CN103608105A - Catalyst for production of ethylene oxide - Google Patents

Catalyst for production of ethylene oxide Download PDF

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Publication number
CN103608105A
CN103608105A CN201280028677.5A CN201280028677A CN103608105A CN 103608105 A CN103608105 A CN 103608105A CN 201280028677 A CN201280028677 A CN 201280028677A CN 103608105 A CN103608105 A CN 103608105A
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Prior art keywords
catalyst
carrier
silver
ethylene oxide
preparation
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T·罗森达尔
T·莫伊雷尔
C·K·杜布纳
J·齐尔克
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BASF SE
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BASF SE
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    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • 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
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • 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
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6522—Chromium
    • 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
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6525—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
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—Tungsten
    • 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
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6567—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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • 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)
  • Epoxy Compounds (AREA)

Abstract

Provided is a catalyst for the production of ethylene oxide, at least comprising silver applied to a carrier, said carrier having a BET constant ranging from 0 to 800 as per DIN ISO 9277.

Description

Catalyst for the preparation of ethylene oxide
The present invention relates to a kind of catalyst for the preparation of ethylene oxide, it at least comprises the silver that puts on carrier, and the BET constant C that wherein carrier has is 0-800, and constant is measured according to DIN ISO9277.The invention further relates to this catalyst carrier itself.The present invention additionally relates to a kind of method of Kaolinite Preparation of Catalyst, and the catalyst that can obtain by the method and this catalyst are being the purposes in ethylene oxide by ethylene.The present invention additionally relates to a kind of method of being prepared ethylene oxide by ethene, and the method is included in described catalyst and has lower ethylene oxide.
Ethylene oxide be a kind of important Essential Chemistry product and industrial conventionally by preparing by oxygen direct oxidation ethene under silver-containing catalyst exists.Conventionally use and wherein catalytically-active metals silver is put on to its catalyst through load by appropriate method.In principle, used carrier material can be for various porous materials be as the mixture of active carbon, titanium dioxide, zirconia or silica or ceramic masses or these materials.Typically, Alpha-alumina is used as to carrier.For example the direct oxidation of ethene can be with reference to DE-A-2300512, DE-A2521906, EP-A-0014457, DE-A-2454972, EP-A-0172565, EP-A-0357293, EP-A-0266015, EP-A-0011356, EP-A-0085237, DE2560684 or DE-A-2753359.
Except the silver as active component, these catalyst comprise co-catalyst conventionally to improve catalytic performance.Example comprises that alkali metal compound and/or alkaline earth metal compound are as co-catalyst.Some teach literatures transition metal as the use of tungsten or molybdenum.A kind of particularly preferred for affect the active of catalyst and/or optionally co-catalyst be rhenium.The catalyst of the combination that comprises rhenium and/or other transition metal co-catalyst and alkali metal compound and/or alkaline earth metal compound due to its high selectivity preferably in industrial use.Selectively mean reaction and form the concentration of the ethene of ethylene oxide.Active other constant conditions as temperature, pressure, gas flow, catalytic amount etc. under ethylene oxide concentration in reactor product characterize.Ethylene oxide concentration in reactor product material stream is higher, and the activity of catalyst is higher.Realize the required temperature of restriction oxyalkylene concentration lower, activity is higher.In order to realize high selectivity, combination active metal and co-catalyst and composition carrier must match each other to obtain the catalyst with best possibility performance.
By prior art, set out, one object of the present invention is to be provided for epoxidized ethylene and to have favourable active and/or raw catelyst optionally.
Another object of the present invention is to be provided for the suitable carrier that preparation has the catalyst of the particularly advantageous Performance Characteristics in epoxidized ethylene.
According to the present invention, this object realizes by the catalyst for the preparation of ethylene oxide, and it comprises the silver that puts on carrier, and the BET constant C that wherein carrier has is determined as 0-800 according to DIN ISO9277.Be surprisingly found out that and use the carrier with the BET constant C in institute's limited range aspect gained catalyst, obtaining particularly advantageous performance.More particularly, catalyst demonstrates favourable selective in ethylene oxide preparation.
Therefore, the invention provides a kind of catalyst for the preparation of ethylene oxide, it comprises the silver that puts on carrier, and the BET constant C that wherein carrier has is determined as 0-800 according to DIN ISO9277.
The present invention further provides carrier itself, a kind of catalyst carrier of the catalyst for the preparation of ethylene oxide in other words, the BET constant C that wherein carrier has is determined as 0-800 according to DIN ISO9277.
The present invention further provides a kind of method for the preparation of preparing the catalyst of ethylene oxide, and the catalyst that can obtain or obtain by the method by the method, described method comprises the steps: that (i) provides the BET constant C having according to DIN ISO9277, to be determined as the carrier of 0-800, and (ii) silver is put on to the carrier from (i).
The present invention further provides catalyst that catalyst of the present invention maybe can obtain by the inventive method purposes in epoxidized ethylene.
With regard to catalyst preparation, all methods that wherein silver put on to carrier in suitable mode are normally suitable.Preferably at least one is comprised to silver-colored mixture here and put on carrier by for example dipping or spraying or mixed method, as hereinafter further described in more detail.
With regard to carrier, it is characterized in that BET constant C is 0-800, preferably 0-700, more preferably 0-600, more preferably 25-500, very preferably 50-450.BET constant C (and C value) is here measured according to DIN ISO9277 (in May, 2003).
