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WO2013164727A1 - Catalyseur pour l'époxydation d'alcènes - Google Patents

Catalyseur pour l'époxydation d'alcènes Download PDF

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Publication number
WO2013164727A1
WO2013164727A1 PCT/IB2013/053169 IB2013053169W WO2013164727A1 WO 2013164727 A1 WO2013164727 A1 WO 2013164727A1 IB 2013053169 W IB2013053169 W IB 2013053169W WO 2013164727 A1 WO2013164727 A1 WO 2013164727A1
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WIPO (PCT)
Prior art keywords
catalyst
ppm
amount
range
carrier
Prior art date
Application number
PCT/IB2013/053169
Other languages
German (de)
English (en)
Inventor
Tobias Rosendahl
Torsten Maeurer
Dirk HENSEL
Andreas Lehr
Original Assignee
Basf Se
Basf Schweiz Ag
Basf (China) Company Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se, Basf Schweiz Ag, Basf (China) Company Limited filed Critical Basf Se
Priority to EP13784593.9A priority Critical patent/EP2844646A4/fr
Priority to BR112014026976A priority patent/BR112014026976A2/pt
Priority to KR1020147034186A priority patent/KR20150013704A/ko
Priority to CN201380022972.4A priority patent/CN104321315A/zh
Priority to JP2015509529A priority patent/JP2015518421A/ja
Publication of WO2013164727A1 publication Critical patent/WO2013164727A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
    • B01J23/686—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
    • 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
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • 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
    • B01J35/64—Pore diameter
    • B01J35/657—Pore diameter larger than 1000 nm
    • 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
    • B01J35/66—Pore distribution
    • B01J35/69—Pore distribution bimodal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0213—Preparation of the impregnating solution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
    • C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a catalyst for the production of alkylene oxides, which is a supported silver catalyst having a novel promoter combination. Furthermore, the present invention also relates to a process for the preparation of the catalyst and the use of the catalyst for the oxidation of alkylene to alkylene oxides. Moreover, the present invention relates to a process for the production of ethylene oxide from ethylene, comprising the oxidation of ethylene in the presence of said catalyst. Ethylene oxide is an important commodity chemical and is often produced on an industrial scale by direct oxidation of ethylene with oxygen in the presence of silver-containing catalysts. Frequently, supported catalysts are used in which the catalytically active metallic silver has been applied to a support by a suitable method. As a carrier can in principle different porous materials such. As activated carbon, titanium, zirconium or silicon dioxide or ceramic compositions or mixtures of these materials can be used. As a rule, alpha-alumina is used as the carrier.
  • these catalysts In addition to silver as an active component, these catalysts often contain promoters to improve the catalytic properties (WO 2007/122090, WO 2010/123856).
  • alkali metal and / or alkaline earth metal compounds may be mentioned as promoters.
  • Some references teach the use of transition metals such as cobalt (EP 0 480 538), tungsten or molybdenum.
  • a particularly preferred promoter for influencing the activity and selectivity of catalysts is rhenium.
  • Catalysts containing rhenium and / or other transition metal promoters in combination with alkali and / or alkaline earth metal compounds are preferably used industrially because of their high selectivity.
  • selectivity refers to the molar percentage of ethylene that reacts to form ethylene oxide.
  • the activity of the catalyst is characterized by the ethylene oxide concentration in the reactor outlet under otherwise constant conditions, such as temperature, pressure, gas flow rate, amount of catalyst, etc.
  • the combination of the active metal with the promoters and the composition of the support are usually matched to one another in order to obtain catalysts having the best possible properties.
  • An object of the present invention was to provide novel catalysts for the epoxidation of alkenes which have advantageous activities and / or selectivities.
  • An object of the invention is therefore a tungsten-free catalyst for the epoxidation of alkenes, comprising silver, molybdenum and tin, applied to a support.
  • the catalyst according to the invention comprises a carrier.
  • Suitable supports according to the invention can be prepared by processes known from the prior art. Examples which may be mentioned are the processes described in US 2009/0198076 A1, WO 2006/133187, WO 03/072244, US 2005/0096219 A1 and EP 0 496 386 B2.
  • Suitable support materials are alumina, silica, silicon carbide, titania, zirconia, and mixtures thereof, with alumina being preferred. According to a preferred embodiment, the present invention accordingly relates to a catalyst whose support is an alumina support.
  • alumina as used herein, includes all conceivable structures such as alpha, gamma or theta alumina.
  • the carrier is an alpha alumina carrier.
  • the present invention also relates to a catalyst wherein the carrier is an alpha-alumina.
  • the alpha-alumina has a purity of at least 75%, preferably a purity of at least 80%, more preferably a purity of at least 85%, more preferably a purity of at least 90%, more preferably a purity of at least 98 %, more preferably a purity of at least 98.5%, and most preferably a purity of at least 99%.
  • alpha-alumina therefore also includes alpha-aluminas containing further constituents, for example elements selected from the group consisting of zirconium, alkali metals, alkaline earth metals, silicon, zinc, gallium, hafnium, boron, fluorine, copper, nickel, manganese, iron , Cerium, titanium, chromium and compounds of these elements and mixtures of two or more of these elements and / or their compounds.
  • elements selected from the group consisting of zirconium, alkali metals, alkaline earth metals, silicon, zinc, gallium, hafnium, boron, fluorine, copper, nickel, manganese, iron , Cerium, titanium, chromium and compounds of these elements and mixtures of two or more of these elements and / or their compounds.
  • a suitable catalyst support for the present invention can be prepared by mixing the alumina with water or other suitable liquid with a burnout material or a pore former and at least one binder.
  • Suitable pore formers are, for example, cellulose and cellulose derivatives, such as, for example, methylcellulose, ethylcellulose, carboxymethylcellulose, or polyolefins, such as polyethylenes and Polypropylene, or natural burnout materials such as walnut shell meal.
  • the pore formers are selected to be completely burned out of the alumina to the final alpha alumina support at the selected kiln temperatures of the calcination.
  • Suitable binders or extrusion or extrusion aids are described, for example, in EP 0 496 386 B2.
  • Examples are alumina gels with nitric acid or acetic acid, cellulose, for example methyl, ethyl cellulose or carboxyethyl cellulose, or methyl or ethyl stearate, polyolefin oxides, waxes and similar substances.
  • the paste formed by mixing can be made into the desired shape by extrusion.
  • Extrusion aids may be used to assist in the extrusion process.
