CN106311353B - A kind of alpha-alumina supports, corresponding silver catalyst and application - Google Patents
A kind of alpha-alumina supports, corresponding silver catalyst and application Download PDFInfo
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- CN106311353B CN106311353B CN201510381538.6A CN201510381538A CN106311353B CN 106311353 B CN106311353 B CN 106311353B CN 201510381538 A CN201510381538 A CN 201510381538A CN 106311353 B CN106311353 B CN 106311353B
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Abstract
The invention discloses a kind of application of alpha-alumina supports and corresponding silver catalyst, their preparation method and the silver catalyst in epoxidation reaction of olefines production epoxide.Using siliceous water aluminium oxide as raw material, fluoride and alkaline earth metal compound as auxiliary agent, wherein element silicon quality is (with SiO in a water aluminium oxide2Meter) Zhan Yishui quality of alumina 0.05~10.0%, by kneading, molding, drying, roasting, prepare alpha-alumina supports, again with the carrier of the solution dipping preparation containing organic amine, silver compound, tungsten auxiliary agent, rhenium auxiliary agent, alkali metal promoter, silver catalyst is made by leaching, activation.The silver catalyst is in alkene epoxidation production epoxide reaction, the selectivity and stability that can especially do well in ethylene epoxidizing production reacting ethylene oxide, and selectivity promotion speed is fast.
Description
Technical field
The invention belongs to catalysis technical fields, are related to a kind of alpha-alumina supports and corresponding silver catalyst, their system
The application of Preparation Method and the silver catalyst in epoxidation reaction of olefines production epoxide.
Background technique
Ethylene oxide is a kind of important basic petrochemical Organic Ingredients, it can derive more than 100 kinds of chemical products
And chemicals, mainly for the production of polyester, antifreezing agent, unsaturated polyester resin, lubricant, plasticizer, non-ionic surface active
Furthermore the industries such as agent and explosive, coating, ink can also be used to produce special solvent, purposes is very extensive.Commercial synthesis at present
The main method of ethylene glycol is to produce ethylene through petrochemical industry route, and under the action of silver catalyst epoxidation reaction occurs for ethylene
Produce ethylene oxide.The silver-colored and one or more additional member of active component that silver catalyst generally comprises carrier, is deposited on carrier
Plain component, these additional elements play the role of auxiliary agent or coassist agent, for improving the catalytic performance of silver catalyst.Silver catalysis
Agent carrier is usually Alpha-alumina resistant to high temperature.The performance of silver catalyst is removed and the composition of catalyst and preparation method have important pass
System is outer, also has important relationship with the performance of alpha-alumina supports and preparation method.
High-temperature roasting is one of the step of preparing alpha-alumina supports.In roasting process, aluminium oxide undergoes phase transition, burns
Knot, causes the sharp fall of carrier specific surface, will cause active constituent aggregation, catalyst inactivation of load etc. in this way, significantly
Affect the popularization and application of the service life and technology of catalyst.It is strong exothermal reaction that ethylene, which produces ethylene oxide, is had
The alpha-alumina supports of suitable specific surface and aperture just have biggish effective catalytic surface, and reactants and products molecule can
Quickly disengaging catalyst surfaces externally and internally, while reaction heat is taken away in time, thermal accumlation is prevented, the activity and stabilization of catalyst are made
Property is improved.The modification of carrier can improve the performance of alpha-alumina supports and silver catalyst, such as improve carrier surface soda acid
Property, improve the specific surface area of carrier and pore structure, improve dispersibility of the active component silver on carrier, adjust silver surface electronics shape
Condition, the adsorption desorption situation of modulation reaction species, to improve the catalytic performance of silver catalyst.But the method has operating process
It is cumbersome, the long deficiency of preparation time.
In industrial processes, not only activity, selectivity, the stability of silver catalyst are paid close attention to, silver catalyst choosing
It is also that people are of interest that selecting property, which promotes speed,.For production efficiency, quickly selectivity, which promotes speed, can be improved production
Efficiency expands yield.For economic benefit, quickly selectivity promotes speed and maintains the stability of catalyst can be obvious
Operating cost is reduced, more products is obtained, increases economic efficiency.
Summary of the invention
In order to improve the performance of silver catalyst, the present inventor has done a large amount of experimental study, and discovery, which is only selected, to be contained
One water aluminium oxide of silicon as raw material, fluoride and alkaline earth metal compound as auxiliary agent, wherein element silicon matter in a water aluminium oxide
Amount is (with SiO2Meter) Zhan Yishui quality of alumina 0.05~10.0%, by kneading, molding, drying, roasting, prepare α-oxygen
Change alumina supporter, then the carrier prepared with the solution dipping containing organic amine, silver compound, tungsten auxiliary agent, rhenium auxiliary agent, alkali metal promoter,
Silver catalyst is made by leaching, activation.The silver catalyst especially exists in alkene epoxidation production epoxide reaction
The selectivity and stability that can be done well in ethylene epoxidizing production reacting ethylene oxide, and selectivity promotes speed
Fastly.
