioned temperature ranges.
  • the reaction gas input mixture C of the reaction zone C is advantageously also supplied at a temperature in the aforementioned range.
  • the silver process at the entrance to the reaction zone C upstream of the actual catalytically active catalyst feed (which is also available with inert shaped bodies) a feed of the reaction zone C with solid inert material or of highly inert catalytically active catalyst feed with such inert material.
  • the temperature of the reaction gas inlet mixture C supplied to the reaction zone C in the silver process can be set comparatively easily to the value at which the reaction gas mixture C is to enter the actual catalytically active catalyst charge of the reaction zone C in the silver process.
  • the temperature of the reaction gas mixture C in the silver process within the reaction zone C is limited to values of 450 to 650 ° C., preferably 500 to 600 ° C.
  • the conversion of methanol is generally ⁇ 90 mol%, frequently ⁇ 85 mol%. % or ⁇ 80 mol%, while the selectivity of formaldehyde formation at values> 90 mol%, often> 93 mol% or> 95 mol%.
  • the water vapor content of the reaction gas input mixture is preferably ⁇ 10% by volume
  • the temperature of the reaction gas mixture C in the silver process within the reaction zone C is therefore 550 to 800.degree. C., preferably 600 to 750.degree. C. and particularly preferably 650 to 750.degree.
  • the water vapor content of the reaction gas input mixture C in the silver process is advantageously adjusted to values> 10% by volume, preferably> 15% by volume and particularly advantageously> 20% by volume. Both the elevated temperature and the increased water vapor content of the reaction gas input mixture C in the silver process have an advantageous effect on the methanol conversion (based on a single pass of the reaction gas mixture C through the reaction zone C).
  • this conversion is> 90 mol%, often> 92 mol%, or> 95 mol% and frequently even> 97 mol% (cf., for example, Ullmann's Encylopedia of Industrial Chemistry, Vol , 5th Ed., VCH Weinheim on page 625 ff)
  • the high methanol conversions to be achieved despite the comparatively low ratios no: ⁇ in the reaction gas input mixture C in the silver process are mainly due to the fact that with increasing temperature of the reaction gas mixture C in the reaction zone C the exothermic partial oxidation CH3OH + 0.5 O2 HCHO + H2O is increasingly accompanied by the endothermic dehydrogenation CH3OH ⁇ HCHO + H2).
  • the silver method can be carried out as described in the prior art references already mentioned in this regard or as described in the specifications US-A 4080383, US-A 3994977, US-A 3987107, US-A 4584412 and US-A 4343954.
  • suitable methanol raw materials in this respect are also aqueous methanol solutions and technical methanol, which can be used after appropriate evaporation to produce the reaction gas input mixture C.
  • the reaction zone C in addition to the reactors recommended in the aforementioned prior art, inter alia those heat exchanger reactors which have already been recommended for the realization of the reaction zone A are also suitable.
  • the loading of the reactor charged with silver crystals with methanol contained in the reaction gas input mixture C will generally be (0.5 to 6) -10 3 kg of methanol per m 2 of the reactor cross section or of the cross section of the fixed catalyst bed.
  • the heterogeneously catalyzed partial gas phase oxidation of methanol to formaldehyde is preferably carried out by the FORMOX process.
  • the FORMOX process is carried out on oxidation catalysts C whose active material is a mixed oxide which has at least one transition metal in the oxidized state (cf., for example, WO 03/053556 and EP-A 2213370).
  • transition metals means the chemical elements of the periodic table with the
  • the aforementioned mixed oxide active compositions preferably contain at least one of the transition metals Mo and V in the oxidized state.
  • the above-mentioned active compounds are mixed oxides containing at least the elements Fe and Mo in the oxidized state (cf., for example, US-A 3983073, US-A
  • the ratio of the molar amount of molecular oxygen (NO) present in the reaction gas input mixture C to the molar amount of methanol (n Me ), NO: n Me contained in the reaction gas input mixture C is normally at least 1 or greater than 1 (> 1), preferably> 1, 1.
  • the ratio no: ⁇ ⁇ in the reaction gas input mixture C in the FORMOX process will not be more than 5, often not more than 4.
  • the content of the Christsgaseingangs- mixture C in methanol in the FORMOX process is usually not more than 15 vol .-%, usually not more than 1 1 vol .-% amount. This is due to the fact that gas mixtures of molecular nitrogen, molecular oxygen and methanol containing not more than about 1 1% by volume of molecular oxygen outside the explosive range.
  • the methanol content of the reaction gas input mixture C in the FORMOX process will be> 2% by volume, preferably from 4 to 10% by volume and more preferably from 6 to 9% by volume or from 5 to 7% by volume.
  • Gas input mixture C can be applied.
  • the FORMOX process also differs from the silver process in that the methanol conversions obtained with this process, based on a single pass of the reaction gas mixture C through the reaction zone C, are generally> 90 mol%, usually independent of the inert diluent gas used in the reaction gas input mixture C. > 92 mol%, usually> 95 mol% and often even> 97 mol% or> 98 mol%, or> 99 mol%.
  • the associated selectivities of formaldehyde formation are regularly> 90 mol%, usually> 92 mol% and often> 94 mol% and often even> 96 mol%.
  • Suitable inert diluent gases in the reaction gas input mixture C according to the invention for the FORMOX process in the reaction zone C are also gases such as H 2 0, N 2 , C0 2 and E- delgase such as Ar and mixtures of the aforementioned gases into consideration.
  • Preferred inert diluent gas other than water vapor is also molecular nitrogen in the FORMOX process in the reaction gas input mixture C.
  • the content of the reaction gas input mixture C of inert diluent gas (the definition of an inert diluent gas for the reaction zone C is analogous to that for the reaction zones A and B) in the FORMOX method 70 to 95 vol .-%, often 70 to 90 vol .-% and advantageously be 70 to 85 vol .-%. That is, the content of the reaction gas input mixture C of molecular nitrogen may be 70 to 95% by volume, or 70 to 90% by volume, or 70 to 85% by volume when the FORMOX method is used in the reaction gas inlet mixture C.
  • the reaction gas input mixture C in the FORMOX process can be free of water vapor.
  • the reaction gas input mixture C will have a low water vapor content when using a FORMOX process in the reaction zone C for similar reasons as in the case of the reaction gas input mixture A.
  • the water vapor content of the reaction gas input mixture C in the FORMOX process in the reaction zone C is> 0.1% by volume and ⁇ 20% by volume or ⁇ 10% by volume, advantageously> 0.2% by volume. and ⁇ 7% by volume, preferably> 0.5 and ⁇ 5% by volume.
  • Another advantage of the application of a FORMOX process in the reaction zone C according to the invention lies in the fact that the high methanol conversions described at set much lower reaction temperatures compared to the application of a silver process.
  • the temperature of the reaction gas mixture C in the FORMOX process in the reaction zone C will normally be in the range of 250 to 500 ° C, preferably in the range of 300 to 450 ° C, and often in the range of 270 to 400 ° C.
