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CN104321315A - Catalyst for epoxidation of alkenes - Google Patents

Catalyst for epoxidation of alkenes Download PDF

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Publication number
CN104321315A
CN104321315A CN201380022972.4A CN201380022972A CN104321315A CN 104321315 A CN104321315 A CN 104321315A CN 201380022972 A CN201380022972 A CN 201380022972A CN 104321315 A CN104321315 A CN 104321315A
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catalyzer
carrier
solution
silver
temperature
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Inventor
T·罗森达尔
T·莫伊雷尔
D·亨泽尔
A·莱尔
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BASF SE
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BASF SE
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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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Epoxy Compounds (AREA)

Abstract

A supported silver catalyst having a novel promoter combination for preparing alkylene oxides is provided. A process for producing the catalyst, the use of the catalyst for the oxidation of alkylenes to alkylene oxides, and a process for preparing ethylene oxide from ethylene in the presence of the catalyst are also provided.

Description

For the catalyzer of epoxidation alkene
The present invention relates to a kind of catalyzer preparing oxyalkylene, it is the loading type silver catalyst with the combination of novel promotor.The invention further relates to a kind of produce this catalyzer method and this catalyzer alkene is being oxidized to the purposes in oxyalkylene.In addition, the present invention relates to a kind of method by ethylene making ethylene oxide, be included in described catalyzer exist under by oxidation of ethylene.
Ethylene oxide is important basic chemical and usually prepares by oxygen to directly oxidize ethene under existing at silver-containing catalyst at industrial scale.Usual working load type catalyzer, wherein catalytically-active metals silver puts on carrier by suitable method.Various porous material can be used in principle as the mixture of gac, titanium dioxide, zirconium dioxide or silicon-dioxide or ceramic composition or these materials as carrier.Usually Alpha-alumina is used as carrier.
Except as except the silver of active ingredient, these catalyzer comprise the promotor (WO 2007/122090, WO 2010/123856) of improving catalytic performance usually.The example of promotor is alkali metal compound and/or alkaline earth metal compound.Some teach literatures use transition metal is as cobalt (EP 0 480 538), tungsten or molybdenum.Rhenium on the particularly preferred promotor of the activity and selectivity affecting catalyzer.Industrially, due to its highly selective, preferably use the catalyzer comprising rhenium and/or other transition metal promoter combined with alkali metal compound and/or alkaline earth metal compound.Selectivity is such as at the ethylene molar percentage ratio that will when oxidation of ethylene be reaction formation ethylene oxide.The activity of catalyzer, by condition constant in other respects, such as, characterizes in the ethylene oxide concentration of reactor exit under temperature, pressure, gas throughput, catalytic amount etc.It is higher that reactor exports ethylene oxide concentration in stream, and the activity of catalyzer is higher.The temperature realized needed for specific ethylene oxide concentration is lower, and activity is higher.In order to realize highly selective, usually active metal is mated mutually with the combination of promotor and the composition of carrier, to obtain the catalyzer with very good performance.
Direct oxidation of ethylene to becomes ethylene oxide to be such as described in DE-A-2300512 by working load type silver catalyst, DE-A 2521906, EP-A-0014457, DE-A-2454972, EP-A-0172565, EP-A-0357293, EP-A-0266015, in EP-A-0011356, EP-A-0085237, DE-A-2560684 and DE-A-2753359.
The object of the invention is the new catalyst that will be provided for epoxidation alkene, it demonstrates favourable activity and/or selectivity.
Therefore, we have found new catalyst, wherein silver and also have molybdenum and tin instead of tungsten to put on carrier as promotor.
Therefore, the invention provides a kind of catalyzer of the not tungstenic for epoxidation alkene, it comprises the silver put on carrier, molybdenum and tin.
Catalyzer of the present invention comprises carrier.The carrier being applicable to the object of the invention can be produced by the method known by prior art.Example is method described in US 2009/0198076 A1, WO 2006/133187, WO 03/072244, US 2005/0096219 A1 and EP 0 496 386 B2.
The example of suitable support material is aluminum oxide, silicon-dioxide, silicon carbide, titanium dioxide, zirconium dioxide and composition thereof, preferential oxidation aluminium.In preferred embodiments, this invention therefore provides its carrier a kind of is the catalyzer of alumina supporter.
Term aluminum oxide used herein comprise all structures expected as α-, γ-or θ-aluminum oxide.In preferred embodiments, this carrier is alpha-alumina supports.Therefore, present invention also offers a kind of wherein this carrier is the catalyzer of Alpha-alumina.
In another preferred embodiment of the present, this Alpha-alumina has at least 75%, and preferably at least 80%, more preferably at least 85%, more preferably at least 90%, more preferably at least 98%, more preferably at least 98.5%, the particularly preferably purity of at least 99%.
Therefore term Alpha-alumina also comprises the Alpha-alumina comprising other compositions, and these other compositions are such as selected among zirconium, basic metal, alkaline-earth metal, silicon, zinc, gallium, hafnium, boron, fluorine, copper, nickel, manganese, iron, cerium, titanium, the element of chromium and the compound of these elements and the mixture also having in these elements and/or its compound two or more.
Usually can by by aluminum oxide and water or another suitable liquid and also have burnout materials (burnout material) or pore former and at least one tackiness agent to mix and produce the support of the catalyst of applicable the object of the invention.Suitable pore former is such as Mierocrystalline cellulose and derivatived cellulose are if methylcellulose gum, ethyl cellulose, carboxymethyl cellulose or polyolefine are if polyethylene and polypropylene or natural burnout materials are as the walnut shell ground.Pore former is selected to form finished product alpha-alumina supports to make them for calcining under selected furnace temperature complete after-flame from aluminum oxide.Suitable tackiness agent or extrusion aid are such as described in EP 0 496 386 B2.Can mention as an example and there is nitric acid or acetic acid, Mierocrystalline cellulose, such as methylcellulose gum, ethyl cellulose or carboxyethyl cellulose or methyl stearate or Stearic ethyl stearate, polyolefin epoxide, the alumina gel of wax and similar substance.
Can be desired shape by extruding by the paste be mixed to form.In order to auxiliary extrusion, extrusion aid can be used.
The formed body obtained as mentioned above after formation usual optionally drying is also calcined and obtains alumina supporter.Calcining is carried out usually at the temperature of 1200-1600 DEG C.Usually this alumina supporter is washed after calcining to remove soluble components.
This Alpha-alumina can comprise other compositions of any suitable form, such as, as element and/or with the form of one or more compounds.If this Alpha-alumina comprises the composition of one or more compound forms, then it such as comprises these with oxide compound or mixed oxide.Therefore, the carrier being applicable to the object of the invention also comprises and comprises the Alpha-alumina that at least one is selected from other compositions of silicon-dioxide, sodium oxide, potassium oxide, calcium oxide and magnesium oxide, nickel oxide, gallium oxide, hafnia, cupric oxide, ferric oxide and composition thereof.
For the amount of other compositions, the total amount of other compositions is preferably less than 25 % by weight based on the gross weight of this carrier, be more preferably less than 20 % by weight, be more preferably less than 15 % by weight, be more preferably less than 10-% by weight, be more preferably less than 5 % by weight, be more preferably less than 2 % by weight, be more preferably less than 1.5 % by weight, be particularly preferably less than 1 % by weight.
If this carrier such as comprises basic metal, then it is preferably based on the gross weight of this carrier and calculates with 10-2500ppm with element, and more preferably 10-1000ppm, more preferably the total amount of 50-850ppm comprises these.In one embodiment, this carrier comprises the basic metal that at least one is selected from sodium and potassium.If this carrier such as comprises sodium, then it is preferably based on the gross weight of this carrier and calculates with 10-1500ppm with element, and more preferably 10-800ppm, more preferably the amount of 10-500ppm comprises sodium.If this carrier such as comprises potassium, then it is preferably based on the gross weight of this carrier and calculates with 10-1000ppm with element, and more preferably 10-500ppm, more preferably the amount of 10-300ppm comprises potassium.In embodiments of the invention, this carrier such as comprises sodium with the amount of 10-1500ppm and comprises potassium with the amount of 10-1000ppm.