Therefore, an object of the present invention is to provide a kind of alpha-alumina supports, the load as loading type silver catalyst
Body has the feature that Alpha-alumina quality accounts for carrier quality >=98%, and silicon content is with SiO2It is calculated as 0.05~
9.0wt%, specific surface are 0.5~4.0m20.35~0.85ml/g of/g, Kong Rongwei, water absorption rate >=30%, crushing strength be 30~
300N/.
The second object of the present invention is to provide a kind of loading type silver catalyst, including metallic silver, tungsten auxiliary agent, rhenium auxiliary agent, alkali
Metal promoter and the alpha-alumina supports.The quality of the metallic silver accounts for the 10~40% of the silver catalyst quality；Tungsten
The quality of element accounts for 5~20000ppm of the silver catalyst quality, preferably 50~5000ppm；The quality of rhenium element accounts for described
10~10000ppm of silver catalyst quality, preferably 100~4000ppm；The quality of alkali metal element accounts for the silver catalyst matter
5~the 5000ppm, preferably 100~3000ppm of amount.
The third object of the present invention is to provide the preparation method of the alpha-alumina supports, includes the following steps: step A,
Siliceous water aluminium oxide, fluoride and alkaline earth metal compound are uniformly mixed and obtain solids, binder is added and water obtains
To mixture；The obtained mixture of step A is mediated, is formed, is dried, is roasted by step B, that is, prepares Alpha-alumina load
Body.Wherein, in a water aluminium oxide described in step A element silicon quality (with SiO2Meter) Zhan Yishui quality of alumina 0.05~
10.0%, preferably 0.05~5.0%.
In the preparation method of alpha-alumina supports of the present invention, a water aluminium oxide is boehmite and/or one
Diaspore.The fluoride is selected from one of hydrogen fluoride, ammonium fluoride, magnesium fluoride and lithium fluoride or a variety of, fluoride
Effect is the transformation of crystal of accelerated oxidation aluminium, and reduces by 0.1 μm of pore below.The alkaline earth metal compound is selected from magnesium
And/or one of oxide, nitrate, sulfate, carbonate, oxalates and chloride of barium or a variety of, alkaline-earth metal
The addition for closing object can improve the mechanical strength of alumina support.
In the preparation method of alpha-alumina supports of the present invention, a water quality of alumina accounts for solids quality
50.0~99.9%.The fluorination amount of substance accounts for the 0.1~10.0% of solids quality.The alkaline earth metal compound matter
Amount accounts for the 0.1~15.0% of solids quality.
In the preparation method of alpha-alumina supports of the present invention, the binder is selected from citric acid, nitric acid, hydrochloric acid, first
One of acid, acetic acid and propionic acid are a variety of.The effect of binder be in solids a water aluminium oxide generate Aluminum sol,
Each component is bonded together, extrudable molding paste is become.The weight ratio of bonding agent and water is 1:1~1:10.
In the preparation method of alpha-alumina supports of the present invention, in order to manufacture macropore, there is alumina support suitable
Pore structure and specific surface area, can be added can after-flame carbonaceous material.This is because carbonaceous material aoxidizes generation in roasting process
Gas evolution, to form macropore in the carrier.Carbonaceous material is selected from polyethylene, polypropylene, petroleum coke, carbon dust, graphite and all
One of intellectual circle is a variety of.Carbonaceous material quality accounts for the 0~30% of solids quality.
In the preparation method of alpha-alumina supports of the present invention, mixture can be dried after mediating, forming to water content
≤ 10%.Drying temperature is 60~150 DEG C, drying time controls 1 according to moisture content~for 24 hours.Formed body after drying exists
2~48h is roasted at 1200~1600 DEG C, and aluminium oxide is made to be substantially transitioned to alpha-alumina supports.
Silver catalyst of the invention is prepared using above-mentioned alpha-alumina supports.Silver catalyst of the invention can be in the usual way
Preparation, such as prepared by impregnating above-mentioned alumina support with the solution of a kind of Ag-containing compound and organic amine.
The addition of active component silver of the present invention can be used traditional infusion process and implement.First by silver nitrate aqueous solution and oxalic acid
Ammonium or oxalic acid aqueous solution react with vigorous stirring and are precipitated silver oxalate precipitate, wash using aging, filtering, deionized water,
Up to no nitrate ion, silver oxalate paste is obtained, then silver oxalate is dissolved in containing in organic amine and compounding agent solution, is prepared
At uniform maceration extract, with the Alpha-alumina of the maceration extract dipping above method preparation under conditions of vacuum degree is less than 10mmHg
Carrier drains, in air or inert gas such as nitrogen, argon gas air-flow in 200~500 DEG C of temperature ranges keep 2~
120min, to be activated.Silver nitrate can also be replaced with silver oxide, silver oxalate can not also analyse filter.In order to improve silver-colored catalysis
The catalytic performance of agent, silver catalyst of the present invention can also add alkali metal promoter, tungsten auxiliary agent and rhenium auxiliary agent simultaneously in the preparation, these
Auxiliary agent can be applied on carrier prior to, concurrently with, or after immersion silver, can also be immersed in after silver compound is reduced
On carrier.The dipping includes primary or multiple, until reaching required silver and auxiliary agent content.
