CN108855237A - Porous alumina carrier and preparation method thereof and silver catalyst and application - Google Patents
Porous alumina carrier and preparation method thereof and silver catalyst and application Download PDFInfo
- Publication number
- CN108855237A CN108855237A CN201710338912.3A CN201710338912A CN108855237A CN 108855237 A CN108855237 A CN 108855237A CN 201710338912 A CN201710338912 A CN 201710338912A CN 108855237 A CN108855237 A CN 108855237A
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- Prior art keywords
- carrier
- weight
- catalyst
- component
- silver
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- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 74
- 239000004332 silver Substances 0.000 title claims abstract description 74
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 21
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- 238000000034 method Methods 0.000 claims abstract description 40
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 33
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- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 239000002562 thickening agent Substances 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
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- 238000004519 manufacturing process Methods 0.000 claims description 17
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- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
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- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
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- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- 206010054949 Metaplasia Diseases 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000428 dust Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
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- 150000007522 mineralic acids Chemical group 0.000 claims description 2
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- 150000003839 salts Chemical class 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
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- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 8
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 5
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- 238000010521 absorption reaction Methods 0.000 description 5
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- 229910052792 caesium Inorganic materials 0.000 description 5
- 239000012876 carrier material Substances 0.000 description 5
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- 239000000047 product Substances 0.000 description 5
- 229940100890 silver compound Drugs 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
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- 150000002500 ions Chemical class 0.000 description 4
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- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
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- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- B01J35/612—
-
- B01J35/635—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention belongs to catalyst carrier field, it is related to a kind of porous alumina carrier and preparation method thereof and silver catalyst and application.The method for preparing porous alumina carrier includes the following steps：Step A forms the mixture comprising following component：I, hydrated alumina；The synthesis high score subclass thickener for being 0.05-30wt% based on component i weight；The binder for being 15~60wt% based on component i weight；The water for being 0-30wt% based on component i weight；The pore creating material for being 0-30wt% based on component i weight；The mineralizer for being 0-5wt% based on component i weight；The auxiliary agent for being 0-5wt% based on component i weight, the auxiliary agent are at least one of base earth metal promoter, silicon additive and zirconium auxiliary agent；Mixture obtained in step A is formed, dried and is roasted by step B.Support preparation method of the invention is simple and easy, and carrier property obtained is uniform, and quality and performance are more preferably.
Description
Technical field
The present invention relates to catalyst carrier fields, more particularly, to a kind of porous alumina carrier and preparation method thereof
With silver catalyst and application.
Background technique
Alumina support is a kind of worldwide widely applied carrier.Such as industrially it is used to be catalyzed ethylene epoxy
Metaplasia produces the silver catalyst of ethylene oxide, and carrier is exactly to select aluminium oxide as carrier.
The primary raw material for preparing alumina support is hydrated alumina (also known as aluminium hydroxide), hydrated alumina dehydration
Louis (L) Acid and basic sites can be generated, and these acid sites L are easy to absorb water and be changed into proton (B) Acid and basic sites.Aluminium oxide
Crystal form type it is very much, impurity and the more or less influence of moisture, cause the surface physics of aluminium oxide, chemical property all non-in addition
It is often complicated.
For the carrier that silver catalyst is selected, the carrier of silver catalyst generally selects the lesser porous α-of specific surface area
Al2O3As carrier.In general, the main method for preparing silver catalyst carrier is to select a variety of different alumina powders former
Material, optional addition pore creating material, binder and various additives etc. through mixing and are mediated uniformly, and then extrusion molding is difference
The green body (Raschig ring, spheric granules, porous cylindrical, shape of a saddle etc.) of shape is finally made in 1200~1700 DEG C of sintering porous
Heat-resisting alpha-alumina supports product, as described in patent US 5063195, US 5703001, US 5801259 etc..
After the completion of carrier preparation, then active component (and auxiliary agent) loaded on the carrier, completes silver catalyst
Preparation.It is industrial that impregnating active method is generally selected to prepare silver catalyst.First with silver salt, optional various auxiliary agents and organic amine
Class is configured to certain density silver-colored ammonia dipping solution, makes Ag ion and organic amine that complex reaction occur and generates silver-organic ammonia complexing
Ion；Then carrier is put into maceration extract and impregnates enough time, ammonia complexing ion silver-colored in this way and various auxiliary agent ions are with solution
It is impregnated into carrier surface；After leaching, it is finally putting into activation zone hot-air (or special atmosphere) activation, in activation process,
The various argentiferous impregnated elements of carrier surface are by heating and gradually decomposing, under the various complicated reductions generated therewith,
Silver ion reduction forms tens of to hundreds of nanometers of particle at elemental silver, and in carrier surface, to obtain finished product silver catalyst.
Above-mentioned silver catalyst is mainly used for being catalyzed ethylene epoxidizing production ethylene oxide.In the reaction, ring is mainly generated
Oxidative ethane, while side reaction occurs and generates carbon dioxide and water etc..The main performance index of silver catalyst includes its activity, selection
Property and stability.Wherein activity generally refers to the reaction temperature that process for ethylene oxide production reaches required when certain reaction load,
Required reaction temperature is lower, and the activity of catalyst is higher；Selectivity refers to that ethylene is converted to the molal quantity of ethylene oxide in reaction
The ratio between with the overall reaction molal quantity of ethylene；Stability is then the fall off rate of activity and selectivity, and fall off rate gets over small catalyst
Stability it is better.