Therefore, invention further describes its carrier a kind of based on the gross weight of this carrier calculates with element in each case and comprises sodium with the amount of 10-1500ppm and comprise potassium with the amount of 10-1000ppm, particularly preferably comprises sodium with the amount of 10-500ppm and comprises the catalyzer of potassium with the amount of 10-300ppm.
If this carrier such as comprises alkaline-earth metal, then it is preferably based on the gross weight of this carrier and calculates such as, with 2500ppm, 10-2500ppm, more preferably 10-1200ppm at the most with element, and more preferably the total amount of 10-700ppm comprises these.In one embodiment, this carrier comprises the alkaline-earth metal that at least one is selected from calcium and magnesium.If this carrier such as comprises calcium, then it is preferably based on the gross weight of this carrier and calculates with 10-1500ppm with element, and more preferably 10-1000ppm, more preferably the amount of 10-500ppm comprises calcium.If this carrier comprises such as magnesium, then it is preferably based on the gross weight of this carrier and calculates with 10-800ppm with element, and more preferably 10-500ppm, more preferably the amount of 10-250ppm comprises magnesium.
Therefore, invention further describes its carrier a kind of in each case based on this carrier gross weight and calculate with element and comprise magnesium with the amount of 10-800ppm and comprise the catalyzer of calcium with the amount of 10-1500ppm.This carrier particularly preferably in each case based on this carrier gross weight and with element calculated example as the amount with 10-1500ppm comprises sodium, comprise potassium with the amount of 10-1000ppm, comprise magnesium with the amount of 10-800ppm and comprise calcium with the amount of 10-1500ppm.
If this carrier comprises such as silicon, then it is preferably based on the gross weight of this carrier and calculates with 50-10000ppm with element, and more preferably 50-5000ppm, more preferably the amount of 50-600ppm comprises silicon.
To the preferred carrier of the object of the invention such as purity is at least 90% and calculate with element in each case and gross weight based on this carrier comprises 50-10000ppm silicon, the Alpha-alumina of 10-1500ppm sodium and altogether 10-2500ppm alkaline-earth metal.This carrier preferably comprises calcium and/or magnesium as alkaline-earth metal.Particularly preferably purity is at least 98 % by weight and calculates with element in each case and gross weight based on this carrier comprises 50-5000ppm silicon, the Alpha-alumina of 10-800ppm sodium and altogether 10-700ppm alkaline-earth metal.
The BET surface-area that catalyzer used carrier of the present invention preferably has is determined as 0.1-5m according to method described in standard ISO 9277 2/ g, more preferably 0.1-2m 2/ g, more preferably 0.5-1.5m 2/ g, more preferably 0.6-1.3m 2/ g, particularly preferably 0.6-1.0m 2/ g.
In addition, the carrier for catalyzer of the present invention preferably has the hole that diameter is 0.1-100 μm, and wherein pore distribution can be unimodal or multimodal, such as bimodal, three peaks or four peaks.Carrier preferably has bimodal pore distribution.It is 0.1-10 μm and 15-100 μm, preferred 0.1-5 μm and 17-80 μm that carrier more preferably has peak-peak, more preferably 0.1-3 μm and 20-50 μm, more preferably the bimodal pore distribution of 0.1-1.5 μm and 20-40 μm.Aperture is measured by Hg porosimetry (as described in standard DIN 66133).Term used " peak-peak is the bimodal pore distribution of 0.1-10 μm and 15-100 μm " represents that one of two peak-peaks are 0.1-10 μm and another peak-peak is 15-100 μm above.
Therefore, invention further describes its carrier a kind of and have bimodal pore distribution, preferably at least to comprise the aperture measured by Hg porosimetry be the hole of 0.1-15 μm and aperture is the catalyzer of the bimodal pore distribution in the hole of 15-100 μm.
The geometrical shape of this carrier is usually not too important, but this carrier should advantageously in the particle form scribbling the very most of and internal surface area of the outer surface area of catalytic activity Argent grain and other promotor optional allowing reactant gases not to be diffused into this carrier with not being obstructed.The carrier geometrical shape chosen should guarantee pressure drop very little in whole reactor length.In preferred embodiments, this carrier as formed body, such as, uses as extrudate, hollow extruded effluent, star extrudate, ball, ring or hollow ring.This carrier preferably has the formed body of ducted body geometrical shape.Particularly preferably there is following geometrical dimension (external diameter × length × internal diameter, in each case with mm record) right cylinder: 5 × 5 × 2,6 × 6 × 3,7 × 7 × 3,8 × 8 × 3,8 × 8.5 × 3,8 × 8.5 × 3.5,8.5 × 8 × 3.5,8.5 × 8 × 3,9 × 9 × 3,9.5 × 9 × 3,9.5 × 9 × 3.5.Tolerance within the scope of length existence ± 0.5mm shown in each.
According to the present invention, catalyzer can also use with the crushing catalyst material forms obtained by formed body described in one or more.
The water-intake rate of this carrier is such as 0.35-0.65ml/g, preferred 0.42-0.52ml/g, by vacuum cold water absorption measurement.
Catalyzer of the present invention comprises silver as active metal.This catalyzer based on this catalyzer gross weight and with element calculate can with such as 5-35 % by weight, especially 10-30 % by weight, the amount of preferred 10-25 % by weight comprises silver.This silver is preferably can put on carrier for the silver compound of salt or silver complex.This silver compound is preferably as solution, and the solution especially in water applies.In order to obtain the silver compound of soluble form, can also in a suitable manner by coordination agent as thanomin, EDTA, 1,3-or 1,2-propylene diamine, quadrol and/or alkaline metal oxalate add this silver compound, such as, in silver suboxide (I) or silver oxalate (I) and this coordination agent can also play reductive agent simultaneously.Silver is particularly preferably with silver-amine compound, and particularly preferably silver-ethylene diamine compound form applies.
In addition, at least one in catalyzer containing element molybdenum of the present invention and tin is as promotor.For the purpose of the present invention, promotor is the composition of this catalyzer, realizes one or more catalytic performances whereby, the improvement compared with not comprising the catalyzer of this composition of such as selectivity, activity, transformation efficiency, productive rate and/or operation lifetime.Preferably basic chemically stable and the compound of any undesirable reaction of not catalysis at reaction conditions.Accelerator-based in this catalyzer gross weight and calculate usually with the total amount of 10-3000ppm and separately with the amount of 5-1500ppm with element summation, more preferably respective with the amount of 10-1300ppm, to use with the amount of 50-1300ppm particularly preferably separately.Promotor preferably puts on carrier with compound form, such as a complex or in the form of salts, such as with halogenide, fluorochemical, bromide or chloride form, or using carboxylate salt, nitrate, vitriol or sulfide, phosphoric acid salt, prussiate, oxyhydroxide, carbonate, oxide compound, oxalate form as the salt of heteropolyacid, such as, with the salt form of the heteropolyacid of rhenium.
Catalyzer of the present invention is preferably based on the gross weight of this catalyzer and calculates with 10-300ppm with element, and more preferably 10-200ppm, more preferably the amount of 10-80ppm comprises molybdenum.Molybdenum preferably applies as compound, such as halogenide, oxyhalogenide, oxide compound, molybdate, permolybdate, or as acid, preferably as the compound being selected from molybdenum oxide, Ammonium Heptamolybdate, ortho-molybdic acid ammonium, molybdenum chloride, molybdenum fluoride, moly-sulfide and molybdic acid.For the purposes of this invention, molybdenum is particularly preferably as molybdic acid (MoO 3h 2o) put on carrier.