The fourth object of the present invention is to provide silver catalyst used in a kind of alkene epoxidation production epoxide, system
1. Preparation Method includes the following steps: step, alpha-alumina supports prepared by the present invention are helped with containing organic amine, silver compound, tungsten
The solution of agent, rhenium auxiliary agent and alkali metal promoter impregnates；2., by the alpha-alumina supports after dipping step carries out leaching and activation,
The silver catalyst is made.
In the preparation method of silver catalyst of the present invention, the organic amine is selected from pyridine, ethylenediamine, 1,2- butanediamine, 1,
3- butanediamine, ethamine, n-propylamine, n-butylamine, isobutylamine, tert-butylamine, sec-butylamine, 1,2- propane diamine, 1,3- the third two
One of amine, ethanol amine, Propanolamine and butanolamine are a variety of.
In the preparation method of silver catalyst of the present invention, the silver compound is in silver oxide, silver nitrate and silver oxalate
It is one or more.The tungsten auxiliary agent is selected from one of oxide, tungsten salt and tungstates of tungsten or a variety of.The rhenium helps
Agent is selected from one of rheium oxide, ammonium perrhenate, perrhenic acid and perrhenic acid caesium or a variety of.The alkali metal promoter be selected from lithium,
One in sodium, potassium, rubidium, the oxide of caesium, hydroxide, nitrate, carbonate, oxalates, sulfate, phosphate and acetate
Kind is a variety of.In order to improve the performance of silver catalyst, the coassist agent of alkaline-earth metal and/or rhenium can be added in the solution, it is described
Base earth metal promoter be selected from magnesium, calcium, strontium, the oxide of barium, hydroxide, oxalates, sulfate, carbonate, nitrate and
One of acetate is a variety of, and the salt or above-mentioned element that coassist agent selected from cerium, sulphur, molybdenum, the chromium of the rhenium are formed are with sour shape
One of oxygen anion existing for formula is a variety of.
In the preparation method of silver catalyst of the present invention, in order to obtain the silver catalysis compared with high silver content and/or auxiliary agent content
Agent can prepare silver-containing catalyst by the method for one or many dippings.
In the preparation method of silver catalyst of the present invention, the activation is in air or oxygen content no more than 21% volume
Nitrogen oxygen atmosphere in carry out.
In the preparation method of silver catalyst of the present invention, the temperature of the activation is 150~400 DEG C, and the time of activation is 1
~120min.
Removing in alpha-alumina supports prepared by the present invention deposited silver, tungsten auxiliary agent, rhenium auxiliary agent and alkali metal promoter, Yi Jiqian
Outside the coassist agent for stating the base earth metal promoter and/or rhenium that may be optionally added, can also by other element depositions on the carrier,
Other elements are selected from one of phosphorus, boron, chromium and titanium or a variety of.
There is provided silver catalysts prepared by the present invention in epoxidation reaction of olefines production epoxy for the fifth object of the present invention
Application in compound, the alkene are selected from one of styrene, propylene, ethylene and 1,3-butadiene or a variety of, and the silver
Catalyst is demonstrated by good catalytic activity and initial selectivity.The epoxide of above method preparation can also further turn
Turn to 1,2- alcohol, 1,2- glycol ethers, alkanolamine.
Specific embodiment
The measurement of silver catalyst catalytic performance:
Various silver catalysts of the invention test its selectivity with laboratory microreactor evaluating apparatus.Microreactor
Reactor used in evaluating apparatus is the stainless steel reaction pipe of internal diameter 4mm, and reaction tube is placed in heating mantle.The filling of catalyst
Volume is 1ml, and inert filler is arranged at lower part, and catalyst bed is made to be located at the flat-temperature zone of heating mantle.
The determination condition for the activity and selectivity that the present invention uses is as shown in table 1:
Table 1
After stably reaching above-mentioned reaction condition, METHOD FOR CONTINUOUS DETERMINATION reactor inlet and exit gas composition.To measurement result
After carrying out volume contraction correction, selectivity is calculated as follows:
Selectivity
Wherein Δ EO is reactor outlet gas and inlet gas ethylene oxide concentration difference, Δ CO2Reactor outlet gas with
Gas concentration lwevel is poor in inlet gas, takes test result of the average of 10 groups or more test datas as the same day.
The present invention is described further below with reference to embodiment, but the scope of the invention is not limited to these embodiments.
Comparative example 1
The preparation of alpha-alumina supports: weighing 491.0g boehmite, wherein element silicon quality in boehmite (with
SiO2Meter) account for boehmite quality 0.01%, 6.0g ammonium fluoride, 3.0g barium sulfate, be put into blender be uniformly mixed, turn
Enter into kneader, dust technology (nitric acid: water=1:3, volume ratio) is added until being kneaded into extrudable molding paste, by cream
Shape object is put into banded extruder, is extruded into five hole columns, is dried more than for 24 hours at 60~90 DEG C, and free water content is reduced to
Then 10% hereinafter, be put into natural gas kiln kiln roasting for five dried hole columns, maturing temperature is 1300 DEG C, constant temperature roasting
20h is burnt, room temperature is finally cooled to, obtains alpha-alumina supports.The related physical performance data of the carrier is shown in Table 2.