  • the term "temperature of the reaction gas mixture C" corresponds to that which has already been given in this document in the silver process.
  • the temperature of the reaction gas mixture C (in this document also referred to as the reaction temperature in the reaction zone C) is advantageously the FORMOX - Process over the entire reaction zone C in the above-mentioned temperature ranges.
  • the reaction gas input mixture C is already supplied to the reaction zone C with a temperature in the aforementioned range Flow direction in advance of the actual catalytically active catalyst charge (which may also be diluted with inert moldings) a feed of the reaction zone C with solid inert material or with such inert material highly diluted catalytically active Katalysatorbeschicku
  • the temperature of the reaction gas input mixture C supplied to the reaction zone C in the FORMOX process can be adjusted comparatively easily to the value with which the reaction gas mixture C in the FORMOX process is converted into the actual catalytically active catalyst feed Reaction zone C should occur.
  • the working pressure in the reaction zone C the statements made in the silver process apply corresponding
  • Particularly suitable mixed oxide active materials for the FORMOX process are those of the general formula III,
  • Mo and / or Fe and, based on the total molar amount of Mo and Fe, a total molar amount of up to 10 mol% (eg 0.01 to 10 mol%, or 0.1 to 10 mol%), preferably not more as 5 mol%,
  • n 1 to 6, with the proviso that the content of both square brackets is electrically neutral, that is, has no electric charge.
  • mixed oxide active materials III contain less than 50 mol%, more preferably less than 20 mol% and particularly preferably less than 10 mol% of the Fe contained in the mixed oxide active material III in the oxidation state +2, and the respective remaining amount of them in them contained Fe in the oxidation state +3. Most preferably, the mixed oxide active material III contains the entire Fe contained in it in the oxidation state +3.
  • the ratio ⁇ 0 : nFe of molar amount of Mo ( ⁇ ⁇ ) TO contained in a mixed oxide active material III in the same mixed oxide active mass of molar amount of Fe (n Fe ) is preferably 1: 1 to 5: 1.
  • favorable mixed oxide III those whose stoichiometry is such that they are considered formally as a mixture of M0O3 and Fe20 3 (represent) are further blank and Mo0 3 content of the mixture 65 to 95 wt .-% and the Fe20 3 Content of the mixture is 5 to 35% by weight.
  • the procedure will be such that from the sources of the catalytically active oxide III a preferably intimate, preferably finely divided, the stoichiometry of the desired oxide composition III correspondingly composed, dry mixture (a precursor composition) and this at temperatures of 300 to 600 ° C, preferably 400 to 550 ° C calcined (thermally treated).
  • the calcination can be carried out both under inert gas and under an oxidative atmosphere such as air (or another mixture of inert gas and oxygen) and under a reducing atmosphere (eg a mixture of inert gas and reducing gases such as NH 3 and CO).
  • the calcination time will usually be a few hours and usually decreases with the height of the calcination temperature.
  • Suitable sources of the elemental constituents of the mixed oxide active materials III are, in particular, those compounds which are already oxides and / or those compounds which can be converted into oxides by heating, at least in the presence of oxygen.
  • the intimate mixing of the starting compounds (sources) can be carried out in dry ner or in wet form. If it takes place in dry form, the starting compounds are expediently used as finely divided powders and subjected to the calcination after mixing and optionally compacting. Preferably, however, the intimate mixing takes place in wet form.
  • the starting compounds are mixed together in the form of aqueous suspensions and / or solutions. Particularly intimate dry mixtures are obtained in the described mixing process when starting exclusively from sources of the elementary constituents present in dissolved form.
  • the solvent used is preferably water. At least two aqueous solutions are preferably prepared from the starting compounds, of which at least one is an acidic solution and at least one is an ammoniacal (basic) solution.
  • the resulting aqueous mass is dried, wherein the drying process can be carried out for example by spray drying.
  • the catalytically active oxide composition obtained after calcination of the dry mass can be used in finely divided form as such, or applied with the aid of a liquid binder to an outer surface of a carrier molding as a shell catalyst for charging the reaction zone C for the FORMOX process.
  • the coated catalyst preparation can also be carried out in such a way that finely divided precursor powder is applied to the outer surface of shaped carrier bodies with the aid of a liquid binder and the calcination of the precursor substance takes place only after the application and drying.
  • the multimetal oxide active compositions III can also be used in pure, undiluted form or diluted with an oxidic, essentially inert diluting material as so-called full catalysts in reaction zone C (this is preferred according to the invention).
  • Suitable inert diluent materials according to the invention include, for example, finely divided aluminum oxide, silicon dioxide, aluminosilicates, zirconium dioxide, titanium dioxide or mixtures thereof.
  • Undiluted unsupported catalysts are preferred according to the invention.
  • the shaping is advantageously carried out with precursor powder, which is calcined only after molding.
  • the shaping is usually carried out with the addition of shaping aids such as graphite (lubricant) or mineral fibers (reinforcing aids).
  • shaping aids such as graphite (lubricant) or mineral fibers (reinforcing aids).
  • Suitable molding methods are tabletting, extrusion and extrusion.
  • the shaping can also be carried out, for example, with a mixture of active material powder and precursor powder, to which shaping in advance shaping aids and optionally inert dilution powders are added in advance.
  • After shaping is calcined again.
  • the shape to full catalysts only be carried out with already prefabricated active composition powder and optionally the said auxiliaries. This procedure is less advantageous.
  • calcination is generally carried out here as well.
  • a favorable Mo source is, for example, ammonium heptamolybdate tetrahydrate (NH 4 ) 6 ( ⁇ 7 ⁇ 24) -4 ⁇ 2 O.
  • Advantageous iron sources are, for example, iron (II) nitrate [Fe (NC> 3) 3], iron (III) chloride [FeC ] or hydrates of the iron (lll) -nitrats such as Fe (N0 3) 3-9 H 2 0th
  • suitable geometries and materials of the carrier moldings and the coating process for the preparation of coated catalysts of Mischoxidgenmassen III apply the statements made in the context of coated catalyst oxidation catalysts A in this document statements in a corresponding manner.
  • Preferred geometries of the carrier shaped bodies are also spheres and rings whose longitudinal extension is 1 to 10 mm, often 2 to 8 mm or 3 to 6 mm.
  • Favorable ring geometries according to the invention have hollow-cylindrical carrier shaped bodies with a length of 2 to 10 mm, an outer diameter of 4 to 10 mm and a wall thickness of 1 to 4 mm.
  • the hollow cylindrical carrier moldings have a length of 3 to 6 mm, an outer diameter of 4 to 8 mm and a wall thickness of 1 to 2 mm.
  • the thickness of the shell of catalytically active oxide mass applied to the carrier shaped bodies in the case of the aforementioned coated catalysts is, in the case of the mixed oxide active materials III, also suitably advantageous in terms of application, generally from 10 to 1000 ⁇ .