Since the commercial scale of production ethylene oxide is extremely huge, the selectivity of reaction, which increases by 1%, can all be saved largely
Raw material generates huge economic benefit.Similarly, the service life of silver catalyst, that is, stability improvement also have it is aobvious
The economic benefit of work.Therefore, this field expectation obtains a kind of better silver catalyst of performance, for the production of ethylene oxide, and
The structure and characteristic of its carrier is even more to improve the key of silver catalyst performance.
Summary of the invention
In view of the situation of the above-mentioned prior art, the present inventor carries out alumina support and its preparation process field
Research extensively and profoundly.It was found by the inventors of the present invention that suitable synthesis macromolecule is added in conventional carriers preparation process
Class thickener can make carrier material form gel, to adjust carrier material rheological characteristic, increase carrier material viscosity and stablize
Property, and then the shaping characteristic of carrier material is improved, and the final mass and performance of final lifting carrier product.This completes this
Invention.
The first aspect of the present invention provides a kind of method for preparing porous alumina carrier, and this method comprises the following steps：
Step A forms the mixture comprising following component：
I, hydrated alumina；
Ii, based on component i weight be 0.05-30wt%, the synthesis high score subclass thickener of preferably 0.1-15wt%；
Iii, the binder for being 15~60wt% based on component i weight；
Iv, the water for being 0-30wt% based on component i weight；And
V, the pore creating material for being 0-30wt% based on component i weight；
Vi, the mineralizer for being 0-5wt% based on component i weight；
Vii, the auxiliary agent for being 0-5wt% based on component i weight, the auxiliary agent are that base earth metal promoter, silicon additive and zirconium help
At least one of agent；
Mixture obtained in step A is formed, dried and is roasted by step B.
The second aspect of the present invention provides porous alumina carrier prepared by the above method.
The third aspect of the present invention provides a kind of silver catalyst of catalysis ethylene production ethylene oxide, the silver catalyst
Silver and optional catalysed promoted amount comprising above-mentioned porous alumina carrier and load catalytically effective amount on this carrier
Alkali metal, the alkaline-earth metal of optional catalysed promoted amount, the rhenium of optional catalysed promoted amount and the collaboration auxiliary agent of optional rhenium.
The fourth aspect of the present invention provides above-mentioned porous alumina carrier and/or silver catalyst and produces ring in alkene epoxidation
Application in oxygen alkane preferably produces the application in ethylene oxide or epoxidation of propylene production propylene oxide in ethylene epoxidizing,
Application particularly preferably in ethylene epoxidizing production ethylene oxide.
It is of the invention beneficial to have technical effect that：Support preparation method of the invention is simple and easy, obtained carrier-mediated
Can be uniform, there is bigger specific surface area and Kong Rong, quality and performance are more preferably.Had by silver catalyst prepared by the carrier higher
Selectivity and activity, can save reaction raw materials, reduce byproduct of reaction, save the cost is particularly suitable for industrially by alkene
Hydrocarbon ring oxidation production epoxyalkane, especially suitable for industrially producing ethylene oxide by ethylene epoxidizing.
Other features and advantages of the present invention will then part of the detailed description can be specified.
Specific embodiment
The first aspect of the present invention provides a kind of method for preparing porous alumina carrier, and this method comprises the following steps：
Step A forms the mixture comprising following component：
I, hydrated alumina；
Ii, based on component i weight be 0.05-30wt%, the synthesis high score subclass thickener of preferably 0.1-15wt%；
Iii, the binder for being 15~60wt% based on component i weight；
It iv, based on component i weight is 0-30wt%, the preferably water of 1-20wt%；And
V, the pore creating material for being 0-30wt% based on component i weight；
Vi, the mineralizer for being 0-5wt% based on component i weight；
Vii, the auxiliary agent for being 0-5wt% based on component i weight, the auxiliary agent are that base earth metal promoter, silicon additive and zirconium help
At least one of agent；
Mixture obtained in step A is formed, dried and is roasted by step B.
Synthesis high score subclass thickener of the present invention can be improved the viscosity of material, change as rheology thickening aids
Become the flow behavior of material.Preferably, the synthesis high score subclass thickener is polyvinyl alcohol, polyacrylamide, vaseline, gathers
Acrylic acid, polyacrylate, polyvinylpyrrolidone, polyurethane, polyethylene glycol oxide, modified paraffin resin, carbomer, modification
Polyureas and low-molecular polyethylene wax it is one or more.
According to the present invention, in the specific preparation process of carrier, it can choose and be directly added into suitable synthesis high score subclass
Thickener, also can choose first will synthesis high score subclass thickener it is soluble in water, after being made into the hydrosol (gel), be then added to it
In his carrier material.
In method of the present invention, hydrated alumina is as alumina raw material, and the hydrated alumina is at least
Including one water A1 of vacation2O3, preferably three water A12O3With one water A1 of vacation2O3, and the three water A12O3With one water A1 of vacation2O3Weight
Than being 0.5~16:1, preferably 1~6:1.The size of the hydrated alumina is not particularly limited in the present invention, and described three
Water A12O3It such as can be 50-500 mesh, the false water A12O3It can be to be more than 200 mesh.