Catalyzer of the present invention based on this catalyzer gross weight and calculate preferably with 10-600ppm with element, more preferably 50-400ppm, more preferably the amount of 80-250ppm comprises tin.Tin preferably applies as compound, such as halogenide, oxyhydroxide, oxalate, oxide compound, stannate, or as acid, preferably as being selected from stannic oxide, tin chloride, Tin tetrafluoride., sodium stannate, six hydrogen-oxygens for the compound of sodium stannate (sodium hexahydroxostannate), stannic acid and tin oxalate.For the object of the invention, tin particularly preferably puts on carrier as tin oxalate.
In addition, catalyzer of the present invention not tungstenic.For the purpose of the present invention, the catalyzer of tungstenic is not the catalyzer that W content is less than 5mg/kg; Tungsten preferably analytically can not detect.Under any circumstance, in the production of this catalyzer, tungsten compound is not used.
In preferred embodiments, this catalyzer comprises silver, molybdenum and tin and also has other promotor of at least one, and such as 5,4,3 or 2 kind of other promotor or other promotor a kind of.All promotor known in the prior art it is contemplated that as other promotor of at least one.Other promotor of this at least one are preferably selected from element lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, manganese, rhenium, cadmium, chromium, sulphur and wherein two or more mixture.This catalyzer particularly preferably comprises other promotor that at least one is selected from element rhenium, caesium, lithium, chromium, manganese, sulphur and the wherein mixture of two or more.This catalyzer very particularly preferably at least comprises rhenium is selected from caesium, lithium, chromium, manganese, sulphur and the wherein mixture of two or more element as other promotor and at least one.
Therefore, invention further describes a kind of catalyzer of not tungstenic, it comprises, and to put on silver on carrier-its amount be 5-35 % by weight based on gross weight of this catalyzer, molybdenum and tin and also have at least rhenium as other promotor.
If this catalyzer such as comprises rhenium, then it is preferably based on the gross weight of this catalyzer and calculates with 50-600ppm with element, and more preferably 100-450ppm, more preferably the amount of 150-400ppm comprises rhenium.Rhenium preferably applies as compound, such as, as halogenide, oxyhalogenide, oxide compound, rhenate, excessively rhenate or conduct acid.To by rhenium be used as promotor, then preferably it can be used as be selected from ammonium perrhenate, chlorination rhenium (III), chlorination rhenium (V), fluoridize rhenium (V), rhenium oxide (VI) and rhenium oxide (VII) compound applying.For the object of the invention, rhenium particularly preferably puts on carrier as ammonium perrhenate.
If this catalyzer such as comprises caesium, then it is preferably based on the gross weight of this catalyzer and calculates with 20-850ppm with element, and especially the amount of 100-600ppm comprises caesium.Caesium preferably puts on carrier as Cesium compound.Here any suitable Cesium compound can be used in principle.Caesium preferably applies with cesium hydroxide form.
If this catalyzer such as comprises lithium, then it is preferably based on the gross weight of this catalyzer and calculates with 10-450ppm with element, and especially the amount of 50-300ppm comprises lithium.Lithium preferably puts on carrier as lithium compound.Here any suitable lithium compound can be used in principle.Lithium preferably applies with lithium nitrate form.
If this catalyzer such as comprises sulphur, then it is preferably based on the gross weight of this catalyzer and calculates with 5-300ppm with element, and especially 5-150ppm comprises sulphur.Sulphur preferably puts on carrier as sulphur compound.Here any suitable sulphur compound can be used in principle.Sulphur preferably applies with ammonium sulfate form.
In particularly preferred embodiments, catalyzer of the present invention comprises rhenium with the amount of 150-450ppm, comprises caesium with the amount of 100-600ppm, comprises lithium and comprise sulphur with the amount of 5-150ppm with the amount of 50-300ppm.
Preferred by promotor before application, more preferably promoter compound is dissolved in suitable solvent, preferably soluble in water.Then preferred by this carrier gained solution impregnation comprising one or more promotor.To add multiple promotor, then can in single impregnation steps or in multiple impregnation steps, these be put on carrier together or separately.For the solution comprising one or more promotor, this can produce in any way as suitable.Such as, promotor separately can be dissolved in separately in a kind of solution and the gained solution comprising a kind of promotor in each case can be used for dipping subsequently.Two or more promotor can be dissolved in together equally in solution and also subsequently gained solution be used for dipping.In addition, the gained solution comprising at least one promotor can be merged before impregnation and the gained solution comprising all promotor is put on carrier.
If such as to major general's molybdenum, tin, caesium, lithium, sulphur and rhenium be used as promotor, then production at least one in particularly preferred embodiments comprise caesium solution, comprise molybdenum another solution, comprise lithium and sulphur another solution, comprise another solution of tin and comprise another solution of rhenium.These solution are put on carrier in the impregnation steps of separating or merges before application and form a kind of solution and be only used for dipping at this moment.These solution preferably together, more preferably with silver-amine compound, the mixture preferably comprising silver with silver-ethylene diamine compound puts on carrier together.
For the applying of silver, this can put on carrier by all dippings of prior art and deposition method for the production of preparing ethylene oxide silver catalyst used, and these methods can comprise one or more dipping and calcining step.Such as can mention DE-A 23005112, DE-A 2521906, EP-A 0 014 457, EP-A 0 085 237, EP-A 0 0,384 312, DE-A 2454927, DE-A 3321895, silver catalyst production method disclosed in EP-A 0 229 465, DE-A 3150205, EP-A 0 172 565 and EP-A 0 357 293.
This silver can separate with one or more promotor or together with apply.Preference is as put on the mixture comprising silver and at least one promotor on carrier by dipping, spraying or blending means.The applying order of promotor and silver can choose at random usually, namely comprises the embodiment wherein silver and promotor simultaneously put on carrier.Equally, comprise the embodiment wherein silver and promotor put on various step on carrier, wherein the order of each step can choose at random usually.In addition, the embodiment wherein part promotor being put on before or after applying silver and apply with silver on carrier and by remainder is simultaneously comprised.Preferably silver and promotor are put on carrier simultaneously.
Invention further provides the method for a kind of production for the catalyzer of the not tungstenic of epoxidation alkene, comprise and silver, molybdenum and tin are put on carrier.
This applying can be undertaken by any appropriate method in principle, such as, pass through impregnated carrier.This applying is particularly preferably undertaken by room temperature vacuum impregnation.In vacuum impregnation, be preferably first no more than 500 millibars, more preferably no more than 250 millibars, under being particularly preferably no more than the pressure of 50 millibars and preferably at 2-50 DEG C, more preferably at the temperature of 5-30 DEG C, particularly preferably at room temperature process this carrier.This vacuum-treat is such as carried out at least 1 minute, preferably at least 5 minutes, more preferably 5-120 minute, especially 10-45 minute, particularly preferably the time of 15-30 minute.After vacuum-treat, by least one solution, such as comprise the solution that the mixture of silver, molybdenum and tin or at least one comprise other promotor of at least one, the mixture preferably comprising silver, molybdenum and tin and other promotor of at least one puts on carrier.This solution preferably drips or sprays, and preferably sprays.Apply in this case preferably to be undertaken by nozzle.Preferred upon application this carrier to be found time further.Find time preferably be no more than 500 millibars, more preferably no more than 250 millibars, under being particularly preferably no more than the pressure of 50 millibars and preferably at 2-50 DEG C, more preferably at the temperature of 5-30 DEG C, particularly preferably at room temperature.This vacuum-treat is such as carried out at least 1 minute, preferably at least 5 minutes, more preferably 5-120 minute, especially 10-45 minute, particularly preferably the time of 10-20 minute.
Silver, molybdenum, tin and optionally other promotor can carry out at least one post-processing step after applying on carrier, such as 1,2 or more drying step.Drying is carried out usually at the temperature of 2-200 DEG C.This post-processing step is by vacuum treated drying, such as mentioned above.
