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CN100577289C - Carrier of silver catalyst for ethylene oxide production, its preparation method and application - Google Patents

Carrier of silver catalyst for ethylene oxide production, its preparation method and application Download PDF

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Publication number
CN100577289C
CN100577289C CN200610002957A CN200610002957A CN100577289C CN 100577289 C CN100577289 C CN 100577289C CN 200610002957 A CN200610002957 A CN 200610002957A CN 200610002957 A CN200610002957 A CN 200610002957A CN 100577289 C CN100577289 C CN 100577289C
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silver
silver catalyst
carrier
catalyst
total weight
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CN101007287A (en
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陈建设
张志祥
李金兵
高政
金积铨
任冬梅
孙欣欣
倪秀
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China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Priority to CN200610002957A priority Critical patent/CN100577289C/en
Priority to KR1020087020995A priority patent/KR20080096678A/en
Priority to PCT/CN2007/000324 priority patent/WO2007085206A1/en
Publication of CN101007287A publication Critical patent/CN101007287A/en
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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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/612—Surface area less than 10 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—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
    • 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
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • 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
    • 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)

Abstract

本发明涉及一种用于乙烯氧化生产环氧乙烷用银催化剂的氧化铝载体及其制备方法以及由该载体制得的银催化剂，还涉及这种催化剂在乙烯氧化生产环氧乙烷中的用途。在本发明载体制备中，采用一定粒度的三水α-氧化铝、假一水α-氧化铝、一定量的可燃尽含碳材料、助熔剂、氟化物、任选的重碱土金属的化合物相混合，混合均匀后加入粘合剂和水，捏合均匀，挤压成型，经干燥焙烧，制成α-氧化铝载体。本发明载体比表面为0.2～2.0m2/g，孔容为0.35～0.85ml/g，吸水率≥30%，压碎强度30～120N/粒。此载体用银胺络合物、碱金属化合物、碱土金属化合物的溶液浸渍，干燥活化后制得银催化剂用于乙烯环氧化制环氧乙烷。The present invention relates to an alumina carrier for a silver catalyst used in the oxidation of ethylene to produce ethylene oxide, a preparation method thereof and a silver catalyst prepared from the carrier, and also relates to the use of the catalyst in the production of ethylene oxide by the oxidation of ethylene use. In the preparation of the carrier of the present invention, a certain particle size of α-alumina trihydrate, α-alumina pseudomonohydrate, a certain amount of burnable carbonaceous material, flux, fluoride, and optional compound phase of heavy alkaline earth metal are used. Mixing, adding binder and water after mixing evenly, kneading evenly, extruding, drying and roasting to make α-alumina carrier. The specific surface of the carrier of the invention is 0.2-2.0m 2 /g, the pore volume is 0.35-0.85ml/g, the water absorption rate is ≥ 30%, and the crushing strength is 30-120N/grain. The carrier is impregnated with the solution of silver amine complex, alkali metal compound and alkaline earth metal compound, dried and activated to prepare silver catalyst for ethylene epoxidation to prepare oxirane.

Description

The carrier of ethylene oxide silver catalyst, its preparation method and application thereof
Technical field
The present invention relates to a kind of carrier, its preparation method and application thereof that is used for silver catalyst, more particularly the present invention relates to a kind of ethene oxidation production oxirane that is used for alumina support, its preparation method of silver catalyst and the silver catalyst that makes by this carrier, also relate to the purposes of this catalyst in ethene oxidation production oxirane.
Background technology
The ethene oxidation mainly generates oxirane under the silver catalyst effect, side reaction takes place simultaneously generate carbon dioxide and water, and wherein activity, selectivity and stability are the main performance index of silver catalyst.So-called activity is meant reaction temperature required when process for ethylene oxide production reaches certain reaction load.Reaction temperature is low more, and activity of such catalysts is high more.So-called selectivity is meant that conversion of ethylene in the reaction becomes the ratio of the overall reaction molal quantity of the molal quantity of oxirane and ethene.So-called stability then is expressed as active and fall off rate optionally, and the fall off rate stability of small catalyst more is good more.The silver catalyst that uses high activity, high selectivity and have good stability in the process of ethene oxidation production oxirane can be increased economic efficiency greatly, and the silver catalyst of therefore making high activity, high selectivity and good stability is the main direction of silver catalyst research.The performance of silver catalyst has the important relationship except that composition and the preparation method with catalyst, and also the performance and the preparation method of the carrier that uses with catalyst have important relationship.
The preparation method of silver catalyst mainly comprise the preparation and administration to active component of porous carrier (as aluminium oxide) and auxiliary agent to as described in this two processes on the carrier.