The binder is inorganic acid, preferably nitric acid, further preferably aqueous solution of nitric acid, wherein the weight of nitric acid and water
Than being 1:1.25-1:10, to provide binder and water simultaneously, additional amount is adjusted according to the amount of hydrated alumina, when
The hydrated alumina includes one water A1 of vacation2O3When, binder and a false water can be partly or entirely replaced with Aluminum sol
A12O3。
In method of the present invention, optional that pore creating material is added in step A, the pore creating material is selected from can after-flame
At least one of carbonaceous material, preferably at least one of petroleum coke, carbon dust and graphite.Carbonaceous material is in roasting process
Oxidation generates gas evolution, so as to form macropore in the carrier.
Also optional to be added mineralizer in step, the mineralizer is fluoride-mineralization agent, selected from hydrogen fluoride,
At least one of aluminum fluoride, ammonium fluoride and ice crystal.The effect of mineralizer is the transformation of crystal of accelerated oxidation aluminium, and eliminates
Pore.
The base earth metal promoter of addition in step and/or silicon additive and/or zirconium auxiliary agent that can also be optional.The alkaline earth
Metal promoter is selected from oxide, sulfate, acetate, nitrate, the carbonate of magnesium, calcium, strontium, barium and magnesium, calcium, strontium and barium
And at least one of oxalates；The silicon additive in elemental silicon, the oxide of silicon, silicate and organosilicon at least
It is a kind of；The zirconium auxiliary agent is in simple substance zirconium, the oxide of zirconium, sulfate, acetate, nitrate, carbonate and oxalates
At least one.
Material needed for carrier will be prepared and suitable thickener after mixing, generally yield gelling material or paste
Object, gained gelling material or paste are formed, and preferably extrusion molding obtains formed body, i.e. carrier blank.The formed body can be done
Hereinafter, drying temperature is 60-200 DEG C, drying time controls according to moisture content at 1-24 hours dry to aqueous 10 weight %.Institute
The shape for obtaining formed body, which can according to need, is made as annular, spherical shape, monoporate column shape, porous column shape or other shapes, of the invention
It is the single hole annular shape particle that 7-9mm internal diameter is 1-6mm that specific embodiment, which provides outer diameter,.
The carrier finished product prepared according to the method provided by the invention is a kind of porous α-A12O3Carrier, can be according to user
Need to adjust molding size, shape and sintering temperature etc., in order to make carrier have enough intensity and good superficiality
Can, the formed body after drying usually roasts at 1000-1500 DEG C, and preferably 1100 DEG C -1400 DEG C, under maturing temperature, usually
Carrier is kept for 2-24 hours.
According to the second aspect of the invention, porous alumina carrier prepared by the above method is provided, the porous aluminas
Carrier has following feature：α-A12O3Content accounts for 85% or more vehicle weight, and specific surface is 0.2~5.0m2/ g, preferably 1.0-
2.0m2/ g, further preferably 1.2-1.8m2/g；Kong Rongwei 0.35-0.85ml/g, preferably 0.45-0.60ml/g, further
Preferably 0.52-0.55ml/g；Water absorption rate>30%, preferably>50%；Crushing strength>20N, preferably>50N.The porous aluminas
Carrier can be in the form of this field be common, such as annular, spherical, monoporate column shape or porous column shape, preferably outer diameter be 7-9mm,
The single hole annular shape particle or outer diameter that internal diameter is 1-6mm are 7-9mm, the seven apertures in the human head or five hole honeycombs circle that hole diameter is 1-2mm
Cylindrical particle.Monoporate column shape or porous column shape herein refers to the overall appearance of carrier, and " more in " porous alumina carrier "
Hole " meaning is different.Porous alumina carrier obtained by the method for the present invention, the especially preferred embodiment in carrier of the present invention
Obtained carrier loaded silver catalyst, and when preparing ethylene oxide for being catalyzed ethylene, there is excellent activity and selection
Property.
Therefore, another aspect of the invention provides a kind of silver catalyst as used in ethylene production ethylene oxide,
The catalyst includes porous alumina carrier of the invention, and the silver for the catalytically effective amount being deposited on the alumina support,
The alkali metal of optional catalysed promoted amount, the alkaline-earth metal of optional catalysed promoted amount, the rhenium of optional catalysed promoted amount, and
The collaboration auxiliary agent of optional rhenium.
In silver catalyst of the invention, silver be dispersed on the surface of porous alumina carrier and hole in, in the present invention
In one preferred embodiment of silver catalyst, the total weight based on silver catalyst, the content of the silver based on the element is 1-
40wt%.
In the preferred embodiment of silver catalyst of the present invention, in silver catalyst, the alkali metal is based on the element
Content is 5-2000ppm, which can be selected from one of Li, Na, K, Rb and Cs or a variety of, preferably in Cs, Li and K
At least one, most preferably Cs.
In a preferred embodiment of silver catalyst of the present invention, the total weight based on silver catalyst, in silver catalyst
The alkaline earth metal content (not including the alkaline-earth metal in carrier) of catalyst promoting amount in terms of alkali earth metal is 5-
2000ppm, the alkaline-earth metal can be selected from one of Mg, Ca, Sr and Ba or a variety of, preferably Sr and/or Ba.