The mensuration of C value is used for measuring by physical absorption gas flow (BET) method of total specific area of measuring porosu solid based on Brunnauer, Emmet and Teller, as Journal of the American Chemical Society, the 60th volume, described in 301-319 page (1938).About describing of gas dynamics model and statistical models, for the physical absorption of gas, Brunnauer, Emmet and Teller obtain the simple relation of the gas flow of gas pressure and absorption, are called BET equation at constant temperature (BET isotherm).Relation is expressed from the next:
V = V M · C · p r ( 1 - p r ) · ( 1 - p r + C · p r )
Wherein V is adsorptivity, the molal volume of the material of the gaseous state that will adsorb, liquid state or dissolving.V mfor forming the required gas volume of individual layer; p r=p/p 0, i.e. relative pressure, wherein p is equalizing pressure and p 0for the gas saturated vapor pressure measuring at temperature.C is BET constant and has following relation:
C＝A·exp[(E 1-E L)/RT]
E wherein 1energy of adsorption while forming for ground floor, E lbe second and more multi-layered energy of adsorption, A is kinetic coefficient, and R is gas constant.T represents the relevant temperature with Kelvinometer.
C value for relate to adsorbed material and carrier interaction energy explanation and the information about the polarity of carrier surface is provided.The characteristic that little C value is apolar surfaces, and large C value is the indication of high polarity or micropore surface.C value for example depends on the composition of carrier, the acidity on surface and the form of porosity and hole.Therefore, for example in preparing carrier calcination condition used or on carrier material the interpolation (interpolation of silicon) of polar compound or the interpolation of non-polar compound (for example wax) there is the impact on C value.
The carrier suitable according to the present invention can be by being prepared by the known method of prior art.For example can be with reference to US2009/0198076A1, WO2006/133187, WO03/072244, US2005/0096219A1 or EP0496386B2.
The example of suitable inert carrier material is aluminium oxide, silica, carborundum, titanium dioxide, zirconia and composition thereof, wherein preferential oxidation aluminium.Therefore, in a preferred embodiment, the invention provides catalyst as above and carrier as above, wherein said carrier is alumina support.In addition, the present invention also provides the catalyst as above that can obtain by said method, and wherein carrier is alumina support.
Term aluminium oxide used herein comprise all possible structure as α-, γ-or θ-aluminium oxide.In a preferred embodiment, carrier is alpha-alumina supports.Therefore, the present invention also provides method as above and the catalyst that can obtain by the method and carrier, and wherein carrier is Alpha-alumina.The present invention additionally also provides catalyst as above itself, and wherein carrier is alpha-alumina supports.
In another preferred embodiment, Alpha-alumina has at least 75% purity, preferably at least 80% purity, more preferably at least 85% purity, more preferably at least 90% purity, more preferably at least 98% purity, more preferably at least 98.5% purity, very preferably at least 99% purity.
Therefore term Alpha-alumina also comprises that the Alpha-alumina that comprises each component, example are two or more mixture in the element of selected among zirconium, alkali metal, alkaline-earth metal, silicon, zinc, gallium, hafnium, boron, fluorine, copper, nickel, manganese, iron, cerium, titanium, chromium and these elements.
Typically, suitable catalyst carrier of the present invention can be prepared with burnout (burn-out) material or pore former and at least one adhesive by mixed aluminium oxides and water or another suitable liquid.The example of suitable pore former comprises cellulose and cellulose derivative, for example methylcellulose, ethyl cellulose, carboxymethyl cellulose, polyolefin is as polyethylene and polypropylene, or natural burnout materials is as walnut shell in small, broken bits.Select pore former that they are burnouted completely under the furnace temperature of selected aluminium oxide calcining, and form final alpha-alumina supports.Proper adhesive and extrusion aid are for example described in EP0496386B2.Example comprises the alumina gel that for example contains nitric acid or acetic acid, and cellulose is as methylcellulose, ethyl cellulose or carboxyethyl cellulose, or methyl stearate or ethyl stearte, polyolefin epoxide, wax etc.
Can make the paste by being mixed to form be required form by extruding.Extrusion aid can be for the auxiliary program of extruding.
After moulding, conventionally by optionally dry and calcining and obtain the alumina support according to (i) of the formed body obtaining as mentioned above.Calcining is carried out conventionally at the temperature of 1200-1600 ℃.Conventionally after calcining, wash alumina support to remove soluble component.
Here Alpha-alumina can comprise component by any suitable form, for example, with element form and/or with one or more compound forms.If here Alpha-alumina comprises one or more components with compound form, it comprises described component with oxide or mixed oxide forms.Therefore, the present invention has also described and has comprised the Alpha-alumina that at least one is selected from other components of silica, sodium oxide molybdena, potassium oxide, calcium oxide, magnesia, nickel oxide, gallium oxide, hafnium oxide, cupric oxide, iron oxide and mixed oxide thereof.
With regard to the amount of other components, the gross weight of the total amount of other components based on carrier is preferably less than 25 % by weight, 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 very preferably less than 1 % by weight.
If carrier comprises for example silicon, its gross weight based on carrier and calculate and preferably comprise 50-10000ppm, more preferably 50-5000ppm, the more preferably silicon of 50-800ppm with element.
If carrier comprises for example alkali metal, to calculate the total amount that preferably comprises these be 10-2500ppm for its gross weight based on carrier and the element of take, more preferably 10-1000ppm, more preferably 50-850ppm.In one embodiment, carrier comprises the alkali metal that at least one is selected from sodium and potassium.If carrier comprises for example sodium, its gross weight based on carrier and calculate to comprise with element and be preferably 10-1500ppm, more preferably 10-800ppm, the more preferably sodium of 10-500ppm.If carrier comprises for example potassium, its gross weight based on carrier and calculate and comprise preferred 10-1000ppm, more preferably 10-500ppm, the more preferably potassium of 10-300ppm with element.In an embodiment of the present invention, carrier comprises for example 10-1500ppm sodium and 10-1000ppm potassium.