In the preparation process of silver catalyst, for α-Al 2O 3Carrier for key component, suitable specific surface and pore structure need, and will reaction heat be spread out for epoxidation of ethylene provides enough spaces on the one hand, also help the timely desorption of product oxirane on the other hand, avoid deep oxidation to generate the accessory substance carbon dioxide.In the manufacture process of alumina support, add pore creating material in the prior art, but, can make carrier obtain desirable pore structure and specific surface, to improve the performance of catalyst as organic after-flame materials such as petroleum coke, walnut parting, carbon dusts.Yet the adding of pore creating material also can bring negative effect, because the residue of pore creating material incomplete combustion in the carrier roasting process can influence the performance of catalyst.U.S. Pat 5801259 is (corresponding to EP0900128, WO9740933 and CN1216940,1998, Shell) and US5733842 (corresponding to EP0900126, CN1216939 and WO9740932,1998, Norton) all proposed not use the alumina support manufacture method of pore creating material, aluminium oxide with at least 80 weight %, 0.01～10 weight % alkaline earth oxides, 0.01～10 weight % silica, 0.01～15 weight % zirconias etc. are mixed with carrier, the granularity of ceramic composition is not more than baked carrier through selecting (15～120 μ m and 1～15 μ m) meticulously with the bulk density that guarantees the dry support precursor, guarantees required voidage.
Although above-mentioned patent documentation is in order to reduce kish ionic impurity after the pore creating material burning to making the influence of catalyst performance, in support material, do not add pore creating material, select varigrained material matching to use for obtaining desirable pore structure, but this method is not brought any improvement to activity of such catalysts and selectivity, therefore this area still needs the manufacture method of carrier is improved, and is beneficial to produce the better silver catalyst of performance.
Chinese patent application publication number CN1634652 has disclosed a kind of manufacture method of not adding the silver catalyst for ethylene oxide carrier of pore creating material.According to this method, can improve gained activity of such catalysts and selectivity simultaneously.But the carrier water absorption rate of this method preparation is on the low side, is unfavorable for the deposition of active component and auxiliary agent; And＜hole of 5 μ m is more, can bring some adverse influences to the mass-and heat-transfer of direct oxidation of ethylene to course of reaction.
Therefore, need in the negative effect that reduces pore creating material as far as possible and brought, obtain having the carrier of perfect apertures structure and specific surface, further obtain well behaved catalyst.
Summary of the invention
In view of the situation of above-mentioned prior art, the present inventor has carried out research extensively and profoundly in the silver catalyst field, thinks along with the aluminium oxide that contains crystallization water roasting at high temperature is converted into α-Al 2O 3, the crystallization water lose the hole that can in carrier, form a certain size, discover that the size in these holes and quantity are suitable for epoxidation of ethylene.Further find when gibbsite and a water aluminium oxide are used as raw material and make carrier, to need not to add too much pore creating material and still can obtain desirable specific surface and pore structure, satisfy the requirement of manufacturing silver catalyst for ethylene oxide porous heat-resistant carrier.Compare with the carrier that the more pore creating material of interpolation is made, silver catalyst intensity and activity that the present invention makes are higher; Compare with not adding the carrier that pore creating material makes, the silver catalyst selectivity that the present invention makes is higher, is specially adapted to the reaction that oxirane is produced in the ethene oxidation.
In alumina raw material, add heavy alkaline earth metal compounds alternatively and make carrier, through the solution that dipping silver compound, organic amine and specific auxiliary agent are mixed with, prepared activity, the selectivity of silver catalyst in ethylene oxidation reactions all is improved after the heat treatment in containing oxygen gas mixture.
Therefore, the purpose of this invention is to provide a kind of novel carriers, in the process of ethene oxidation production oxirane, demonstrate good activity and selectivity by its silver catalyst of making.
Another object of the present invention provides a kind of preparation method of above-mentioned carrier.
A further object of the present invention provides a kind of silver catalyst by above-mentioned preparing carriers.
An also purpose of the present invention provides the application of above-mentioned silver catalyst in ethene oxidation production oxirane.
These and other purposes of the present invention, feature and advantage will become more clear after reading this specification.