In a preferred embodiment of silver catalyst of the present invention, the total weight based on silver catalyst, in silver catalyst
Rhenium content in terms of rhenium element is 5-1500ppm.If if using rhenium and its collaboration auxiliary agent, the total weight based on silver catalyst,
In silver catalyst the content of the collaboration auxiliary agent of rhenium based on the element be 5-1000ppm, the collaboration auxiliary element of the rhenium can be chromium,
One of molybdenum, tungsten and boron are a variety of.
Silver catalyst carrier of the invention uses the carrier of support preparation method provided by the present invention preparation.Silver catalysis
Agent can be prepared in the usual way, for example, by with the solution of Ag-containing compound and organic amine a kind of impregnate above-mentioned alumina support come
Preparation.If if use, alkali metal, alkaline-earth metal, the collaboration auxiliary agent of rhenium and rhenium can be each independently in load silver
Before, load silver while or load silver after be carried on porous alumina carrier of the invention, preferably load silver while
Load.
In one embodiment of the invention, the preparation method of silver catalyst of the present invention includes the following steps：
1) with containing sufficient amount silver compound, organic amine, optional alkali metal promoter, optional base earth metal promoter, appoint
The solution of the collaboration auxiliary agent of the rhenium auxiliary agent and optional rhenium of choosing impregnates porous alumina carrier of the invention；
2) leaching maceration extract；With
3) step 2) resulting vehicle is activated in air or inert gas, the silver catalyst is made.
In order to prepare silver catalyst of the invention, silver compound used can be to be urged suitable for preparation ethylene oxide production with silver
Any silver compound of agent.Present invention preferably uses silver oxide, silver nitrate and/or silver oxalates.
In order to prepare catalyst of the invention, organic amine compound used can be for suitable for preparation ethylene oxide production silver
Any organic amine compound of catalyst, as long as the organic amine compound can form argent-amine complex with silver compound.
For the purpose of the present invention, it is preferable to use or mixtures thereof pyridine, butylamine, ethylenediamine, 1,3- propane diamine, ethanol amine, such as ethylenediamine
With the mixture of ethanol amine.
In order to prepare catalyst of the invention, the alkali metal promoter optionally employed can be the change of lithium, sodium, potassium, rubidium or caesium
It closes or mixtures thereof object (such as nitrate, sulfate and hydroxide), preferred as alkali auxiliary agent is the chemical combination selected from lithium, potassium and caesium
One of object is a variety of, including but not limited at least one of cesium nitrate, lithium nitrate and potassium hydroxide.
In order to prepare catalyst of the invention, the base earth metal promoter optionally employed can be the chemical combination of magnesium, calcium, strontium and barium
One of object is a variety of, one of such as oxide, oxalates, sulfate, acetate and nitrate of the element or more
Kind, the preferably compound of the compound of barium and/or strontium, such as barium acetate and/or strontium acetate.
In order to prepare catalyst of the invention, the rhenium auxiliary agent optionally employed can be the oxide, perrhenic acid, perrhenic acid of rhenium
Or mixtures thereof salt, preferred at least one in perrhenic acid and/or perrhenate, such as perrhenic acid, perrhenic acid caesium and ammonium perrhenate
Kind.In addition to silver compound, organic amine, optional alkali metal promoter, optional base earth metal promoter and optional in dipping solution
Other than rhenium auxiliary agent, the collaboration auxiliary agent of rhenium auxiliary agent can also be added, be further improved gained silver catalyst activity, selectivity with
And stability.The collaboration auxiliary agent of rhenium auxiliary agent in the present invention can be selected from one of chromium, molybdenum, tungsten and boron compound or more
Kind.
It in the impregnation step, is the uniform abundant load for guaranteeing silver, carrier preferably vacuumizes in advance.
After porous alumina carrier impregnates argentiferous maceration extract, leaching maceration extract, then in air or inert gas
Carrier in step 3) through impregnating is activated.For this purpose, can be by the carrier through impregnating at 180-700 DEG C, preferably 200-500
DEG C moving air or inert gas such as nitrogen, argon gas air-flow in activate, activation time typically at least 2 minutes, such as 2-120
Minute, preferably 2-60 minutes.To guarantee that catalyst activity with higher, the activation temperature should not be greater than 500 DEG C.
In a preferred embodiment for preparing silver catalyst of the present invention, make the aqueous solution and ammonium oxalate of silver nitrate first
Or oxalic acid aqueous solution reaction, silver oxalate precipitate is precipitated, after filtering, is washed with deionized, up to no nitrate ion, through drying
Afterwards, silver oxalate is dissolved in the aqueous solution of or mixtures thereof organic amine such as pyridine, butylamine, ethylenediamine, 1,3- propane diamine, ethanol amine
In, each auxiliary agent is added, is made into dipping solution；Then gained dipping solution is used to impregnate this under conditions of vacuum degree is less than 10mmHg
The porous alumina carrier of invention 10-60 minutes, drains, in air or inert gas within the temperature range of 200-500 DEG C
Holding 2-120 minutes, preferably 2-60 minutes, to be activated.Silver nitrate can also be replaced with silver oxide, silver oxalate can not also analyse
Filter is directly complexed with organic amine, then impregnated carrier.