  • the molded article obtained as described above is optionally dried following the molding and calcined to obtain the alumina support.
  • the calcining is usually carried out at temperatures in the range of 1200 ° C to 1600 ° C. It is common to wash the alumina support after calcining to remove soluble components.
  • the alpha-alumina may contain the further constituents in any suitable form, for example as an element and / or in the form of one or more compounds. If the alpha-alumina contains one or more constituents in the form of a compound, it contains these, for example, as oxide or mixed oxide. Suitable supports according to the invention are therefore also alpha-aluminas containing at least one further constituent selected from the group consisting of silicon dioxide, sodium oxide, potassium oxide, calcium oxide and magnesium oxide, nickel oxide, gallium oxide, hafnium oxide, copper oxide, iron oxide and
  • the total content of the further constituents is preferably in a range of less than 25% by weight, more preferably less than 20% by weight, more preferably less than 15% by weight, more preferably less than 10% by weight, more preferably less than 5% by weight, more preferably less than 2% by weight, more preferably less than 1.5% by weight and particularly preferably less than 1% by weight, based on the total weight of the carrier.
  • the carrier contains alkali metals, it preferably contains them in a total amount in the range of 10 to 2500 ppm, more preferably in an amount of 10 to 1000 ppm, further preferably in an amount of 50 to 850 ppm based on the total weight of the carrier and calculated as an element.
  • the carrier contains at least one alkali metal selected from the group consisting of sodium and potassium.
  • the carrier when the carrier contains sodium, it preferably contains them in an amount in the range of 10 to 1500 ppm, more preferably in an amount of 10 to 800 ppm, further preferably in an amount of 10 to 500 ppm based on the total weight of the carrier and calculated as an element.
  • the carrier if the carrier contains potassium, it preferably contains them in an amount in the range of 10 to 1000 ppm, more preferably in an amount of 10 to 500 ppm, further preferably in an amount of 10 to 300 ppm based on the total weight of the carrier and calculated as an element.
  • the carrier contains sodium in an amount of 10 to 1500 ppm and potassium in an amount of 10 to 1000 ppm.
  • the present invention also describes a catalyst whose support comprises sodium in an amount of 10 to 1500 ppm and potassium in an amount of 10 to 1000 ppm, more preferably sodium in an amount of 10 to 500 ppm and potassium in an amount of 10 to 300 ppm, based on the total weight of the carrier and calculated in each case as an element.
  • the carrier contains, for example, alkaline earth metals, it preferably contains these in a total amount in the range of not more than 2500 ppm, for example in the range of from 10 to
  • the carrier comprises at least one alkaline earth metal selected from the group consisting of calcium and magnesium.
  • the carrier preferably contains calcium in an amount in the range of 10 to 1500 ppm, more preferably in an amount of 10 to 1000 ppm, further preferably in an amount of 10 to 500 ppm, based on the total weight of the carrier and calculated as an element.
  • the carrier when it contains magnesium, it preferably contains them in an amount in the range of 10 to 800 ppm, more preferably in an amount of 10 to 500 ppm, further preferably in an amount of 10 to 250 ppm based on the total weight of the carrier and calculated as an element.
  • the present invention also describes a catalyst whose support comprises magnesium in an amount of 10 to 800 ppm and calcium in an amount of 10 to 1500 ppm, each based on the total weight of the support and calculated as element.
  • the carrier comprises, for example, sodium in an amount of 10 to 1500 ppm, potassium in an amount of 10 to 1000 ppm, magnesium in an amount of 10 to 800 ppm, and calcium in an amount of 10 to 1500 ppm, based on the total weight of the carrier and calculated as an element.
  • the carrier when it contains silicon, it preferably contains it in an amount in the range of 50 to 10,000 ppm, more preferably in an amount of 50 to 5,000 ppm, further preferably in an amount of 50 to 600 ppm based on the total weight of the carrier and calculated as an element.
  • a preferred carrier in accordance with the present invention is, for example, an alpha alumina in a purity of at least 90%, which contains from 50 to 10,000 ppm silicon, of 10 to 1500 ppm of sodium and from 10 to 2500 ppm of total alkaline earth metals, calculated in each case as an element and based on the total weight of the carrier.
  • the support preferably comprises calcium and / or magnesium as the alkaline earth metal.
  • the supports used for the catalyst according to the invention preferably have a BET surface, determined in accordance with the method described in ISO standard 9277, of 0.1 to 5 m 2 / g, more preferably in the range of 0.1 to 2 m 2 / g, more preferably in the range of 0.5 to 1, 5 m 2 / g, more preferably in the range of 0.6 to 1, 3 m 2 / g, and particularly preferably in the range of 0.6 to 1, 0 m 2 / g.
  • the supports used for the catalyst according to the invention preferably have pores having diameters in the range from 0.1 to 100 ⁇ m, the pore distribution being monomodal or polymodal, for example bimodal, trimodal or tetramodal.
  • the carriers have a bimodal pore distribution.
  • the supports furthermore preferably have a bimodal pore distribution with peak maxima in the range from 0.1 to 10 ⁇ m and 15 to 100 ⁇ m, preferably in the range from 0.1 to 5 ⁇ m and 17 to 80 ⁇ m, more preferably in the range from 0.1 to 3 ⁇ and 20 to 50 ⁇ , more preferably in the range of 0.1 to 1, 5 ⁇ and 20 to 40 ⁇ on.
  • the pore diameters are determined by Hg porosimetry (as described in DIN standard 66133).
  • the present invention also describes a catalyst whose carrier has a bimodal pore distribution, preferably a bimodal pore distribution at least containing pores having a pore diameter in the range of 0.1 to 15 ⁇ and pores having a pore diameter in the range of 15 to 100 ⁇ , determined by Hg porosimetry.
  • the carrier is used as a shaped body, for example as a strand, hollow strand, star strand, sphere, ring or hollow ring.
  • the carrier is preferably a shaped body with the geometry of a hollow body.
  • cylinders with the following geometries (outer diameter x length x inner diameter, each indicated in FIG mm): 5x5x2, 6x6x3, 7x7x3, 8x8x3, 8x8,5x3, 8x8,5x3, 5, 8,5x8x3,5, 8,5x8x3, 9x9x3, 9,5x9x3, 9,5x9x3, 9,5x9x3,5.
  • Each length specification includes tolerances in the range of ⁇ 0.5 mm.
