Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/30—Loose or shaped packing elements, e.g. Raschig rings or Berl saddles, for pouring into the apparatus for mass or heat transfer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
  • B01J27/198—Vanadium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• • 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
  • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D307/60—Two oxygen atoms, e.g. succinic anhydride
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/30—Details relating to random packing elements
  • B01J2219/302—Basic shape of the elements
  • B01J2219/3023—Triangle
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/30—Details relating to random packing elements
  • B01J2219/304—Composition or microstructure of the elements
  • B01J2219/30475—Composition or microstructure of the elements comprising catalytically active material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
  • B01J35/31—Density
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/613—10-100 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/633—Pore volume less than 0.5 ml/g

Definitions

• the present invention relates to a catalyst article for the production of malic acid anhydride containing mixed oxides of vanadium and phosphorus as a catalyst component
• Maleic anhydride is a chemical intermediate of considerable commercial interest. It is used, for example, in the preparation of alkyd and polyester resins, alone or in combination with other acids. In addition, it is also a versatile intermediate for chemical synthesis, for example for the synthesis of Gamma-butyrolactone, tetrahydrofuran and 1,4-butanediol, which in turn are used in turn as a solvent or to polymers such as polytetrahydrofuran or Polyvmylpyrrolidon further processed
• the preparation of maleic anhydride is usually carried out by partial oxidation of hydrocarbons xn the gas phase mic molecular oxygen or with a molecular oxygen-containing gas in the presence of a vanadium-phosphorus oxide catalyst (VPO)
• VPO vanadium-phosphorus oxide catalyst
• the oxidation catalysts contain mixed oxides of vanadium and phosphorus, with such vanadium m oxidation catalysts having a valence of +3.8 to +4.8 being particularly suitable for the production of maleic anhydride from saturated hydrocarbons having at least four carbon atoms in a straight chain.
• the VPO catalysts may also contain promoters, such as metals, which may be present in the form of their oxides in the oxidation catalyst.
• No. 4,283,307 describes a mixed oxide of the vanadium and the phosphorus-containing catalyst moldings for the partial oxidation of n-butane, which has a cylindrical geometry and is penetrated along its longitudinal axis by a through-bore.
• EP 1 261 424 B1 relates to a catalyst for the production of maleic anhydride by heterogeneously catalyzed gas-phase oxidation of a hydrocarbon having at least 4 carbon atoms.
• This catalyst contains a catalytically active composition of a vanadium-phosphorus mixed oxide and has a substantially hollow cylindrical structure.
• the hollow cylinder is designed such that the ratio of the height to the diameter of the passage opening is at most 1.5 and the ratio of the geometric surface to the geometric volume of the molding at least 2 mm "1 .
• EP 0 552 287 B1 relates to a shaped catalyst body for producing maleic anhydride, wherein the shaped body comprises a solid geometric shape with at least one cavity arranged in the outer surface.
• the shaped body is formed from mixed oxides of vanadium and phosphorus and has a geometric volume of 30% to 67% of that occupies the cavity-free massive moldings, wherein the ratio of the geometric surface of the shaped body to the geometric volume of the shaped body at least 20 cm "1 Detragt
• the object of the present invention is to provide a Katalysatorformkorper for the preparation of Malemsaureanhyd ⁇ d MSA) by heterogeneously catalyzed gas-phase oxidation of hydrocarbons of the type mentioned above, which allows the preparation of maleic anhydride with a higher selectivity and with a higher productivity compared to the prior art and wherein the end product has a low content of acetic and acrylic acid than in the case of previously known shaped articles.