The fourth aspect of the present invention provides above-mentioned alumina support and/or silver catalyst and produces alkylene oxide in alkene epoxidation
Application in hydrocarbon preferably produces the application in ethylene oxide or epoxidation of propylene production propylene oxide in ethylene epoxidizing, especially
It is preferred that the application in ethylene epoxidizing production ethylene oxide.
Herein, " optional " referring to may include that can also not include, such as optional alkali metal promoter refers to described
In catalyst alkali metal promoter can also be free of with alkali metal containing auxiliary agent.
In the present invention, unless expressly stated otherwise, all contents as unit of ppm are content by weight.
To keep the present invention easier to understand, below in conjunction with embodiment, present invention be described in more detail, these implementations
Example only serves illustrative, is not intended to limit application range of the invention.
In following embodiment, various silver catalysts of the invention test its activity with laboratory microreactor evaluating apparatus
And selectivity.Reactor used in microreactor evaluating apparatus is the stainless steel reaction pipe of internal diameter 4mm, and reaction tube, which is placed in, to be added
In hot jacket.The admission space of catalyst is 1ml, and there is inert filler in lower part, catalyst bed is made to be located at the flat-temperature zone of heating mantle.
Shown in the determination condition following table for the activity and selectivity that the present invention uses.
Table 1
METHOD FOR CONTINUOUS DETERMINATION reactor inlet and exit gas composition after stably reaching above-mentioned reaction condition.Measurement result carries out
Selectivity is calculated as follows after volume contraction correction：
Selectivity
Wherein, EO is reactor outlet gas and inlet gas ethylene oxide concentration difference, CO2It is reactor outlet gas and import
Gas concentration lwevel is poor in gas, takes test result of the average of 10 groups or more test datas as the same day.
Below with reference to embodiment and comparative example, the invention will be further described.
Carrier comparative example 1
By three water A1 of 50-500 purpose2O3400g crosses the one water A1 of vacation of 200 meshes2O3100g is put into blender and mixes
It closes uniformly, is transferred in kneader, be added 120 milliliters of 20wt% aqueous solution of nitric acid, be kneaded into extrudable molding paste.It squeezes out
It is shaped to the single hole column of outer diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, it is 2 hours dry at 80-120 DEG C, make free contain
Water is reduced to 10 weight % hereinafter, obtaining green compact.Then it puts the green body into electric furnace, is increased to 1300 DEG C from room temperature, and
Constant temperature 2 hours under the high temperature obtain white α-A12O3Sample, referred to as comparative example carrier DS1.
Carrier comparative example 2
By three water A1 of 50-500 purpose2O3400g crosses the one water A1 of vacation of 200 meshes2O3100g, petroleum coke 20g, fluorination
Ammonium 10g, BaSO41g, SiO21g, ZrO21g is put into blender and is uniformly mixed, and is transferred in kneader, and 20wt% nitric acid is added
120 milliliters of aqueous solution, it is kneaded into extrudable molding paste.Extrusion molding is outer diameter 8.0mm, long 6.0mm, internal diameter 1.0mm
Single hole column so that free water content is reduced to 10 weight % hereinafter, obtaining green compact dry 2 hours at 80-120 DEG C.So
After put the green body into electric furnace, be increased to 1300 DEG C from room temperature, and constant temperature 2 hours at such high temperatures, obtain white α-A12O3Sample
Product, referred to as comparative example carrier DS2.
Carrier embodiment 1
By three water A1 of 50-500 purpose2O3400g crosses the one water A1 of vacation of 200 meshes2O3100g, polyvinyl alcohol (PVA-
124) 20g is put into blender and is uniformly mixed, is transferred in kneader, is added 120 milliliters of 20wt% aqueous solution of nitric acid, is kneaded into
Extrudable molding paste.Extrusion molding is the single hole column of outer diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, in 80-120
It is 2 hours dry at DEG C, so that free water content is reduced to 10 weight % hereinafter, obtaining green compact.Then it puts the green body into electric furnace, from
Room temperature is increased to 1300 DEG C, and constant temperature 2 hours at such high temperatures, obtains white α-A12O3Sample, referred to as invention carrier S 1, as
Silver catalyst carrier of the invention uses.
Carrier embodiment 2
By three water A1 of 50-500 purpose2O3400g crosses the one water A1 of vacation of 200 meshes2O3100g, polyacrylamide 20g,
Be put into blender be uniformly mixed, be transferred in kneader, be added 120 milliliters of 20wt% aqueous solution of nitric acid, be kneaded into it is extrudable at
The paste of type.Extrusion molding is the single hole column of outer diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, dry at 80-120 DEG C
2 hours, free water content is made to be reduced to 10 weight % hereinafter, obtaining green compact.Then it puts the green body into electric furnace, is increased from room temperature
To 1300 DEG C, and constant temperature 2 hours at such high temperatures, obtain white α-A12O3Sample, referred to as invention carrier S 2, as of the invention
Silver catalyst carrier uses.