  • the catalyst it is also possible for the catalyst to be used in the form of a catalyst split which is obtained from one or more of the shaped bodies mentioned.
  • the water absorption of the carriers is, for example, in the range from 0.35 ml / g to 0.65 ml / g, preferably in the range from 0.42 ml / g to 0.52 ml / g, determined by a vacuum cold water absorption.
  • the catalyst according to the invention contains silver as the active metal.
  • the catalyst may contain silver in an amount of, for example, from 5 to 35% by weight, in particular from 10 to 30% by weight, preferably in an amount of from 10 to 25% by weight, based on the total weight of the catalyst and calculated as an element.
  • the silver is preferably applied to the support in the form of a silver compound, which may be a salt or a silver complex.
  • the silver compound is preferably dissolved, in particular dissolved in water.
  • the silver compound such as silver (I) oxide or silver (I) oxalate may further suitably contain a complexing agent such as ethanolamine, EDTA, 1, 3 or 1, 2-propanediamine, ethylenediamine and / or alkali metal oxalate can be added, which can act simultaneously as a reducing agent. More preferably, silver is applied in the form of a silver amine compound, more preferably a silver ethylenediamine compound.
  • the catalyst according to the invention comprises at least the elements molybdenum and tin as promoters.
  • promoter is understood as meaning a constituent of the catalyst by which, as compared to a catalyst which does not contain the constituent, an improvement in one or more catalytic properties, e.g. As selectivity, activity, conversion, yield and / or life is achieved.
  • Preferred compounds which are chemically stable under the reaction conditions and do not catalyze undesirable reactions.
  • Promoters are usually used in a total amount of 10 to 3000 ppm and in an amount of 5 to 1500 ppm, more preferably in an amount of 10 to 1300 ppm, and particularly preferably in an amount of 50 to 1300 ppm, based on the total weight of the catalyst and calculated as the sum of the elements used.
  • Promoters are preferably applied in the form of compounds on the support, for example in the form of complexes or in the form of salts, for example in the form of halides, fluorides, bromides or chlorides, or in the form of carboxylates, nitrates, sulfates or sulfides, phosphates, cyanides , Hydroxides, carbonates, oxides, oxalates or as salts of heteropolyacids, for example in the form of salts of the heteropolyacids of rhenium.
  • the catalyst of the present invention preferably contains molybdenum in an amount of from 10 to 300 ppm, more preferably in an amount of from 10 to 200 ppm, more preferably in an amount of 10 to 80 ppm, based on the total weight of the catalyst and calculated as element.
  • Molybdenum is preferably applied as a compound, for example as a halide, oxyhalide, oxide, molybdate, permolybdate or acid, preferably as a compound selected from the group consisting of molybdenum oxide, ammonium heptamolybdate, ammonium orthomolybdate, molybdenum chloride, molybdenum fluoride, molybdenum sulfide and molybdic acid.
  • Molybdenum as molybdic acid is particularly preferably applied to the support in the context of the invention.
  • the catalyst of the present invention preferably contains tin in an amount of 10 to 600 ppm, more preferably in an amount of 50 to 400 ppm, further preferably in an amount of 80 to 250 ppm based on the total weight of the catalyst and calculated as an element.
  • Tin is preferably applied as a compound, for example as a halide, hydroxide, oxalate, oxide, stannate or acid, preferably as a compound selected from the group consisting of tin oxide, tin chloride, tin fluoride, sodium stannate, sodium hexahydroxoate, tin acid and tin oxalate.
  • tin is particularly preferably applied to the carrier as tin oxalate.
  • the catalyst according to the invention is tungsten-free.
  • a tungsten-free catalyst is understood as meaning a catalyst which has a tungsten content of less than 5 mg / kg, and tungsten is preferably not detectable analytically. In any case, the use of tungsten compounds is dispensed with during catalyst preparation.
  • the catalyst comprises at least one further promoter, for example five, four, three or two further promoters or a further promoter.
  • at least one further promoter all known in the art promoters are conceivable.
  • the at least one further promoter is preferably selected from the group consisting of the elements lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, manganese, rhenium, cadmium, chromium, sulfur and mixtures of two or more from that.
  • the catalyst particularly preferably contains at least one further promoter selected from the group consisting of the elements rhenium, cesium, lithium, chromium, manganese, sulfur and mixtures of two or more thereof. Most preferably, the catalyst contains at least rhenium as a further promoter and at least one element selected from the group consisting of cesium, lithium, chromium, manganese, sulfur and mixtures of two or more thereof.
  • the present invention also describes a tungsten-free catalyst comprising silver in an amount of 5 to 35 wt .-%, based on the total weight of the catalyst, molybdenum and tin and at least rhenium as a further promoter, applied to a support.
  • the catalyst when it contains rhenium, it preferably contains rhenium in an amount of 50 to 600 ppm, more preferably in an amount of 100 to 450 ppm, further preferably in an amount of 150 to 400 ppm based on the total weight of the catalyst and calculated as an element.
  • Rhenium is preferably applied as a compound, for example as a halide, oxyhalide, oxide, rhenate, perrhenate or as acid.
  • rhenium is used as a promoter, it is preferably used as a compound selected from the group consisting of ammonium perrhenate, rhenium (III) chloride, rhenium (V) chloride, rhenium (V) fluoride, rhenium (VI) oxide and Rhenium (VII) oxide applied.
  • rhenium as ammonium perrhenate to the carrier.
  • the catalyst contains, for example, cesium, it preferably contains this in an amount of from 20 to 850 ppm, in particular in an amount of from 100 to 600 ppm, based on the total weight of the catalyst and calculated as an element.
  • Cesium is preferably applied to the support as a cesium compound.
  • any suitable cesium compound can be used.
  • cesium is applied in the form of cesium hydroxide.
  • the catalyst when it contains lithium, it preferably contains it in an amount of 10 to 450 ppm, more preferably in an amount of 50 to 300 ppm, based on the total weight of the catalyst and calculated as an element.
  • Lithium is preferably applied to the carrier as a lithium compound.
  • any suitable lithium compound is usable.
  • lithium is applied in the form of lithium nitrate.
  • the catalyst contains, for example, sulfur, it preferably contains this in an amount of 5 to 300 ppm, in particular in an amount of 5 to 150 ppm, based on the total weight of the catalyst and calculated as an element.
  • Sulfur is preferably applied to the carrier as a sulfur compound.
  • any suitable sulfur compound is usable.