  • the shell thickness is 10 to 500 ⁇ , more preferably 100 to 500 ⁇ and most preferably 200 to 300 ⁇ .
  • Preferred unsupported catalyst bodies comprising mixed oxide active materials III are solid cylinders, hollow cylinders and trilobes.
  • the outer diameter of cylindrical unsupported catalysts is suitably 3 to 10 mm, preferably 4 to 8 mm and especially 5 to 7 mm.
  • Their height is advantageously 1 to 10 mm, preferably 2 to 6 mm and especially 3 to 5 mm.
  • the inner diameter of the opening running from top to bottom is advantageously 1 to 8 mm, preferably 2 to 6 mm and most preferably 2 to 4 mm.
  • the wall thickness of hollow cylinders is 1 to 3 mm.
  • Mixed oxide active material III oxidation catalysts C can also be used in the reaction zone C as supported catalysts.
  • Methanol raw materials which are suitable in this regard according to the invention are also aqueous methanol solutions and technical methanol which, after appropriate evaporation, can be used to produce the reaction gas input mixture C.
  • the reaction zone C can also be charged with a fixed catalyst bed which has FORMOX oxidation catalysts C in a form diluted with inert shaped bodies.
  • the loading of the catalyst fixed bed in reaction zone C with reaction gas starting mixture C in a FORMOX process used according to the invention will generally be 3500 Nl / l-h to 75000 Nl / l-h, preferably 25000 Nl / l-h to 35000 Nl / l-h.
  • the term load is used as defined in DE-A 19927624.
  • the heat exchanger reactors which have already been recommended for the realization of the reaction zone A are also suitable (cf., for example, WO 2005/063375).
  • reaction zone C leaving product gas mixture C is used to produce the reaction gas input mixture B as a formaldehyde source, which is the product of a carried out in the reaction zone C FORMOX process.
  • reaction zone C is also because such a product gas mixture C, unlike a product gas mixture C after the silver process is free of molecular hydrogen.
  • the product gas mixture C of a heterogeneously catalyzed partial gas phase oxidation of methanol to formaldehyde by the FORMOX process is (without previously subjecting it to a separation process without first carrying out a separation process on it) the ideal formaldehyde source for formaldehyde required in the reaction gas input mixture B.
  • the product gas mixture C falls in the FORMOX process at a temperature with which it can be used to produce the reaction gas input mixture B without further thermal pretreatment.
  • the temperature of the product gas mixture C leaving the reaction zone C is not limited to both the silver process and the FORMOX process.
  • the method differs from the temperature with which it is to be used to generate the reaction gas input mixture B.
  • the stream of the product gas mixture C can flow through an indirect heat exchanger on its way out of the reaction zone C into the reaction zone B, in order to adapt its temperature to the mixing temperature intended for the generation of the reaction gas input mixture B.
  • the feed of reaction zone C with at least one oxidation catalyst C can be designed as a fluidized bed. From an application point of view, however, the feed of the reaction zone C with the oxidation catalyst C is carried out as a fixed bed.
  • the stream Z produced in the separation zone T in the process according to the invention forms a suitable inert gas source for the inert gas required in the reaction gas input mixture C and, suitably in terms of application, a substream of the material.
  • Stream Z is recycled to generate the reaction gas input mixture C in the reaction zone C.
  • the separation can be carried out by fractional condensation, as is recommended in DE-A 102007004960, DE-A 10 2007055086, DE-A 10243625, DE-A 10235847 and DE-A 19924532.
  • the temperature of the product gas mixture B is optionally initially reduced by direct and / or indirect cooling and the product gas mixture B then passed into a condensation column equipped with separation-active internals (eg mass transfer trays) and optionally provided with cooling circuits and within itself within the condensation column ascending fractionally condensed.
  • separation-active internals eg mass transfer trays
  • the streams X, Y and Z can be led out as separate fractions with the particular desired degree of enrichment from the condensation column.
  • stream X is generally separated off with an acrylic acid content of> 90% by weight, preferably> 95% by weight, and taken out of the condensation column. If the purity requirement is increased, stream X can advantageously be further purified in terms of application technology by crystallization (preferably suspension crystallization) (compare the abovementioned publications of the prior art and WO 01/77056). Of course, the led out of the condensation column stream X can also be purified by rectification. In both ways can be so with relatively little effort Acrylic acid units> 99.9 wt .-% can be achieved, which are suitable for the preparation of water-absorbing resins by free radical polymerization of acrylic acid and / or their sodium salt comprising monomer mixtures. The preparation of the water-absorbing resins can be carried out, for example, as in the documents WO
  • the stream Y is normally led out of the condensation column with an acetic acid content> 90% by weight, preferably> 95% by weight.
  • the thus separated stream Y can be recycled as such for generating the Christsgaseingangs- mixture B in the reaction zone B.
  • the acetic acid content of which enriches further rectificatively and / or crystallisatively eg to acetic acid contents> 99 wt .-%), or by increasing the number of theoretical plates in the condensation column to separate the stream Y in the same directly with such increased purity.
  • the stream Z leaves the condensation column usually overhead.
  • the product gas mixture B in this procedure in an advantageous equipped with separating internals absorption column in countercurrent to a normal pressure (10 5 Pa) higher than acrylic acid boiling organic solvent (such as, for example, the in DE-A 102009027401 and in DE-A 10336386 mentioned organic solvent into consideration) and the acetic acid contained in the product gas mixture B and acrylic acid in the organic solvent, while a stream Z leaves the absorption column at the top.
  • acrylic acid boiling organic solvent such as, for example, the in DE-A 102009027401 and in DE-A 10336386 mentioned organic solvent into consideration
  • streams X and Y can be separated by appropriate selection of the number of theoretical separation stages (the theoretical plates) in a manner known per se by rectification (fractional distillation) in a rectification column having the respectively desired degree of enrichment.
  • this degree of enrichment of acrylic acid or acetic acid will be at least 90% by weight, preferably at least 95% by weight.
  • a subsequent crystallisative further purification of the separated stream X leads to comparatively little effort to acrylic acid units> 99.9 wt .-%, for the production of water-absorbing resins by free-radical polymerization of acrylic acid and / or its sodium salt comprehensive monomer mixtures are suitable.
  • the material stream Y which has been separated off by rectification as described can be recycled as such or after any crystallization and / or rectification (eg to acetic acid contents> 99% by weight) of the reaction gas input mixture B into the reaction zone B.
  • any crystallization and / or rectification eg to acetic acid contents> 99% by weight
  • the material stream Y can also be separated from the absorbate directly with such a degree of enrichment.
  • the acrylic acid contained in the product gas mixture B and acetic acid from selbigem in an absorption column can also be included in an aqueous absorbent, while a stream Z the absorption column leaves at the head. Subsequent rectificative separation of the aqueous absorbate, with the optional inclusion of an azeotropic entraining agent, gives the desired mass flows X and Y.