Therefore, present invention also offers the method for a kind of production for the catalyzer of the not tungstenic of epoxidation alkene, comprise and silver, molybdenum and tin are applied on carrier and drying step.
At applying silver, molybdenum, tin and optionally after other promotor, optionally after the drying step, preferably calcine this solid support material.Calcining is preferred at 150-750 DEG C, preferred 200-500 DEG C, more preferably 220-350 DEG C, more preferably 250 DEG C to being less than 300 DEG C, particularly preferably carry out at the temperature of 270-295 DEG C, wherein calcination time is generally at least 5 minutes or longer, such as 5 minutes to 24 hours or 10 minutes to 12 hours.Calcination time is particularly preferably 5 minutes to 3 hours.Calcining can be carried out at a constant temperature.In addition, the embodiment of wherein continuous in calcination process or discontinuous change temperature is comprised.
Calcining can any be applicable to the gas atmosphere of this object under, such as carry out in the mixture of rare gas element or rare gas element and 10ppm-21 volume % oxygen.The rare gas element that can mention is such as the mixture of nitrogen, argon gas, carbonic acid gas, helium and above-mentioned rare gas element.If calcining is carried out in rare gas element, then particularly preferably nitrogen.In the preferred embodiment of replacing, use air and/or poor air.
In addition, calcining is preferably carried out in retort furnace, convection oven, rotary kiln and/or belt calciner.
Therefore, present invention also offers the method for producing for the catalyzer of the not tungstenic of epoxidation alkene, comprise and silver, molybdenum and tin are put on carrier, optional drying step and calcining, preferably at the temperature lower calcination of 270-295 DEG C.
In a preferred embodiment of the invention, obtained by aforesaid method and there is calcining in multistep method with the solid support material of silver, molybdenum and tin dipping of temperature T0.The method at least comprises the following steps:
(1) at least 30K/min, preferred 30-80K/min, under the heating rate of more preferably 40-75K/min by impregnated solid support material by temperature T 0be heated to temperature T 1;
(2) temperature T will be heated to 1solid support material remain on temperature T 2under, wherein T 2be preferably 0.95T 1-1.1T 1;
(3) temperature T will be remained on 2under solid support material be cooled to temperature T 3, wherein T 3be no more than 60 DEG C.
If in dipping, especially in a particularly preferred step dipping, be greater than T 0temperature under obtain impregnated solid support material, be first cooled to temperature T according to the present invention 0.
It is contemplated that temperature T in principle 0for 35 DEG C at the most, such as at the most 30 DEG C.Temperature T 0be preferably 5-20 DEG C, more preferably 10-15 DEG C.
In preferred embodiments, temperature T 0the solid support material that gained should be made to flood according to the present invention need not carry out predrying before being heated with the heating rate of at least 30K/min in step (1) according to the present invention.
Therefore, the present invention preferably provides following method, wherein by aforesaid method obtain be impregnated with silver, molybdenum, tin and optional other promotor solid support material before with the heating rate of at least 30K/min without undergoing being greater than 35 DEG C, be preferably greater than 30 DEG C, more preferably greater than 25 DEG C, more preferably greater than the temperature of 20 DEG C.
In the step (1) of method for calcinating of the present invention, by temperature T 0under the impregnated solid support material that provides the heating rate of at least 30K/min.
It is contemplated that 150K/min at the most, the heating rate of such as 100K/min or 80K/min at the most.Heating rate in step (1) is preferably 30-80K/min, more preferably 40-75K/min.
In the step (1) of method for calcinating of the present invention, by solid support material by temperature T 0be heated to temperature T 1.
According to the present invention, heating proceeds to the temperature T being applicable to this impregnated solid support material of calcining 1.Here it is contemplated that 350 DEG C at the most in principle, such as 340 DEG C or 330 DEG C or 320 DEG C or 310 DEG C or the temperature T of 300 DEG C at the most at the most at the most at the most at the most 1.Preferred minimum temperature T 1it is about 250 DEG C.Therefore, it is contemplated that the temperature T of 250-310 DEG C or 250-300 DEG C 1.But, have been found that calcining temperature can be set smaller than 300 DEG C according to the present invention.Therefore, the invention provides method as above, wherein temperature T 1be less than 300 DEG C, be preferably less than or equal to 299 DEG C.
According to the present invention, temperature T 1be preferably 250-295 DEG C, more preferably 260-295 DEG C, more preferably 270-295 DEG C, more preferably 270-290 DEG C, such as 270-285 DEG C, 275-290 DEG C or 275-285 DEG C.
With regard to realizing the mode of heating rate of the present invention, do not limit in principle.Preferably make to take temperature as T 0exist solid support material contact with gas in heat-processed, further preferred by this solid support material of this gas heating and this gas therefore have permission this solid support material is heated to temperature T 1temperature.
For the chemical constitution contacting the gas heating this solid support material with solid support material, do not limit in principle.Therefore it is contemplated that this gas comprises oxygen, the oxygen content wherein can mentioning this gas is as an example 100 volume % or at the most 25 volume % at the most.Such as also air can be used.More the oxygen of low levels is also possible, the mixture of such as likely nitrogen and air, such as poor air.The oxygen content of the gas that can mention is 20 volume % or 15 volume % or at the most 10 volume % or 5 volume % or at the most 1 volume % at the most at the most at the most.For the purpose of the present invention, particularly preferably use the mixture of rare gas element or two or more rare gas elementes as heating gas, wherein oxygen content is preferably less than 10ppm, more preferably 5-9ppm.As rare gas element, for example nitrogen, carbonic acid gas, argon gas and/or helium can be mentioned.For the purpose of the present invention, nitrogen is particularly preferably used as rare gas element.
Therefore, the invention provides method as above, being heated by wherein in step (1) makes this solid support material and rare gas element I 1contact and carry out.
The present invention preferably provides method as above, and being heated by wherein in step (1) makes this solid support material and comprise to be less than 10ppm, the rare gas element I of preferred 5-9ppm oxygen 1contact and carry out.
More preferably the invention provides method as above, being heated by wherein in step (1) makes this solid support material and rare gas element I 1contact and carrying out, wherein this rare gas element is nitrogen and this rare gas element comprises and is less than 10ppm, the oxygen of preferred 5-9ppm.
Statement " comprises and is less than 10ppm, the rare gas element I of the oxygen of preferred 5-9ppm 1" here refer to and comprise rare gas element I 1with the gaseous mixture of oxygen, the oxygen content being wherein less than 10ppm or 5-9ppm relates to the oxygen content of gaseous mixture and this rare gas element I 1it can be the mixture of two or more rare gas elementes.
For the purpose of the present invention, the gas contacted with this solid support material in heat-processed in step (1) is very particularly preferably technical grade nitrogen, the technical grade nitrogen preferably obtained by air distillation, it comprises 99.995-99.9999 nitrogen usually, 6-8ppm oxygen and trace rare gas.
The temperature of the gas contacted with this solid support material in heat-processed is selected make can become possibility according to heating rate of the present invention and this solid support material can be made to reach temperature T in principle 1.The temperature that the gas be in contact with it in the heat-processed of this solid support material in step (1) preferably has is T 1-1.1T 1, more preferably T 1-1.07T 1, more preferably T 1-1.05T 1.
This solid support material and the contact of this gas in step (1) can be carried out in principle in any desired manner, as long as guarantee to realize according to heating rate of the present invention this solid support material.Thus, particularly preferably make this solid support material and this gas streams, preferred rare gas element I 1stream contact, even if this gas is by this solid support material.Here substantially select the volumetric flow rate of this gas to make to realize according to heating rate of the present invention.Specifically, the volumetric flow rate of this gas is selected to realize according to heating rate of the present invention with the combination of the temperature and volumetric flow rate that make the gas by contacting with this solid support material.This volumetric flow rate is particularly preferably 2500-5000m 3/ h, especially 3200-4500m 3/ h.
