CN105435792A - Alumina carrier, preparation method and silver catalyst - Google Patents

Alumina carrier, preparation method and silver catalyst Download PDF

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Publication number
CN105435792A
CN105435792A CN201410393211.6A CN201410393211A CN105435792A CN 105435792 A CN105435792 A CN 105435792A CN 201410393211 A CN201410393211 A CN 201410393211A CN 105435792 A CN105435792 A CN 105435792A
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nickel
carrier
silicon
alpha
water
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CN105435792B (en
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李贤丰
王辉
蒋军
孙欣欣
任冬梅
林强
高立新
李金兵
陈建设
张志祥
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • 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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Abstract

The present invention discloses an alpha-alumina carrier, which comprises silicon element and nickel element, and the nickel element and the silicon element are uniformly distributed in the carrier. The mass ratio of nickel element to silicon element in the carrier is 0.1: 1-20: 1. Widespread and extensive researches on the field of a silver catalyst and the alumina catalyst carrier of the silver catalyst are performed, by creative addition (bulk phase addition) of the nickel element and the silicon element in the process of preparation of the alumina carrier for the silver catalyst, the obtained carrier contains the silicon element and the nickel element, the nickel element and the silicon element are uniformly distributed in the carrier, the specific surface and the strength of the carrier are improved, and when the silver catalyst prepared by the carrier is used in the preparation of ethylene oxide by ethylene oxidation, the silver catalyst has lower reaction temperature (higher reactivity), and has high selectivity.

Description

Alumina support, preparation method and silver catalyst
Technical field
The present invention relates to a kind of carrier for silver catalyst, preparation method and application thereof.More particularly, the present invention relates to a kind of alumina support for the preparation of ethylene production oxirane silver catalyst and preparation method thereof.The invention still further relates to the catalyst and application thereof that comprise above-mentioned alumina support.
Background technology
Ethene is oxidized and mainly generates oxirane under silver catalyst effect, side reaction occurs simultaneously and generates carbon dioxide and water etc., and wherein active, selective is the main performance index of silver catalyst.So-called activity refers to the reaction temperature that process for ethylene oxide production reaches required when necessarily reacting load.Reaction temperature is lower, and the activity of catalyst is higher.What is called is selective refers to that in reaction, ethylene conversion becomes the ratio of the molal quantity of oxirane and the overall reaction molal quantity of ethene.
Producing at ethylene in the process of oxirane uses the silver catalyst of high activity, high selectivity greatly to increase economic efficiency, and therefore manufactures high activity, the silver catalyst of high selectivity is the Main way that silver catalyst is studied.
In prior art the preparation method of silver catalyst 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 carrier.In recent years, bibliographical information is had about some novel silver catalyst carrier technologies of preparing.
Summary of the invention
Therefore, the object of this invention is to provide a kind of alumina support, and the method for this alumina support of preparation.The silver catalyst be made up of this carrier or the method gained carrier is produced in the process of oxirane at ethylene and is demonstrated good activity (namely having lower reaction temperature) and good selective.
Another object of the present invention is to provide a kind of silver catalyst prepared by above-mentioned carrier.
Another object of the present invention is to provide the application of above-mentioned silver catalyst in ethylene production oxirane.
According to an aspect of the present invention, provide a kind of alpha-alumina supports, it comprises nickel element and element silicon, and described nickel element and element silicon are uniformly distributed in the carrier.
In above-mentioned carrier, the mass ratio of described nickel element and element silicon is 0.1:1-20:1.In a specific embodiment, the mass ratio of described nickel element and element silicon is 0.1:1-10:1, preferred 0.5:1-5:1.
In above-mentioned carrier, described alpha-alumina supports have in following characteristics one or more:
1) specific area is 0.7-2.0m 2/ g,
2) pore volume is 0.35-0.85ml/g,
3) water absorption rate >=30%,
4) crushing strength is 60-200N/ grain,
5) α-A1 2o 3content is 70 % by weight or higher, based on the gross weight of described carrier.
According to carrier provided by the invention, described nickel element and element silicon be body Entropy density deviation in the carrier, is also namely uniformly distributed in the carrier, has higher specific area, lower water absorption rate and higher crushing strength.