Detailed Description Of The Invention
One aspect of the present invention provides a kind of preparation to be used for the ethene oxidation and has produced the method for oxirane with the porous alpha-alumina supports of silver catalyst, comprises the steps:
I) preparation has the mixture of following composition:
A) based on the solid mixture gross weight be 50 orders～500 orders, the three water α-Al of 5～90% weight 2O 3
B) be that the granularity of 5～70% weight is greater than the false water Al of 200 purposes based on the solid mixture gross weight 2O 3
C) but be after-flame carbonaceous material based on the solid mixture gross weight greater than 0～6.6% weight;
D) based on the solid mixture gross weight be the flux of 0.01～3.0% weight;
E) based on the solid mixture gross weight be the fluoride-mineralization agent of 0.01～3.0% weight;
F) based on containing of solid mixture gross weight 0～5.0% weight of heavy alkaline earth metal compounds;
G) binding agent that is 25～60% weight based on above solid mixture gross weight; And
H) an amount of water;
II) with I) in the mixture that obtains mediate evenly and extrusion molding; With
III) product that obtains dry II), at high temperature roasting becomes α-Al then 2O 3
The porous alumina carrier of the present invention's preparation has following feature: specific surface is 0.2m 2/ g～2.0m 2/ g, preferred 0.5m 2/ g～1.5m 2/ g; Pore volume is 0.35～0.85ml/g, preferred 0.40～0.80ml/g; Water absorption rate 〉=30%, preferred 〉=35%; And crushing strength is 30N/ grain～120N/ grain, preferred 35N/ grain～90N/ grain.
Further aspect of the present invention provides a kind of novel silver catalyst, and described catalyst is prepared by a method comprising the following steps:
1) usefulness contains the above-mentioned porous alpha-alumina supports of solution impregnation of silver compound, organic amine, alkali metal promoter and the base earth metal promoter of q.s;
2) elimination maceration extract, dry impregnated carrier; With
3) in containing oxygen gas mixture to step 2) the gained carrier activates, and makes described silver catalyst.
The present invention also relates in one aspect to the application of above-mentioned novel silver catalyst in ethene oxidation production oxirane.
In order to make carrier that enough intensity and good surface properties be arranged, preferably between 1250 ℃～1550 ℃, temperature is too high can to influence activity of such catalysts and the selectivity of making to sintering temperature, and the too low then support strength of sintering temperature is relatively poor.
But the adding of after-flame carbonaceous material is in order to make macropore, thereby makes carrier have proper pore structure and specific surface.Described carbonaceous material comprises a kind of or its mixture in petroleum coke, carbon dust, graphite, polyethylene, polypropylene, the rosin etc.Carbonaceous material is oxidation in roasting process, generates gas and overflows, and forms macropore in carrier.Granularity according to carbonaceous material of the present invention is 20～300 orders.The addition of described carbonaceous material be the mixture total weight amount greater than 0～6.6%, preferred 0.01～5%.
The adding of flux is in order to make carrier have good intensity under low sintering temperature.The example of flux comprises magnesium compound, for example the mixture of one or more in magnesia, magnesium sulfate, magnesium nitrate and the magnesium carbonate.
The fluoride-mineralization agent that the present invention selects for use comprises hydrogen fluoride, ammonium fluoride, aluminum fluoride, magnesium fluoride, ice crystal etc. or its mixture, and the crystal formation that its role is to accelerated oxidation aluminium transforms, and reduces the following pore of 0.1 μ m.
The heavy alkaline earth metal compound that the present invention adds comprises oxide, sulfate, acetate, nitrate and the oxalates etc. of strontium and/or barium, its role is to carrier is improved, addition is 0～5% of a solid mixture gross weight, preferred 0.01～2.0%.
The present invention is by adding binding agent, the vacation one water Al in it and the mixture 2O 3Generation aluminium colloidal sol bonds together each component, but becomes the paste of extrusion molding.Used binding agent comprises acid, as nitric acid, formic acid, acetate, propionic acid and hydrochloric acid etc., or with a false water Al 2O 3Replace with aluminium colloidal sol with acid.When using acid as binding agent, aqueous solution of nitric acid preferably, wherein the weight ratio of nitric acid and water is 1: 1.25～10.
Can be dried to moisturely below 10% after the extrusion molding of gained paste, support shapes can be annular, spherical, cylindricality or porous cylindricality.Baking temperature is 80～120 ℃, and be controlled at 1 hour～24 hour according to moisture drying time.
Dried paste makes aluminium oxide whole substantially 1250～1550 ℃ of following roastings 2～6 hours, for example is converted into α-Al more than 90% 2O 3The specific surface of this carrier is 0.2m 2/ g～2.0m 2/ g, preferred 0.5m 2/ g～1.5m 2/ g; Pore volume is 0.35～0.85ml/g, preferred 0.40～0.80ml/g; Water absorption rate 〉=30%, preferred 〉=35%; And crushing strength is 30N/ grain～120N/ grain, preferred 35N/ grain～90N/ grain.
Silver catalyst of the present invention can prepare in the usual way, for example by preparing with the above-mentioned alumina support of the solution impregnation of a kind of Ag-containing compound, organic amine, alkali metal promoter and base earth metal promoter.