In preferred embodiments, the invention provides method as above, wherein make rare gas element I 1, preferred nitrogen is by treating the solid support material of heating in step (1), wherein I 1preferably comprise and be less than 10ppm, more preferably the oxygen of 5-9ppm, I 1the temperature preferably had is T 1-1.1T 1and I 1preferably with 2500-5000m 3/ h, more preferably 3200-4500m 3the volumetric flow rate of/h flows through this solid support material.
In the heat-processed of this solid support material according to step (1), heating rate can be constant or can change, as long as guarantee by the temperature difference (T 1-T 0) be at least 30K/min, preferred 30-80K/min, more preferably 30-75K/min, more preferably 30-70K/min divided by the total heating rate calculated heating required total time.Heating rate in whole heating operation process is preferably at least 30K/min, more preferably 30-80K/min, more preferably 30-75K/min, more preferably 30-70K/min.
The heating rate scope possible according to the present invention is such as 35-80K/min or 40-75K/min or 40-70K/min or 45-70K/min or 50-70K/min or 55-70K/min or 60-70K/min or 65-70K/min.
Temperature T is heated in step (2) process of method for calcinating of the present invention 1solid support material after heating, preferably directly maintain the temperature T that applicable the present invention calcines object after heating 2under.Here preferable temperature T 2at temperature T 1scope in.Particularly preferably temperature T 2for 0.95-1.1T 1, such as 0.95-1.05T 1, 0.96-1.04T 1, 0.97-1.03T 1, 0.98-1.02T 1or 0.99-1.01T 1.Preferred selective temperature T 2to make it be less than 300 DEG C, be preferably less than or equal to 299 DEG C.
Solid support material is at temperature T 2under maintenance also comprise wherein T 2value non-constant within the hold-time, but the embodiment changed in above-mentioned limit.Therefore, the present invention especially also comprises wherein that this remains on two or more and is positioned at above-mentioned limit T 2the embodiment of carrying out under interior differing temps.
This solid support material is at temperature T 2unrestricted in the time principle of lower maintenance.For the purpose of the present invention, preferably in step (2) by this carrier at temperature T 2lower maintenance 1-15 minute, preferred 2-10 minute, the more preferably time of 3-5 minute.
For the mode wherein realized in step (2) according to maintenance of the present invention, do not limit in principle.At temperature T 2in the process of lower maintenance, preferably make this solid support material and be in allow this solid support material to be maintained temperature T 2temperature under gas contact.
Contact that this solid support material is maintained temperature T for this solid support material 2under the chemical constitution of gas do not limit in principle.Therefore, such as, it is contemplated that this gas comprises oxygen, the oxygen content of such as this gas can be 100 volume % or at the most 25 volume % at the most.It is also contemplated that use air.It is also contemplated that lower oxygen content, such as, it is contemplated that the mixture of nitrogen and air, such as poor air.The oxygen content can mentioning this gas is 20 volume % or 15 volume % or at the most 10 volume % or 5 volume % or at the most 1 volume % at the most at the most at the most.For the purpose of the present invention, as in order to remain on temperature T 2under gas, particularly preferably use the mixture of rare gas element or two or more rare gas elementes, wherein oxygen content is preferably less than 10ppm, more preferably 5-9ppm.As rare gas element, for example nitrogen, carbonic acid gas, argon gas and helium can be mentioned.For the purpose of the present invention, particularly preferably use nitrogen as rare gas element.
Therefore, the invention provides method as above, wherein make this solid support material and rare gas element I according to being maintained by of step (2) 2contact and carry out.
The present invention preferably provides method as above, and being maintained by wherein in step (2) makes this solid support material and comprise to be less than 10ppm, the rare gas element I of preferred 5-9ppm oxygen 2contact and carry out.
The present invention more preferably provides method as above, and being maintained by wherein in step (2) makes this solid support material and rare gas element I 2contact and carrying out, wherein this rare gas element is nitrogen and this rare gas element comprises and is less than 10ppm, the oxygen of preferred 5-9ppm.
Statement " comprises and is less than 10ppm, the rare gas element I of preferred 5-9ppm oxygen 2" here refer to and comprise rare gas element I 2with the gaseous mixture of oxygen, the oxygen content being wherein less than 10ppm or 5-9ppm relates to the oxygen content of gaseous mixture and rare gas element I 2it can be the mixture of two or more rare gas elementes.
For the object of the invention, this solid support material is very particularly preferably technical grade nitrogen with the gas contacted in its keep-process in step (2), the technical grade nitrogen preferably obtained by air distillation, it comprises 99.995-99.9999 volume % nitrogen, 6-8ppm oxygen and trace rare gas usually.
This solid support material of basic selection becomes possibility with the temperature of the gas contacted in its keep-process in step (2) to make it possible to maintenance temperature according to the present invention.This solid support material preferably has T with the gas contacted in its keep-process in step (2) 2-1.1T 2, more preferably T 2-1.07T 2, more preferably T 2-1.05T 2, such as T 2-1.04T 2or T 2-1.03T 2or T 2-1.02T 2or T 2-1.01T 2temperature.
This solid support material and the contact of this gas in step (2) can be carried out in principle in any desired manner, as long as guarantee to realize this solid support material according to the present invention at temperature T 2under maintenance.Thus, particularly preferably make this solid support material and gas streams, preferred rare gas element I 2stream contact, even if this gas is by this solid support material.Here the volumetric flow rate of this gas is substantially selected to remain on temperature T to make realizing support according to the present invention material 2under.Specifically, the volumetric flow rate of this gas is selected to realize this carrier according to the present invention at temperature T to make the temperature of gas by contacting with this solid support material and the combination of volumetric flow rate 2under maintenance.This volumetric flow rate is particularly preferably 1000-3000m 3/ h, more preferably 1500-2000m 3/ h.
In preferred embodiments, the invention provides method as above, wherein make rare gas element I 2, preferred nitrogen is by treating to remain on temperature T in step (2) 2under solid support material, wherein I 2preferably comprise and be less than 10ppm, more preferably the oxygen of 5-9ppm, I 2the temperature preferably had is T 2-1.05T 2and I 2preferably with 1000-3000m 3/ h, more preferably 1500-2000m 3the volumetric flow rate of/h flows through this carrier.
Preferably but it is not necessary that by rare gas element I 1as rare gas element I 2for the object of the invention, wherein I described above 2volumetric flow rate can be different from I 1volumetric flow rate/or I 2temperature can be different from I 1temperature.
In the step (3) of method for calcinating of the present invention, maintenance after, preferably direct maintenance after will remain on temperature T 2under solid support material be cooled to temperature T 3.For T 3value, be not particularly limited in principle.For the purpose of the present invention, preferable temperature T 3be no more than 60 DEG C.
For the mode realized in step (3) according to cooling of the present invention, do not limit in principle.Be cooled to temperature T 3process in preferably make this solid support material and the temperature that has allow this solid support material to be cooled to temperature T 3gas contact.
Contact that this solid support material is cooled to temperature T for this solid support material 3the chemical constitution of gas, do not limit in principle.Therefore, such as it is contemplated that the rare gas element of such as use in step (1) or (2) as gas.For the purpose of the present invention, as being cooled to temperature T 3gas, particularly preferably use oxygen content be at least 5 volume %, preferably at least 10 volume %, more preferably at least 15 volume %, the more preferably gas of at least 20 volume %.Specifically, according to the present invention, air is used for carrying out the cooling in step (3).
In the methods of the invention, solid support material is preferably with 30-80K/min, and preferred 40-60K/min, more preferably the rate of cooling of 45-55K/min cools in step (3).
Obtain in this way calcine and the solid support material cooled can be used as catalyzer or can store in a suitable manner after being close to step (3).