• the geometric basic body enclosing the shaped catalyst is a prism having a first and a second triangular surface and the catalyst former is provided with three continuous openings extending from a first Flat surface of the molded body, which spans the first triangular surface of the prism, to a second surface of the shaped body, which spans the second triangular surface of the prism extend
• the catalyst moldings according to the invention are distinguished by an increased specific activity per g / catalyst and an increased selectivity, resulting in an increased productivity of maleic anhydride and an increased malemic anhydride selectivity by suppression of overoxidation of maleic anhydride can be obtained.
• productivity means the mass flow of MSA kg (MSA) per volume / reactor, expressed in units of
• the erfmdungsgedorfen Katalysatorforrrkorper have a high mechanical stability, so that, for example, during transport of erfmdungsgeloisen Formkorper and Befullen a Rohrbundelreaktors with the erfmdungsgedorfen Katalysatorform- corpuscles substantially no damage to the Formkorper.
• novel catalyst moldings it is advantageous in the novel catalyst moldings that they have relatively short diffusion paths.
• the short diffusion paths cause a high pore utilization, so that a lower catalyst mass can be used to achieve a desired hydrocarbon conversion and a higher MSA selectivity, since the total oxidation of MSA to CO and CO 2 is suppressed.
• Prismatic catalyst moldings generally have a relatively low stability along their long edges, so that, for example, during the filling process of a reactor with the corresponding catalyst moldings, flaking in the region of the long edges can occur.
• the shaped body has a substantially triangular cross-section with rounded apexes.
• the Katalysatorformkorper has a substantially trilobal cross section, each Lobus is provided with a through opening.
• the through-holes have a circular or oval cross-section.
• the through openings of the erfformungshacke Katalysatorformkorpers according to a particularly preferred embodiment, a diameter of 0.5 mm to 3 mm.
• the through openings have the same diameter.
• the continuous openings have a diameter different from each other.
• the through openings are substantially parallel to each other.
• the ratio of the gap between the continuous openings to the diameter of the openings amounts to 1.15 to 1.5.
• the ratio of the gap between the continuous openings to the diameter of the openings amounts to 1.15 to 1.5.
• relatively high space velocities of the gas mixture passing through the reactor bed can be obtained by such a design.
• a factor which determines the filling density of shaped catalyst bodies in a reactor is the geometry of the shaped catalyst bodies. In order to influence the filling density and thus to influence the space velocities of the gas passing through the catalyst bed, according to a further preferred embodiment of the shaped catalyst body according to the invention it can be provided that two of the three lobes have the same outside diameter. According to an alternative embodiment, all prongs have a different outer diameter.
• the filling density of a reactor loaded with shaped catalyst bodies depends on the size of the corresponding shaped bodies.
• the shaped bodies preferably have a length of 2 to 20 mm, in particular of 3 to 10 mm.
• the ratio of the length of the shaped body according to the invention to the minimum width of the end face of the trilobal shaped body is 0.5 to 2.
• the minimum width of the end face is defined in FIG. 1 by the reference numeral 170.
• the catalyst moldings of the invention the ratio of the volume of the shaped body V Fo rmSystem to the volume of the enveloping primate V Prisrna 0.71 to 0.9.
• the volume of the shaped body but also of the enveloping prism is calculated as the volume of the solid shaped body, ie without consideration of the through openings.
• the shaped article according to the invention usually has a geometric surface area of 0.15 cm 2 to 5 cm 2 , preferably 0.5 cm 2 to 4 cm 2 , more preferably 1 cm 2 to 3.5 cm 2 , in particular 1, 5 cm 2 to 3 cm 2 .
• the erfir.dungs- gerra touch Katalysatorformkorpers amounts to the ratio of the geometric surface of the molded article to the volume of the molded body pers 0.5 to 20 mm “1 , preferably 1.4 to 4 mm “ 1 and in particular the ratio of geometric surface of the shaped body to its volume greater than 2.1 mm "1 .