Therefore, the present invention has also described the method for Kaolinite Preparation of Catalyst as above and the catalyst that can obtain by the method, the gross weight of carrier based on carrier and calculate and comprise 10-1500ppm sodium, 10-1000ppm potassium and 0-1000ppm caesium with element wherein, carrier more preferably comprises 10-500ppm sodium, 10-300ppm potassium and 0-100ppm caesium.Additional description of the present invention catalyst and the carrier itself that can obtain by the method.In addition, the present invention also provides catalyst as above and carrier as above itself, carrier comprises 10-1500ppm sodium, 10-1000ppm potassium and 0-100ppm caesium, more preferably 10-500ppm sodium, 10-300ppm potassium and 0-100ppm caesium, calculate based on total weight of carrier and with element in each case.
If carrier comprises for example alkaline-earth metal, the gross weight of the total amount of its alkaline-earth metal comprising based on carrier and calculate and be preferably not more than 2500ppm with element, for example, be 10-2500ppm, more preferably 10-1200ppm, more preferably 10-700ppm.In one embodiment, carrier comprises the alkaline-earth metal that at least one is selected from calcium and magnesium.If carrier comprises for example calcium, its gross weight based on carrier and calculate and comprise preferred 10-1500ppm, more preferably 10-1000ppm, the more preferably calcium of 10-500ppm with element.If carrier comprises for example magnesium, its gross weight based on carrier and calculate and comprise 10-800ppm, more preferably 10-500ppm, the more preferably magnesium of 10-250ppm with element.
Therefore, the present invention has also described the method for Kaolinite Preparation of Catalyst as above and the catalyst that can obtain by the method, and wherein carrier comprises 10-800ppm magnesium and 10-1500ppm calcium, in each case the gross weight based on carrier and calculating with element.In addition, the present invention also provides catalyst as above and carrier as above itself, and wherein carrier comprises 10-800ppm magnesium and 10-1500ppm calcium, in each case the gross weight based on carrier and calculating with element.Particularly preferably carrier comprises for example 10-1500ppm sodium, 10-1000ppm potassium, 10-800ppm magnesium and 10-1500ppm calcium, in each case the gross weight based on carrier and calculating with element.
If carrier comprises for example silicon, its gross weight based on carrier and calculate and comprise preferred 50-10000ppm, more preferably 50-5000ppm, the more preferably silicon of 50-600ppm with element.
According to the present invention, preferred carrier is for example an Alpha-alumina, and its purity is at least 90%, comprises the alkaline-earth metal that 50-10000ppm silicon, 10-1500ppm sodium and total amount are 10-2500ppm, calculates in each case and the gross weight based on carrier with element.Carrier preferably comprises calcium and/or magnesium as alkaline-earth metal.Alpha-alumina particularly preferably, its purity is at least 98 % by weight, comprises the alkaline-earth metal that 50-5000ppm silicon, 10-800ppm sodium and total amount are 10-700ppm, calculates in each case and the gross weight based on carrier with element.
The BET surface area that carrier used according to the invention preferably has is surveyed as 0.1-5m according to DIN ISO9277 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, very preferably 0.6-1.0m 2/ g, measures according to DIN ISO9277.
In addition, carrier of the present invention preferably has the hole that diameter is 0.1-100 μ m, wherein distribution of pores can be that unimodal or multimodal-is for example bimodal, three peaks or four peaks.Carrier preferably has bimodal distribution of pores.It is 0.1-10 μ m and 15-100 μ m that further preferred vector has peak maximum, preferably 0.1-5 μ m and 17-80 μ m, more preferably 0.1-3 μ m and 20-50 μ m, the more preferably bimodal distribution of pores of 0.1-1.5 μ m and 20-40 μ m.Pore diameter is measured by Hg porosimetry (DIN66133).Above term used " peak maximum is the bimodal distribution of pores of 0.1-10 μ m and 5-100 μ m " mean one of two peak maximums for 0.1-10 μ m and another peak maximum be 15-100 μ m.
Therefore, the present invention also describes the method for Kaolinite Preparation of Catalyst as above and the catalyst that can prepare by the method, wherein carrier has bimodal distribution of pores, preferably at least comprises that by Hg porosimetry, according to DIN66133, to measure pore diameter be that hole and the pore diameter of 0.1-10 μ m is the bimodal distribution of pores of the hole of 15-100 μ m.In addition, the present invention also provides catalyst as above and carrier as above itself, wherein said carrier has bimodal distribution of pores, preferably at least comprises that by Hg porosimetry, according to DIN66133, to measure pore diameter be that hole and the pore diameter of 0.1-10 μ m is the bimodal distribution of pores of the hole of 15-100 μ m.
The geometry of carrier is conventionally less important; Yet, carrier should usefully be allow reacting gas not to be obstructed to diffuse to carrier be coated with catalytically active silver particle and the optionally large as far as possible outer surface of part or the particle form of inner surface area of other co-catalysts.The geometry of the carrier that must select in addition, is guaranteed along the pressure loss of whole reactor length minimum.In a preferred embodiment, carrier is used with formed body form, for example, as extrudate, hollow extrudate, star extrudate, bead, ring or hollow ring.Carrier is preferably the formed body of the geometry with ducted body.Particularly preferably there is the following geometry cylinder of (external diameter * length * internal diameter, represents with mm in each case): 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.Shown in the tolerance of comprise approximately ± 0.5mm of each length numerical value.