  • the conversion of the acetic acid contained in the reaction gas mixture B and acrylic acid in the condensed phase, leaving a gaseous stream Z, can also be used e.g. by one-stage condensation of those contained in the reaction gas mixture B components whose boiling point is not above that of acetic acid at atmospheric pressure, take place. Subsequently, the condensate containing acrylic acid and acetic acid can again be separated into at least one stream Y and at least one stream X in the respectively desired degree of enrichment.
  • At least 90 mol%, preferably at least 95 mol%, particularly preferably at least 98 mol% or at least 99 mol% of the acetic acid present in the product gas mixture B are recycled to the reaction zone B to produce the reaction gas input mixture B in the process according to the invention.
  • acrylic acid contained in the stream X or a mixture of acrylic acid contained in stream X and one or more of acrylic acid, at least monoethylenically unsaturated monomers polymerized to form polymers eg free radical; the polymerization may be, for example, a solution polymerization or an aqueous emulsion polymerization or a suspension polymerization
  • the process according to the invention may also be followed by a process in which acrylic acid contained in the stream X has at least one, eg 1 to 8 carbon atoms, alcohol (e.g., such an alkanol as methanol,
  • Ethanol, n-butanol, tert-butanol and 2-ethylhexanol) to the corresponding acrylic acid ester (acrylate) is esterified.
  • the process of acrylic acid ester preparation can then be followed by a process in which the acrylic ester prepared or a mixture of the acrylic ester prepared and one or more, at least monoethylenically unsaturated monomers different from the acrylic ester produced are polymerized to form polymers (eg free-radical polymerization; may be, for example, a solution polymerization or an aqueous emulsion polymerization or a suspension polymerization).
  • deactivation of the various catalysts in the various reaction zones of the process according to the invention can be counteracted by correspondingly increasing the reaction temperature in the respective reaction zone (by a single pass of the reaction gas mixture) to keep the catalyst charge related reactant turnover stable).
  • the oxidic active materials of the reaction zones A, B and C can be regenerated in a manner corresponding to that described for comparable oxidic catalysts in WO 2005/042459 by passing over an oxidizing oxygen-containing gas at elevated temperature.
  • the inventive method captivates on the one hand by its broad and time-consuming raw material base. On the other hand, it is a method which, in contrast to the prior art methods while maintaining the procedure allows a sliding transition from "fossil acrylic acid” to "renewable acrylic acid”.
  • acrylic acid is meant acrylic acid, for which the ratio of the molar amount of 4 C atomic nuclei contained in this acrylic acid to the molar amount of 12 C atomic nuclei contained in the same acrylic acid, n 14 C: n 12 C, disappears
  • new acrylic acid is meant acrylic acid, for which the ratio n 14 C: n 12 C corresponds to the ratio V * of n 14 C: n 12 C present in the atmosphere in the atmosphere on the Earth Ratio n 14 C: n 12 C according to the procedure developed by Willard Frank Libby
  • 14 C In the upper layers of the Earth's atmosphere, 14 C is constantly being re-formed by nuclear reaction. At the same time 14 C decomposes with a half-life of 5700 years by ß-decay. Between constant regeneration and continual decay, equilibrium is established in the Earth's atmosphere, so that the proportion of 14 C nuclei in the atmosphere's carbon on Earth is constant over long periods of time in the atmosphere on Earth stable ratio V * is present.
  • the radiocarbon produced in the atmosphere combines with atmospheric oxygen to form CO2, which then enters the biosphere through photosynthesis. In this way, living beings (plants, animals, humans) constantly metabolize carbon with their metabolism.
  • n 14 C In living organisms, the same distribution ratio of the three carbon isotopes and therefore the same ratio n 14 C: n 12 C arises as exists in the surrounding atmosphere. If this exchange is interrupted at the time of the death of the living being, the ratio between 14 C and 12 C in the dead organism changes because the decaying 14 C atomic nuclei are no longer replaced by new ones (the carbon contained in the dead organism becomes fossil). If the death of the organism (living thing) is more than 50,000 years old, its 14 C content is below the detection limit.
  • a further advantage of the procedure according to the invention is that neither the target product of the reaction zone A nor the target product of the reaction zone C require separation from the product gas mixture A or C in order to be used to produce the reaction gas inlet mixture B. This ensures both a high economy and an efficient energy balance for the method according to the invention.
  • the inventive method ensures a high space-time yield at the same time high, based on the reacted reactants target product selectivity.
  • a process for preparing acrylic acid from ethanol and formaldehyde comprising the steps of: passing through a first reaction zone A charged with at least one oxidation catalyst A, a stream of one of the reactants is ethanol and molecular oxygen and at least one other than water vapor Heterogeneously catalysed by heterogeneously catalysed ethanol oxidized to acetic acid and water vapor, so that an acetic acid, water vapor, molecular oxygen and at least one of water vapor different inert diluent gas containing product gas mixture A is formed and a stream of the reaction gas A contained in the reaction gas input mixture A
  • Product gas mixture A leaves the reaction zone A, wherein the reaction gas mixture A flowing through the reaction zone A on its way through the reaction zone A optionally further molecular oxygen and / or further inert V a stream of acetic acid, water vapor, molecular oxygen, at least one non-aqueous inert diluent gas and formaldehyde-containing reaction gas input
  • the acrylic acid stream contained in the stream X is greater than the combined in the streams Y and Z together contained acrylic acid stream contained in the stream Y is greater than that contained in the streams X and Z taken together acetic acid stream
  • the contained in the stream Z stream of water vapor different inert diluent gas is greater than that contained in the streams X and Y combined stream of water vapor different inert diluent gas
  • the stream Y is recycled to the reaction zone B and to produce the Reaction gas input mixture B also used.
  • the at least one oxidation catalyst A has a catalytically active composition which contains at least one vanadium oxide.
  • the at least one oxidation catalyst A comprises a catalytically active composition which contains at least one vanadium oxide and additionally at least one oxide from the group of the oxides of titanium of aluminum, zirconium and tin.
  • the catalytically active composition contains from 1 to 50 wt .-% V2O5.
  • the catalytically active material to 3 to 40 wt .-% V2O5.
  • the at least one oxidation catalyst A is a shell catalyst, which has applied the catalytically active material as a shell on the surface of an inert carrier molding.
  • Longest extent of the carrier molded body is 1 to 10 mm.
  • the at least one oxidation catalyst A of the section 1 comprises a catalytically active composition 1 which contains at least one vanadium oxide and at least one oxide from the group of the oxides of titanium, aluminum, zirconium and tin
  • the at least one oxidation catalyst A of the Section 2 has a catalytically active material 2, which is a multimetal, in addition to V and Mo additionally at least one of W, Mo, Ta, Cr and Ce and at least one of Cu, Ni, Co, Fe, Mn and Zn.
  • the catalytically active composition 1 contains from 1 to 50% by weight of V 2 Os as the at least one vanadium oxide and from 50 to 99% by weight of ⁇ O 2 as the oxide of the titanium (preferably in the anatase Modification) or consists of.