• the bulk density of the inventive shaped body is 0.4 g / cm 3 to 1.4 g / cm 3 , preferably 0.5 g / cm 3 to 1.1 g / cm 3 .
• the B ⁇ T surface of the erfmdungsgewillen Katalysatorformkorpers amounts to 10 to 300 m 2 / g, preferably 15 to 80 m 2 / g, particularly preferably 20 - 50 m 2 / g.
• the BET surface is determined by the one-point method by adsorption of nitrogen according to DIN 66132.
• the integral pore volume (determined according to DIN 66133 (Hg porosimetry)) is> 100, preferably> 180 mmVg.
• a maximum of 10% of the pore volume is formed by pores of ⁇ 10 nm radius and a maximum of 10% of the pore volume is formed by pores> 500 nm radius.
• the shaped catalyst bodies according to the invention may contain the mixed oxides of vanadium and phosphorus, for example in pure, undiluted form as a so-called “full catalyst” or diluted with a preferably oxidic support material as a so-called supported “mixed catalyst”.
• Suitable support materials for the mixed catalysts are, for example, aluminum oxide, silicon dioxide, aluminum silicates, zirconium dioxide, titanium dioxide or mixtures thereof.
• the content of the catalyst component in the shaped catalyst body according to the invention is preferably from 3 to 50% by weight, based on the total weight of the shaped catalyst body.
• the content of the catalyst component in the inventive shaped catalyst body 3 is 50% by weight, preferably 5 to 30% by weight, based on the total weight of the shaped catalyst body.
• the shaped catalyst body according to the invention may contain as further catalytically active component a promoter selected from metals of the Periodic Table of the Elements.
• the catalyst component corresponds to the general formula
• M is at least one promoter
• x represents a number from 0.1 to 3
• y is a number adapted to the valences of V
• P and M and z represents a number from 0 to 1.5.
• the promoter may be selected from the metals.
• the promoter is selected from chromium, nickel, magnesium, aluminum, silicon, tungsten, niobium, antimony and / or cesium
• the promoter is further selected from lithium, zinc, iron, or bismuth, tellurium, silver, and / or molybdenum
• the proportion of the promoter in the form of an oxide or in the form of a compound which can be converted into an oxide is 0.005% by weight to 5% by weight, based on the total weight of the molded article.
• auxiliaries such as tableting aids or pore formers, to be added to the catalyst moldings according to the invention.
• Tablettierosmittel are generally added when the shaping of erfmdungsgeEnglishen Katalysatorformkorpers takes place via a tabletting.
• Tableting aids are generally catalytically inert and improve the tabletting properties of the so-called catalyst precursor powder, for example by increasing the lubricious and / or free-flowing properties.
• a particularly suitable tableting aid is, for example, graphite.
• the added tabletting aids may remain in the activated catalyst and are generally of the order of 1 to 5% by weight of the catalyst article, based on the total weight of the catalyst article
• pore formers are pore forming agents, which for targeted adjustment of the pore structure in the meso- and macropores area are used. These are usually compounds containing carbon, hydrogen, oxygen and / or nitrogen, which are added to the catalyst precursor powder before shaping and decompose or evaporate during the subsequent activation of the catalyst molding, for example by calcination, and thus for the most part from the resulting Moldings emerge and thereby create pores.
• the invention further relates to the use of the shaped catalyst body according to the invention for the production of maleic anhydride from hydrocarbons.
• Non-aromatic hydrocarbons having 4 to 10 carbon atoms can be used as hydrocarbons. It is required that the hydrocarbon contains not less than 4 carbon atoms in a straight chain or in a ring. Particularly suitable is the hydrocarbon n-butane. In addition to n-butane, pentanes, hexanes, heptanes, octanes, nonanes, decanes or mixtures of any of these compounds with or without n-butane are also suitable, provided they contain at least 4 straight chain carbon atoms.
• Unsaturated hydrocarbons may also be used for conversion to maleic anhydride.
• Suitable unsaturated hydrocarbons are for example butenes (1-butene and 2-butene), 1, 3-butadiene, the pentenes, the hexenes, the heptenes, the octenes, the nonenes, the decenes, and mixtures be ⁇ Kunststoffiger of these compounds, with the proviso that they contain at least 4 carbon cofactors in straight chain.