  • sulfur is applied in the form of ammonium sulfate.
  • the catalyst according to the invention contains rhenium in an amount of 150 to 450 ppm, cesium in an amount of 100 to 600 ppm, lithium in an amount of 50 to 300 ppm and sulfur in an amount of 5 to 150 ppm.
  • the promoters are preferably dissolved before application in a suitable solvent, preferably in water.
  • the support is then preferably impregnated with the resulting solution comprising one or more of the promoters. If more promoters are added, they can be applied to the support either together or separately in a single impregnation step or in several impregnation steps.
  • the solution comprising one or more of the promoters it may be prepared in any suitable manner.
  • the promoters can each be separately dissolved in each case in a solution and the resulting solutions, each containing a promoter, are then used for impregnation.
  • At least molybdenum, tin, cesium, lithium, sulfur and rhenium are used as promoters
  • at least one solution containing cesium, another solution containing molybdenum, another solution containing lithium and sulfur, containing a further solution Tin and another solution containing rhenium are either applied to the carrier in separate impregnation steps, or combined before application to a solution and only then used for impregnation.
  • the solutions are applied together, more preferably together with the mixture containing silver as a silver amine compound, preferably as Silberethylendiamintress applied to the support.
  • silver it may be applied to the support by any prior art impregnation and deposition process for the preparation of silver catalysts for the production of ethylene oxide, which processes may comprise one or more impregnation and calcination steps.
  • any prior art impregnation and deposition process for the preparation of silver catalysts for the production of ethylene oxide which processes may comprise one or more impregnation and calcination steps.
  • mention may be made of the preparation processes for silver catalysts, as described in DE-A 230051 12, DE-A 2521906, EP-A 0 014 457, EP-A 0 085 237, EP-A 0 0384 312, DE-A 2454927, DE-A A 3321895, EP-A 0 229 465, DE-A 3150205, EP-A 0 172 565 and EP-A 0 357 293 are disclosed.
  • the silver may be applied separately or together with one or more promoters.
  • a mixture containing silver and at least one promoter is applied to the carrier, for example by impregnation, spraying or mixing processes.
  • the order of application of the promoters and the silver is generally arbitrary, i. Embodiments are contemplated in which silver and the promoters are simultaneously applied to the support. Also included are embodiments in which silver and the promoters are applied to the support in various steps, the order of the steps being generally arbitrary. Furthermore, embodiments are encompassed in which a part of the promoters is applied to the carrier before or after application of the silver, and the remaining part is applied simultaneously with silver. Preferably, silver and the promoters are applied simultaneously to the support.
  • Another object of the invention is a process for the preparation of tungsten-free catalysts for the epoxidation of alkenes, comprising the application of silver, molybdenum and tin on a support.
  • the application can in principle be carried out by any suitable method, for example by soaking the carrier. Particularly preferably, the application is carried out by vacuum impregnation at room temperature.
  • the support is preferably initially added a pressure in the range of at most 500 mbar, more preferably at a pressure of at most 250 mbar, and more preferably at a pressure of at most 50 mbar, and preferably at a temperature in the range of 2 ° C to 50 ° C, more preferably at a temperature in the range of 5 ° C to 30 ° C, and most preferably at room temperature.
  • the vacuum treatment is carried out, for example, for a time of at least 1 min, preferably of at least 5 min, more preferably for a time in the range of 5 min to 120 min, in particular in the range of 10 min to 45 min, particularly preferably in the range of 15 min up to 30 min.
  • the at least one solution for example the mixture containing silver, molybdenum and tin or at least one solution containing at least one further promoter, preferably the mixture containing silver, molybdenum and tin and the at least one further promoter, on the support applied.
  • the solution is dropped or sprayed on, preferably sprayed on.
  • the application is preferably carried out by means of a nozzle.
  • the carrier preferably further evacuated.
  • the evacuation is carried out at a pressure in the range of at most 500 mbar, more preferably at a pressure of at most 250 mbar and particularly preferably at a pressure of a maximum of 50 mbar, and preferably at a temperature in the range of 2 ° C to 50 ° C, more preferably at a temperature in the range of 5 ° C to 30 ° C, and more preferably at room temperature.
  • the vacuum treatment is carried out, for example, for a time of at least 1 min, preferably of at least 5 min, more preferably for a time in the range of 5 min to 120 min, in particular in the range of 10 min to 45 min, particularly preferably in the range of 10 min up to 20 min.
  • At least one after-treatment step for example one, two or more drying steps, can follow.
  • the drying is usually carried out at temperatures in the range of 2 to 200 ° C.
  • the post-treatment step is drying by vacuum treatment as described above.
  • the present invention also relates to a process for the preparation of tungsten-free catalysts for the epoxidation of alkenes, comprising the application of silver, molybdenum and tin to a support and a drying step.
  • the support material is preferably calcined after the application of silver, molybdenum, tin and optionally further promoters, optionally after a drying step.
  • the calcining is preferably carried out at temperatures in the range of 150 to 750 ° C, preferably in the range of 200 to 500 ° C, more preferably in the range of 220 to 350 ° C, more preferably in the range of 250 to less than 300 ° C and especially preferably in the range of 270 to 295 ° C, wherein the Klazinianssdauer is generally at least 5 minutes or more, for example in the range of 5 minutes to 24 hours or in the range of 10 minutes to 12 hours. More preferably, the calcination time is in the range of 5 minutes to 3 hours.
  • the calcination can be carried out at a constant temperature. Furthermore are Embodiments in which the temperature during the calcination period is changed continuously or discontinuously.
  • the calcination can be carried out under any suitable gas atmosphere, for example in an inert gas or a mixture of an inert gas and 10 ppm to 21 vol .-% oxygen.
  • an inert gas for example, nitrogen, argon, carbon dioxide, helium and mixtures of the aforementioned inert gases may be mentioned.
  • nitrogen is particularly preferred.
  • air and / or lean air is used.
  • the calcination is preferably carried out in a muffle furnace, convection oven, in a rotary kiln and / or a belt calcination furnace.
  • the present invention also relates to a process for the preparation of tungsten-free catalysts for the epoxidation of alkenes, comprising the application of silver, molybdenum and tin to a support, optionally a drying step and a calcination, preferably at a temperature in the range from 270 to 295 ° C.
  • the silver, molybdenum and tin impregnated support material obtained according to the method described above, which has a temperature To is calcined in a multi-stage process.