According to the present invention, catalyst can also be used with the crushing catalyst material form being obtained by formed body described in one or more.
The water absorption rate of carrier is for example 0.35-0.65ml/g by vacuum cold water absorption measurement, preferably 0.42-0.52ml/g.
Catalyst of the present invention comprises silver as active metal.Here, catalyst for example can comprise the gross weight based on catalyst and be calculated as 5-35 % by weight with element, more especially 10-30 % by weight, the preferably silver of 10-25 % by weight.
Therefore, the catalyst that the present invention has also described method as above and can obtain by the method, and catalyst as above itself, its gross weight that comprises based on catalyst is the silver of 5-35 % by weight.
In a preferred embodiment, except silver, catalyst for example further comprises at least one Zhu Cuiization Ji –, and 6,5,4,3 or 2 kind of co-catalyst or a kind of co-catalyst.For the purpose of the present invention, the component that co-catalyst is catalyst, compares with the catalyst that does not contain this component, by it, has realized one or more catalyst performances as the improvement of selective, activity, conversion ratio and/or productive rate or space-time yield.Preferred compound be those of the chemical basicly stable and undesirable reaction of not catalysis under reaction condition.
With regard at least one co-catalyst, the known co-catalyst of all prior aries is possible.Described at least one co-catalyst is preferably selected from lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, manganese, rhenium, cadmium, tungsten, molybdenum, chromium, sulphur and the mixture of two or more wherein.Particularly preferably catalyst comprises at least one and is selected from rhenium, caesium, lithium, tungsten, chromium, manganese, sulphur and the co-catalyst of the mixture of two or more wherein.Catalyst more preferably comprises as at least rhenium of co-catalyst and at least one and is selected from caesium, lithium, tungsten, chromium, manganese, sulphur and other co-catalysts of the mixture of two or more wherein.
Therefore, the catalyst that the present invention has also described method as above and can obtain by the method, and catalyst as above itself, comprise at least rhenium as co-catalyst, preferably comprise gross weight based on catalyst and be the silver of 5-35 % by weight and at least rhenium as co-catalyst.
If catalyst comprises rhenium as mentioned above, its gross weight based on catalyst and calculate and preferably comprise 50-600ppm, more preferably 100-450ppm, the more preferably rhenium of 150-400ppm with element.
In an especially preferred embodiment, catalyst further comprises at least one and is selected from lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, manganese, rhenium, cadmium, tungsten, chromium, molybdenum, sulphur and other co-catalysts of the mixture of two or more wherein.More preferably, catalyst further comprises at least one and is selected from caesium, lithium, tungsten, chromium, manganese, sulphur and two or more mixture and the co-catalyst of the mixture of two or more wherein wherein.In an especially preferred embodiment, catalyst at least further comprises caesium, lithium, tungsten and sulphur; More particularly, catalyst comprise rhenium and in addition caesium, lithium, tungsten and sulphur as co-catalyst.
If catalyst comprises at least one other co-catalyst, the gross weight of its total amount that preferably comprises these co-catalysts based on catalyst and be calculated as 10-2000ppm with element summation, preferred 10-1500ppm in each case, more preferably 50-1300ppm in each case, is particularly preferably 80-1300ppm in each case.
If catalyst comprises for example tungsten, it comprises preferred 10-500ppm, preferably the tungsten of 50-300ppm.
If catalyst comprises for example caesium, its gross weight based on catalyst and calculate and preferably comprise 20-850ppm, the more especially caesium of 100-600ppm with element.
If catalyst comprises for example lithium, its gross weight based on catalyst and calculate and preferably comprise 10-450ppm, the more especially lithium of 50-300ppm with element.
If catalyst comprises for example sulphur, its gross weight based on catalyst and calculate and preferably comprise 5-300ppm, the more especially sulphur of 5-150ppm with element.
In an especially preferred embodiment, catalyst comprises 150-450ppm rhenium, 50-300ppm tungsten, 100-600ppm caesium, 50-300ppm lithium and 5-150ppm sulphur.
With regard to regard to the applying of silver, it can put on carrier for the preparation of dipping and the deposition process of the silver catalyst for the preparation of ethylene oxide by all prior aries, and wherein these methods can comprise one or more dippings and calcining step.For example can be with reference to the preparation method of disclosed silver catalyst in DE-A2300512, DE-A2521906, EP-A0014457, EP-A0085237, EP-A00384312, DE-A2454972, DE-A3321895, EP-A0229465, DE-A3150205, EP-A0172565 and EP-A0357293.
If catalyst comprises at least one co-catalyst except silver, its mixture that preferably at least one is comprised to silver and at least one co-catalyst puts on carrier, for example, by dipping or spraying or mixed method.In this case, at least one co-catalyst and silver applies order conventionally arbitrarily; In other words, comprise the embodiment that wherein silver and at least one co-catalyst is put on simultaneously to carrier.Also comprise the embodiment that wherein silver and at least one co-catalyst is put in different step to carrier, wherein step order is conventionally any.Additionally comprise wherein described at least one co-catalyst of a part is only put on to the embodiment that carrier and remainder and silver apply simultaneously after applying silver.Preferably silver and at least one co-catalyst are put on to carrier simultaneously.