In the preparation of silver catalyst of the present invention, at first make the aqueous solution and the ammonium oxalate or the oxalic acid aqueous solution reaction of silver nitrate, separate out the silver oxalate precipitation, after the filtration, spend deionised water, until no nitrate ion, then silver oxalate is dissolved in organic amine such as pyridine, butylamine, ethylenediamine, 1, in the aqueous solution of 3-propane diamine, monoethanolamine or its mixture, add auxiliary agent, be made into dipping solution.Then with the gained dipping solution vacuum less than the condition of 10mmHg under the above-mentioned alumina support of dipping 30 minutes, drain, in being not more than the nitrogen oxygen atmosphere of 21% (as containing oxygen 8.0%), air stream or oxygen content in 180～700 ℃, preferred 200-500 ℃ temperature range, kept 1 minute～120 minutes, preferred 2 minutes～60 minutes, to carry out thermal decomposition.Also available silver oxide replaces silver nitrate, and silver oxalate also can not analysed filter, direct and organic amine complexing, impregnated carrier then.The amount of the silver compound that uses in the dipping process of the present invention should be enough to make argentiferous 1～30% weight in the finally prepd catalyst, and preferred 5～25% weight are in total catalyst weight.
Alkali metal promoter among the present invention can be compound or its any two kinds combination of compounds of lithium, sodium, potassium, rubidium or caesium, and alkali-metal content is 5～2000ppm in the final catalyst, preferred 10～1500ppm.Alkali metal promoter can be before dipping silver, simultaneously or be applied to afterwards on the carrier, also can after silver compound is reduced, be immersed on the carrier.
Base earth metal promoter among the present invention can be the compound of magnesium, calcium, strontium or barium, as oxide, oxalates, sulfate, acetate or nitrate, or its mixture, the compound of preferred barium or strontium.The total content of alkaline-earth metal is 5ppm～22000ppm in the final catalyst, preferred 10ppm～15000ppm.Base earth metal promoter can be before dipping silver, simultaneously or be applied to afterwards on the carrier, also can after silver compound is reduced, be immersed on the carrier.
Except alkali metal promoter above-mentioned and base earth metal promoter, can also add other auxiliary agents such as rhenium compound and coassist agent thereof, as ammonium perrhenate and coassist agent chromium thereof, molybdenum, tungsten, boron etc., with the activity of further improvement gained silver catalyst, selectivity and active and stability optionally.These other auxiliary agents can be before dipping silver, simultaneously or be applied to afterwards on the carrier, also can after silver compound is reduced, be immersed on the carrier.
The mensuration of catalyst performance
Various silver catalyst of the present invention is tested its initial performance and stability with laboratory reaction device (following letter " little anti-") evaluating apparatus.The reactor that the micro anti-evaluation device uses is the stainless steel tube of internal diameter 4mm, and reactor places heating jacket.The admission space of catalyst is 1ml, and inert filler is arranged at the bottom, makes beds be positioned at the flat-temperature zone of heating jacket.
Initial activity, optionally measure
The activity that the present invention uses and optionally condition determination is as follows:
Reacting gas is formed (mol%)
Ethene (C 2H 4) 28.0 ± 1.0
Oxygen (O 2) 7.4 ± 0.2
Carbon dioxide (CO 2)＜8.0
Cause steady gas (N 2) surplus
Inhibitor dichloroethanes 0.1ppm～2.0ppm
Reaction pressure 2.1MPa
Air speed 7000/h
Reactor goes out EO concentration 1.35%
Space-time yield 185gEO/mlCat./h
When stable reach above-mentioned reaction condition after the METHOD FOR CONTINUOUS DETERMINATION reactor go into, exit gas forms.Measurement result carries out calculating as follows after volume contraction is proofreaied and correct selectivity:
Figure C20061000295700111
Wherein Δ EO works off one's feeling vent one's spleen poorly with the inlet gas ethylene oxide concentration, gets the result of the test of the average of 10 groups of above test datas as the same day.
The present invention compares following advantage with prior art: porous alumina carrier is not subjected to the influence of pore creating material quality made in accordance with the present invention, make the stable performance of silver catalyst, and have higher activity, be specially adapted to the reaction that oxirane is produced in the ethene oxidation.
Embodiment
The present invention is described further below in conjunction with embodiment, but scope of the present invention is not limited to these embodiment.
Carrier comparative example 1 and 2 preparation
With 50～500 purposes, three water α-Al 2O 3312g is greater than the false water Al of 200 purposes 2O 392g, petroleum coke are respectively 0 and 81g, NH 4F 7g and Mg (NO 3) 2Mix 8.5g put into blender, change in the kneader, add 0.12 liter in rare nitric acid (nitric acid: water=1: 3, weight ratio), but be kneaded into the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, dries more than 2 hours down at 80～120 ℃, and free water content is reduced to below 10%.