• substituted and unsubstituted furans for.
• tetrahydrofuran also aromatic compounds, such as benzene and its derivatives.
• the shaped catalyst body according to the invention can be produced, for example, as described in WO 97/12674, the shaping taking place in accordance with the geometry according to the invention.
• a pentavalent vanadium compound for example, V 2 Os
• a reducing solvent for example isobutanol
• a pentavalent phosphorus compound for example, o-phosphoric acid or another phosphoric acid such as pyrophosphoric acids and / or mixtures thereof, etc.
• a promoter for example, o-phosphoric acid or another phosphoric acid such as pyrophosphoric acids and / or mixtures thereof, etc.
• the abovementioned reaction can be carried out in the presence of a carrier material which is, for example, pulverulent and is dispersed in the solvent.
• Drying and optionally calcining the catalyst precursor If appropriate, pulverulent carrier material and / or a pore-forming agent can be mixed in with the dried catalyst precursor.
• the drying can be carried out, for example, under reduced pressure under protective gas or under excess oxygen.
• a tableting aid may be added to the dried catalyst precursor.
• an atmosphere which may contain oxygen, nitrogen, noble gases, carbon dioxide, carbon monoxide and / or water vapor or mixtures thereof.
• the shaped catalyst body according to the invention can be prepared, for example, by first mixing the dried catalyst precursor powder with a binder or with a lubricant. The production of the shaped body is then for example in a tablet press having a turntable, a plurality of openings uer4.000 at its periphery with a corresponding Q, beis p ielsweise are arranged a trilobal cross-section or a triangular cross-section. In this opening (dies), the mixture is filled, which is held from below by a stamp, through which during the rotation of the turntable, for example, three pins which are located at the locations of the openings to be generated, are pushed upwards.
• FIG. 2 shows a catalyst according to the invention according to a second embodiment.
• FIG. 1 shows a shaped catalyst body according to a first embodiment taken overall by the reference numeral 100.
• the shaped catalyst body 100 is formed from mixed oxides of vanadium and phosphorus and has a trilobal cross section.
• the three lobes 110, 120, 130, each having the same outer diameter 150, are each penetrated by a circular opening 111, 121, 131.
• the three through holes 111, 121 and 131 have the same diameter 140 and are aligned parallel to each other, wherein the longitudinal axes of the openings 111, 121 and 131 define the vertices of a substantially equilateral triangle in cross section.
• the ratio of the length 160 of the molding 100 to the minimum width of the end face 170 of the trilobal molding is on the order of 0.5 to 2.
• the geometric basic body enveloping the trilobal shaped catalyst body 100 is a prism 180.
• FIG. 2 shows a shaped catalyst body according to the invention, designated in total by the reference numeral 200, according to a second embodiment.
• the molded body 200 has a triangular cross section with rounded apexes and is penetrated by three mutually parallel through holes 211, 221 and 231 as openings, all of which have the same diameter 240.
• the longitudinal axes The through-holes 211, 221 and 231 form in cross section the vertices of a substantially equilateral triangle.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Catalysts (AREA)

Applications Claiming Priority (3)

Publications (1)

Family

ID=37686103

Family Applications (1)

Country Status (6)

Families Citing this family (20)

Family Cites Families (11)

• 2006
  • 2006-10-14 TW TW095137834A patent/TW200719968A/zh unknown
  • 2006-10-31 US US12/092,012 patent/US8048820B2/en not_active Expired - Fee Related
  • 2006-10-31 WO PCT/EP2006/010487 patent/WO2007051602A1/de active Application Filing
  • 2006-10-31 EP EP06806647A patent/EP1945353A1/de not_active Ceased
  • 2006-10-31 CA CA2627481A patent/CA2627481C/en not_active Expired - Fee Related
  • 2006-10-31 RU RU2008121944/04A patent/RU2008121944A/ru not_active Application Discontinuation

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events