  • This process includes at least the following steps:
  • T2 Maintaining the carrier material heated to the temperature Ti at a temperature T2, wherein T2 is preferably in the range of 0.95 Ti to 1, 1 Ti;
  • the impregnated support material is obtained at a temperature of greater than 0, it is first cooled according to the invention to the temperature To.
  • temperatures To in the range of up to 35 ° C such as in the range of up to 30 ° C conceivable.
  • the temperature To is in the range of 5 to 20 ° C, more preferably in the range of 10 to 15 ° C.
  • the resulting impregnated support material no pre-drying must be exposed before it is heated according to the invention in step (1) with a heating rate of at least 30 K / min.
  • the present invention thus preferably relates to a process in which the carrier material impregnated with silver, molybdenum, tin and optionally further promoters, obtained according to the process described above, is not exposed to a temperature greater than or equal to, before heating at a heating rate of at least 30 K min 35 ° C, preferably greater than 30 ° C, more preferably greater than 25 ° C and more preferably greater than 20 ° C.
  • the impregnated support material provided at the temperature To is heated at a heating rate of at least 30 K / min.
  • heating rates of up to 150 K min for example up to 100 K min or up to 80 K / min are conceivable.
  • the heating rate in step (1) is preferably in the range from 30 to 80 K / min, more preferably in the range from 40 to 75 K / min.
  • step (1) of the calcination process according to the invention the carrier material is heated from the temperature To to the temperature Ti.
  • temperatures Ti which are suitable for calcination of the impregnated carrier material.
  • temperatures Ti of up to 350 ° C such as up to 340 ° C or up to 330 ° C or up to 320 ° C or up to 310 ° C or up to 300 ° C conceivable.
  • Preferred minimum temperatures Ti are in the range of 250 ° C. Accordingly, temperatures Ti are conceivable in the range from 250 to 310 ° C. or in the range from 250 to 300 ° C. According to the invention, however, it has been found that it is possible to set calcination temperatures of less than 300 ° C. Therefore, the present invention relates to the method as described above, wherein the temperature Ti is less than 300 ° C, preferably less than or equal to 299 ° C.
  • the temperature Ti is preferably in the range from 250 to 295.degree. C., more preferably in the range from 260 to 295.degree. C., more preferably in the range from 270 to 295.degree. C., more preferably in the range from 270 to 290.degree Range from 270 to 285 ° C, 275 to 290 ° C, or 275 to 285 ° C.
  • the carrier material present at the temperature To is preferably brought into contact with a gas, more preferably the heating of the carrier material takes place via this gas, ie the gas has a temperature which allows the carrier material to reach the temperature To heat up Ti.
  • the gas contains oxygen, for example, oxygen contents of the gas of up to 100 vol .-% or up to 25 vol .-% may be mentioned.
  • the present invention relates to the method as described above, wherein the heating according to step (1) is carried out by contacting the carrier material with an inert gas.
  • the present invention relates to the method as described above, wherein the heating according to step (1) is carried out by contacting the carrier material with an inert gas, wherein the inert gas contains less than 10 ppm, preferably from 5 to 9 ppm oxygen.
  • the present invention relates to the method as described above, wherein the heating according to step (1) is carried out by contacting the carrier material with an inert gas, wherein the inert gas is nitrogen and the inert gas contains less than 10 ppm, preferably from 5 to 9 ppm oxygen ,
  • inert gas containing less than 10 ppm, preferably from 5 to 9 ppm of oxygen in this case denotes a gas mixture consisting of the inert gas and oxygen, wherein the oxygen content of less than 10 ppm and 5 to 9 ppm, respectively, on the oxygen content refers to the gas mixture and wherein the inert gas may be a mixture of 2 or more inert gases.
  • the use of technical nitrogen preferably obtained from air separation, which typically has nitrogen in the range from 99.995 to 99, is very particularly preferred as the gas with which the carrier material is brought into contact during the heating in step (1).
  • 9999 oxygen in the range of 6 to 8 ppm and contains traces of noble gases.
  • the temperature of the gas with which the carrier material is brought into contact in the course of heating is basically chosen so that the heating rates according to the invention can be made possible and the carrier material can be brought to the temperature Ti.
  • the gas with which the carrier material is brought into contact during the heating in step (1) a temperature in the range of Ti to 1, 1 Ti, more preferably in the range of Ti to 1, 07 Ti, more preferably in Range from Ti to 1, 05 Ti up.
  • the contacting of the carrier material with the gas in the context of step (1) can in principle be carried out arbitrarily, as long as it is ensured that the heating rate of the carrier material according to the invention is achieved.
  • the volumetric flow of the gas is in principle selected such that the heating rate according to the invention is achieved.
  • the volume flow of the gas is selected such that the heating rate according to the invention is achieved with the combination of the temperature and the volume flow of the gas which is brought into contact with the carrier material.
  • the volume flow is particularly preferably in the range from 2500 to 5000, particularly preferably in the range from 3200 to 4500 m 3 / h.
  • the present invention relates to the method as described above, wherein the carrier material to be heated according to step (1) is flowed through by an inert gas, preferably by nitrogen, wherein preferably contains less than 10 ppm, more preferably from 5 to 9 ppm oxygen, wherein preferably has a temperature in the range of Ti to 1, 1 Ti and wherein h the carrier material preferably flows through a volume flow in the range of 2500 to 5000, more preferably from 3200 to 4500 m 3 / h.
  • an inert gas preferably by nitrogen, wherein preferably contains less than 10 ppm, more preferably from 5 to 9 ppm oxygen, wherein preferably has a temperature in the range of Ti to 1, 1 Ti and wherein h the carrier material preferably flows through a volume flow in the range of 2500 to 5000, more preferably from 3200 to 4500 m 3 / h.
  • the heating rate may be constant or vary, as long as it is ensured that the total heating rate calculated from the temperature difference ( ⁇ - ⁇ -To) divided by the total for heating time required, at least 30 K / min, and preferably in the range of 30 to 80 K / min, more preferably in the range of 30 to 75 K / min, more preferably in the range of 30 to 70 K / min.
  • the heating rate is preferably at least 30 K / min, more preferably in the range from 30 to 80 K / min, more preferably in the range from 30 to 75 K / min, even more preferably in the range from 30 to 70 K. / min.