Silver preferably puts on carrier of the present invention with silver compound form, and wherein silver compound can be salt or silver complex.Silver compound, preferably with solution, more especially applies with the solution in water.In order to obtain the silver compound that is soluble form, also can be suitably by silver compound as silver oxide (I) or silver oxalate (I) with complexing agent as monoethanolamine, EDTA, 1,3-or 1,2-propane diamine, ethylenediamine and/or alkaline metal oxalate (can simultaneously also as reducing agent) mix.Particularly preferably silver is with silver-colored amines, and more preferably the form of silver-colored ethylene diamine compound applies.
Therefore, the present invention also provides method as above, wherein, in step (ii), will comprise and be silver-colored amines form, and the silver-colored mixture that is preferably silver-colored ethylene diamine compound form puts on above-mentioned carrier.The present invention provides a kind of catalyst that can obtain by the method equally.
Applying of silver can be at least one post-processing step afterwards, and example is drying steps, for example one, two or more drying steps.In this case, be dried and conventionally at the temperature of 10-200 ℃, carry out.Post-processing step preferably includes reduced pressure treatment.Therefore, in a preferred embodiment, carrier is found time after applying.Find time to be preferably not more than under the pressure of 500 millibars, be more preferably not more than under the pressure of 250 millibars, very preferably, being not more than under the pressure of 30 millibars and preferably the temperature of 2-50 ℃, more preferably, at the temperature of 5-30 ℃, very preferably at room temperature carry out.Here reduced pressure treatment is carried out for example at least 1 minute, and preferably at least 5 minutes, more preferably 5 minutes to 120 minutes, more especially 10 minutes to 45 minutes, particularly preferably 10 minutes to 20 minutes.Silver-colored applies and optionally after at least one drying steps, is preferably at least one calcining step.
Therefore, the present invention also describes as mentioned above for the preparation of the method for catalyst and the catalyst that can obtain by the method, and wherein said method further comprises step (iii):
(iii) calcining is optionally through the carrier being obtained by (ii) of post processing.
This calcining, at for example 150-750 ℃, is generally 200-500 ℃, and preferably 220-500 ℃, more preferably carries out at the temperature of 250-350 ℃, and wherein calcination time is generally at least 5 minutes or is longer, for example, be 5 minutes to 24 hours or be 10 minutes to 12 hours.Calcination time is particularly preferably 5 minutes to 3 hours.Here, calcining can be carried out under steady temperature; In addition the embodiment that comprises wherein, the continuous or discontinuous variation of in calcination time temperature.Calcining can be carried out under any gas atmosphere that is applicable to this object, preferably air, nitrogen and/or poor air.In addition, calcining is preferably carried out in Muffle furnace, revolving burner, convection furnace and/or belt calcining furnace.
If catalyst comprises at least one co-catalyst, in the inventive method of Kaolinite Preparation of Catalyst, described at least one co-catalyst is preferably with compound form, for example, with complex form or with salt form, for example, with halide mode, for example, with fluoride, bromide or chloride form, or using carboxylate, nitrate, sulfate or sulfide, phosphate, cyanide, hydroxide, carbonate form or as the salt of heteropoly acid, with salt form, as for example salt form with the heteropolyacid salt of rhenium and/or tungsten, put on carrier.
If catalyst comprises for example rhenium, rhenium is preferably as compound, for example, using halide, oxyhalide, oxide form or apply as acid.In addition, in preparation method of the present invention, rhenium for example can be applied with rhenate or perrhenate.If rhenium is used as co-catalyst, its preferably compound form use to be selected from ammonium perrhenate, chlorination rhenium (III), chlorination rhenium (V), to fluoridize rhenium (V), rheium oxide (VI) and rheium oxide (VII).For the purpose of the present invention, rhenium particularly preferably puts on carrier with ammonium perrhenate form.
If catalyst comprises tungsten as co-catalyst as mentioned above, tungsten preferably puts on carrier as tungsten compound.Can use in principle any suitable tungsten compound here.For example tungsten applies with tungstates or wolframic acid form.
If catalyst is containing lithium as co-catalyst as mentioned above, lithium preferably puts on carrier as lithium compound.Can use in principle any suitable lithium compound here.Lithium preferably applies with lithium nitrate form.
If catalyst comprises caesium as co-catalyst as mentioned above, caesium preferably puts on carrier as cesium compound.Can use in principle any suitable cesium compound here.Caesium preferably applies with cesium hydroxide form.
If catalyst comprises sulphur as co-catalyst as mentioned above, sulphur preferably puts on carrier as sulphur compound.Can use in principle any suitable sulphur compound here.Sulphur preferably applies with ammonium sulfate form.
Before applying by least one other co-catalyst, the more preferably molten appropriate solution that is preferable over of at least one cocatalyst compound, preferred water.Then the solution impregnation that preferably makes carrier comprise one or more co-catalysts with gained.If add two or more co-catalysts, these can together or separate in independent impregnation steps or put on carrier in two or more impregnation steps.With regard to the solution that comprises one or more co-catalysts, this can prepare in any suitable manner.For example, co-catalyst can separately be dissolved in a kind of solution separately, and the solution that gained can be comprised in each case subsequently to a kind of co-catalyst is for dipping.Two or more co-catalysts can be dissolved in together equally in a kind of solution and subsequently by gained solution for dipping.The solution that in addition, gained can be comprised at least one co-catalyst merged before dipping and solution that gained is comprised to all co-catalysts puts on carrier.