The preparation of silver catalyst: it weighs 140.0g silver nitrate and is dissolved in 150.0ml deionized water, weigh 64.0g ammonium oxalate
It is dissolved in 520.0ml deionized water, sufficiently dissolves, obtain silver nitrate solution and ammonium oxalate solution, mix institute with vigorous stirring
The two kinds of solution obtained generate white silver oxalate precipitate.Filter cake is washed with deionized until without nitre in filtrate in aging 1h, filtering
Acid ion obtains silver oxalate paste filter cake.The filter cake about 60wt% containing metallic silver, aqueous about 15wt%.In the glass with stirring
60.0g ethylenediamine, 22.0g ethanol amine and 75.0g deionized water are added in glass flask, lasting stirring dissolves silver oxalate all,
And keep mixed solution temperature at -5~10 DEG C.Then 0.17g ammonium metatungstate, 0.24g perrhenic acid are sequentially added to mixed solution
Ammonium, 0.53g cesium sulfate, adding deionized water makes solution gross mass reach 400g, is uniformly mixed that dipping solution is made is stand-by.It takes
Carrier 20g prepared by comparative example 1, puts it into the glass container that can be vacuumized, pours into the dipping solution prepared, be totally submerged
Carrier is evacuated to lower than 10mmHg, keeps about 15min, then extra solution is removed in leaching.It finally will be impregnated
Support samples are placed in 320 DEG C of air and heat 3min, cooling, that is, silver catalyst is made.
The selectivity of catalyst sample made of being measured under the conditions of previous process using microreactor evaluating apparatus, examination
It tests result and is listed in table 3.
Embodiment 1
The preparation of alpha-alumina supports: weighing 491.0g boehmite, wherein element silicon quality in boehmite (with
SiO2Meter) account for boehmite quality 0.05%, 6.0g ammonium fluoride, 3.0g barium sulfate, be put into blender be uniformly mixed, turn
Enter into kneader, dust technology (nitric acid: water=1:3, volume ratio) is added until being kneaded into extrudable molding paste, by cream
Shape object is put into banded extruder, is extruded into five hole columns, is dried more than for 24 hours at 60~90 DEG C, and free water content is reduced to
Then 10% hereinafter, be put into natural gas kiln kiln roasting for five dried hole columns, maturing temperature is 1300 DEG C, constant temperature roasting
20h is burnt, room temperature is finally cooled to, obtains alpha-alumina supports.The related physical performance data of the carrier is shown in Table 2.
The preparation method of silver catalyst is identical as comparative example 1.
The selectivity of catalyst sample made of being measured under the conditions of previous process using microreactor evaluating apparatus, examination
It tests result and is listed in table 3.
Comparative example 2
The preparation of alpha-alumina supports: weighing 491.0g boehmite, wherein element silicon quality in boehmite (with
SiO2Meter) account for boehmite quality 0.10%, 6.0g ammonium fluoride, 3.0g barium sulfate, be put into blender be uniformly mixed, turn
Enter into kneader, dust technology (nitric acid: water=1:3, volume ratio) is added until being kneaded into extrudable molding paste, by cream
Shape object is put into banded extruder, is extruded into five hole columns, is dried more than for 24 hours at 60~90 DEG C, and free water content is reduced to
Then 10% hereinafter, be put into natural gas kiln kiln roasting for five dried hole columns, maturing temperature is 1250 DEG C, constant temperature roasting
20h is burnt, room temperature is finally cooled to, obtains alpha-alumina supports.The related physical performance data of the carrier is shown in Table 2.
The preparation of silver catalyst: it weighs 140.0g silver nitrate and is dissolved in 150.0ml deionized water, weigh 64.0g ammonium oxalate
It is dissolved in 520.0ml deionized water, sufficiently dissolves, obtain silver nitrate solution and ammonium oxalate solution, mix institute with vigorous stirring
The two kinds of solution obtained generate white silver oxalate precipitate.Filter cake is washed with deionized until without nitre in filtrate in aging 1h, filtering
Acid ion obtains silver oxalate paste filter cake.The filter cake about 60wt% containing metallic silver, aqueous about 15wt%.In the glass with stirring
60.0g ethylenediamine, 22.0g ethanol amine and 75.0g deionized water are added in glass flask, lasting stirring dissolves silver oxalate all,
And keep mixed solution temperature at -5~10 DEG C.Then to mixed solution sequentially add 0.50g strontium acetate, 0.24g ammonium perrhenate,
0.53g cesium sulfate, adding deionized water makes solution gross mass reach 400g, is uniformly mixed that dipping solution is made is stand-by.It takes pair
Carrier 20g prepared by ratio 1, puts it into the glass container that can be vacuumized, pours into the dipping solution prepared, be totally submerged load
Body is evacuated to lower than 10mmHg, keeps about 15min, then extra solution is removed in leaching.Finally by impregnated load
Body sample is placed in 320 DEG C of air and heats 3min, cooling, that is, silver catalyst is made.
The selectivity of catalyst sample made of being measured under the conditions of previous process using microreactor evaluating apparatus, examination
It tests result and is listed in table 3.
Embodiment 2
Alpha-alumina supports preparation method is identical as comparative example 2.