  • the catalytically active composition 1 contains from 3 to 40% by weight of V 2 Os as the at least one vanadium oxide and from 60 to 97% by weight of TO 2 as oxide of titanium (preferably in the anatase). Modification) contains or consists of.
  • the catalytically active composition 1 contains from 5 to 30% by weight of V 2 Os as the at least one vanadium oxide and from 70 to 95% by weight of TO 2 as the oxide of titanium (preferably in the anatase). Modification) contains or consists of.
  • a method according to embodiment 33 characterized in that the carrier shaped body is a ball or a ring.
  • Method according to one of the embodiments 33 to 36 characterized in that the thickness of the shell of catalytically active mass 1 10 to 2000 ⁇ , or 10 to 500 ⁇ , or 100 to 500 ⁇ , or 200 to 300 ⁇ .
  • Method according to one of the embodiments 27 to 37 characterized in that the catalytically active material 1 has no Mo.
  • X 1 W, Nb, Ta, Cr and / or Ce
  • X 2 Cu, Ni, Co, Fe, Mn and / or Zn,
  • X 3 Sb and / or Bi
  • X 4 one or more alkali metals
  • X 5 one or more alkaline earth metals
  • X 6 Si, Al, Ti and / or Zr
  • n the stoichiometric coefficient of the element oxygen, which is determined by the stoichiometric coefficients of the elements other than oxygen and their charge number in I,
  • the catalytically active composition 2 comprises at least one multimetal oxide of the general formula I
  • X 1 W, Nb and / or Cr
  • X 2 Cu, Ni, Co, Fe, Mn and / or Fe,
  • X 5 Ca, Sr and / or Ba
  • n the stoichiometric coefficient of the element oxygen, which is determined by the stoichiometric coefficients of the elements other than oxygen and their charge number in I,
  • Method according to one of the embodiments 27 to 40 characterized in that the at least one oxidation catalyst A of the section 2 is a shell catalyst, which has the catalytically active material 2 applied as a shell on the surface of an inert support molding.
  • Longest extent of the carrier molded body is 1 to 10 mm.
  • Method according to embodiment 49 characterized in that 2 is at least 10 ° C greater than T 1 .
  • Method according to embodiment 49 characterized in that 2 is at least 20 ° C greater than T 1 .
  • T 2 is not more than 80 ° C greater than 1 .
  • reaction gas input mixture A contains 0.3 to 20% by volume of ethanol.
  • reaction gas input mixture A contains 0.5 to 15% by volume of ethanol.
  • reaction gas input mixture A contains 0.75 to 10% by volume or 1 to 5% by volume of ethanol.
  • reaction gas input mixture A contains the molecular oxygen in a molar amount no and the ethanol in a molar amount n ⁇ and the ratio no: n ⁇ at least 1.3.
  • na is at least 1.75.
  • reaction gas input mixture A contains 1 to 40% by volume of H 2 0.
  • reaction gas input mixture A contains 1 to 20% by volume of H 2 0.
  • reaction gas input mixture A contains 5 to 15% by volume of H 2 0.
  • reaction gas input mixture A as at least one other than water vapor inert diluent gas contains at least 40% by volume of molecular nitrogen.
  • reaction gas input mixture A contains at least one of different than water vapor inert diluent gas not more than 90% by volume of molecular nitrogen.
  • reaction gas input mixture A based on the weight of the ethanol contained therein, at least 1 ppm by weight of a chemical compound containing the element sulfur, calculated as the amount of sulfur contained.
  • reaction gas input mixture A based on the weight of the ethanol contained therein, 2 bis
  • reaction gas input mixture A based on the weight of the contained ethanol, 0 to ⁇ 1 ppm by weight of a chemical compound containing the element sulfur, calculated as the amount of sulfur contained ,
  • Solution of bioethanol is. 83.
  • the method according to embodiment 82 characterized in that as the source of the ethanol contained in the reaction gas input mixture A, the filtrate is used in a bioethanol production resulting, the bioethanol dissolved aqueous mash.
  • a process according to any of embodiments 1 to 83 characterized in that at least one of trioxane, paraformaldehyde, formalin, methylal, aqueous paraformaldehyde solution, aqueous formaldehyde solution and the product gas mixture of a heterogeneously catalyzed partial gas phase phase oxidation of formaldehyde source for the formaldehyde contained in the reaction gas input mixture B.
  • Methanol is used to formaldehyde, from which either optionally contained therein unreacted methanol is separated.
  • reaction temperature in the reaction zone B is 260 to 400 ° C.
  • reaction temperature in the reaction zone B is 280 to 380 ° C.
  • reaction temperature in the reaction zone B is 300 to 370 ° C.
  • reaction gas input mixture B contains the acetic acid in a molar amount ⁇ and the formaldehyde in a molar amount nFd and the ratio ⁇ : nFd is greater than 1 and ⁇ 10.
  • the ratio ⁇ : n F d is 1, 1 to 5.
  • Method according to one of the embodiments 1 to 99 characterized in that the water vapor content of the reaction gas input mixture B does not exceed 20 vol .-% and 2 vol .-% does not fall below.
  • reaction gas input mixture B contains at least 50% by volume of N 2 as at least one inert diluent gas other than water vapor.
  • the at least one aldol condensation catalyst B is a zeolite with anionic framework charge, on the inner and outer surface of which at least one cation species from the group of alkali metal and alkaline earth metal ions is present Neutralize framework charge.
  • Method according to embodiment 108 characterized in that the hydroxide applied to the amorphous silica is KOH, NaOH, Ca (OH) 2 or Mg (OH) 2 .
  • the at least one aldocondensation catalyst B comprises a catalytically active composition which is a vanadium phosphorus oxide or a Vanadin phosphorus oxide doped with elements other than vanadium and phosphorus.
  • a catalytically active composition which is a vanadium phosphorus oxide or a Vanadin phosphorus oxide doped with elements other than vanadium and phosphorus.
  • the catalytically active composition is a multielement oxide active composition of the general formula II,
  • X 1 Mo, Bi, Co, Ni, Si, Zn, Hf, Zr, Ti, Cr, Mn, Cu, B, Sn and / or Nb,
  • X 2 Li, K, Na, Rb, Cs and / or TI
  • n the stoichiometric coefficient of the element oxygen, which is determined by the stoichiometric coefficients of the elements other than oxygen and their number of charges in II.
  • X 1 Nb, Mo, Zn and / or Hf.
  • Method according to one of the embodiments 1 13 to 16, characterized in that X 1 Mo.
  • vanadium and phosphorus elements contained in the catalytically active composition are one or more than one element selected from the group consisting of lithium, potassium, sodium, rubidium, cesium , Thallium, molybdenum, zinc, hafnium, zirconium, titanium, chromium, manganese, nickel, copper, iron, boron, silicon, tin, niobium, cobalt and bismuth.
  • Process according to embodiment 121 characterized in that the total content of elements different from vanadium and phosphorus in the catalytically active composition, by weight, is not more than 5% by weight, the respective element other than vanadium and phosphorus being electrical neutral oxide is calculated, in which the element has the same charge number as in the active composition.