For the equipment for above-mentioned method for calcinating, substantially do not limit, as long as guarantee according to the heating of the present invention in step (1), the preferably also maintenance of with good grounds the present invention in step (2), preferably also the cooling of with good grounds the present invention in step (3) can be carried out as mentioned above.According to the heating of the present invention preferably wherein at least in step (1), the heating preferably in step (1) and the maintenance in step (2) and the embodiment also having the cooling in step (3) to carry out continuously.Particularly preferably the inventive method is with regard to step (1), preferably at least carries out in belt calciner with regard to step (1) and (2).
For the time applying promotor, they also can apply after the above calcination.Also together with silver compound, promotor can be put on carrier.
Therefore, the present invention includes wherein by other promotor of this at least one, that is such as 5 kinds different other promotor, 4 kinds of different other promotor, 3 kinds of different other promotor, 2 kinds of different other promotor or other promotor a kind of to put on carrier and only subsequently as mentioned above the carrier that processes in this way of calcining to obtain the embodiment of catalyzer of the present invention.
Invention further provides a kind of method by ethylene making ethylene oxide, be included in for the not tungstenic of epoxidation alkene catalyzer exist under by oxidation of ethylene, this catalyzer comprises the silver put on carrier, molybdenum and tin.
In addition, present invention also offers the purposes of catalyzer in epoxidation alkene of the not tungstenic comprising the silver put on carrier, molybdenum and tin.
According to the present invention, epoxidation can be undertaken by all methods that those skilled in the art are known.Here all reactors that may be used in the ethylene oxide production method of prior art can be used, the shell-tube type reactor of such as exterior cooling is (see Ullmann ' s Encyclopedia of Industrial Chemistry, 5th edition, A-10 rolls up, 117-135 page, 123-125, VCH-Verlagsgesellschaft, Weinheim 1987), or there is the reactor of loose catalyst bed and cooling tube, such as DE-A 3414717, EP 0082609 and the reactor described in EP-A 0339748.Epoxidation, preferably at least one tubular reactor, preferably carries out in shell-tube type reactor.Catalyzer of the present invention can be used alone or with the mixture of other catalyzer for combine or in structural catalyst bed.
Preparing ethylene oxide by ethene and oxygen can such as DE 25 21 906 A1 according to the present invention, EP 0 014 457 A2, DE 2 300 512 A1, EP 0 172 565 A2, DE 24 54 972 A1, EP 0 357 293 A1, EP 0 266 015 A1, carry out under popular response condition described in EP 0 085 237 A1, EP 0 082 609 A1 and EP 0 339 748 A2.Can additionally by rare gas element if nitrogen or the gas at reaction conditions in inertia are as water vapour and methane and optional reaction control agent, such as halogenide, hydro carbons is as ethyl chloride, and vinylchlorid or 1,2-ethylene dichloride are mixed in the reactant gases comprising ethene and molecular oxygen.The oxygen content of reactant gases does not advantageously exist in the scope of explosive gas mixture wherein.It is 10-80 volume % that the composition being applicable to the reactant gases preparing ethylene oxide such as can comprise based on reactant gases cumulative volume, preferred 20-60 volume %, more preferably 25-50 volume %, the particularly preferably ethene of 30-40 volume %.The oxygen content of reactant gases is advantageously being no more than 10 volume % based on reactant gases cumulative volume, preferably more than 9 volume %, more preferably no more than 8 volume %, is very particularly preferably no more than in the scope of 7 volume %.
Reactant gases is preferably with 0-15ppm, and the amount of preferred 0.1-8ppm comprises chloride reaction control agent as ethyl chloride, methyl chloride, vinyl chloride or ethylene dichloride.The remainder of this reactant gases generally includes hydrocarbon if methane or rare gas element are as nitrogen.In addition, this reactant gases can also comprise other materials as water vapour, carbonic acid gas or rare gas.
The mentioned component of reaction mixture can optionally comprise a small amount of impurity.Such as ethene can use with the epoxidised purity of any applicable the present invention.Suitable purity includes but not limited to polymer grade ethylene, and its purity usually had is at least 99%, and chemical grade ethene, and it has the more low-purity being usually less than 95%.Impurity mainly comprises ethane, propane and/or propylene usually.
Epoxidation carries out usually at elevated temperatures.Preferable temperature is 150-350 DEG C, more preferably 180-300 DEG C, more preferably 190-280 DEG C, particularly preferably 200-280 DEG C.Therefore, present invention also offers and be wherein oxidized at 180-300 DEG C, the aforesaid method carried out at the temperature of preferred 200-280 DEG C.
Oxidation is preferably carried out under a pressure comprised between 5 and 30 bars.Oxidation is more preferably at 5-25 bar, and preferred 10-20 bar, carries out under the pressure that especially 14-20 clings to.Therefore, present invention also offers the aforesaid method being wherein oxidized and carrying out under the pressure of 14-20 bar.
Oxidation is preferably carried out in a continuous process.If this reaction is carried out continuously, the GHSV (gas hourly space velocity) then used is as selected type of reactor, size/the cross-sectional area of such as reactor, the function of the shape and size of catalyzer is preferred 800-10000/h, preferred 2000-6000/h, more preferably 2500-5000/h, wherein numeral is based on the volume of this catalyzer.
Prepare ethylene oxide by ethene and oxygen can advantageously carry out with circulation means.Here make reaction mixture cycle through reactor, wherein the new ethylene oxide formed and the by product formed in the reaction each by taking-up after the ethene of supplementary aequum, oxygen and reaction control agent, product stream being fed in reactor again from product gas flow afterwards.Ethylene oxide is separated from product gas flow and aftertreatment can be undertaken (see Ullmann ' s Encyclopedia of Industrial Chemistry by the ordinary method of prior art, 5th edition, A-10 rolls up, 117-135 page, 123-125, VCH-Verlagsgesellschaft, Weinheim 1987).
The present invention is described as follows by embodiment.
1. the universal method of production catalyzer of the present invention
1.1 alumina supporters used
Use the bimodal Alpha-alumina with performance shown in hollow ring geometrical shape and table 1.
Table 1: used carrier
? Carrier A
Ring geometrical dimension (external diameter × length × internal diameter) [mm] 7.91×8.41×2.62
? ?
BET[m 2/g] 0.82
Water-intake rate [ml/g] 0.444
The peak-peak [μm] of Hg porosimetry 1.09，53.2
Ca[ppm] 300
Fe[ppm] 200
K[ppm] 300
Mg[ppm] 100
Na[ppm] 400
Si[ppm] 600
1.2 produce silver complex solution
Under agitation at 40 DEG C, 550g Silver Nitrate is dissolved in 1.5L water.402.62g potassium hydroxide solution (47.8%) is mixed with 1.29L water.Then 216.31g oxalic acid is added in this potassium hydroxide solution and also dissolve completely, this solution is heated to 40 DEG C.Then in about 45 minutes, by volume pump, this Potassium Oxalate Solution is added (40 DEG C) in silver nitrate solution (volumetric flow rate=about 33ml/min).Upon completion of the addition gained solution is stirred 1 hour again at 40 DEG C.The silver oxalate of precipitation to be leached and by the water washing (altogether about 10L) of gained filter cake every part of 1L, until it (is not determined by the conductivity measurement of washings containing potassium and nitrate radical; For the purpose of the present invention, electric conductivity <40 μ S/cm is not referred to containing potassium and nitrate radical).As far as possible from filter cake completely except anhydrating and measuring the residual moisture content of filter cake.Obtain the silver oxalate that 620g water-content is 20.80%.
In ice bath, 306g quadrol be cooled to about 10 DEG C and add 245g water with aliquot.In about 30 minutes, 484.7g gained (still moist) silver oxalate is added with aliquot after water reinforced completes.This mixture is at room temperature stirred and to spend the night and centrifugation goes out resistates subsequently.Measure the Ag content of residue clear solution with refractometry and measure density by 10ml graduated cylinder.
This solution comprise 29.35 % by weight with element calculate silver and density for 1.536g/ml.