Carrier embodiment 3
18g deionized water is added in 2g polyvinyl alcohol (PVA-124), heats and stirs completely soluble to polyvinyl alcohol
Middle formation colloidal sol (gel).Then by three water A1 of 50-500 purpose2O3400g crosses the one water A1 of vacation of 200 meshes2O3100g, stone
Oil coke 20g, ammonium fluoride 10g, BaSO41g, SiO21g, ZrO21g and above-mentioned polyvinyl alcohol colloidal sol (gel) are put into togerther mixing
It is uniformly mixed, is transferred in kneader in device, be added 100 milliliters of 24wt% aqueous solution of nitric acid, be kneaded into extrudable molding paste
Object.Extrusion molding is the single hole column of outer diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, 2 hours dry at 80-120 DEG C, is made
Free water content is reduced to 10 weight % hereinafter, obtaining green compact.Then it puts the green body into electric furnace, is increased to 1300 from room temperature
DEG C, and constant temperature 2 hours at such high temperatures, obtain white α-A12O3Sample, referred to as invention carrier S 3, as silver catalysis of the invention
Agent carrier uses.
Carrier embodiment 4
19.4g deionized water is first added in 0.6g polyvinyl alcohol (PVA-124), heats and stirs complete to polyvinyl alcohol
Formation colloidal sol (gel) soluble in water.Then by three water A1 of 50-500 purpose2O3400g crosses the one water A1 of vacation of 200 meshes2O3
100g is put into blender and is uniformly mixed, be transferred in kneader with above-mentioned polyvinyl alcohol colloidal sol (gel), and 24wt% nitre is added
100 milliliters of aqueous acid, it is kneaded into extrudable molding paste.Extrusion molding is outer diameter 8.0mm, long 6.0mm, internal diameter
The single hole column of 1.0mm, it is 2 hours dry at 80-120 DEG C, so that free water content is reduced to 10 weight % hereinafter, being given birth to
Base.Then it puts the green body into electric furnace, is increased to 1300 DEG C from room temperature, and constant temperature 2 hours at such high temperatures, obtain white α-
A12O3Sample, referred to as invention carrier S 4, use as silver catalyst carrier of the invention.
Carrier embodiment 5
By three water A1 of 50-500 purpose2O3400g crosses the one water A1 of vacation of 200 meshes2O3100g, polyvinyl alcohol (PVA-
124) 70g is put into blender and is uniformly mixed, is transferred in kneader, is added 120 milliliters of 20wt% aqueous solution of nitric acid, is kneaded into
Extrudable molding paste.Extrusion molding is the single hole column of outer diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, in 80-120
It is 2 hours dry at DEG C, so that free water content is reduced to 10 weight % hereinafter, obtaining green compact.Then it puts the green body into electric furnace, from
Room temperature is increased to 1300 DEG C, and constant temperature 2 hours at such high temperatures, obtains white α-A12O3Sample, referred to as invention carrier S 5, as
Silver catalyst carrier of the invention uses.
Carrier embodiment 6
Porous alumina carrier is prepared according to the method for carrier embodiment 1, unlike, polyethylene is replaced with vaseline
Alcohol.Obtain white α-A12O3Sample, referred to as invention carrier S 6.
Carrier embodiment 7
Porous alumina carrier is prepared according to the method for carrier embodiment 1, unlike, polyethylene is replaced with polyacrylic acid
Alcohol.Obtain white α-A12O3Sample, referred to as invention carrier S 7.
Carrier embodiment 8
Porous alumina carrier is prepared according to the method for carrier embodiment 1, unlike, poly- second is replaced with polyacrylate
Enol.Obtain white α-A12O3Sample, referred to as invention carrier S 8.
Carrier embodiment 9
Porous alumina carrier is prepared according to the method for carrier embodiment 1, unlike, it is replaced with polyvinylpyrrolidone
Polyvinyl alcohol.Obtain white α-A12O3Sample, referred to as invention carrier S 9.
Carrier embodiment 10
Porous alumina carrier is prepared according to the method for carrier embodiment 1, unlike, polyethylene is replaced with polyurethane
Alcohol.Obtain white α-A12O3Sample, referred to as invention carrier S 10.
Carrier embodiment 11
Porous alumina carrier is prepared according to the method for carrier embodiment 1, unlike, poly- second is replaced with polyethylene glycol oxide
Enol.Obtain white α-A12O3Sample, referred to as invention carrier S 11.
Carrier embodiment 12
Porous alumina carrier is prepared according to the method for carrier embodiment 1, unlike, it is replaced with modified paraffin resin poly-
Vinyl alcohol.Obtain white α-A12O3Sample, referred to as invention carrier S 12.
Carrier embodiment 13
Porous alumina carrier is prepared according to the method for carrier embodiment 1, unlike, polyethylene is replaced with carbomer
Alcohol.Obtain white α-A12O3Sample, referred to as invention carrier S 13.
Carrier embodiment 14
Porous alumina carrier is prepared according to the method for carrier embodiment 1, unlike, polyethylene is replaced with modified polyurea
Alcohol.Obtain white α-A12O3Sample, referred to as invention carrier S 14.
Carrier embodiment 15
Porous alumina carrier is prepared according to the method for carrier embodiment 1, unlike, it is replaced with low-molecular polyethylene wax
Polyvinyl alcohol.Obtain white α-A12O3Sample, referred to as invention carrier S 15.