The preparation of carrier embodiment 1-3
With 50～500 purposes, three water α-Al 2O 3312g is greater than the false water Al of 200 purposes 2O 392g, petroleum coke are respectively 5,11 and 21g, NH 4F 7g and Mg (NO 3) 2Mix 8.5g put into blender, change in the kneader, add 0.12 liter in rare nitric acid (nitric acid: water=1: 3, weight ratio), but be kneaded into the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, dries more than 2 hours down at 80～120 ℃, and free water content is reduced to below 10%.
The preparation of carrier comparative example 3
With 50～500 purposes, three water α-Al 2O 3212g is greater than the false water Al of 200 purposes 2O 3192g, petroleum coke 81g, the barium sulfate of 4g porphyrize, NH 4F 7g and Mg (NO 3) 2Mix 8.5g put into blender, change in the kneader, add 0.12 liter in rare nitric acid (nitric acid: water=1: 3, weight ratio), but be kneaded into the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, dries more than 2 hours down at 80～120 ℃, and free water content is reduced to below 10%.
The preparation of carrier embodiment 4
Different with comparative example 3 is in batching Jiao's of PetroChina Company Limited. addition is 21g, mixes then, mediates, extrudes, dries, and free water content is reduced to below 10%.
Above-mentioned nine kind of five hole column put into top-hat kiln, and through being elevated between 1350 ℃～1550 ℃ from room temperature about 30 hours, constant temperature 2 hours obtains white α-Al 2O 3Support samples.
The carrier property data of measuring are listed in table 1.
The physical data of table 1 comparative example 1 and embodiment 1～5
Comparative example 1 Comparative example 2 Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 3 Embodiment 4
Crushing strength (N/ grain) 84 34 79 71 63 42 55
Water absorption rate (%) 47 70 50 54 58 74 73
Bulk density (gram per centimeter 3) 0.64 0.52 0.63 0.62 0.60 0.49 0.54
Specific surface (rice 2/ gram) 0.91 0.90 0.88 0.84 0.72 0.78 1.05
Pore volume (milliliter/gram) 0.58 0.64 0.60 0.61 0.61 0.65 0.62
Distribute (accounting for total pore volume %)＜1 microns 1～5 micron 5～10 microns 10～30 microns 30～50 microns＞50 microns of pore radius 6.2 74.5 9.0 7.5 0.8 2.0 4.6 53.7 11.7 17.8 4.9 7.3 5.4 72.1 10.2 8.5 1.0 2.8 5.8 71.6 9.8 9.1 2.3 1.4 8.2 68.5 9.6 9.4 1.9 2.4 5.6 56.2 10.8 16.2 5.8 5.4 6.9 60.7 10.6 14.8 3.1 3.9
The preparation of catalyst comparative example 1～3 and embodiment 1～4
Getting the 700g silver nitrate is dissolved in the 750ml deionized water.Get in the deionized water that the 325g ammonium oxalate is dissolved in 50 ℃ of 250ml.Under vigorous stirring, mix two kinds of solution, generate white silver oxalate precipitation.Aging more than 30 minutes, filter, spend deionised water and be precipitated to no nitrate ion.Filter cake argentiferous about 60%, moisture about 15%.
In the glass flask that band stirs, add the 300g ethylenediamine, 110g monoethanolamine, 375g deionized water.Stir following silver oxalate paste that makes and slowly add in the mixed liquor, temperature remains on below 40 ℃, and silver oxalate is all dissolved, and the addition of silver oxalate makes the maceration extract argentiferous 22% (weight) that makes.Add 2.2g cesium sulfate, 1.4g strontium acetate, add deionized water again and make the solution gross mass reach 2000g, make solution for later use.
Get the support samples of 100g carrier comparative example 1～3 and embodiment 1～4 preparation and put into the container that can vacuumize.Be evacuated to more than the 10mmHg, put into above maceration extract, the submergence carrier kept 30 minutes.Excessive solution is gone in leaching.Soaked carrier heated 5 minutes in 450 ℃ air stream, and silver catalyst for ethylene oxide is promptly made in cooling.
Silver and auxiliary agent content to the catalyst made are analyzed, and wherein content is in metal; Use the microreactor evaluating apparatus to measure the activity and the selectivity of catalyst sample under aforementioned process conditions, result of the test is listed in table 2.