  • Process according to any of embodiments 112 to 122 characterized in that the arithmetic mean oxidation state of the vanadium in the catalytically active composition is +3.9 to +4.4 or +4.0 to +4.3.
  • Method according to one of the embodiments 1 12 to 123 characterized in that the BET specific surface area of the catalytically active composition is> 15 to 50 m 2 / g.
  • Method according to one of the embodiments 1 12 to 124 characterized in that the total pore volume of the catalytically active composition is 0.1 to 0.5 ml / g.
  • Method according to one of the embodiments 1 12 to 125 characterized in that the total pore volume of the catalytically active composition is 0.15 to 0.4 ml / g.
  • Method according to one of the embodiments 1 12 to 126 characterized in that the at least one oxidation catalyst B is a full catalyst or a supported catalyst.
  • Method according to embodiment 127 characterized in that the geometry of the solid catalyst is selected from the group consisting of ball, ring and solid cylinder, and has a longitudinal extension in the range of 1 to 10 mm.
  • a method according to the embodiment 127 characterized in that the geometry of the full catalyst is a ring (a hollow cylinder) having an outer diameter in the Range of 3 to 10 mm, a height of 1 to 10 mm, an inner diameter of 1 to 8 mm and a wall thickness of 1 to 3 mm.
  • Method according to embodiment 130 characterized in that the carrier shaped body is a ball or a ring.
  • Longest extent of the carrier molded body is 1 to 10 mm. 133.
  • a process according to any of embodiments 1 to 134 characterized in that it comprises a further, a third reaction zone C, which is charged with at least one oxidation catalyst C, and comprises the following additional measures: by a third reaction zone C, the is fed with at least one oxidation catalyst C, a stream of the reactants methanol and molecular oxygen and at least one of different water vapor inert diluent gas containing Mattersgaseingangsgemischs C is passed through and heterogeneously catalyzed when flowing through the reaction zone C in the reaction gas input mixture C methanol to formaldehyde and steam, so that a formaldehyde, water vapor and at least one of different water vapor inert diluent gas containing product gas mixture C is formed and a stream of product gas mixture C leaves the reaction zone C, wherein the flowing through the reaction zone C. en reaction gas mixture C on his
  • reaction zone C optionally further molecular oxygen and / or further inert diluent gas can be added through the reaction zone C; optionally, unreacted methanol still present in the product gas mixture C is separated from the product gas mixture C in a separation zone T * in the product gas mixture C, a product gas mixture C containing formaldehyde being separated off * remains, and the product gas mixture C or the product gas mixture C * is fed into the reaction zone B to produce the reaction gas input mixture B.
  • Method according to one of the embodiments 138 to 140 characterized in that the at least one oxidation catalyst C comprises silver crystals whose
  • reaction gas input mixture contains C> 0 to 50 vol .-% of H 2 0.
  • reaction gas input mixture C contains 15 to 35 vol.% Or 20 to 30 vol.% Of H 2 O.
  • reaction gas input mixture C contains as at least one other than water vapor inert diluent N 2 .
  • reaction gas input mixture C contains 20 to 80 vol .-% N 2 .
  • reaction gas input mixture C contains 30 to 70 vol .-% N 2 .
  • reaction gas input mixture C contains 40 to 60% by volume of N 2 .
  • methanol is oxidized in the reaction zone C at a reaction temperature in the range of 400 to 800 ° C to formaldehyde and water.
  • Method according to embodiment 161 characterized in that the at least one transition metal comprises Mo and / or V.
  • Mo and / or Fe and, based on the total molar amount of Mo and Fe, a total molar amount of up to 10 mol% (eg 0.01 to 10 mol%, or 0.1 to 10 mol%), preferably not to more than 5 mol%, one or more elements from the group consisting of Ti, Sb, Sn, Ni, Cr, Ce, Al, Ca, Mg, V, Nb, Ag, Mn, Cu, Co, Si, Na, K, TI, Zr, W, Ir, Ta, As, P and B, q 0 to 5,
  • n 1 to 6 is. 165.
  • Method according to one of the embodiments 164 to 168 characterized in that less than 10 mol% of the Fe contained in the mixed oxide III in the oxidation state +2 is present. 172. Method according to one of the embodiments 164 to 168, characterized in that the total amount of Fe contained in the mixed oxide III is in the oxidation state +3.
  • Method according to one of the embodiments 164 to 172 characterized in that the ratio n Mo : n Fe , formed from the molar amount of Mo contained in the mixed oxide III and the molar amount of Fe, 1: 1 to 5: 1.
  • the catalytically active composition can formally be represented as a mixture of M0O3 and Fe20 3 , wherein the content of the mixture of M0O3 65 to 95 wt .-% and the content of the Mixture of Fe2Ü 3 5 to 35 wt .-% is.
  • the solid catalyst has the geometry of a ring having an outer diameter of 3 to 10 mm, a height of 1 to 10 mm and an inner diameter of 1 to 8 mm. 79.
  • the at least one oxidation catalyst C is a shell catalyst, which has the catalytically active mixed oxide applied as a shell on the surface of an inert support molding. 181.
  • Method according to embodiment 180 characterized in that the shaped support body is a ball or a ring.
  • the inert support molding is a ring with a length of 2 to 10 mm, an outer diameter of 4 to 10 mm and a wall thickness of 1 to 4 mm.
  • the shell of catalytically active mixed oxide has a thickness of 10 to 2000 ⁇ , or 10 to 500 ⁇ , or 100 to 500 ⁇ , or 200 to 300 ⁇ .
  • reaction gas input mixture C contains not more than 15 vol .-% methanol.
  • reaction gas input mixture C contains not more than 1 1 vol .-% methanol.
  • reaction gas input mixture C contains 2 to 10 vol .-% of methanol.
  • reaction gas input mixture C contains 6 to 9 vol .-% of methanol.
  • reaction gas input mixture C contains the molecular oxygen in a molar amount no and the methanol in a molar amount ⁇ ⁇ and the ratio no: nMe at least 1 or greater than 1.
  • Method according to embodiment 190 characterized in that the ratio no: ⁇ ⁇ is 1, 1 to 5. 192. Method according to embodiment 190 or 191, characterized in that the ratio no: n Me is 1.5 to 3.5.
  • reaction gas input mixture C contains at least one non-steam-diluting inert diluent gas N 2 .
  • reaction gas input mixture C contains 70 to 95 vol .-% N 2 . 195.
  • reaction gas input mixture C 0 to 20 vol .-% H 2 0 contains.
  • reaction gas input mixture C contains 0.1 to 10 vol .-% H 2 0.
  • reaction gas input mixture C contains 0.2 to 7 vol .-% H 2 0.
  • Condensation column is condensed fractionally and the streams X, Y and Z are led out as separate fractions from the condensation column.