If by for example at least caesium, tungsten, lithium, sulphur and rhenium are used as co-catalyst, another solution that according to a particularly preferred embodiment, prepare at least one solution that comprises caesium and tungsten, comprises lithium and sulphur and the another solution that comprises rhenium.In impregnation steps separately, solution is put on to carrier and maybe this solution was merged before applying and form a kind of solution and only subsequently for flooding.Solution preferably together, more preferably with comprise as silver-colored amines, preferably the silver-colored mixture as silver-colored ethylene diamine compound puts on carrier together.
Apply in principle and can in any suitable method, for example, by impregnated carrier, be undertaken.Apply particularly preferably and undertaken by room temperature vacuum impregnation.In vacuum-impregnated situation, make carrier preferably start be not more than under the pressure of 500 millibars, more preferably be not more than under the pressure of 250 millibars, very preferably be not more than under the pressure of 30 millibars and preferably the temperature of 2-50 ℃, more preferably at the temperature of 5-30 ℃, more preferably at room temperature process.Application of vacuum is here for example carried out at least 1 minute, and preferably at least 5 minutes, more preferably 5 minutes to 120 minutes, more especially 10 minutes to 45 minutes, very preferably 15 minutes to 30 minutes.After application of vacuum, by least one solution, for example, comprise silver-colored mixture, or at least one solution that comprises at least one co-catalyst, the mixture that preferably comprises silver and at least one co-catalyst puts on carrier.Solution preferably drips or applies by spraying, preferably by spraying, applies.In these cases, apply preferably and undertaken by nozzle.After applying, preferably make carrier further find time.Find time to be preferably not more than under the pressure of 500 millibars, be more preferably not more than under the pressure of 250 millibars, very preferably, being not more than under the pressure of 30 millibars and preferably the temperature of 2-50 ℃, more preferably, at the temperature of 5-30 ℃, very preferably at room temperature carry out.Application of vacuum is here for example carried out at least 1 minute, and preferably at least 5 minutes, more preferably 5 minutes to 120 minutes, more especially 10 minutes to 45 minutes, very preferably 10 minutes to 20 minutes.
With regard to the time point applying with regard to co-catalyst, this can carry out after the calcining of above-mentioned steps (iii).As an alternative, at least one co-catalyst can be put on to carrier together with silver compound.
Therefore, the present invention includes wherein at least one co-catalyst, for example 5 kinds of different co-catalysts, 4 kinds of different co-catalysts, 3 kinds of different co-catalysts, 2 kinds of different co-catalysts or a kind of co-catalyst put on carrier and the carrier then so processed is only calcined as mentioned above and obtain the embodiment of catalyst of the present invention.
Therefore, the present invention also describes the method for Kaolinite Preparation of Catalyst and the catalyst that can obtain by the method, and described method comprises the steps:
(i) provide the BET constant C having according to DIN ISO9277, to be determined as the carrier of 0-800,
(ii) by applying the solution that comprises silver and at least one co-catalyst, silver and at least one co-catalyst are put on to carrier, and
(iii) calcine the optionally carrier from (ii) of drying.
Co-catalyst preferably applies together with silver in step (ii).
Catalyst of the present invention and the catalyst that can obtain by the present invention are especially suitable as prepares the catalyst of ethylene oxide for what comprise ethylene oxide by ethene.Realized under high selection and excellent activity.
According on the other hand, therefore, the present invention also provide under the catalyst for the preparation of putting on the silver of carrier and BET constant C that carrier has comprising of ethylene oxide and be determined as according to DIN ISO9277 0-800 maybe can exist by the catalyst obtaining for the preparation of the method for preparing the catalyst of ethylene oxide as mentioned above, comprise ethylene oxide by ethene, prepare the method for ethylene oxide.
In another embodiment, therefore, the present invention also provide as above comprise ethylene oxide by ethene, prepare the method for ethylene oxide, wherein catalyst further comprises rhenium.
In addition, the present invention is also provided for preparing and puts on the silver of carrier at least comprising of ethylene oxide and BET constant C that carrier has is determined as the purposes of the catalyst of 0-800 according to DIN ISO9277.
According to the present invention, epoxidation can be undertaken by the known any method of those of skill in the art.Can use all reactors that can use in the ethene preparation method of prior art, the shell-and-tube reactor that wherein example is external refrigeration is (referring to Ullmann's Encyclopedia of Industrial Chemistry, the 5th edition, A-10 volume, 117-135 page, 123-125, VCH-Verlagsgesellschaft, Weinheim1987) or have that loose catalyst is filled and the reactor of cooling tube, wherein example is the reactor being described in DE-A3414717, EP0082609 and EP-A0339748.Epoxidation, preferably at least one tubular reactor, preferably carries out in shell-and-tube reactor.Catalyst of the present invention can be used separately or with the mixture with other catalyst in combination and/or structural catalyst bed.
In order to prepare ethylene oxide by ethene and oxygen, according to the present invention, can under popular response condition, operate, it is for example as described in DE2521906A1, EP0014457A2, DE2300512A1, EP0172565A2, DE2454972A1, EP0357293A1, EP0266015A1, EP0085237A1, EP0082609A1 and EP0339748A2.In this case can be additionally by inert gas as nitrogen or the gas that is inertia under reaction condition as steam, methane and optionally reaction control agent (example is halide, hydrocarbon is as ethyl chloride, vinyl chloride or 1,2-dichloroethanes) sneak in the reacting gas that comprises ethene and molecular oxygen.In the oxygen content of reacting gas advantageously in not there is not the scope of explosive gas mixture.The cumulative volume that can for example comprise based on reacting gas for the preparation of the suitable composition of the reacting gas of ethylene oxide is 10-80 volume %, preferably 20-60 volume %, more preferably 25-50 volume %, the very preferably ethene of 30-40 volume %.In this case, the oxygen content of the reacting gas advantageously cumulative volume based on reacting gas is not more than 10 volume %, is preferably not more than 9 volume %, more preferably no more than 8 volume %, is very preferably not more than 7 volume %.