The result of the test of the sample of table 2 Preparation of Catalyst comparative example 1～3 and embodiment 1～4
The sample title Silver content (%) The content of caesium (ppm) The content of strontium (ppm) Reaction temperature (℃) EO (％) Selectivity (%)
Comparative example 1 13.8 538 218 216 1.35 83.9
Comparative example 2 16.9 645 252 223 1.35 83.6
Embodiment 1 14.2 542 223 218 1.35 84.2
Embodiment 2 14.4 550 222 217 1.35 84.5
Embodiment 3 15.2 564 229 218 1.35 84.1
Comparative example 3 17.0 654 255 225 1.34 83.8
Embodiment 4 15.4 586 231 218 1.35 84.5
The preparation of catalyst comparative example 4 and embodiment 5
In the glass flask that band stirs, add the 300g ethylenediamine, 110g monoethanolamine, 375g deionized water.Stir following silver oxalate paste that makes as catalyst comparative example 1～3 and embodiment 1～4 and slowly add in the mixed liquor, temperature remains on below 40 ℃, and silver oxalate is all dissolved, and the addition of silver oxalate makes the maceration extract argentiferous 22% (weight) that makes.Add 2.2g cesium sulfate, 2.6g barium acetate, 0.3g lithium sulfate, add deionized water again and make the solution gross mass reach 2000g, make solution for later use.
Get the support samples of 100g carrier comparative example 2 and embodiment 3 preparations and put into the container that can vacuumize.Be evacuated to more than the 10mmHg, put into above maceration extract, the submergence carrier kept 30 minutes.Excessive solution is gone in leaching.Soaked carrier heated 10 minutes in 350 ℃ air stream, and silver catalyst for ethylene oxide is promptly made in cooling.
Silver and auxiliary agent content to the catalyst made are analyzed, and wherein content is in metal; Use the microreactor evaluating apparatus to measure the activity and the selectivity of catalyst sample under aforementioned process conditions, result of the test is listed in table 3.
The result of the test of the sample of table 3 Preparation of Catalyst comparative example 4 and embodiment 5
The sample title Silver content (%) The content of caesium (ppm) The content of lithium (ppm) The content of barium (ppm) Reaction temperature (℃) EO (％) Selectivity (%)
Comparative example 4 17.2 650 15 417 222 1.35 83.5
Embodiment 5 15.2 583 13 347 217 1.35 84.0

Claims (27)

1.一种制备用于乙烯氧化生产环氧乙烷用银催化剂的多孔α-氧化铝载体的方法，包括如下步骤：1. A method for preparing a porous α-alumina carrier for the production of ethylene oxide silver catalyst for ethylene oxidation, comprising the steps: I)制备具有如下组成的混合物：1) Prepare a mixture with the following composition: a)基于固体混合物总重量为5～90％重量的50目～500目三水α-Al2O3；a) 50 to 500 mesh α-Al 2 O 3 trihydrate of 5 to 90% by weight based on the total weight of the solid mixture; b)基于固体混合物总重量为5～70％重量的粒度大于200目的假一水α-Al2O3；b) Pseudo monohydrate α-Al 2 O 3 with a particle size greater than 200 mesh of 5 to 70% by weight based on the total weight of the solid mixture; c)基于固体混合物总重量为大于0至小于5％重量的可燃尽含碳材料；c) greater than 0 to less than 5% by weight of burnable carbonaceous material, based on the total weight of the solid mixture; d)基于固体混合物总重量为0.01～3.0％重量的助熔剂；d) 0.01 to 3.0% by weight of a flux based on the total weight of the solid mixture; e)基于固体混合物总重量为0.01～3.0％重量的氟化物矿化剂；e) 0.01 to 3.0% by weight of fluoride mineralizer based on the total weight of the solid mixture; f)基于固体混合物总重量为0～5.0％重量的重碱土金属的化合物；f) based on the total weight of the solid mixture, 0 to 5.0% by weight of heavy alkaline earth metal compounds; g)基于组分a)-f)的总重量为25～60％重量的粘结剂；以及g) 25 to 60% by weight of binder based on the total weight of components a)-f); and h)适量的水；h) appropriate amount of water; II)将I)中得到的混合物捏合均匀并挤出成型；和II) kneading the mixture obtained in I) uniformly and extruding; and III)干燥II)中得到的产品，然后在高温下焙烧成α-Al2O3。