  • Acrylic acid for which the ratio V of the molar amount of n 14 C contained in this acrylic acid to 14 C atomic nuclei to the molar in the same acrylic acid
  • Amount n 12 C on 12 C nuclei, V n 14 C: n 12 C, greater than 0 and less than the corresponding molar ratio V * of 14 C atomic nuclei to 12 C atomic nuclei in the atmosphere's carbon dioxide , 208.
  • Acrylic acid according to embodiment 207, characterized in that V (1/3) -V *.
  • the solution 2 was continuously stirred while maintaining the 60 ° C in the solution 1.
  • the mixture was then stirred for 5 min at 60 ° C.
  • the resulting aqueous suspension was then spray dried at an inlet temperature of 340 ° C and an outlet temperature of 1 10 ° C in air flow within 1, 5 h
  • the spray powder thus obtained was, based on its weight, 1 wt .-% of graphite TIM REX ® T44 Timcal AG homogeneously mixed (in an adequate mixer; wheel diameter (cf. WO 2008/0871. 16): 650 mm, drum volume: 5 I, speed: about 30 rpm, mixing time: 30 min).
  • the resulting mixture was then compacted in a RCC 100x20 roll compact from Powtec with 2 counter-rotating steel rolls at a pressure of 12 bar and then forced through a sieve with square meshes of 0.8 mm mesh.
  • the resulting Kompaktat (it had a bulk density of 1050 g / l and a substantially uniform grain size of> 0.4 mm and ⁇ 0.8 mm) was then in the aforementioned Rhönradmischer at a speed of about 30 U / min within 30 min with, based on its weight, 3
  • the catalyst precursor moldings were evenly divided into 4 juxtaposed grids with a square base area of 150 mm x 150 mm (height: about 40 mm) and in an air-flow circulating air oven (Heraeus Instruments GmbH, D-63450 Hanau , Type: K 750/2) treated as follows.
  • the air flow was 100 Nl / h and initially had a temperature of 120 ° C.
  • the 120 ° C was initially maintained for 10 h.
  • the temperature was increased substantially linearly to 460 ° C within 10 hours and then the 460 ° C was maintained for a further 4 hours. It was then cooled to 25 ° C within 5 h.
  • the 150 g steatite chippings were introduced into a rotating coating drum (with an inner radius of 15 cm and an inner volume of 1800 cm 3 ) as a coating system.
  • the speed of the coating drum was 200 rpm.
  • the aqueous dispersion was applied to the surface of the steatite chips by spraying the aqueous dispersion with the aid of a two-component atomizing nozzle.
  • the dispersion stream was 100 ml / h at a temperature of the aqueous dispersion of 25 ° C.
  • the atomization mold was a circular solid cone (10 ° -40 °).
  • the Zerstäubungsart was fog, with a droplet size ⁇ 50 to 150 ⁇ .
  • the diameter of the flow cross section for the dispersion was 1 mm.
  • the internal temperature of the coating drum was kept at 120 ° C during the coating process.
  • the coated carrier particles were placed in a porcelain dish and calcined therein in a muffle furnace (1, 5 l internal volume) under air (not flowing).
  • the temperature in the calcination good was raised from 100 ° C. to 500 ° C. at a heating rate of 3 ° C./min and then kept at this temperature for 3 h.
  • the calcination was within 12 h in a muffle furnace located substantially linearly cooled to 25 ° C.
  • the oxidation catalyst A (1) was obtained as a shell catalyst whose cata- lytically active mixed oxide shell averaged stoichiometry
  • the 25 ° C having solution 1 was then within 5 min. in the 80 ° C warm solution 2 while maintaining the 80 ° C stirred.
  • the resulting solution was then spray dried at an inlet temperature of 350 ° C and an outlet temperature of 1 10 ° C within 3 h in the air stream (spray tower Mobile Minor 2000 type (MM-I) from Niro A / S, Gladsaxevej 305, 2860th Soborg, Denmark, with a type F0 A1 centrifugal atomizer and a type SL24-50 atomizer wheel).
  • MM-I spray tower Mobile Minor 2000 type
  • the kneaded mass was first heated at a heating rate of 10 ° C / min from 30 ° C to 300 ° C (each temperature of Calcinationsguts) and then held at this temperature for 6 h. Thereafter, the calcination was at a heating rate of
  • Feed (calculated as the ratio of the internal volume of the recirculating air oven and the supplied volume flow of the supplied at a temperature of 25 ° C oxygen / nitrogen mixture) was 135 sec.
  • the internal volume of the recirculating oven was 3 I.
  • the resulting catalytically active mixed oxide had the stoichiometry Moi2V3Wi , 2 Cui, 60 n .
  • the catalytically active oxide composition was then ground in a ZM 200 mill from Retsch to give a finely divided powder whose particle diameter (longitudinal expansion) was substantially in the range from 0.1 to 50 ⁇ m (a favorable diameter distribution of the fine-particle powder according to the invention)
  • Figure 2 of DE-A
  • vanadium pentoxide V2O5
  • the mixture was heated with stirring and under reflux to temperatures in the range of 100 to 108 ° C and held for 14 hours in this temperature range. Subsequently, the obtained hot suspension was cooled substantially linearly to 60 ° C. within 75 minutes and 22.7 kg of Fe (III) -phosphate hydrate were added (Fe content: 29.9% by weight; supplier: Dr Paul Lohmann, Free from Fe (II) Impurities). The mixture was then heated under reflux to temperatures of 100 to 108 ° C and the suspension was kept at this temperature with further stirring for 1 hour.
  • the about 105 ° C hot suspension was discharged into a previously inertized with nitrogen and heated to 100 ° C pressure suction filter and abs at a pressure above the Filutterutsche of about 0.35 MPa abs. filtered off.
  • the resulting filter cake was blown dry by continuous introduction of nitrogen with stirring and at 100 ° C within one hour. After dry-blowing was heated to 155 ° C and abs to a pressure of 15 kPa. (150 mbar abs.) Evacuated.
  • the dry powder was further treated in a stainless steel inclined rotary tube through which 100 m 3 / h of air (whose inlet temperature was 150 ° C.) flowed and had spiral spirals inside.
  • the tube length was 6.5 m, the inside diameter 0.9 m and the rotary tube wall thickness was 2.5 cm.
  • the speed of the rotary tube was 0.4 rpm.
  • the dry powder was supplied to the rotary tube interior in an amount of 60 kg / h at its upper end.
  • the helical coils ensured a uniform trickling (downwards) movement of the dry powder within the rotary tube.
  • the rotary tube length was divided into five heating zones of the same length, which were tempered from the outside. The temperatures of the five heating zones measured on the outer wall of the rotary tube were from top to bottom 250 ° C, 300 ° C, 345 ° C, 345 ° C and 345 ° C.
  • reaction zone A The contents of all reaction gas input mixtures and starting materials were determined by gas chromatography.