According to another aspect of the present invention, provide a kind of method preparing above-mentioned alpha-alumina supports, comprise the steps:
I) preparation comprises the solid mixture of following component: a) 50 order-500 order three water α-A1 2o 3; B) the false water A1 of>=200 objects 2o 3; C) optionally contain or do not contain heavy alkaline earth metal compound; D) fluoride-mineralization agent; E) in element silicon and nickel element, based on the nickel of the 0.01-3.0wt% of solid mixture gross weight and/or nickel compound containing and silicon and/or silicon-containing compound;
II) in above-mentioned solid mixture, add binding agent and water, then mediate even and shaping, obtain formed body; And
III) drying steps II) in the formed body that obtains, then roasting obtains alpha-alumina supports.
In the above-mentioned methods, based on the gross weight of described solid mixture, component amount a) is 45-90wt%, is preferably 65-85wt%; Components b) amount be 5-50wt%, be preferably 11-32wt%; Amount of component b) amount be 0-1.5wt%, be preferably 0.1-1.0wt%; Component d) amount be 0.1-3.0wt%, be preferably 1.0-2.0wt%, with component e) amount be element in 0.01-1.5wt% (equally in component e)), the addition of described binding agent is 15-60wt%, is preferably 15-20wt%.
In the above-mentioned methods, the mass ratio of described nickel and/or nickel compound containing and silicon and/or siliceous compound counts 0.1:1-20:1 with nickel element and element silicon.In a specific embodiment, the mass ratio of described nickel and/nickel compound containing and silicon and/siliceous compound counts 0.1:1-10:1 with nickel element and element silicon, preferred 0.5:1-5:1.
In the method for the invention, described amount of component b) optionally contain or containing weighing alkaline earth metal compound, being also that said method includes containing or do not contain the technical scheme of amount of component b, also namely containing containing or do not contain the technical scheme weighing alkaline earth metal compound.
In the above-mentioned methods, described nickel compound containing, be selected from nickel monoxide, nickel sesquioxide, nickel hydroxide, nickelous sulfate, nickel chloride and nickel nitrate one or more, be preferably selected from nickel nitrate, nickel sesquioxide or its mixture; Described silicon-containing compound, be selected from sodium metasilicate, ethyl orthosilicate, nano-silicon, silica gel one or more, be preferably selected from ethyl orthosilicate, nano-silicon or its mixture.
For the purpose of the present invention, based on step I) in preparation mixture in all solids gross weight of dividing, the addition of nickel element and element silicon is generally 0.01-3.0 % by weight, such as, be 0.02-1.5 % by weight, be such as 0.03-1.0 % by weight, or be such as 0.04-0.7 % by weight.
In the above-mentioned methods, the consumption of described water in right amount, i.e. usual amounts in this area.Vacation one water A1 in binding agent, water and solid mixture 2o 3generate Alumina gel, each component be bonded together, becoming can the paste of extrusion molding.In a specific embodiment of said method, described binding agent is acid, as nitric acid, formic acid, acetic acid, propionic acid and hydrochloric acid etc.; Preferred nitric acid, more preferably the weight ratio of described nitric acid and water is 1:1.25-1:10.In a specific embodiment, the weight ratio of described nitric acid and water is 1:2-1:4.
In a specific embodiment of said method, described acid, water and a false water A1 2o 3partly or entirely replace with Alumina gel.When all replacing with Alumina gel, also namely described method comprises: by component a) 50 order-500 order three water α-A1 2o 3; C) optionally contain or do not contain heavy alkaline earth metal compound; D) fluoride-mineralization agent; E) in element silicon and nickel element, based on the nickel of the 0.01-3.0wt% of solid mixture gross weight and/or nickel compound containing and silicon and/or silicon-containing compound; And f) Alumina gel; Then said components kneading is even and shaping, obtains formed body; Dry described formed body, obtains alpha-alumina supports after roasting.The consumption of described Alumina gel can be the conventional amount used in this area, as in the aluminium oxide in Alumina gel, accounts for the 5-50wt% of component a), c), d), e) and f) total consumption, is preferably 11-32wt%.In like manner, when replacing for part, a false water A1 2o 3with in the Alumina gel of aluminium oxide, account for the 5-50wt% of component a), b), c), d), e) and f) total consumption, be preferably 11-32wt%.