III) drying the product obtained in II), and then calcining at high temperature into α-Al 2 O 3 . 2.如权利要求1所述的方法，其中所述助熔剂是选自氧化镁、硫酸镁、硝酸镁、碳酸镁及其混合物的镁化合物；所述含碳材料是石油焦、碳粉、石墨、松香、聚乙烯、聚丙烯或其混合物；所述氟化物矿化剂为氟化氢、氟化铝、氟化铵、氟化镁、冰晶石中的一种或几种的混合物。2. The method as claimed in claim 1, wherein said fluxing agent is a magnesium compound selected from magnesium oxide, magnesium sulfate, magnesium nitrate, magnesium carbonate and mixtures thereof; said carbonaceous material is petroleum coke, carbon powder, graphite , rosin, polyethylene, polypropylene or a mixture thereof; the fluoride mineralizer is one or a mixture of hydrogen fluoride, aluminum fluoride, ammonium fluoride, magnesium fluoride, and cryolite. 3.如权利要求2所述的方法，其特征在于所述含碳材料的用量为所述混合物总重量的0.01～5％。3. The method according to claim 2, characterized in that the amount of the carbonaceous material is 0.01-5% of the total weight of the mixture. 4.如权利要求2所述的方法，其特征在于所述含碳材料的粒度为20～300目。4. The method according to claim 2, characterized in that the particle size of the carbonaceous material is 20-300 mesh. 5.如权利要求1所述的方法，其中所述粘结剂为酸。5. The method of claim 1, wherein the binder is an acid. 6.如权利要求5所述的方法，其中用铝溶胶代替酸和假一水α-Al2O3。6. The method as claimed in claim 5, wherein the acid and pseudomonohydrate α-Al 2 O 3 are replaced by aluminum sol. 7.如权利要求5所述的方法，其中所述酸为硝酸水溶液，其中硝酸与水的重量比为1∶1.25～10。7. The method according to claim 5, wherein the acid is an aqueous solution of nitric acid, wherein the weight ratio of nitric acid to water is 1:1.25˜10. 8.如权利要求1所述的方法，其特征在于所述重碱土金属的化合物为锶和/或钡的氧化物、硝酸盐、醋酸盐、草酸盐或硫酸盐。8. The method according to claim 1, characterized in that the compound of the heavy alkaline earth metal is an oxide, nitrate, acetate, oxalate or sulfate of strontium and/or barium. 9.如权利要求1所述的方法，其中所述III)中得到的产品在1250℃～1550℃的高温下焙烧。9. The method according to claim 1, wherein the product obtained in said III) is calcined at a high temperature of 1250°C to 1550°C. 10.一种如权利要求1-9中任一项所述的方法得到的多孔氧化铝载体，其特征在于所述多孔氧化铝载体具有以下特征：比表面为0.2m2/g～2.0m2/g；孔容为0.35～0.85ml/g；吸水率≥30％；以及压碎强度为30N/粒～120N/粒。10. A porous alumina carrier obtained by the method according to any one of claims 1-9, characterized in that the porous alumina carrier has the following characteristics: the specific surface is 0.2m 2 /g-2.0m 2 /g; pore volume of 0.35-0.85ml/g; water absorption ≥30%; and crushing strength of 30N/grain-120N/grain. 11.如权利要求10所述的多孔氧化铝载体，其特征在于所述多孔氧化铝载体具有以下特征：比表面为0.5m2/g～1.5m2/g；孔容为0.40～0.80ml/g；吸水率≥35％；以及压碎强度为35N/粒～90N/粒。11. The porous alumina carrier according to claim 10, characterized in that the porous alumina carrier has the following characteristics: the specific surface is 0.5m 2 /g-1.5m 2 /g; the pore volume is 0.40-0.80ml/ g; water absorption ≥ 35%; and crushing strength of 35N/grain to 90N/grain. 12.如权利要求10所述的多孔氧化铝载体，其中所述重碱土金属化合物的量以重碱土金属计为所述混合物总重量的0.01～2.0％。12. The porous alumina carrier according to claim 10, wherein the amount of the heavy alkaline earth metal compound is 0.01-2.0% of the total weight of the mixture in terms of heavy alkaline earth metal. 13.如权利要求10-12中任一项所述的多孔氧化铝载体，其中α-Al2O3含量为90％以上。13. The porous alumina support according to any one of claims 10-12, wherein the α-Al 2 O 3 content is above 90%. 14.一种由乙烯氧化生产环氧乙烷所用的银催化剂，通过包括以下步骤的方法制备：14. A silver catalyst for the production of ethylene oxide by the oxidation of ethylene, prepared by a process comprising the steps of: 1)用含足够量的银化合物、有机胺、碱金属助剂和碱土金属助剂的溶液浸渍根据权利要求1所述方法制备的多孔α-氧化铝载体；1) impregnating the porous α-alumina carrier prepared according to the method described in claim 1 with a solution containing a sufficient amount of silver compound, organic amine, alkali metal additives and alkaline earth metal additives; 2)滤去浸渍液，干燥浸渍过的载体；和2) filtering off the impregnation solution, drying the impregnated carrier; and 3)在含氧混合气体中对步骤2)所得载体进行活化，制成所述银催化剂。3) activating the carrier obtained in step 2) in an oxygen-containing mixed gas to prepare the silver catalyst. 