The preparation of silver catalyst: it weighs 140.0g silver nitrate and is dissolved in 150.0ml deionized water, weigh 64.0g ammonium oxalate
It is dissolved in 520.0ml deionized water, sufficiently dissolves, obtain silver nitrate solution and ammonium oxalate solution, mix institute with vigorous stirring
The two kinds of solution obtained generate white silver oxalate precipitate.Filter cake is washed with deionized until without nitre in filtrate in aging 1h, filtering
Acid ion obtains silver oxalate paste filter cake.The filter cake about 60wt% containing metallic silver, aqueous about 15wt%.In the glass with stirring
60.0g ethylenediamine, 22.0g ethanol amine and 75.0g deionized water are added in glass flask, lasting stirring dissolves silver oxalate all,
And keep mixed solution temperature at -5~10 DEG C.Then 0.21g ammonium metatungstate, 0.24g perrhenic acid are sequentially added to mixed solution
Ammonium, 0.53g cesium sulfate, adding deionized water makes solution gross mass reach 400g, is uniformly mixed that dipping solution is made is stand-by.It takes
Carrier 20g prepared by comparative example 1, puts it into the glass container that can be vacuumized, pours into the dipping solution prepared, be totally submerged
Carrier is evacuated to lower than 10mmHg, keeps about 15min, then extra solution is removed in leaching.It finally will be impregnated
Support samples are placed in 320 DEG C of air and heat 3min, cooling, that is, silver catalyst is made.
The selectivity of catalyst sample made of being measured under the conditions of previous process using microreactor evaluating apparatus, examination
It tests result and is listed in table 3.
Embodiment 3
Alpha-alumina supports preparation method is identical as comparative example 2.In addition to ammonium metatungstate is added in silver catalyst preparation method
Quality is 0.25g, ammonium perrhenate addition quality is outside 0.40g, other are same as Example 2.
The selectivity of catalyst sample made of being measured under the conditions of previous process using microreactor evaluating apparatus, examination
It tests result and is listed in table 3.
Embodiment 4
The preparation of alpha-alumina supports: weighing 491.0g boehmite, wherein element silicon quality in boehmite (with
SiO2Meter) account for boehmite quality 0.35%, 6.0g ammonium fluoride, 3.0g barium sulfate, be put into blender be uniformly mixed, turn
Enter into kneader, dust technology (nitric acid: water=1:3, volume ratio) is added until being kneaded into extrudable molding paste, by cream
Shape object is put into banded extruder, is extruded into five hole columns, is dried more than for 24 hours at 60~90 DEG C, and free water content is reduced to
Then 10% hereinafter, be put into natural gas kiln kiln roasting for five dried hole columns, maturing temperature is 1350 DEG C, constant temperature roasting
20h is burnt, room temperature is finally cooled to, obtains alpha-alumina supports.The related physical performance data of the carrier is shown in Table 2.
The preparation of silver catalyst: it weighs 140.0g silver nitrate and is dissolved in 150.0ml deionized water, weigh 64.0g ammonium oxalate
It is dissolved in 520.0ml deionized water, sufficiently dissolves, obtain silver nitrate solution and ammonium oxalate solution, mix institute with vigorous stirring
The two kinds of solution obtained generate white silver oxalate precipitate.Filter cake is washed with deionized until without nitre in filtrate in aging 1h, filtering
Acid ion obtains silver oxalate paste filter cake.The filter cake about 60wt% containing metallic silver, aqueous about 15wt%.In the glass with stirring
60.0g ethylenediamine, 22.0g ethanol amine and 75.0g deionized water are added in glass flask, lasting stirring dissolves silver oxalate all,
And keep mixed solution temperature at -5~10 DEG C.Then to mixed solution sequentially add 0.20g ammonium tungstate, 0.39g ammonium perrhenate,
0.65g cesium nitrate, adding deionized water makes solution gross mass reach 400g, is uniformly mixed that dipping solution is made is stand-by.It takes pair
Carrier 20g prepared by ratio 1, puts it into the glass container that can be vacuumized, pours into the dipping solution prepared, be totally submerged load
Body is evacuated to lower than 10mmHg, keeps about 15min, then extra solution is removed in leaching.Finally by impregnated load
Body sample is placed in 320 DEG C of air and heats 3min, cooling, that is, silver catalyst is made.
The selectivity of catalyst sample made of being measured under the conditions of previous process using microreactor evaluating apparatus, examination
It tests result and is listed in table 3.
Embodiment 5
The preparation of alpha-alumina supports: weighing 491.0g boehmite, wherein element silicon quality in boehmite (with
SiO2Meter) account for boehmite quality 0.50%, 6.0g ammonium fluoride, 3.0g barium sulfate, be put into blender be uniformly mixed, turn
Enter into kneader, dust technology (nitric acid: water=1:3, volume ratio) is added until being kneaded into extrudable molding paste, by cream
Shape object is put into banded extruder, is extruded into five hole columns, is dried more than for 24 hours at 60~90 DEG C, and free water content is reduced to
Then 10% hereinafter, be put into natural gas kiln kiln roasting for five dried hole columns, maturing temperature is 1350 DEG C, constant temperature roasting
20h is burnt, room temperature is finally cooled to, obtains alpha-alumina supports.The related physical performance data of the carrier is shown in Table 2.