In the above-mentioned methods, in order to prepare alpha-alumina supports of the present invention, need use three water α-A1 2o 3, namely component a).This three water α-A1 2o 3for graininess, require that granularity is 50 order-500 orders, such as 200 order-500 orders.Based on step I) in the gross weight of solid mixture, three water α-A1 2o 3consumption be generally 50-90 % by weight, be such as 65-80 % by weight, such as 73-77 % by weight.
In the above-mentioned methods, in order to prepare alpha-alumina supports of the present invention, also need to use a false water A1 2o 3, i.e. components b).This false water A1 2o 3for graininess, require that granularity is>=200 orders, such as>=250 orders, such as 200 order-400 orders.Based on step I) in the gross weight of solid mixture, as components b) vacation one water A1 2o 3consumption be generally 5-50 % by weight, be such as 10-20 % by weight, such as 14-16 % by weight.
In the above-mentioned methods, as component d) adding of fluoride-mineralization agent be transformation of crystal in order to accelerated oxidation aluminium.Described fluoride-mineralization agent is one or more in hydrogen fluoride, aluminum fluoride, ammonium fluoride, magnesium fluoride and ice crystal.Described heavy alkaline earth metal compound is one or more in the oxide of strontium and barium, sulfate, acetate, nitrate and oxalates, preferential oxidation barium, barium sulfate, barium nitrate, brium carbonate or its mixture.Based on step I) in the gross weight of solid mixture, the addition of heavy alkaline earth metal compound is 0-1.5 % by weight, such as 0.1-1.0 % by weight, such as 0.1-0.5 % by weight.
By Step II) mediate evenly, usually obtain paste.To the present invention advantageously, usually after first component a, b, c (if the words used), d and e being mixed, proceed in kneader, then add adhesive and water is mediated, evenly be kneaded into paste, being especially kneaded into can the paste of extrusion molding.After gained paste is shaping, especially after extrusion molding, obtain formed body.This formed body can be dried to moisture less than 10 % by weight, and baking temperature is 80-120 DEG C, and drying time controls at 1-24 hour according to moisture.The shape of gained formed body can be annular, spherical, cylindricality or porous column shape, or other shape.
In the above-mentioned methods, dried formed body is usually at the roasting temperature of 1000 DEG C-1500 DEG C, preferably 1000 DEG C-1400 DEG C, and roasting time is no less than 1 hour, is generally 2-24 hour, preferred 2-8 hour.Aluminium oxide is made substantially all to be converted into α-A1 by roasting 2o 3, such as more than 90% is converted into α-A1 2o 3, obtain described α-A1 2o 3carrier.
The alpha-alumina supports obtained according to said method, this carrier has following characteristics: specific area is 0.7-2.0m 2/ g, pore volume is 0.35-0.85ml/g, water absorption rate>=30%, and crushing strength is 60-200N/ grain.Preferably, α-A1 in this alpha-alumina supports 2o 3content is 70 % by weight or higher, based on the gross weight of this alpha-alumina supports.The mass ratio of the nisiloy element in described carrier is 0.1-20:1, is preferably 0.1-10:1, more preferably 0.5-5:1.
In the present invention, the specific area of carrier adopts nitrogen physisorption BET method to measure according to international test standards ISO-9277.U.S. Kang Ta company NOVA2000e type nitrogen physisorption instrument such as can be used to measure the specific area of carrier.
The pore volume of carrier adopts mercury injection method to measure.Such as, Merck & Co., Inc of U.S. AutoPore9510 type mercury injection apparatus can be used to measure the pore volume of carrier.
In carrier, the amount of alkaline earth metal compound can obtain by calculating or measure (as adopted x-ray fluorescence analysis).
The side pressure strength of carrier such as can adopt Dalian Chemical Research &. Design Inst. to produce DLII type intelligence detector for strength of particles, and random selecting 30 support samples, average after measuring radial crushing strength and obtain.