  • Possible ranges for the heating rate according to the invention are, for example, 35 to 80 K / min or 40 to 75 K / min or 40 to 70 K / min or 45 to 70 K / min or 50 to 70 K / min or 55 to 70 K / min or 60 to 70 K / min or 65 to 70 K / min.
  • the support material heated to the temperature Ti is maintained at a temperature T2 which is suitable for the purposes of the calcination according to the invention after the heating, preferably in direct connection to the heating.
  • temperatures T2 which are in the region of the temperature Ti are preferred.
  • temperatures T 2 ranging from 0.95 to 1, 1 Ti, such as in the range of 0.95 to 1, 05 Ti, 0.96 to 1, 04 Ti, 0.97 to 1, 03 Ti . 0.98 to 1, 02 Ti, or 0.99 to 1, 01 Ti lie.
  • the temperature T2 is preferably chosen so that it is less than 300 ° C, preferably less than or equal to 299 ° C.
  • Holding the substrate at temperature T2 also includes embodiments in which, while held, the value of T2 is not constant but varies within the limits described above.
  • the present invention thus also includes embodiments according to which the holding takes place at two or more different temperatures, wherein these temperatures are within the limits T2 described above.
  • the duration of holding the support material at the temperature T2 is basically not limited. In the context of the present invention, it is preferred that in step (2) the support be maintained at the temperature T2 for a time in the range of 1 to 15 minutes, preferably 2 to 10 minutes, more preferably 3 to 5 minutes. As regards the manner in which the holding according to the invention is achieved according to step (2), there are basically no restrictions.
  • the carrier material is brought into contact with a gas, wherein the gas has a temperature which makes it possible to keep the carrier material at the temperature T2.
  • the gas contains oxygen, for example, oxygen contents of the gas of up to 100 vol .-% or up to 25 vol .-%. It is conceivable, for example, the use of air. Also, lower levels of oxygen are conceivable, for example, mixtures of nitrogen and air such as lean air are conceivable.
  • Oxygen contents of the gas of up to 20 vol.% Or up to 15 vol.% Or up to 10 vol.% Or up to 5 vol.% Or up to 1 vol.% Can be mentioned.
  • inert gases include nitrogen, carbon dioxide, argon and helium. Nitrogen is particularly preferably used as the inert gas in the context of the present invention.
  • the present invention relates to the method as described above, wherein the holding according to step (2) is carried out by contacting the carrier material with an inert gas I2.
  • the present invention relates to the method as described above, wherein the holding according to step (2) is carried out by contacting the carrier material with an inert gas I2, wherein the inert gas contains less than 10 ppm, preferably from 5 to 9 ppm oxygen. More preferably, the present invention relates to the method as described above, wherein the holding according to step (2) is carried out by contacting the carrier material with an inert gas b, wherein the inert gas is nitrogen and the inert gas less than 10 ppm, preferably from 5 to 9 ppm oxygen contains.
  • inert gas b which contains less than 10 ppm, preferably from 5 to 9 ppm of oxygen
  • inert gas b which contains less than 10 ppm, preferably from 5 to 9 ppm of oxygen
  • here denotes a gas mixture consisting of the inert gas b and oxygen, wherein the oxygen content of less than 10 ppm and 5 to 9 ppm, respectively refers to the oxygen content of the gas mixture and wherein the inert gas b may be a mixture of 2 or more inert gases.
  • step (2) in the context of the present invention, very particular preference is given to using as the gas with which the support material is brought into contact during the holding in step (2), technical nitrogen, preferably obtained from air separation, typically nitrogen in the range from 99.995 to 99 , 9999 vol .-%, oxygen in the range of 6 to 8 ppm and traces of noble gases.
  • technical nitrogen preferably obtained from air separation, typically nitrogen in the range from 99.995 to 99 , 9999 vol .-%, oxygen in the range of 6 to 8 ppm and traces of noble gases.
  • the temperature of the gas with which the carrier material is brought into contact in the context of holding in accordance with step (2) is in principle selected such that the holding temperature according to the invention can be made possible.
  • the gas with which the carrier material is brought into contact in the context of holding in step (2) preferably has a temperature in the range from T2 to 1.1 T2, more preferably in the range from T2 to 1.7.07 T2, more preferably in the range from Range from T2 to 1, 05 T2 as in the range of T2 to 1, 04 T2 or in the range of T2 to 1, 03 T2 or in the range of T2 to 1, 02 T2 or in the range of T2 to 1, 01 T2 on ,
  • the contacting of the carrier material with the gas in the context of step (2) can basically be carried out arbitrarily, as long as it is ensured that the holding of the carrier material according to the invention is achieved at the temperature T2.
  • the volume flow of the gas is basically chosen so that the holding of the carrier material according to the invention is achieved at the temperature T2.
  • the volumetric flow rate of the gas is chosen such that, with the combination of the temperature and the volumetric flow rate of the gas which is brought into contact with the carrier material, the holding of the carrier according to the invention is achieved at the temperature T2.
  • the volume flow is particularly preferably in the range from 1000 to 3000, more preferably from 1500 to 2000 m 3 / h.
  • the present invention relates to the method as described above, wherein the according to step (2) to be held at the temperature T2 carrier material is traversed by an inert gas b, preferably by nitrogen, b preferably less than 10 ppm, more preferably of Contains 5 to 9 ppm oxygen, wherein b preferably has a temperature in the range of T2 to 1, 05 T2 and wherein b is the carrier preferably with flows through a volume flow in the range of 1000 to 3000, more preferably from 1500 to 2000 m 3 / h.
  • an inert gas b preferably by nitrogen, b preferably less than 10 ppm, more preferably of Contains 5 to 9 ppm oxygen
  • b preferably has a temperature in the range of T2 to 1, 05 T2 and wherein b is the carrier preferably with flows through a volume flow in the range of 1000 to 3000, more preferably from 1500 to 2000 m 3 / h.
  • the inert gas is used in the context of the present invention as the inert gas, wherein, as described above, the volume flow of the volume flow of and / or the temperature of the temperature may be different from or may be.
  • step (3) of the calcining process according to the invention the carrier material held at the temperature T2 is cooled to a temperature T3 following the holding, preferably immediately following the holding.
  • a temperature T3 following the holding, preferably immediately following the holding.
  • temperatures T3 are preferred.
  • the carrier material is brought into contact with a gas, wherein the gas has a temperature which makes it possible to cool the carrier material to the temperature T3.