1.3 produce cobalt or palladium complex solution
By ice/water mixture, 12g is water-cooled to 8 DEG C and also slowly adds 10g quadrol in batches.Then 12.7g acid chloride (45.9-48.4%Pd) or 10.0g cobaltous acetate (about 33%Co) is slowly added in the mode making temperature be no more than 20 DEG C.
1.4 produce tin oxalate solution
The tin oxalate of aequum is weighed and with 4 parts of distilled water and 1 part of H 2o 2(concentration is 30%) mixes.At room temperature stirred reaction mixture is until form clear solution.
1.5 productions comprise the universal method of the solution of silver and promotor
The silver complex solution produced according to method 1.2 is put into reaction vessel.Optionally will comprise lithium and sulphur (lithium nitrate and (NH 4) 2sO 4) the aqueous solution, comprise caesium (CsOH) the aqueous solution, comprise caesium (CsOH) and tungsten (H 2wO 4) the aqueous solution, palladium-ethylene diamine complex aqueous solution, cobalt-ethylene diamine complex aqueous solution, comprise tin (tin oxalate, SnC 2o 4) the aqueous solution, comprise molybdenum (molybdic acid, H 2moO 4) the aqueous solution and/or the aqueous solution that comprises rhenium (ammonium perrhenate) to add wherein and by this solution stirring 5 minutes.Be shown in detail in the embodiment under the 2nd for the solution of special catalyst and amount thereof.
Solution puts on carrier by 1.6
The carrier A (see table 1) of aequum is put into rotatory evaporator and found time.Vacuum is 50 millibars.This carrier is found time in advance about 10 minutes.
Under reduced pressure the solution produced according to method 1.5 was added drop-wise in 15 minutes on carrier and also subsequently the carrier of dipping is under reduced pressure rotated 15 minutes again.Then at room temperature and pressure by this carrier indwelling gentle mixing in 1 hour and every 15 minutes in the device.
The impregnated carrier of 1.7 calcining
At 283 DEG C by impregnated carrier convection oven (from HORO, 129ALV-SP type, sequence number: at 8.3m per hour 53270) 3n 2lower process 13 minutes, heating rate is 40K/min, is 360s heat-up time and hold-time at 283 DEG C is 420s.Room temperature is cooled in 420s.
1.8 produce crushing catalyst material
In porcelain dish by mortar by the coarse reduction of gained catalyst rings.Then by sieve apparatus (from Fritsch) and 2 sintering oxidation aluminum balls by the material disintegrating pulverized to desired particle size fraction
(500-900μm)。Pulverize stone ring completely by mortar and sieve subsequently.
1.9 epoxidation
Epoxidation is 6mm and length is carry out in the test reactor of the vertical reaction tubes of 2200mm comprising the internal diameter be made up of stainless steel.The reaction tubes providing chuck heats under temperature T by the deep fat flowing through chuck.Oil temperature corresponds to the temperature in reaction tubes very approx and therefore corresponds to temperature of reaction.
In order to epoxidation, this catalyzer uses with the form of crushing catalyst material (granularity fraction 500-900 μm).Upwards fill the height of reaction tubes to 212mm with inertia talcum ball (1.0-1.6mm) by bottom, the crushing catalyst material being 0.5-0.9mm to the height 38.2g granularity of 1100mm more than this height is filled and is filled to height inertia talcum ball (1.0-1.6mm) of 707mm more than this height.Feed gas enters reactor by top and after by this catalyst bed again in bottom out.
Feed gas comprises 35 volume % ethene, 7 volume % oxygen, 1 volume %CO2, EC conditioning agent.Start time by 2.0ppm EC (vinylchlorid) for start.Depend on catalyzer and performance, EC concentration rises to maximum 8ppm in every 24 hours.Remaining feed gas comprises methane.Test is at the pressure of 15 bar, the gas hourly space velocity (GHSV) of 4750L/h and 250kg EO/ (m 3cat × h) space-time yield under carry out.
Regulate temperature of reaction with the defined ethylene oxide exhaust gas concentration providing 2.7%.In order to optimize this selectivity of catalyst and transformation efficiency, 2.2-4.0ppm vinylchlorid is added in feed gas as conditioning agent.
The gas leaving reactor is analyzed by online MS.By analytical results determination selectivity.
The results are summarized in table 2.This be presented at the operation phase of >100 hour catalyzer operating time after under best EC regulates at the performance number of steady state operation.
2. produced catalyzer
2.1 catalyzer 1 (comparative example)
According to universal method 1.2-1.7,300g carrier A is changed into corresponding catalyst.
Following amounts is used for produce in solution according to universal method 1.5:
190.25g silver complex solution (28.83%Ag)
2.3698g comprises the solution of 2.85% lithium and 0.21% sulphur
3.5593g comprises the solution of 2.00% tungsten and 4.00% caesium
3.2991g comprises the solution of 4.1% rhenium
The catalyzer produced comprises 15.4 % by weight silver medals, 200 weight ppm tungsten, 400 weight ppm caesiums, 190 weight ppm lithiums, 14 weight ppm sulphur and 380ppm rhenium.Then according to universal method
1.9 test gained catalyzer.Result is shown in Table 2.
2.2 catalyzer 2 (comparative example)
According to universal method 1.2-1.7,119.9g carrier A is changed into corresponding catalyst.
Following amounts is used for produce in solution according to universal method 1.5:
75.64g silver complex solution (29.14%Ag)
0.95g comprises the solution of 2.85% lithium and 0.21% sulphur
1.4241g comprises the solution of 4.00% caesium
1.3210g comprises the solution of 4.1% rhenium
0.0681g water
The catalyzer produced comprises 15.5 % by weight silver medals, 400 weight ppm caesiums, 190 weight ppm lithiums, 14 weight ppm sulphur and 380ppm rhenium.
Then gained catalyzer is tested according to universal method 1.9.Result is shown in Table 2.
2.3 catalyzer 3 (the present invention)
According to universal method 1.2-1.7,120.2g carrier A is changed into corresponding catalyst.
Following amounts is used for produce in solution according to universal method 1.5:
73.63g silver complex solution (29.14%Ag)
0.9458g comprises the solution of 2.85% lithium and 0.21% sulphur
1.4182g comprises the solution of 4.00% caesium
0.3576g comprises the solution of 2.00% molybdenum
1.0632g comprises the solution of 2.00% tin
1.3136g comprises the solution of 4.1% rhenium
The catalyzer produced comprises 15.2 % by weight silver medals, 400 weight ppm caesiums, 190 weight ppm lithiums, 14 weight ppm sulphur, 50ppm molybdenum, 150ppm tin and 380ppm rhenium.
Then gained catalyzer is tested according to universal method 1.9.Result is shown in Table 2.
2.4 catalyzer 4 (comparative example)
According to universal method 1.2-1.7,119.9g carrier A is changed into corresponding catalyst.
Following amounts is used for produce in solution according to universal method 1.5:
71.83g silver complex solution (29.24%Ag)
0.9439g comprises the solution of 2.85% lithium and 0.21% sulphur
1.4125g comprises the solution of 4.00% caesium
0.3551g comprises the solution of 2.00% molybdenum
1.3101g comprises the solution of 4.1% rhenium
2.5033g water
The catalyzer produced comprises 14.9 % by weight silver medals, 400 weight ppm caesiums, 190 weight ppm lithiums, 14 weight ppm sulphur, 50ppm molybdenum and 380ppm rhenium.
Then gained catalyzer is tested according to universal method 1.9.Result is shown in Table 2.
2.5 catalyzer 5 (comparative example)
According to universal method 1.2-1.7,120.0g carrier A is changed into corresponding catalyst.