Water absorption rate refers to the volume of the carrier saturated adsorption water of unit mass, and unit is ml/g.Assay method is as follows, first a certain amount of carrier (assuming that its quality is m1) is taken, boil 1h in boiling water after, carrier is taken out to be erected on the moderate wet gauze of water content and remove the unnecessary moisture of carrier surface, finally weigh the quality (being assumed to m2) of the carrier after adsorbed water, calculate the water absorption rate of carrier as follows.
Water absorption rate=(m2-m1)/m1/ ρ water
Wherein ρ waterthe density of water under mensuration temperature, atmospheric pressure.
Nickel/silicon (Ni/Si) mass ratio in carrier obtains by calculating or measure (as adopted x-ray fluorescence analysis).
The alpha-alumina supports that support according to the present invention preparation method obtains can in the common form in this area, such as annular, spherical, cylindricality or porous column shape, or other shape.
In a specific embodiment, the alpha-alumina supports in the present invention is the alpha-alumina supports that ethylene epoxidizing produces oxirane silver catalyst.
According to another aspect of the present invention, provide a kind of silver catalyst used by ethylene production oxirane, comprising:
The alpha-alumina supports that above-mentioned alpha-alumina supports or said method prepare;
In silver, content is the silver compound of 1 ~ 40wt%, preferred 5-25wt%;
With alkali metal, content is 0-2000ppm, preferred 5-2000ppm, more preferably the alkali metal promoter of 5-1500ppm;
In alkaline-earth metal, content is the base earth metal promoter of 0-10000ppm, preferred 0-8000ppm;
In rhenium atom, content is 0-2000ppm, preferred 10-2000ppm, more preferably the rhenium auxiliary agent of 100-1000ppm.
In a specific embodiment, the method preparation of above-mentioned silver catalyst by comprising the following steps:
1) by alpha-alumina supports prepared by the above-mentioned alpha-alumina supports of the solution impregnation of the coassist agent containing the silver compound of q.s, organic amine, optional alkali metal promoter, optional base earth metal promoter and optional rhenium auxiliary agent and optional rhenium auxiliary agent or dipping said method;
2) leaching maceration extract; With
Optionally 3), as required, to step 2 in oxygen-containing gas) gained carrier activates, and makes described silver catalyst.
In the present invention, described silver compound is silver oxide, silver nitrate and/or silver oxalate, and the consumption of silver compound should make silver in the content of atom in described silver catalyst for 1-40%, and preferred 5-25%, based on the gross weight of described silver catalyst.
In the present invention, described alkali metal promoter be selected from the compound of lithium, sodium, potassium, rubidium and caesium one or more, preferably sulfuric acid caesium, cesium nitrate, lithium nitrate and/or potassium hydroxide, particularly preferably cesium nitrate, cesium sulfate, and the addition of alkali metal promoter in maceration extract should make described alkali metal in the content of atom in described silver catalyst for 0-2000 weight ppm, preferred 5-2000 weight ppm, more preferably 5-1500 weight ppm, based on the gross weight of described silver catalyst.
In the present invention, described base earth metal promoter be selected from the compound of magnesium, calcium, strontium and barium one or more, be such as be selected from the oxide of magnesium, calcium, strontium and barium, oxalates, sulfate, acetate and nitrate one or more, and the addition of base earth metal promoter in maceration extract should make alkaline-earth metal in the total content of atom in described silver catalyst for 0-10000 weight ppm, preferred 0-8000 weight ppm, based on the gross weight of described silver catalyst.
In the present invention, described rhenium auxiliary agent be selected from the oxide of rhenium, perrhenic acid, perrhenic acid caesium and ammonium perrhenate one or more, be preferably ammonium perrhenate, and the addition of rhenium auxiliary agent in maceration extract should make rhenium auxiliary agent in the total content of atom in described silver catalyst for 0-2000 weight ppm, preferred 10-2000 weight ppm, more preferably 100-1000 weight ppm, based on the gross weight of described silver catalyst.When comprising rhenium auxiliary agent in dipping solution, the coassist agent of rhenium auxiliary agent can also be added in this maceration extract, to improve the activity of gained silver catalyst, selective and stability further.The coassist agent of the rhenium auxiliary agent in the present invention can be the compound of arbitrary transition metal in the periodic table of elements, or the mixture of several transistion metal compound, the oxyacid of preferred group vib and VIIB race element and salt thereof, such as wolframic acid, sodium tungstate, potassium tungstate, ammonium tungstate, wolframic acid caesium, molybdic acid, ammonium molybdate, ammonium metatungstate etc.The consumption of the coassist agent of rhenium auxiliary agent should make the content of the coassist agent metal of rhenium auxiliary agent in final catalyst be 0-1000 weight ppm, preferred 0-500 weight ppm by weight.