Reacting gas preferably comprises 0-15 ppm by weight, and preferably the chloride reaction control agent of 0.1-8ppm is as ethyl chloride, vinyl chloride or dichloroethanes.The remainder of reacting gas comprises hydrocarbon conventionally if methane or inert gas are as nitrogen.In addition, in reacting gas, also can exist other materials as steam, carbon dioxide or rare gas.
The said components of reactant mixture optionally contains a small amount of impurity separately.Ethene can for example be used with any purity that is suitable for gaseous oxidation of the present invention.Suitable purity includes but not limited to conventionally to have the polymer grade ethylene of at least 99% purity and conventionally has the chemical grade ethene of the low-purity that is less than 95%.Impurity mainly comprises ethane, propane and/or propylene conventionally.
Epoxidation carries out conventionally at elevated temperatures.Preferably temperature is 150-350 ℃, more preferably 180-300 ℃, more preferably 190-280 ℃, very preferably 200-280 ℃.Therefore, the present invention also provides method as above, is wherein oxidized at 180-300 ℃, preferably at the temperature of 200-280 ℃, carries out.The present invention provides the catalyst that can be obtained by the method equally.
Preferably under the pressure of 5-30 bar, operate.Further preferential oxidation, under the pressure of 5-25 bar, preferably, under the pressure of 10-20 bar, more especially carries out under the pressure of 14-20 bar.Therefore, the present invention also provides method as above, is wherein oxidized under the pressure of 14-20 bar and carries out.The present invention provides the catalyst that can be obtained by the method equally.
Oxidation is preferably carried out with continuation method.If reaction is carried out continuously, GHSV (gas hourly space velocity) depends on that selected reactor character is preferably 800-10000/h as the shape of the size/average area of reactor, catalyst and size, preferred 2000-6000/h, more preferably 2500-5000/h, wherein each numerical value is based on catalyst volume.
By ethene and oxygen, preparing ethylene oxide can advantageously carry out with cyclic program.In this case, by the ethylene oxide of reactant mixture and new formation and at the accessory substance forming taking out after each logical journey, cycle through reactor with supplementing ethene, the oxygen of aequum and lead to back product gas material in reactor reaction control agent after together with flowing in product gas material stream in reaction.The taking-up of ethylene oxide from product gas material stream with and processing can be undertaken by the conventional method of prior art (referring to Ullmann's Encyclopedia of Industrial Chemistry, the 5th edition, A-10 volume, 117-135 page, 123-125, VCH-Verlagsgesellschaft, Weinheim1987).
Therefore, in addition, the present invention be also provided for preparing put on that the silver of carrier and BET constant C that carrier has are determined as 0 to 800 catalyst according to DIN ISO9277 at least comprising of ethylene oxide or the catalyst that can obtain by the method for the preparation of preparing the catalyst of ethylene oxide as mentioned above as mentioned above as the purposes of the catalyst for the preparation of ethylene oxide.
Embodiment
1. catalyst
Based on 5 kinds of different carrier Kaolinite Preparation of Catalysts, the C value that wherein carrier is measured according to DIN ISO9277 is different:
The composition of carrier is presented in table 1.
Table 1: used carrier
Figure BDA0000434545010000151
The carrier that is marked with * is comparative example
1.1 prepare silver complex solution
Under agitation 550g silver nitrate is added in the initial charge of completely softening (FD) water of 1.5L and it is dissolved in wherein completely.Here solution is heated to 40 ℃.402.62g potassium hydroxide aqueous solution (47.8%) is mixed with 1.29L FD water.Add subsequently 216.31g oxalic acid and it is dissolved completely, this solution is heated to 40 ℃.Subsequently Potassium Oxalate Solution was added in approximately 45 minutes to liquor argenti nitratis ophthalmicus (40 ℃) (volume flow rate=about 33ml/min) by measuring pump.After having fed in raw material, gained solution is under agitation placed 1 hour at 40 ℃ again.The silver oxalate of precipitation is washed until it (is not measured wash solution by conductivity measurement containing potassium and nitrate anion with the water (about 10L) of 1L part by isolated by filtration and by gained filter cake; Containing potassium and nitrate anion, do not mean respectively conductance <40 μ S/cm in this case).As much as possible water is removed from filter cake and the residual moisture content of definite filter cake.Obtain the silver oxalate that 620g has 20.80% water content.
Using ice bath that 306g ethylenediamine is cooled to approximately 10 ℃ also divides a fraction to add 245g water.Water add end after, 484.7g gained (still moistening) silver oxalate minute fraction in approximately 30 minutes is added.This mixture is at room temperature stirred and spends the night and subsequently residue centrifugation gone out.The Ag content of the clear solution that this obtains is measured by refraction process and density is used 10ml graduated cylinder to measure.
Gained solution comprises with element and is calculated as the silver of 29.14 % by weight and has the density of 1.532g/ml.
The preparation of 1.2 solution that comprise silver and co-catalyst
Introduce 97.1004g silver complex solution.To the aqueous solution that adds the aqueous solution (2.85 % by weight are the sulphur from ammonium sulfate from the lithium of lithium nitrate and 0.21 % by weight), 1.791g tungsten and the caesium of 1.1047g lithium and sulphur in this initial charge, (2 % by weight are the caesium from cesium hydroxide from the tungsten of wolframic acid and 3.5 % by weight, 50%, at H 2in O) and the 1.6492g rhenium aqueous solution (3.1% ammonium perrhenate), and solution is stirred 5 minutes.