  • Design of reaction zone A The realization of the reaction zone A was carried out in a tubular reactor A (inner diameter: 12 mm, wall thickness: 1, 5 mm, length: 2000 mm, material: stainless steel, DIN material
  • Section 1 300 mm of a steatite chippings infill (1 to 1.5 mm long stope, Steatite C220 from CeramTec) at the reactor inlet;
  • Section 2 15 mm with 1.7 ml of coated catalyst A (2);
  • Sections 1 and 2 bordered directly on each other.
  • the temperature of tubular reactor A was set to 185 ° C. in the region of section 1 and to 220 ° C. in the region of section 2 (in each case the outside wall temperature of
  • reaction gas input mixture A 41.8 Nl / h of reaction gas input mixture A were fed to the bed of steatite chippings at an inlet temperature of 150.degree. The pressure at the entrance to the tubular reactor A was 2.0 bar abs.
  • the reaction gas input mixture A had the following contents:
  • the last 1326 mm of tube reactor A were unheated.
  • the loading of the catalyst charge with reaction gas input mixture A was about 5000 h 1 .
  • the loading with ethanol was 80 Ir 1 (Nl / lh).
  • Reaction zone B was carried out in a tubular reactor B (internal diameter: 15 mm, wall thickness: 1.2 mm, length: 2000 mm, material: stainless steel DIN material 1.4541), which could be heated electrically from the outside.
  • the catalyst charge in the tubular reactor B was designed as follows:
  • the contents of the reaction gas input mixture B were:
  • the reaction gas input mixture B was the feed of steatite chippings supplied with an inlet temperature of 350 ° C.
  • the pressure at the entrance into the tubular reactor B carried 1.5 bar abs.
  • the temperature of tube reactor B was adjusted to 375 ° C along the length of its fixed bed feed (outer wall temperature of tube reactor B).
  • the residual length of the tubular reactor B was unheated.
  • the loading of the catalyst feed with reaction gas input mixture B was 340 h 1 .
  • the obtained acrylic acid yield was 87.0 mol%.
  • the reaction zone A and the reaction zone B were designed as in II) A) and charged with the same catalyst beds.
  • the bed length of the catalytically active part in section 1 was 62 mm (homogeneous mixture of 3.5 ml of oxidation catalyst A (1) and 3.5 ml of steatite grit).
  • the implementation of the heterogeneously catalyzed partial oxidation of ethanol to acetic acid was carried out as in II) A), but the feed stream of the reaction gas input mixture A was 43.3 Nl / h. Obtained 43.4 Nl / h of product gas mixture A.
  • the composition of the product gas mixture A corresponded to that in II) A).
  • the loading of the catalyst charge in the tubular reactor A with reaction gas inlet mixture A was about 5000 Ir 1 .
  • the contents of the evaporated acetic acid were: 99% by volume of acetic acid.
  • the contents of the reaction gas input mixture B were:
  • the reaction gas input mixture B was the feed from steatite chippings supplied with an inlet temperature of 320 ° C.
  • the pressure at the entrance to the tubular reactor B was 1.5 bar abs.
  • the temperature of the tubular reactor B was set to 340 ° C. along the length of its packed bed (outer wall temperature of the tubular reactor B).
  • the residual length of the tubular reactor B was unheated.
  • the loading of the catalyst feed with reaction gas input mixture B was 340 fr 1 (Nl / lh).
  • the product gas mixture B leaving the tubular reactor B (45.1 Nl / h) had the following contents (online GC analysis):
  • the obtained acrylic acid yield was 88 mol%.
  • reaction zone A and the reaction zone B were designed as in II) A) and charged with the same catalyst beds.
  • the heterogeneously catalyzed partial oxidation of ethanol to acetic acid was carried out as in II) A), but the reaction gas input mixture A had the following contents
  • the contents of the reaction gas input mixture B were:
  • the reaction gas input mixture B was the feed from steatite chippings supplied with an inlet temperature of 320 ° C.
  • the pressure at the entrance to the tubular reactor B was 1.5 bar abs.
  • the temperature of the tubular reactor B was set to 340 ° C. along the length of its packed bed (outer wall temperature of the tubular reactor B).
  • the residual length of the tubular reactor B was unheated.
  • the load of the catalyst feed with reaction gas input mixture B was 340 h.
  • the product gas mixture B leaving the tubular reactor B (45.1 l / h) had the following contents:
  • the obtained acrylic acid yield was 88 mol%.
  • the reaction zone A and the reaction zone B were designed as in II) A) and charged with the same catalyst beds.
  • the bed length of the catalytically active part in section 1 was 43 mm (homogeneous mixture of 2.4 ml of oxidation catalyst A (1) and 2.4 ml of steatite grit) and the bed length of the catalytically active part in section 2 was only 11 mm (1, 2 ml of the coated catalyst A (2)).
  • the heterogeneously catalyzed partial oxidation of ethanol to acetic acid was carried out as in II) A)
  • Reaction gas input mixture A had the following contents:
  • the contents of the product gas mixture C were:
  • the reaction gas input mixture B was the feed from steatite chippings supplied with an inlet temperature of 320 ° C.
  • the pressure at the entrance to the tubular reactor B was 1.5 bar abs.
  • the temperature of the tubular reactor B was set to 340 ° C. along the length of its packed bed (outer wall temperature of the tubular reactor B).
  • Residual length of the tubular reactor B was unheated.
  • the loading of the catalyst feed with reaction gas input mixture B was 340 h 1 .
  • the product gas mixture B leaving the tubular reactor B (45.1 Nl / h) had the following contents: 0.01% by volume of methanol,
  • the realization of the reaction zone C took place in a tube reactor C (inside diameter: 8 mm, wall thickness: 1 mm, length: 100 mm, material: stainless steel DIN material 1.4541), which could be electrically heated from the outside.
  • the catalyst charge in the tubular reactor C was designed as follows:
  • the contents of the reaction gas input mixture C were:
  • the reaction gas input mixture C (12.2 Nl / h) was fed to the bed of steatite chippings with an inlet temperature of 265 ° C.
  • the pressure at the entrance to the tubular reactor C was 2 bar abs.
  • the temperature of the tubular reactor C was adjusted to 265 ° C along the length of its fixed bed charge (outer wall temperature of the tubular reactor C).
  • the residual length of the tubular reactor C was unheated.
  • the loading of the catalyst feed with reaction gas input mixture C was 6500 lr 1 .

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EP11758439.1A 2010-09-16 2011-09-13 Verfahren zur herstellung von acrysläure aus ethanol und formaldehyd Withdrawn EP2616427A1 (de)

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CN103221378A (zh) 2013-07-24
BR112013006305A2 (pt) 2016-06-07
ZA201302644B (en) 2014-05-25
US20120071687A1 (en) 2012-03-22
DE102010040923A1 (de) 2012-03-22
CN103221378B (zh) 2015-07-15
RU2013116997A (ru) 2014-10-27
RU2606623C2 (ru) 2017-01-10
US8507721B2 (en) 2013-08-13
CN104817450A (zh) 2015-08-05
WO2012035019A1 (de) 2012-03-22

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