  • Temperature T3 a gas having an oxygen content of at least 5 vol .-%, preferably at least 10 vol .-%, more preferably at least 15 vol .-%, more preferably at least 20 vol .-% use. Particular preference is given to using air according to the invention for cooling according to step (3).
  • the support material is preferably cooled in step (3) at a cooling rate which is in the range from 30 to 80 K / min, preferably in the range from 40 to 60 K / min, more preferably in the range from 45 to 55 K / min lies.
  • step (3) the correspondingly obtained, calcined and cooled carrier material can either be used directly as a catalyst or else be stored in a suitable manner.
  • the heating according to the invention according to step (1) preferably further holding according to the invention according to step (2), preferably further cooling according to the invention according to step (3) like can be performed as described above.
  • Embodiments according to which at least the heating according to step (1), preferably the heating according to step (1) and the holding according to step (2), and optionally also the cooling according to step (3), are preferably carried out continuously.
  • the method according to the invention is carried out in a ribbon calciner, at least as regards step (1), preferably at least with regard to steps (1) and (2).
  • the time of application of the promoters may also be applied subsequent to the calcination described above.
  • embodiments are encompassed in which the at least one further promoter, for example five different further promoters, four different further promoters, three different further promoters, two different further promoters or another promoter, are applied to the carrier and so on treated support is subsequently calcined as described above to obtain a catalyst according to the invention.
  • the at least one further promoter for example five different further promoters, four different further promoters, three different further promoters, two different further promoters or another promoter
  • the present invention further relates to a process for the production of ethylene oxide from ethylene, comprising an oxidation of ethylene in the presence of a tungsten-free catalyst for the epoxidation of alkenes comprising silver, molybdenum and tin supported on a support.
  • the present invention also relates to the use of a tungsten-free catalyst comprising silver, molybdenum and tin supported on a support for the epoxidation of alkenes.
  • the epoxidation can be carried out by all methods known to the person skilled in the art.
  • Any of the reactors which can be used in the ethylene oxide preparation processes of the prior art can be used here, for example externally cooled tube bundle reactors (compare Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Vol. A-10, pages 1 17-135, 123-125 VCH-Verlagsgesellschaft, Weinheim 1987) or also reactors with loose catalyst bed and cooling tubes, for example the reactors described in DE-A 3414717, EP 0082609 and EP-A 0339748.
  • the epoxidation takes place in at least one tubular reactor, preferably in a tube bundle reactor.
  • the catalyst according to the invention can be used either alone or in admixture with other catalysts in a combined or structured catalyst bed.
  • inert gases such as nitrogen or gases behaving inertly under the reaction conditions such as water vapor, methane and optionally reaction moderators, for example halides, hydrocarbons such as ethyl chloride, vinyl chloride or 1, 2-dichloroethane can be admixed with the reaction gas containing ethylene and molecular oxygen.
  • reaction moderators for example halides, hydrocarbons such as ethyl chloride, vinyl chloride or 1, 2-dichloroethane
  • the oxygen content of the reaction gas is in a range in which no explosive gas mixtures are present.
  • a suitable composition of the reaction gas for the production of ethylene oxide may, for.
  • an amount of ethylene in the range of 10 to 80 vol .-%, preferably from 20 to 60 vol .-%, more preferably from 25 to 50% by volume, and particularly preferably in the range of 30 to 40 vol. %, based on the total volume of the reaction gas include.
  • the oxygen content of the reaction gas is expediently in a range of at most 10 vol .-%, preferably of at most 9 vol .-%, more preferably of at most 8 vol .-%, and most preferably of at most 7 vol .-%, based on the total volume of the reaction gas.
  • the reaction gas contains a chlorine-containing reaction moderator such as ethyl chloride, methyl chloride, vinyl chloride or dichloroethane in an amount of 0 to 15 ppm, preferably in an amount of 0.1 to 8 ppm.
  • the remainder of the reaction gas usually consists of hydrocarbons, such as methane, or of inert gases such as nitrogen.
  • other substances such as water vapor, carbon dioxide or noble gases may also be present in the reaction gas.
  • the components of the reaction mixture described above may optionally each have small amounts of impurities.
  • ethylene can be used at any purity level suitable for the epoxidation of the present invention. Suitable levels of purity include, but are not limited to, polymer grade ethylene, which typically has a purity of at least 99%, and chemical grade ethylene, which has a lower purity, typically less than 95%.
  • the impurities typically consist mainly of ethane, propane and / or propene. The epoxidation is usually carried out at elevated temperature.
  • the present invention also relates to a process as described above, wherein the oxidation takes place at a temperature in the range of 180 to 300 ° C, preferably in the range of 200 to 280 ° C.
  • the oxidation is carried out at a pressure in the range of 5 bar to 25 bar, preferably at a pressure in the range of 10 bar to 20 bar and in particular in the range of 14 bar to 20 bar.
  • the present invention also relates to a process as described above, wherein the oxidation takes place at a pressure in the range of 14 bar to 20 bar.
  • the oxidation is carried out in a continuous process.
  • a GHSV gas hourly space velocity
  • the size / average area of the reactor preferably in the range of 800 to 10000 / h, preferably in the range of 2000 to 6000 / h, more preferably in the range of 2500 to 5000 / h, wherein the data relate to the volume of the catalyst.
  • the production of ethylene oxide from ethylene and oxygen can be carried out in a cyclic process.
  • the reaction mixture is circulated through the reactor, where after each pass the newly formed ethylene oxide and the by-products formed in the reaction are removed from the product gas stream, which is fed back into the reactor after addition of the required amounts of ethylene, oxygen and Mattersmoderatoren becomes.
  • the separation of the ethylene oxide from the product gas stream and its work-up can be carried out according to the customary processes of the state of the art (see Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Vol. A-10, pp. 17-135, 123-125 VCH Verlagsgesellschaft, Weinheim 1987).
  • the precipitated silver oxalate was filtered off and washed the filter cake obtained with 1 liter portions of water (in total about 10 I) until it was potassium or nitrate-free (determined by conductivity measurement of the washing solution, potassium or nitrate-free means in the present case a conductivity ⁇ 40 ⁇ 5 / ⁇ ).
  • the water was as completely as possible removed from the filter cake and the residual moisture of the filter cake determined. There were obtained 620 g of silver oxalate with a water content of 20.80%.
  • the desired amount of tin oxalate was weighed and mixed with four parts of distilled water and one part of H2O2 (30%). The reaction mixture was stirred at room temperature until a clear solution had formed.