In the present invention, described organic amine is pyridine, butylamine, ethylenediamine, 1,3-propane diamine, monoethanolamine or its mixture, the mixture of preferred ethylenediamine and monoethanolamine.If no special instructions, the ppm in the present invention refers to weight ppm.
In order to carry out step 1) dipping, advantageously, with gained dipping solution lower than oxide impregnation alumina supporter under atmospheric pressure, oxide impregnation alumina supporter under the condition of 10mmHg is preferably less than in absolute pressure, dip time is generally 10-60 minute, afterwards leaching maceration extract, then in oxygen-containing gas to step 2) gained carrier activates, namely carry out step 3), make described silver catalyst.Step 3) activation be advantageously not more than at air or oxygen content in the nitrogen oxygen atmosphere of 21 volume % and carry out, activation temperature is generally 180-700 DEG C, preferred 200-500 DEG C, and soak time is generally 1-120 minute, preferred 2-60 minute.
According to another aspect of the present invention, additionally provide a kind of method of being produced oxirane by ethylene, described ethene carries out oxidation and generates oxirane under the effect of above-mentioned silver catalyst.According to provided by the invention carrier loaded after the silver catalyst that obtains to produce at ethylene in the process of oxirane and demonstrate good activity and selectivity.
These and other objects of the present invention, feature and advantage will become more clear after reading this description.
The present inventor has carried out research extensively and profoundly at silver catalyst and alumina support field thereof, creatively by adding nickel element and element silicon (namely body adds mutually) in the process preparing silver catalyst alumina support, containing element silicon and nickel element in obtained described carrier, described nickel element and element silicon are uniformly distributed in the carrier, specific surface and the intensity of gained carrier improve, the silver catalyst be made up of this carrier is when for preparing oxirane by ethylene, there is lower reaction temperature (having higher reactivity), and have higher selective.
Detailed description of the invention
The present invention is described further below in conjunction with specific embodiment, but scope of the present invention is not limited to these embodiments.
Alpha-alumina supports of the present invention is the alpha-alumina supports adopting nickel element and element silicon modification.This carrier can be used for ethylene and produces oxirane.In certain embodiments, in this carrier, nisiloy element mass ratio is 0.1:1-20:1.In certain embodiments, in this carrier, nisiloy element mass ratio is 0.5:1-1.5:1.In certain embodiments, in this carrier, nisiloy element mass ratio is 1.5:1-2.5:1.In certain embodiments, in this carrier, nisiloy element mass ratio is 2.5:1-3.5:1.In certain embodiments, in this carrier, nisiloy element mass ratio is 8.0:1-10.0:1.
the mensuration of catalyst performance
The various silver catalyst laboratories microreactor that relates in the present invention (following letter " micro-anti-") evaluating apparatus tests its initial activity and selective.The reactor that micro anti-evaluation device uses is the stainless steel tube of internal diameter 4mm, and reactor is placed in heating jacket.The admission space of catalyst is 1ml, and inert filler is arranged at bottom, makes beds be positioned at the flat-temperature zone of heating jacket.
The condition determination of the activity and selectivity that the present invention uses is as follows:
Reacting gas composition (mol%)
When stable reach above-mentioned reaction condition after METHOD FOR CONTINUOUS DETERMINATION reactor enter, exit gas composition.Measurement result calculates selective S after carrying out volume contraction correction as follows:
Wherein Δ EO be work off one's feeling vent one's spleen poor with inlet gas ethylene oxide concentration, Δ CO 2be work off one's feeling vent one's spleen poor with inlet gas gas concentration lwevel, get the result of the test of average as the same day of more than 10 groups test datas.