The preparation of silver catalyst: it weighs 140.0g silver nitrate and is dissolved in 150.0ml deionized water, weigh 64.0g ammonium oxalate
It is dissolved in 520.0ml deionized water, sufficiently dissolves, obtain silver nitrate solution and ammonium oxalate solution, mix institute with vigorous stirring
The two kinds of solution obtained generate white silver oxalate precipitate.Filter cake is washed with deionized until without nitre in filtrate in aging 1h, filtering
Acid ion obtains silver oxalate paste filter cake.The filter cake about 60wt% containing metallic silver, aqueous about 15wt%.In the glass with stirring
60.0g ethylenediamine, 22.0g ethanol amine and 75.0g deionized water are added in glass flask, lasting stirring dissolves silver oxalate all,
And keep mixed solution temperature at -5~10 DEG C.Then to mixed solution sequentially add 0.27g ammonium tungstate, 0.25g ammonium perrhenate,
0.61g cesium sulfate, adding deionized water makes solution gross mass reach 400g, is uniformly mixed that dipping solution is made is stand-by.It takes pair
Carrier 20g prepared by ratio 1, puts it into the glass container that can be vacuumized, pours into the dipping solution prepared, be totally submerged load
Body is evacuated to lower than 10mmHg, keeps about 15min, then extra solution is removed in leaching.Finally by impregnated load
Body sample is placed in 320 DEG C of air and heats 3min, cooling, that is, silver catalyst is made.
The selectivity of catalyst sample made of being measured under the conditions of previous process using microreactor evaluating apparatus, examination
It tests result and is listed in table 3.
Embodiment 6
The preparation of alpha-alumina supports: weighing 491.0g boehmite, wherein element silicon quality in boehmite (with
SiO2Meter) account for boehmite quality 1.70%, 6.0g ammonium fluoride, 3.0g barium sulfate, be put into blender be uniformly mixed, turn
Enter into kneader, dust technology (nitric acid: water=1:3, volume ratio) is added until being kneaded into extrudable molding paste, by cream
Shape object is put into banded extruder, is extruded into five hole columns, is dried more than for 24 hours at 60~90 DEG C, and free water content is reduced to
Then 10% hereinafter, be put into natural gas kiln kiln roasting for five dried hole columns, maturing temperature is 1380 DEG C, constant temperature roasting
20h is burnt, room temperature is finally cooled to, obtains alpha-alumina supports.The related physical performance data of the carrier is shown in Table 2.
The preparation of silver catalyst: it weighs 140.0g silver nitrate and is dissolved in 150.0ml deionized water, weigh 64.0g ammonium oxalate
It is dissolved in 520.0ml deionized water, sufficiently dissolves, obtain silver nitrate solution and ammonium oxalate solution, mix institute with vigorous stirring
The two kinds of solution obtained generate white silver oxalate precipitate.Filter cake is washed with deionized until without nitre in filtrate in aging 1h, filtering
Acid ion obtains silver oxalate paste filter cake.The filter cake about 60wt% containing metallic silver, aqueous about 15wt%.In the glass with stirring
60.0g ethylenediamine, 22.0g ethanol amine and 75.0g deionized water are added in glass flask, lasting stirring dissolves silver oxalate all,
And keep mixed solution temperature at -5~10 DEG C.Then 0.25g ammonium metatungstate, 0.40g perrhenic acid are sequentially added to mixed solution
Ammonium, 0.65g cesium nitrate, adding deionized water makes solution gross mass reach 400g, is uniformly mixed that dipping solution is made is stand-by.It takes
Carrier 20g prepared by comparative example 1, puts it into the glass container that can be vacuumized, pours into the dipping solution prepared, be totally submerged
Carrier is evacuated to lower than 10mmHg, keeps about 15min, then extra solution is removed in leaching.It finally will be impregnated
Support samples are placed in 320 DEG C of air and heat 3min, cooling, that is, silver catalyst is made.
The selectivity of catalyst sample made of being measured under the conditions of previous process using microreactor evaluating apparatus, examination
It tests result and is listed in table 3.
Embodiment 7
The preparation of alpha-alumina supports: weighing 491.0g boehmite, wherein element silicon quality in boehmite (with
SiO2Meter) account for boehmite quality 3.80%, 6.0g ammonium fluoride, 3.0g barium sulfate, be put into blender be uniformly mixed, turn
Enter into kneader, dust technology (nitric acid: water=1:3, volume ratio) is added until being kneaded into extrudable molding paste, by cream
Shape object is put into banded extruder, is extruded into five hole columns, is dried more than for 24 hours at 60~90 DEG C, and free water content is reduced to
Then 10% hereinafter, be put into natural gas kiln kiln roasting for five dried hole columns, maturing temperature is 1400 DEG C, constant temperature roasting
20h is burnt, room temperature is finally cooled to, obtains alpha-alumina supports.The related physical performance data of the carrier is shown in Table 2.
The preparation method of silver catalyst is identical as comparative example 1.
The selectivity of catalyst sample made of being measured under the conditions of previous process using microreactor evaluating apparatus, examination
It tests result and is listed in table 3.