1.3 are applied to carrier by solution
140.61g carrier 1 (referring to table 1) is introduced on rotary evaporator and found time.Decompression is 20 millibars.Carrier is found time approximately 10 minutes in advance.
The solution obtaining according to explanation 1.2 was dripped and is applied to carrier through 15 minute, after this make under reduced pressure to rotate again 15 minutes through the carrier of dipping.Then under room temperature and atmospheric pressure, carrier is placed in to device 1 hour, wherein soft mixing the every 15 minutes.
1.4 calcinings are through the carrier of dipping
By through dipping carrier at 283 ℃ at 8.3m 3air/hour under at convection furnace, (HORO, model 129ALV-SP manufacture numbering: 53270), process 12 minutes.
The catalyst material that 1.5 preparations crush
By mortar pregrounding in porcelain dish for gained catalyst rings.Use subsequently screening machine, circular sieve and ball that the material of grinding is reached to desired particle size fraction (500 – 900 μ m).Stone ring grinds completely with mortar, then sieves.
2. epoxidation
Epoxidation carries out in laboratory reaction device, and this reactor comprises that internal diameter is that 6mm and length are the vertical stainless steel reaction pipe of 2200mm.The reaction tube that provides chuck is used the deep fat heating of the temperature T of the chuck of flowing through.In order to reach extraordinary, approach, the temperature of oil is corresponding to the temperature in reaction tube and reaction temperature therefore.
For epoxidation, use and be the catalyst that crushes catalyst material form.Reaction tube is upwards filled to the height of 212mm with inertia talcum ball (1.0-1.6mm) by bottom, the crushing catalyst that is 0.5-0.9mm by 38.2g granularity on this is filled to the height of 1100mm, is filled to the height of 707mm on this with inertia talcum ball (1.0-1.6mm).Feed gas enters reactor by top and it leaves at low side after by catalyst bed again.
Feed gas comprises 35 volume % ethene, 7 volume % oxygen, 1 volume %CO 2(EC (ethlyene dichloride) adjusting).When starting, 2.5ppm EC is used for starting.Depend on catalyst and performance, EC concentration was increased to the maximum of 4ppm every 24 hours.The remainder of feed gas consists of methane.Test is at the pressure of 15 bar and the gas hourly space velocity of 4750/h (GHSV) and 250kgEO/ (m 3(cat) under space-time yield * h), carry out.
Reaction temperature is regulated according to 2.7% given ethylene oxide exhaust gas concentration.For optimization of catalysts with regard to selective and conversion ratio, 2.2-4.0ppm ethlyene dichloride conditioning agent is metered into feed gas.
Leaving the gas of reactor analyzes by online MS.Selectively by analysis result, measured.
Result is summarised in following table 2.
Table 2: the test carrier sample with different C values
The carrier that is marked with * is comparative example

Claims (15)

1. for the preparation of a catalyst for ethylene oxide, at least comprise the silver that puts on carrier, the BET constant C that wherein carrier has is determined as 0-800 according to DIN ISO9277.
2. according to the catalyst of claim 1, wherein carrier is alumina support, preferably alpha-alumina supports.
3. according to the catalyst of claim 2, wherein aluminium oxide has at least 85% purity.
4. according to the catalyst of any one in claim 1-3, wherein carrier has bimodal distribution of pores, preferably at least comprises that by Hg porosimetry, according to DIN66133, to measure pore diameter be that hole and the pore diameter of 0.1-10 μ m is the bimodal distribution of pores of the hole of 12-100 μ m.
5. according to the catalyst of any one in claim 1-4, wherein catalyst comprises 5-35 % by weight silver.
6. according to the catalyst of any one in claim 1-5, wherein catalyst comprises rhenium, is preferably based on the gross weight of catalyst and is calculated as 50-600ppm with element.
7. according to the catalyst of any one in claim 1-6, wherein catalyst further comprises at least one other co-catalyst, is preferably selected from tungsten, lithium, sulphur, caesium, chromium, manganese, molybdenum, potassium and the co-catalyst of the mixture of two or more wherein.
8. for the preparation of a catalyst carrier for the catalyst of ethylene oxide, the BET constant C that wherein carrier has is determined as 0-800 according to DIN ISO9277.
9. carrier according to Claim 8, wherein carrier is alumina support, preferably alpha-alumina supports.
10. according to the carrier of claim 9, wherein aluminium oxide has at least 85% purity.
The carrier of any one in 11. according to Claim 8-10, wherein carrier has bimodal distribution of pores, preferably at least comprises that by Hg porosimetry, according to DIN66133, to measure pore diameter be that hole and the pore diameter of 0.1-10 μ m is the bimodal distribution of pores of the hole of 12-100 μ m.
12. 1 kinds for the preparation of the method for preparing the catalyst of ethylene oxide, at least comprises the steps:
(i) provide the BET constant C having according to DIN ISO9277, to be determined as the carrier of 0-800,
(ii) silver is put on to the carrier from (i).
13. 1 kinds can be by obtaining according to the method for claim 12 or by the catalyst obtaining according to the method for claim 12.
14. 1 kinds of methods of being prepared ethylene oxide by ethene, are included according to the catalyst of any one in claim 1-7 or 13 and have lower ethylene oxide.
15. are being prepared the purposes in ethylene oxide according to the catalyst of any one in claim 1-7 or 13 by ethene.
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