the preparation of carrier
embodiment 1 (contrast)
By 200 ~ 500 object three water α-A1 2o 3the false water A1 of 372g, 200 ~ 400 objects 2o 3112g, MgF 23g and Ba (NO 3) 2the solid mixture of 0.5g puts into blender mixing, then proceeds in kneader, adds dust technology (nitric acid: water=1:3, weight ratio) 90ml, and being kneaded into can the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, and dry 10h at 80 ~ 120 DEG C, makes free water content be reduced to below 10wt%, obtained shaping alpha-alumina supports green compact.Then these green compact are put into electric furnace, be elevated to 1400 DEG C through 30h from room temperature, constant temperature 2h, by obtained white α-A1 2o 3carrier called after Z-1, and measure its crushing strength, water absorption rate and specific area, the results are shown in Table 1.
embodiment 2 (contrast)
By 200 ~ 500 object three water α-A1 2o 3the false water A1 of 372g, 200 ~ 400 objects 2o 3112g, MgF 23g, Ba (NO 3) 20.5g and SiO 2the solid mixture of 0.51g puts into blender mixing, then proceeds in kneader, adds dust technology (nitric acid: water=1:3, weight ratio) 90ml, and being kneaded into can the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, and dry 10h at 80 ~ 120 DEG C, makes free water content be reduced to below 10wt%, obtained shaping alpha-alumina supports green compact.Then these green compact are put into electric furnace, be elevated to 1400 DEG C through 30h from room temperature, constant temperature 2h, by obtained white α-A1 2o 3carrier called after Z-2, and measure its crushing strength, water absorption rate and specific area, the results are shown in Table 1.
embodiment 3
By 200 ~ 500 object three water α-A1 2o 3the false water A1 of 372g, 200 ~ 400 objects 2o 3112g, MgF 23g, Ba (NO 3) 20.5g, Ni (NO 3) 2.6H 2o1.21g and SiO 2the solid mixture of 0.51g puts into blender mixing, then proceeds in kneader, adds dust technology (nitric acid: water=1:3, weight ratio) 90ml, and being kneaded into can the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, and dry 10h at 80 ~ 120 DEG C, makes free water content be reduced to below 10wt%, obtained shaping alpha-alumina supports green compact.Then these green compact are put into electric furnace, be elevated to 1400 DEG C through 30h from room temperature, constant temperature 2h, by obtained white α-A1 2o 3carrier called after Z-3, and measure its crushing strength, water absorption rate and specific area, the results are shown in Table 1.
embodiment 4
Step is with embodiment 3, and difference is, containing Ni (NO in described solid mixture 3) 2.6H 2o2.41g, by obtained white α-A1 2o 3carrier called after Z-4, and measure its crushing strength, water absorption rate and specific area, the results are shown in Table 1.
embodiment 5
Step is with embodiment 3, and difference is, containing Ni (NO in described solid mixture 3) 2.6H 2o3.62g, by obtained white α-A1 2o 3carrier called after Z-5, and measure its crushing strength, water absorption rate and specific area, the results are shown in Table 1.
embodiment 6
Step is with embodiment 3, and difference is, containing Ni (NO in described solid mixture 3) 2.6H 2o10.85g, by obtained white α-A1 2o 3carrier called after Z-6, and measure its crushing strength, water absorption rate and specific area, the results are shown in Table 1.
The physical data of table 1 carrier
Support samples Z-1 Z-2 Z-3 Z-4 Z-5 Z-6
Crushing strength (N/ grain) 48 106 94 129 55 52
Water absorption rate (%) 51.14 51.28 50.23 49.33 50.63 50.43
Specific area (rice 2/ gram) 0.752 1.06 1.435 1.392 1.445 1.208
Ni/Si (mass ratio) 0 0 1.0 2.0 3.1 9.0
As can be seen from Table 1, according to alumina support provided by the invention, its crushing strength improves, and water absorption rate reduces, and is conducive to the use of carrier.According to alumina support provided by the invention, its specific area improves, and is conducive to the dispersion of active metal.
the preparation of catalyst
Get 700g silver nitrate to be dissolved in 750ml deionized water, obtain solution.Get 325g ammonium oxalate to be dissolved in the deionized water of 250ml50 DEG C, obtain solution.Mix gained two kinds of solution with vigorous stirring, generate white silver oxalate precipitate.Aging 1 hour, filter, spend deionized water filter cake until without nitrate ion in filtrate, obtain silver oxalate paste filter cake.Filter cake containing metal silver about 60 % by weight, moisture about 15 % by weight.