Following amounts is used for produce in solution according to universal method 1.5:
71.90g silver complex solution (29.24%Ag)
0.9439g comprises the solution of 2.85% lithium and 0.21% sulphur
1.4149g comprises the solution of 4.00% caesium
1.0622g comprises the solution of 2.00% tin
1.3121g comprises the solution of 4.1% rhenium
1.7943g water
The catalyzer produced comprises 14.9 % by weight silver medals, 400 weight ppm caesiums, 190 weight ppm lithiums, 14 weight ppm sulphur, 150ppm tin and 380ppm rhenium.
Then gained catalyzer is tested according to universal method 1.9.Result is shown in Table 2.
2.6 catalyzer 6 (comparative example)
According to universal method 1.2-1.7,120.1g carrier A is changed into corresponding catalyst.
Following amounts is used for produce in solution according to universal method 1.5:
74.16g silver complex solution (29.55%Ag)
0.9490g comprises the solution of 2.85% lithium and 0.21% sulphur
1.4256g comprises the solution of 4.00% caesium and 2.00% tungsten
0.3558g comprises the solution of 2.00% molybdenum
1.0683g comprises the solution of 2.00% tin
1.3191g comprises the solution of 4.1% rhenium
The catalyzer produced comprises 15.3 % by weight silver medals, 400 weight ppm caesiums, 190 weight ppm lithiums, 14 weight ppm sulphur, 200ppm tungsten, 50ppm molybdenum, 150ppm tin and 380ppm rhenium.
Then gained catalyzer is tested according to universal method 1.9.Result is shown in Table 2.
2.7 catalyzer 7 (comparative example)
According to universal method 1.2-1.7,120.1g carrier A is changed into corresponding catalyst.
Following amounts is used for produce in solution according to universal method 1.5:
75.17g silver complex solution (29.35%Ag)
0.9506g comprises the solution of 2.85% lithium and 0.21% sulphur
1.4247g comprises the solution of 4.00% caesium
0.2410g comprises the solution of 9.00% cobalt
0.0701g comprises the solution of 10.6% palladium
1.3220g comprises the solution of 4.1% rhenium
0.4253g water
The catalyzer produced comprises 15.5 % by weight silver medals, 400 weight ppm caesiums, 190 weight ppm lithiums, 14 weight ppm sulphur, 50ppm palladium, 150ppm cobalt and 380ppm rhenium.
Then gained catalyzer is tested according to universal method 1.9.Result is shown in Table 2.
2.8 catalyzer 8 (comparative example)
According to universal method 1.2-1.7,120.1g carrier A is changed into corresponding catalyst.
Following amounts is used for produce in solution according to universal method 1.5:
75.19g silver complex solution (29.35%Ag)
0.9502g comprises the solution of 2.85% lithium and 0.21% sulphur
1.4270g comprises the solution of 4.00% caesium and 2.00% tungsten
0.2428g comprises the solution of 9.00% cobalt
0.0693g comprises the solution of 10.6% palladium
1.3199g comprises the solution of 4.1% rhenium
0.4134g water
The catalyzer produced comprises 15.5 % by weight silver medals, 400 weight ppm caesiums, 200ppm tungsten, 190 weight ppm lithiums, 14 weight ppm sulphur, 50ppm palladium, 150ppm cobalt and 380ppm rhenium.
Then gained catalyzer is tested according to universal method 1.9.Result is shown in Table 2.
2.9 catalyzer 9 (comparative example)
According to universal method 1.2-1.7,120.2g carrier A is changed into corresponding catalyst.
Following amounts is used for produce in solution according to universal method 1.5:
75.23g silver complex solution (29.35%Ag)
0.9505g comprises the solution of 2.85% lithium and 0.21% sulphur
1.4260g comprises the solution of 4.00% caesium
0.2408g comprises the solution of 9.00% cobalt
0.3582g comprises the solution of 2.00% molybdenum
1.3222g comprises the solution of 4.1% rhenium
0.1344g water
The catalyzer produced comprises 15.5 % by weight silver medals, 400 weight ppm caesiums, 190 weight ppm lithiums, 14 weight ppm sulphur, 150ppm cobalt, 50ppm molybdenum and 380ppm rhenium.
Then gained catalyzer is tested according to universal method 1.9.Result is shown in Table 2.
2.10 catalyzer 10 (comparative example)
According to universal method 1.2-1.7,120.2g carrier A is changed into corresponding catalyst.
Following amounts is used for produce in solution according to universal method 1.5:
74.38g silver complex solution (29.35%Ag)
0.9496g comprises the solution of 2.85% lithium and 0.21% sulphur
1.4263g comprises the solution of 4.00% caesium
0.2388g comprises the solution of 9.00% cobalt
1.0707g comprises the solution of 2.00% tin
1.3101g comprises the solution of 4.1% rhenium
The catalyzer produced comprises 15.5 % by weight silver medals, 400 weight ppm caesiums, 190 weight ppm lithiums, 14 weight ppm sulphur, 150ppm cobalt, 150ppm tin and 380ppm rhenium.
Then gained catalyzer is tested according to universal method 1.9.Result is shown in Table 2.
Catalytic result shows that catalyzer 3 of the present invention demonstrates best combination that is active and highly selective.Under selected test parameter, require that the temperature more than 245 DEG C is not suitable for the usually required operation lifetime of about 1 year with the catalyzer realizing ethylene oxide exhaust gas concentration needed for 2.7%.
Table 2: catalytic result contrasts
Catalyzer sequence number Carrier Composition [ppm] Selectivity [%] Temperature [DEG C]
1 A 200W, standard 90.2 242.8
2 A 0W，0Mo，0Sn 86.7 237.6
3 A 0W，50Mo，150Sn 90.5 240.3
4 A 0W，50Mo，0Sn 90.2 247.8
5 A 0W，0Mo，150Sn 81.9 222.6
6 A 200W，50Mo，150Sn 90.8 248.3
7 A 0W，50Pd，150Co 83.7 236.0
8 A 200W，50Pd，150Co 86.1 242.0
9 A 0W，50Mo，150Co 88.3 242.0
10 A 0W，150Sn，150Co 84.5 243.1

Claims (13)

1., for a catalyzer for the not tungstenic of epoxidation alkene, comprise the silver be applied on carrier, molybdenum and tin.
2. catalyzer according to claim 1, wherein said carrier is alumina supporter.
3. catalyzer according to claim 2, the purity that wherein said aluminum oxide has is at least 85%.
4. catalyzer as claimed in one of claims 1-3, wherein said carrier has bimodal pore distribution, and preferably at least to comprise aperture be the hole of 0.1-10 μm and aperture is the bimodal pore distribution in the hole of 15-100 μm.
5. catalyzer as claimed in one of claims 1-4, wherein said catalyzer comprises silver with the amount of 5-35 % by weight.
6. catalyzer as claimed in one of claims 1-5, wherein said catalyzer based on described catalyzer gross weight and calculate with element and comprise molybdenum with the amount of 10-300ppm and comprise tin with the amount of 10-600ppm.
7. catalyzer as claimed in one of claims 1-6, wherein said catalyzer additionally comprises other promotor of at least one, is preferably selected from the promotor of rhenium, lithium, sulphur, caesium, chromium, manganese and the wherein mixture of two or more.
8. catalyzer as claimed in one of claims 1-7, wherein said catalyzer based on described catalyzer gross weight and with element calculate comprise rhenium with the amount of 50-600ppm.
9. produce a method for the catalyzer of the not tungstenic being used for epoxidation alkene, comprise and silver, molybdenum and tin are put on carrier.
10. method according to claim 9, comprises drying step.
11. methods according to claim 9 or 10, are included in the temperature lower calcination of 270-295 DEG C.
12. 1 kinds of methods by ethylene making ethylene oxide, be included in catalyzer as claimed in one of claims 1-8 exist under by oxidation of ethylene.
The purposes of 13. catalyzer as claimed in one of claims 1-8 in epoxidation alkene.
CN201380022972.4A 2012-05-04 2013-04-22 Catalyst for epoxidation of alkenes Pending CN104321315A (en)

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