Embodiment 8
The preparation of alpha-alumina supports: weighing 491.0g boehmite, wherein element silicon quality in boehmite (with
SiO2Meter) account for boehmite quality 7.10%, 6.0g ammonium fluoride, 3.0g barium sulfate, be put into blender be uniformly mixed, turn
Enter into kneader, dust technology (nitric acid: water=1:3, volume ratio) is added until being kneaded into extrudable molding paste, by cream
Shape object is put into banded extruder, is extruded into five hole columns, is dried more than for 24 hours at 60~90 DEG C, and free water content is reduced to
Then 10% hereinafter, be put into natural gas kiln kiln roasting for five dried hole columns, maturing temperature is 1420 DEG C, constant temperature roasting
20h is burnt, room temperature is finally cooled to, obtains alpha-alumina supports.The related physical performance data of the carrier is shown in Table 2.
The preparation of silver catalyst: it weighs 140.0g silver nitrate and is dissolved in 150.0ml deionized water, weigh 64.0g ammonium oxalate
It is dissolved in 520.0ml deionized water, sufficiently dissolves, obtain silver nitrate solution and ammonium oxalate solution, mix institute with vigorous stirring
The two kinds of solution obtained generate white silver oxalate precipitate.Filter cake is washed with deionized until without nitre in filtrate in aging 1h, filtering
Acid ion obtains silver oxalate paste filter cake.The filter cake about 60wt% containing metallic silver, aqueous about 15wt%.In the glass with stirring
60.0g ethylenediamine, 22.0g ethanol amine and 75.0g deionized water are added in glass flask, lasting stirring dissolves silver oxalate all,
And keep mixed solution temperature at -5~10 DEG C.Then 0.20g ammonium metatungstate, 0.25g perrhenic acid are sequentially added to mixed solution
Ammonium, 0.65g cesium nitrate, adding deionized water makes solution gross mass reach 400g, is uniformly mixed that dipping solution is made is stand-by.It takes
Carrier 20g prepared by comparative example 1, puts it into the glass container that can be vacuumized, pours into the dipping solution prepared, be totally submerged
Carrier is evacuated to lower than 10mmHg, keeps about 15min, then extra solution is removed in leaching.It finally will be impregnated
Support samples are placed in 320 DEG C of air and heat 3min, cooling, that is, silver catalyst is made.
The selectivity of catalyst sample made of being measured under the conditions of previous process using microreactor evaluating apparatus, examination
It tests result and is listed in table 3.
Table 2
| Silicone content (wt%) | Specific surface area (m2/g) | Crushing strength (N/) | |
| Comparative example 1 | 0.01 | 1.41 | 209 |
| Comparative example 2 | 0.06 | 1.87 | 196 |
| Embodiment 1 | 0.08 | 2.59 | 154 |
| Embodiment 2 | 0.08 | 2.59 | 154 |
| Embodiment 3 | 0.08 | 2.59 | 154 |
| Embodiment 4 | 0.27 | 2.43 | 231 |
| Embodiment 5 | 0.39 | 2.71 | 243 |
| Embodiment 6 | 1.97 | 2.68 | 246 |
| Embodiment 7 | 4.61 | 2.66 | 261 |
| Embodiment 8 | 7.96 | 2.75 | 272 |
Table 3
| * selectivity (%) | # selectivity (%) | |
| Comparative example 1 | 83.0 | 83.2 |
| Comparative example 2 | 83.4 | 84.5 |
| Embodiment 1 | 84.6 | 84.9 |
| Embodiment 2 | 85.1 | 85.5 |
| Embodiment 3 | 85.9 | 85.8 |
| Embodiment 4 | 86.0 | 86.1 |
| Embodiment 5 | 84.7 | 85.1 |
| Embodiment 6 | 86.2 | 85.9 |
| Embodiment 7 | 85.7 | 85.9 |
| Embodiment 8 | 85.3 | 85.8 |
* selectivity is the selectivity that silver catalyst evaluates the 3rd day, and # is selectively the selection that silver catalyst evaluates the 30th day
Property.
It can be seen that in a water aluminium oxide suitable silicon content by 2 data of contrast table and prepared in silver catalyst
Suitable silver-colored auxiliary agent is added in the process and content can be improved the performance of silver catalyst.Suitable element silicon can increase alpha-oxidation
The specific surface area of alumina supporter improves the dispersibility of silver and its auxiliary agent on the surface of the carrier, improves the catalytic performance of silver catalyst.?
The silver catalyst that suitable silver-colored auxiliary agent and content preparation is added is up to 84.0% or more in the selectivity of evaluation the 3rd day, with evaluation
30th day selectivity is close, this illustrates silver catalyst catalytic selectivity with higher and stability, and selectivity
Promotion speed quickly.In addition, embodiment 2 compared with the comparative example 2 that wolfram element is not added in silver catalyst preparation process, is evaluated
3rd day and the 30th day selectivity is improved.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (14)
1. a kind of silver catalyst, preparation method include the following steps:
Step 1., by alpha-alumina supports with containing organic amine, silver compound, tungsten auxiliary agent, rhenium auxiliary agent and alkali metal promoter solution
Dipping；
2., by the alpha-alumina supports after dipping step carries out leaching and activation, obtain the silver catalyst；
Wherein, the alpha-alumina supports are prepared by a method comprising the following steps:
Siliceous water aluminium oxide, fluoride and alkaline earth metal compound are uniformly mixed and obtain solids, add viscous by step A
Knot agent and water obtain mixture；
The obtained mixture of step A is mediated, is formed, dried and is roasted, obtains the alpha-alumina supports by step B；
Wherein, with SiO2It counts, the 0.05~10.0% of element silicon quality Zhan Yishui quality of alumina in a water aluminium oxide.