In the glass flask that band stirs, add 300g ethylenediamine, 110g monoethanolamine and 375g deionized water, obtain mixed liquor.Under stirring, obtained silver oxalate paste is slowly added in mixed liquor, temperature remains between-5 DEG C to 10 DEG C, silver oxalate is all dissolved, then 2.37g cesium nitrate and 1.25g strontium sulfate is added, adding deionized water again makes solution gross mass reach 2000g, make maceration extract M stand-by, the silver content of described maceration extract M is 22 % by weight.
Get respectively support samples Z-1 to Z-6 that 100g embodiment 1-6 obtains put into can be different the container vacuumized.Absolute pressure is evacuated to lower than 10mmHg, puts into the above described maceration extract prepared respectively, submergence carrier, keeps 30 minutes.Then unnecessary solution is removed in leaching.Heated 5 minutes in the air stream of 350 DEG C by carrier after dipping, cooling, namely makes silver catalyst, respectively called after CZ-1, CZ-2, CZ-3 to CZ-6.The content of the silver in wherein from CZ-1 to CZ-6 and auxiliary agent (caesium and strontium) is substantially identical, and wherein silver content is 16.1wt%.
In above-mentioned maceration extract M, add the nickel nitrate of 1.21 grams, obtain nickeliferous maceration extract.The support samples Z-1 got in the embodiment 1 of 100g puts into the container that can vacuumize, and is evacuated to lower than 10mmHg by the absolute pressure in container, then adds the above-mentioned nickeliferous maceration extract prepared, submergence carrier, keeps 30 minutes.Then unnecessary solution is removed in leaching.Heated 5 minutes in the air stream of 350 DEG C by carrier after dipping, cooling, namely makes silver catalyst, called after CZ-7.In CZ-7 and CZ-1, the content of silver and auxiliary agent (caesium and strontium) is substantially identical.
Catalyst CZ-1, CZ-2, CZ-3, CZ-4, CZ-5, CZ-6 and CZ-7 of making are carried out separately use microreactor evaluating apparatus above " the mensuration of catalyst performance" measuring the activity and selectivity of each catalyst under the described process conditions of part, temperature when reaction proceeds to the 7th day and selective data are listed in table 2.
Table 2
As can be seen from Table 2, according to catalyst prepared by carrier provided by the invention, compare, under the optionally prerequisite that improve silver catalyst with the catalyst prepared with the carrier of nickel not siliceous in prior art, its reaction temperature reduces, and namely its reactivity significantly improves.The catalyst prepared with only siliceous carrier is compared, and under ensureing that catalyst has the prerequisite of comparatively low reaction temperatures (namely comparatively high reaction activity), its selective raising is remarkable.With surface impregnation, the catalyst of nickel is compared, under ensureing that catalyst has the prerequisite of more low reaction temperatures (namely comparatively high reaction activity), and its selective raising.
As can be seen from Table 2, the only catalyst (CZ-2 or CZ-7) of siliceous or surface impregnation nickel element, although it is compared with catalyst (CZ-1) prepared by the carrier of nickel with not siliceous in prior art, reaction temperature reduces, namely reactivity improves, but after adding silicon or surface impregnation nickel element, the selective of catalyst all have dropped.Then, according to the catalyst (CZ-3 to CZ-6) of the siliceous and nickel element that the present invention obtains, not only ensure that higher reactivity, the selective of catalyst improves on the contrary, demonstrate the synergy of silicon and nickel, can, under the prerequisite keeping comparatively low reaction temperatures (namely comparatively high reaction activity), improve selective.Especially catalyst CZ-3 to CZ-5, namely significantly improves reactivity, selectively also improves.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.

Claims (12)

1. an alpha-alumina supports, it comprises nickel element and element silicon, and described nickel element and element silicon are uniformly distributed in the carrier.