It is detected through XRD, the α phase-A1 in above-mentioned carrier2O3Content is more than 90%.Carrier comparison to above-mentioned all preparations
Example measures its crushing strength, water absorption rate, specific surface area and Kong Rong with embodiment, is as a result listed in the table below in 2.In the present invention, it carries
The crushing strength of body refers to side crush intensity, is measured by intensity of pressure instrument；Specific surface area uses nitrogen physisorption BET method
Measurement；Water absorption rate is measured by densimetry；Kong Rong is using pressure mercury method measurement.
Table 2
| Number | Crushing strength (N) | Water absorption rate (%) | Specific surface area (m2/g) | Kong Rong (ml/g) |
| DS1 | 111 | 49 | 0.91 | 0.50 |
| DS2 | 134 | 50 | 1.13 | 0.51 |
| S1 | 97 | 52 | 1.34 | 0.52 |
| S2 | 88 | 52 | 1.30 | 0.52 |
| S3 | 62 | 56 | 1.57 | 0.55 |
| S4 | 80 | 54 | 1.42 | 0.53 |
| S5 | 74 | 56 | 1.61 | 0.55 |
| S6 | 105 | 51 | 1.28 | 0.52 |
| S7 | 88 | 52 | 1.33 | 0.53 |
| S8 | 92 | 52 | 1.36 | 0.52 |
| S9 | 66 | 54 | 1.55 | 0.54 |
| S10 | 79 | 53 | 1.47 | 0.53 |
| S11 | 94 | 52 | 1.30 | 0.52 |
| S12 | 71 | 54 | 1.31 | 0.53 |
| S13 | 84 | 53 | 1.26 | 0.54 |
| S14 | 65 | 53 | 1.42 | 0.52 |
| S15 | 77 | 52 | 1.34 | 0.53 |
As can be seen from Table 2, catalyst carrier made from embodiment 1-15 has equal or higher compared with the carrier of comparative example
Water absorption rate, bigger specific surface area and Kong Rong.
The preparation of catalyst impregnating solution
175g ethylenediamine, 70g ethanol amine and 200g deionized water are added in the glass flask with stirring, is mixed
Liquid.Silver oxalate is slowly added into gained mixed liquor under stirring, temperature is maintained at 10-25 DEG C, dissolves silver oxalate all, oxalic acid
The additional amount of silver makes 24 weight % of argentiferous in final maceration extract obtained.Add 2.5g cesium nitrate, 0.5g strontium acetate and 2.25g high
Rehenic acid ammonium, then plus deionized water so that solution gross mass is reached 1000g, maceration extract is made, for use.
COMPARATIVE CATALYST EXAMPLE 1~2
Comparative example carrier DS1 and each 40g of comparative example carrier DS2 are taken, is respectively put into the container that can be vacuumized.It is evacuated to
Vacuum degree is lower than 10mmHg, is put into the above catalyst impregnating solution thereto, submerges carrier, is kept for 30 minutes.Leaching later removes
Extra maceration extract.Carrier after dipping is heated 5 minutes in 350 DEG C of air stream, it is cooling, that is, silver catalyst is made, it is right
Ratio carrier DS1 load is known as comparative catalyst DC1, and comparative example carrier DS2 load is known as comparative catalyst DC2.
CATALYST EXAMPLE 1~15
It is identical with the preparation method of COMPARATIVE CATALYST EXAMPLE, invention carrier S each 40g of 1-S15 is taken respectively, is then successively put respectively
Enter in the container that can be vacuumized.Vacuum degree is evacuated to lower than 10mmHg, is put into the above catalyst impregnating solution thereto, submergence carries
Body is kept for 30 minutes.Leaching later removes extra maceration extract.Carrier after dipping is heated 5 points in 350 DEG C of air stream
Clock, it is cooling, that is, silver catalyst is made, invention carrier S 1-S15 load is referred to as catalyst C1-C15.
Using being measured under microreactor evaluating apparatus above " measurement of catalyst performance " part process conditions
The activity and selectivity of above-mentioned comparative catalyst and catalyst prod of the invention, test result are listed in table 3.
Table 3
| Catalyst | * reaction temperature (DEG C) | * selectivity (%) |
| Comparative catalyst DC1 | 244 | 83.1 |
| Comparative catalyst DC2 | 235 | 82.9 |
| Catalyst C1 | 229 | 84.1 |
| Catalyst C2 | 234 | 83.7 |
| Catalyst C3 | 224 | 84.1 |
| Catalyst C4 | 223 | 84.0 |
| Catalyst C5 | 231 | 84.3 |
| Catalyst C6 | 225 | 83.8 |
| Catalyst C7 | 229 | 84.2 |
| Catalyst C8 | 228 | 83.9 |
| Catalyst C9 | 233 | 84.7 |
| Catalyst C10 | 231 | 84.0 |
| Catalyst C11 | 230 | 83.9 |
| Catalyst C12 | 229 | 83.8 |
| Catalyst C13 | 230 | 84.1 |
| Catalyst C14 | 233 | 84.2 |
| Catalyst C15 | 228 | 83.9 |
[note]：* reaction temperature and * selective presentation EO yield are accumulative up to 300T/m in table 33When reaction temperature and average
Selectivity.