2. silver catalyst according to claim 1, which is characterized in that with SiO2It counts, element silicon in a water aluminium oxide
The 0.05~5.0% of quality Zhan Yishui quality of alumina.
3. silver catalyst according to claim 1, which is characterized in that a water aluminium oxide described in step A is the soft aluminium of a water
Stone and/or diaspore；The fluoride is selected from one of hydrogen fluoride, ammonium fluoride, magnesium fluoride and lithium fluoride or a variety of；
The alkaline earth metal compound is selected from oxide, nitrate, sulfate, carbonate, oxalates and the chloride of magnesium and/or barium
One of or it is a variety of；And/or
The binder is selected from one of citric acid, nitric acid, hydrochloric acid, formic acid, acetic acid and propionic acid or a variety of.
4. silver catalyst according to claim 3, which is characterized in that the weight ratio of the binder and water is 1:1~1:
10。
5. silver catalyst according to claim 1, which is characterized in that in step A, a water quality of alumina accounts for solid
The 50.0~99.9% of body amount of substance；The fluorination amount of substance accounts for the 0.1~10.0% of solids quality；The alkaline earth gold
Belong to compound quality and accounts for the 0.1~15.0% of solids quality.
6. silver catalyst according to claim 1, which is characterized in that Alpha-alumina quality accounts for carrier quality in the carrier
>=98%, silicon content is with SiO2It is calculated as 0.05~9.0wt%, specific surface is 0.5~4.0m2/ g, Kong Rongwei 0.35~
0.85mL/g, water absorption rate >=30%, crushing strength are 30~300N/.
7. silver catalyst according to claim 1, which is characterized in that the organic amine is selected from pyridine, ethylenediamine, 1,2- fourth
Diamines, 1,3- butanediamine, ethamine, n-propylamine, n-butylamine, isobutylamine, tert-butylamine, sec-butylamine, 1,2- propane diamine, 1,
One of 3- propane diamine, ethanol amine, Propanolamine and butanolamine are a variety of.
8. silver catalyst according to claim 1, which is characterized in that the silver compound be selected from silver oxide, silver nitrate and
One of silver oxalate is a variety of；The tungsten auxiliary agent is selected from one of oxide, tungsten salt and tungstates of tungsten or a variety of；Institute
The rhenium auxiliary agent stated is selected from one of rheium oxide, ammonium perrhenate, perrhenic acid and perrhenic acid caesium or a variety of；The alkali metal promoter
Selected from lithium, sodium, potassium, rubidium, the oxide of caesium, hydroxide, nitrate, carbonate, oxalates, sulfate, phosphate and acetic acid
One of salt is a variety of.
9. silver catalyst according to claim 1, which is characterized in that the activation is not more than in air or oxygen content
It is carried out in the nitrogen oxygen atmosphere of 21% volume.
10. silver catalyst according to claim 9, which is characterized in that the activation temperature is 150~400 DEG C, and the time is
1~120min.
11. the silver catalyst according to any of claims 1 to 10, which is characterized in that silver-colored quality accounts for the silver catalysis
The 10~40% of agent quality；The quality of wolfram element accounts for 5~20000ppm of the silver catalyst quality；The quality of rhenium element accounts for institute
State 10~10000ppm of silver catalyst quality；The quality of alkali metal element accounts for 5~5000ppm of the silver catalyst quality.
12. silver catalyst according to claim 11, which is characterized in that the quality of wolfram element accounts for the silver catalyst quality
50~5000ppm；The quality of rhenium element accounts for 100~4000ppm of the silver catalyst quality；The quality of alkali metal element accounts for
100~3000ppm of the silver catalyst quality.
13. the described in any item silver catalysts of claim 1 to 12 answering in epoxidation reaction of olefines production epoxide
With.
14. application according to claim 13, which is characterized in that the alkene is selected from styrene, propylene, ethylene and 1,3-
One of butadiene is a variety of.
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| CN111659469A (en) * | 2019-03-05 | 2020-09-15 | 中国石油化工股份有限公司 | Silver catalyst for producing ethylene oxide by ethylene oxidation and preparation method and application thereof |
| CN112295561B (en) * | 2019-08-02 | 2023-07-25 | 中国石油天然气股份有限公司 | Epoxidation catalyst and preparation method thereof |
| CN112705196B (en) * | 2019-10-24 | 2023-02-24 | 中国石油化工股份有限公司 | Silver-gold bimetal supported catalyst and preparation method and application thereof |
| CN113694941B (en) * | 2020-05-20 | 2024-05-07 | 中国石油化工股份有限公司 | Supported metal catalyst and preparation method and application thereof |
| CN114425373B (en) * | 2020-09-25 | 2023-09-08 | 中国石油化工股份有限公司 | Alpha-alumina carrier, preparation method, silver catalyst and application |
| CN117427666B (en) * | 2023-12-22 | 2024-02-27 | 橙雨化学(大连)有限公司 | Te modified alumina carrier and preparation method thereof |
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