15.如权利要求14所述的银催化剂，其中银化合物为氧化银、硝酸银或草酸银且其加入量应使银在所述银催化剂中的含量为1％～30％，基于所述银催化剂的总重量。15. The silver catalyst as claimed in claim 14, wherein the silver compound is silver oxide, silver nitrate or silver oxalate and its addition should make the content of silver in the silver catalyst be 1%～30%, based on the silver The total weight of the catalyst. 16.如权利要求15所述的银催化剂，其中银化合物的加入量应使银在所述银催化剂中的含量为5％～25％，基于所述银催化剂的总重量。16. The silver catalyst as claimed in claim 15, wherein the silver compound is added in such an amount that the silver content in the silver catalyst is 5%-25%, based on the total weight of the silver catalyst. 17.如权利要求14所述的银催化剂，其中所述碱金属助剂为锂、钠、钾、铷或铯的化合物或其任意两种的组合，且其加入量应使所述碱金属在所述银催化剂中的含量为5ppm～2000ppm，基于所述银催化剂的总重量。17. silver catalyst as claimed in claim 14, wherein said alkali metal promoter is the compound of lithium, sodium, potassium, rubidium or cesium or its combination of any two, and its addition should make described alkali metal in The content of the silver catalyst is 5 ppm to 2000 ppm, based on the total weight of the silver catalyst. 18.如权利要求17所述的银催化剂，其中所述碱金属助剂的加入量应使所述碱金属在所述银催化剂中的含量为10ppm～1500ppm，基于所述银催化剂的总重量。18. The silver catalyst as claimed in claim 17, wherein the addition amount of the alkali metal promoter is such that the content of the alkali metal in the silver catalyst is 10 ppm to 1500 ppm, based on the total weight of the silver catalyst. 19.如权利要求17或18所述的银催化剂，其中所述碱金属为铯或铯和锂的组合。19. A silver catalyst as claimed in claim 17 or 18 wherein the alkali metal is cesium or a combination of cesium and lithium. 20.如权利要求14所述的银催化剂，其中所述碱土金属助剂为镁、钙、锶或钡的化合物或其混合物且其加入量应使碱土金属在所述银催化剂中的总含量为5ppm～22000ppm，基于所述银催化剂的总重量。20. silver catalyst as claimed in claim 14, wherein said alkaline earth metal additive is the compound or its mixture of magnesium, calcium, strontium or barium and its addition should make the total content of alkaline earth metal in described silver catalyst be 5ppm-22000ppm, based on the total weight of the silver catalyst. 21.如权利要求20所述的银催化剂，其中所述碱土金属助剂的加入量应使碱土金属在所述银催化剂中的总含量为10ppm～15000ppm，基于所述银催化剂的总重量。21. The silver catalyst as claimed in claim 20, wherein the alkaline earth metal promoter is added in an amount such that the total content of the alkaline earth metal in the silver catalyst is 10 ppm to 15000 ppm, based on the total weight of the silver catalyst. 22.如权利要求20或21所述的银催化剂，其中所述碱土金属为钡或锶。22. A silver catalyst as claimed in claim 20 or 21 wherein the alkaline earth metal is barium or strontium. 23.如权利要求14所述的银催化剂，其中所述助剂在浸渍银之前、同时或之后施加到载体上，或在银化合物被还原以后浸渍在载体上。23. The silver catalyst of claim 14, wherein the auxiliary agent is applied to the support before, simultaneously with or after impregnating the silver, or impregnated on the support after the silver compound is reduced. 24.如权利要求14所述的银催化剂，其中所述活化过程是在空气或氧含量不大于21％的氮氧混合气中进行的。24. The silver catalyst as claimed in claim 14, wherein the activation process is carried out in air or a nitrogen-oxygen mixture with an oxygen content not greater than 21%. 25.如权利要求14所述的银催化剂，其中所述活化过程的温度控制在180℃～700℃之间且所述活化过程的时间是1分钟～120分钟。25. The silver catalyst as claimed in claim 14, wherein the temperature of the activation process is controlled between 180°C to 700°C and the time of the activation process is 1 minute to 120 minutes. 26.如权利要求25所述的银催化剂，其中所述活化过程的温度控制在200℃～500℃之间且所述活化过程的时间是2分钟～60分钟。26. The silver catalyst as claimed in claim 25, wherein the temperature of the activation process is controlled between 200° C. and 500° C. and the time of the activation process is 2 minutes to 60 minutes. 27.一种由乙烯氧化生产环氧乙烷的方法，其中使用如权利要求14～26中任一项所述的银催化剂。27. A process for the production of ethylene oxide by oxidation of ethylene, wherein a silver catalyst as claimed in any one of claims 14 to 26 is used.
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