As can be seen from Table 3, using the reaction of the carrier loaded silver catalyst C1-C15 of the method provided by the present invention preparation
Temperature is below the reaction temperature of comparative catalyst, illustrates that the activity of catalyst of the present invention is higher than comparative catalyst, also, be catalyzed
The selectivity of agent C1-C15 is above the selectivity of comparative catalyst, and therefore, the carrier property prepared with method of the invention is excellent
It is good, it is particularly suitable for use as the silver catalyst carrier of catalysis ethylene epoxidizing production ethylene oxide, by the method provided by the present invention system
Silver catalyst made of standby carrier, activity is higher, and selectivity is higher.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.
Claims (10)
1. a kind of method for preparing porous alumina carrier, which is characterized in that this method comprises the following steps：
Step A forms the mixture comprising following component：
I, hydrated alumina；
Ii, based on component i weight be 0.05-30wt%, the synthesis high score subclass thickener of preferably 0.1-15wt%；
Iii, the binder for being 15~60wt% based on component i weight；
Iv, the water for being 0-30wt% based on component i weight；And
V, the pore creating material for being 0-30wt% based on component i weight；
Vi, the mineralizer for being 0-5wt% based on component i weight；
Vii, the auxiliary agent for being 0-5wt% based on component i weight, the auxiliary agent are in base earth metal promoter, silicon additive and zirconium auxiliary agent
At least one；
Mixture obtained in step A is formed, dried and is roasted by step B.
2. according to the method described in claim 1, wherein, the synthesis high score subclass thickener is polyvinyl alcohol, polyacrylamide
Amine, vaseline, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyurethane, polyethylene glycol oxide, modified paraffin resin,
One of carbomer, modified polyurea and low-molecular polyethylene wax are a variety of.
3. according to the method described in claim 1, wherein, the hydrated alumina includes at least one water A1 of vacation2O3, preferably
Three water A12O3With one water A1 of vacation2O3, and the three water A12O3With one water A1 of vacation2O3Weight ratio be 0.5~16:1, preferably 1~
6:1。
4. according to the method described in claim 1, wherein, the binder is inorganic acid, preferably nitric acid.
5. according to the method described in claim 1, wherein, the pore creating material selected from can in the carbonaceous material of after-flame at least one
Kind, preferably at least one of petroleum coke, carbon dust and graphite；The mineralizer is selected from hydrogen fluoride, aluminum fluoride, ammonium fluoride and ice crystal
At least one of stone；The base earth metal promoter is selected from oxide, the sulfuric acid of magnesium, calcium, strontium, barium and magnesium, calcium, strontium and barium
At least one of salt, acetate, nitrate, carbonate and oxalates；The silicon additive is selected from the oxidation of elemental silicon, silicon
At least one of object, silicate and organosilicon；The zirconium auxiliary agent be selected from simple substance zirconium, the oxide of zirconium, sulfate, acetate,
At least one of nitrate, carbonate and oxalates.
6. according to the method described in claim 1, wherein, in step B, dry condition includes：Temperature is 60 DEG C -200 DEG C, when
Between be 1-24 hours；The condition of roasting includes：Temperature be 1000 DEG C -1500 DEG C, preferably 1100 DEG C -1400 DEG C, time 2-
24 hours.
7. porous alumina carrier made from the method as described in any one of claim 1-6.
8. a kind of silver catalyst of catalysis ethylene production ethylene oxide, which is characterized in that the silver catalyst is wanted comprising right
The silver of the catalytically effective amount of porous alumina carrier described in asking 7 and load on this carrier and optional catalysed promoted amount
Alkali metal, the collaboration of the alkaline-earth metal of optional catalysed promoted amount, the rhenium and optional rhenium of optional catalysed promoted amount helps
Agent.
9. silver catalyst according to claim 8, wherein total weight based on silver catalyst, the silver is based on the element
Content is 1~40wt%；The content of the alkali metal based on the element is 5~2000ppm；The alkaline earth gold of the catalyst promoting amount
The content belonged to based on the element is 5-2000ppm；The content of the rhenium based on the element is 5~1500ppm, the collaboration auxiliary agent of the rhenium
Content based on the element is 5~1000ppm.
10. silver catalyst described in porous alumina carrier as claimed in claim 7 and/or claim 8 or 9 is in olefin epoxide
Metaplasia produces the application in epoxyalkane, preferably produces in ethylene oxide or epoxidation of propylene production propylene oxide in ethylene epoxidizing
Application, particularly preferably ethylene epoxidizing production ethylene oxide in application.
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| CN111375394A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Alumina carrier and preparation method and application thereof |
| CN111375393A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Alumina carrier and preparation method and application thereof |
| CN111517346A (en) * | 2020-03-16 | 2020-08-11 | 河北铭万精细化工有限公司 | Preparation method of high-purity nano aluminum oxide |
| CN112121780A (en) * | 2019-06-25 | 2020-12-25 | 中国石油化工股份有限公司 | Alpha-alumina carrier and preparation method thereof, silver catalyst and application |
| CN114433043A (en) * | 2020-11-05 | 2022-05-06 | 中国石油化工股份有限公司 | Alumina carrier and preparation method thereof, silver catalyst and application |
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