  • the desired amount of carrier A (see Table 1) was placed in a rotary evaporator and evacuated. The vacuum was 50 mbar. The carrier was pre-evacuated for about 10 min.
  • the impregnated support was for 13 min at 283 ° C under 8.3 m 3 N 2 per hour with a heating rate of 40 K / min, a heating time of 360 s and a hold time at 283 ° C of 420 s in a convection oven (HORO , Type 129 ALV-SP, make no .: 53270).
  • the cooling to room temperature took place within 420 s.
  • the epoxidation was carried out in a test reactor consisting of a vertical reaction tube made of stainless steel with an inner diameter of 6 mm and a length of 2200 mm.
  • the jacketed reaction tube was heated with hot oil of temperature T flowing through the jacket. With a very good approximation, the temperature of the oil corresponds to the temperature in the reaction tube and thus the reaction temperature.
  • the reaction temperature was controlled according to the specified ethylene oxide exhaust gas concentration of 2.7%.
  • ethylene oxide exhaust gas concentration 2.7%.
  • 2.2 and 4.0 ppm of ethylene chloride were added as a moderator to the input gas.
  • the prepared catalyst contains 15.4% by weight of silver, tungsten in an amount of 200 ppm by weight, cesium in an amount of 400 ppm by weight, lithium in an amount of 190 ppm by weight, sulfur in an amount of 14 Ppm by weight and rhenium in an amount of 380 ppm.
  • the prepared catalyst contains 15.5% by weight of silver, cesium in an amount of 400 ppm by weight, lithium in an amount of 190 ppm by weight, sulfur in an amount of 14 ppm by weight and rhenium in an amount of 380 ppm.
  • the catalyst prepared contains 15.2% by weight of silver, cesium in an amount of 400 ppm by weight, lithium in an amount of 190 ppm by weight, sulfur in an amount of 14 ppm by weight, molybdenum in an amount of 50 ppm, tin in an amount of 150 ppm and rhenium in an amount of 380 ppm.
  • the prepared catalyst contains 14.9% by weight of silver, cesium in an amount of 400 ppm by weight, lithium in an amount of 190 ppm by weight, sulfur in an amount of 14 ppm by weight, molybdenum in an amount of 50% ppm and rhenium in an amount of 380 ppm.
  • the prepared catalyst contains 14.9% by weight of silver, cesium in an amount of 400 ppm by weight, lithium in an amount of 190 ppm by weight, sulfur in an amount of 14 ppm by weight, tin in an amount of 150 ppm and rhenium in an amount of 380 ppm.
  • the prepared catalyst contains 15.3% by weight of silver, cesium in an amount of 400 ppm by weight, lithium in an amount of 190 ppm by weight, sulfur in an amount of 14 ppm by weight, tungsten in an amount of 200 ppm, molybdenum in an amount of 50 ppm, tin in an amount of 150 ppm and rhenium in an amount of 380 ppm.
  • the prepared catalyst contains 15.5% by weight of silver, cesium in an amount of 400 ppm by weight, lithium in an amount of 190 ppm by weight, sulfur in an amount of 14 ppm by weight, palladium in an amount of 50% ppm, cobalt in an amount of 150 ppm and rhenium in an amount of 380 ppm.
  • Catalyst 8 (Comparative Example) 120.1 g of the carrier A were converted into the corresponding catalyst according to general instructions 1.2 to 1 .7.
  • the prepared catalyst contains 15.5% by weight of silver, cesium in an amount of 400 ppm by weight, tungsten in an amount of 200 ppm, lithium in an amount of 190 ppm by weight, sulfur in an amount of 14% by weight ppm, palladium in an amount of 50 ppm, cobalt in an amount of 150 ppm and rhenium in an amount of 380 ppm.
  • the resulting catalyst was then tested according to General Procedure 1.9. The result is shown in Table 2.
  • the prepared catalyst contains 15.5% by weight of silver, cesium in an amount of 400 ppm by weight, lithium in an amount of 190 ppm by weight, sulfur in an amount of 14 ppm by weight, cobalt in an amount of 150 ppm, molybdenum in an amount of 50 ppm and rhenium in an amount of 380 ppm.
  • the catalyst prepared contains 15.5% by weight of silver, cesium in an amount of 400 ppm by weight, lithium in an amount of 190 ppm by weight, sulfur in an amount of 14 ppm by weight, cobalt in an amount of 150 ppm, tin in an amount of 150 ppm and rhenium in an amount of 380 ppm.
  • the catalytic results show that the catalyst 3 according to the invention has the best combination of activity and high selectivity. Under the selected experimental parameters, a catalyst which requires a temperature of more than 245 ° C. to achieve the desired ethylene oxide concentration of 2.7% of the exhaust gas of ethylene is not suitable for achieving the typically required service life of about 1 year.

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Abstract

La présente invention concerne un catalyseur pour la préparation d'oxydes d'alkylène, ce catalyseur étant un catalyseur à l'argent supporté comprenant une nouvelle combinaison de promoteurs. La présente invention concerne en outre un procédé de préparation de ce catalyseur, l'utilisation dudit catalyseur pour l'oxydation d'alkylènes en oxydes d'alkylène, ainsi qu'un procédé de préparation d'oxyde d'éthylène à partir d'éthylène en présence dudit catalyseur.
PCT/IB2013/053169 2012-05-04 2013-04-22 Catalyseur pour l'époxydation d'alcènes WO2013164727A1 (fr)

Priority Applications (5)

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EP13784593.9A EP2844646A4 (fr) 2012-05-04 2013-04-22 Catalyseur pour l'époxydation d'alcènes
BR112014026976A BR112014026976A2 (pt) 2012-05-04 2013-04-22 catalisador sem tungstênio para a epoxidação de alcenos, processo para a produção de catalisadores sem tungstênio para a epoxidação de alcenos e uso de um catalisador
KR1020147034186A KR20150013704A (ko) 2012-05-04 2013-04-22 알켄의 에폭시화용 촉매
CN201380022972.4A CN104321315A (zh) 2012-05-04 2013-04-22 用于环氧化链烯烃的催化剂
JP2015509529A JP2015518421A (ja) 2012-05-04 2013-04-22 アルケンのエポキシ化のための触媒

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EP12166830 2012-05-04

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CN116196922A (zh) * 2021-12-01 2023-06-02 中国石油化工股份有限公司 一种银催化剂及其制备方法与应用

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