2. described alpha-alumina supports according to claim 1, it is characterized in that, the mass ratio of described nickel element and element silicon is 0.1:1-20:1, is preferably 0.1:1-10:1, is more preferably 0.5:1-5:1.
3. the alpha-alumina supports described in claim 1 or 2, is characterized in that, described alpha-alumina supports have in following characteristics one or more:
1) specific area is 0.7-2.0m 2/ g,
2) pore volume is 0.35-0.85ml/g,
3) water absorption rate >=30%,
4) crushing strength is 60-200N/ grain,
5) α-A1 2o 3content is more than 70wt%, based on the gross weight of described carrier.
4. prepare a method for alpha-alumina supports described in any one in claims 1 to 3, comprise the steps:
I) preparation comprises the solid mixture of following component: a) 50 order-500 order three water α-A1 2o 3; B) the false water A1 of>=200 objects 2o 3; C) optionally contain or do not contain heavy alkaline earth metal compound; D) fluoride-mineralization agent; E) in element silicon and nickel element, based on the nickel of the 0.01-3.0wt% of solid mixture gross weight and/or nickel compound containing and silicon and/or silicon-containing compound;
II) in above-mentioned solid mixture, add binding agent and water, then mediate even and shaping, obtain formed body; And
III) drying steps II) in the formed body that obtains, then roasting obtains alpha-alumina supports.
5. method according to claim 4, is characterized in that, based on the gross weight of described solid mixture, component amount a) is 45-90wt%, is preferably 65-85wt%; Components b) amount be 5-50wt%, be preferably 11-32wt%; Amount of component b) amount be 0-1.5wt%, be preferably 0.1-1.0wt%; Component d) amount be 0.1-3.0wt%, be preferably 1.0-2.0wt%, and component e) amount be 0.01-1.5wt%, the addition of described binding agent is 15-60wt%, be preferably 15-20wt%.
6. the method according to claim 4 or 5, is characterized in that, the mass ratio of described nickel and/or nickel compound containing and silicon and/or silicon-containing compound counts 0.1:1-20:1 with nickel element and element silicon, is preferably 0.1:1-10:1, is more preferably 0.5:1-5:1.
7. according to the method in claim 4 ~ 6 described in any one, it is characterized in that, described nickel compound containing, be selected from nickel monoxide, nickel sesquioxide, nickel hydroxide, nickelous sulfate, nickel chloride and nickel nitrate one or more, be preferably selected from nickel nitrate, nickel sesquioxide or its mixture; Described silicon-containing compound, be selected from sodium metasilicate, ethyl orthosilicate, nano-silicon, silica gel one or more, be preferably selected from ethyl orthosilicate, nano-silicon or its mixture.
8. according to the method in claim 4 ~ 7 described in any one, it is characterized in that, described binding agent is acid, and preferred nitric acid, the weight ratio of described nitric acid and water is 1:1.25-1:10, preferred 1:2-1:4.
9. method according to claim 8, is characterized in that, described acid, water and a false water A1 2o 3partly or entirely replace with Alumina gel.
10. according to the method in claim 4 ~ 9 described in any one, it is characterized in that, in described carrier, the mass ratio of nisiloy element is 0.1:1-20:1, is preferably 0.1:1-10:1, is more preferably 0.5:1-5:1.
Produce oxirane silver catalyst used by ethylene, comprising for 11. 1 kinds:
The alpha-alumina supports that in alpha-alumina supports in claims 1 to 3 described in any one or claim 4 ~ 10, described in any one, method prepares;
In silver, content is the silver compound of 1 ~ 40wt%, preferred 5-25wt%;
With alkali metal, content is 0-2000ppm, preferred 5-2000ppm, more preferably the alkali metal promoter of 5-1500ppm;
In alkaline-earth metal, content is the base earth metal promoter of 0-10000ppm, preferred 0-8000ppm;
In rhenium atom, content is 0-2000ppm, preferred 10-2000ppm, more preferably the rhenium auxiliary agent of 100-1000ppm;
In coassist agent metal, content is 0-1000ppm, the coassist agent of the rhenium auxiliary agent of preferred 0-500ppm.
Produce the method for oxirane by ethylene for 12. 1 kinds, described ethene carries out oxidation and generates oxirane under the effect of silver catalyst according to claim 11.
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