CN106955744A - The alpha-alumina supports of alkene epoxidation silver catalyst and its preparation and application - Google Patents
The alpha-alumina supports of alkene epoxidation silver catalyst and its preparation and application Download PDFInfo
- Publication number
- CN106955744A CN106955744A CN201610010169.4A CN201610010169A CN106955744A CN 106955744 A CN106955744 A CN 106955744A CN 201610010169 A CN201610010169 A CN 201610010169A CN 106955744 A CN106955744 A CN 106955744A
- Authority
- CN
- China
- Prior art keywords
- alpha
- alumina supports
- component
- catalyst
- alumina
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- B01J23/38—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
-
- 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
-
- 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 present invention relates to a kind of alpha-alumina supports of alkene epoxidation silver catalyst and preparation method thereof, by adding alpha-alumina supports made from the gibbsite and surge aluminium stone of Suitable weight ratio in the preparation process of carrier with higher specific surface area and pore volume.Application the invention further relates to the silver catalyst being made up of the alpha-alumina supports and its in ethylene epoxidizing produces oxirane, the silver catalyst is used in ethylene epoxidizing production oxirane, has higher activity and selectivity concurrently.
Description
Technical field
The invention belongs to catalyst carrier and catalyst preparation technical field, and in particular to a kind of alkene epoxidation is used
The alpha-alumina supports of silver catalyst and its preparation and application.
Background technology
In alkene epoxidation production epoxide reaction, under certain reaction condition, containing alkene and
The reaction mixture gas of oxygen reacted in the presence of catalyst production epoxide and a small amount of carbon dioxide,
The accessory substances such as water.Wherein activity, selectivity and stability are the main performance index of silver catalyst.Activity is
Refer to process for ethylene oxide production and reach reaction temperature required during certain reaction load, reaction temperature is lower, catalysis
The activity of agent is higher；Selectivity refer to reaction in ethene change into oxirane molal quantity and ethene overall reaction
The ratio between molal quantity；Stability is then expressed as the fall off rate of activity and selectivity, and fall off rate gets over small catalyst
Stability is better.
Oxirane, can be in the presence of silver catalyst, with ethene and oxygen as one kind in epoxide
Gas is obtained as reaction gas.So far, silver catalyst is still industrial ethylene epoxidizing production oxirane
(EO) unique effective catalyst, silver catalyst carrier is generally made up of resistant to elevated temperatures Alpha-alumina.
The material for preparing the alpha-alumina supports of silver catalyst is generally comprised：Alpha-alumina powder and/or its forerunner
Body；Binding agent, for shortening the sintering time for being bonded together particle；Thermal decomposition burnout materials, are used for
Serve as duct and form material；Lubricant, is conducive to carrier to be molded；Auxiliary agent, for improve alpha-alumina supports and
/ or silver catalyst performance.In general, prepare alpha-alumina supports method be by these raw materials carry out batch mixing,
Mediate, be then molded according to molding blank of different shapes, eventually pass high temperature sintering and alpha-alumina supports are made.
Alpha-alumina supports have very important effect to silver catalyst, such as：Improve the dispersiveness of active component；Subtract
The consumption of few active component, reduces cost；Increasing effective specific surface area, there is provided suitable pore volume；Improve
The heat endurance of catalyst.The particularly specific surface area and pore volume of alpha-alumina supports, due to ethylene epoxidizing
It is strong exothermal reaction to produce reacting ethylene oxide, and their performances to silver catalyst play particularly important effect.
Specific surface area such as alpha-alumina supports is too low, then is unfavorable for active component dispersed on carrier；Such as α-
The pore volume of alumina support is too low, then is unfavorable for catalytic reaction process reactant or product and inhales de- in time
It is attached, and also result in reaction produce heat can not take away in time, local temperature is too high, causes silver catalyst
Performance reduction is even inactivated.
Prior art largely improves the ratio surface of alpha-alumina supports by thermal decomposition burnout materials, auxiliary agent
Product and pore volume, but its specific surface area can be improved simultaneously and the prior art of pore volume is less.Therefore, mesh
It is preceding to be badly in need of researching and developing a kind of alkene epoxidation silver catalyst with good specific surface area and pore volume
Alpha-alumina supports.
The content of the invention
The technical problems to be solved by the invention are that there is provided a kind of olefin epoxide for above-mentioned the deficiencies in the prior art
The alpha-alumina supports of change silver catalyst, the alpha-alumina supports have good specific surface area and pore volume concurrently.
Present invention also offers a kind of preparation method of above-mentioned alpha-alumina supports, this method is same in carrier preparation process
The gibbsite of Shi Tianjia Suitable weight ratios and surge aluminium stone, the specific surface area of prepared alpha-alumina supports and
Pore volume is all higher.The silver catalyst prepared by above-mentioned alpha-alumina supports is used for ethylene epoxidizing and produces epoxy
Ethane, catalyst activity and selectivity can be improved simultaneously.
Therefore, first aspect present invention provides a kind of alpha-alumina supports of alkene epoxidation silver catalyst,
It is that alpha-alumina supports precursor mixture is made through shaping, dry and roasting, the alpha-alumina supports precursor
Mixture is included：
Component a, three water α-Al2O3；
Component b, boehmite；
Component c, weight alkaline earth metal compound；
Component d, fluorine compounds；
Component e, binding agent；And
Water；
Wherein, the gibbsite includes gibbsite and surge aluminium stone；The weight of the gibbsite and surge aluminium stone
Amount is than being (1-8):1.
According to the present invention, the alpha-alumina supports precursor mixture presses the composition of solid constituent a-d gross weight meters
It is as follows：
In some embodiments of the invention, the alpha-alumina supports precursor mixture is total by solid constituent a-d
The composition of weight meter is as follows：
According to the present invention, the heavy alkaline earth metal compound includes the oxide, sulfate, carbon of weight alkaline-earth metal
One or more in hydrochlorate, nitrate and oxalates；It is preferred that the heavy alkaline-earth metal is strontium and/or barium.
In some embodiments of the invention, the fluorine compounds include hydrogen fluoride, aluminum fluoride, ammonium fluoride, fluorine
Change the one or more in magnesium and ice crystal.
In other embodiments of the present invention, the weight ratio of the binding agent and water is 1:(1-10)；It is described viscous
Tying agent includes the one or more in citric acid, nitric acid, formic acid, acetic acid, propionic acid and hydrochloric acid.
According to the present invention, the compression strength of the carrier is 50-350N/；Specific surface area is 0.5-3.0m2/g；
Pore volume is 0.4-1.2ml/g；Water absorption rate >=30%.
Second aspect present invention provides a kind of preparation of alpha-alumina supports as described in the first aspect of the invention
Method, it includes：
Step S1, solid mixture is mixed to form by component a-d；
Step S2, component e and water are mixed with solid mixture, and alpha-alumina supports precursor mixture is made；
Step S3, alpha-alumina supports precursor mixture is molded, and is dried, is calcined, and α-oxygen is made
Change alumina supporter.
In some embodiments of the invention, in step s3, the temperature of the drying is 60-120 DEG C；Institute
The temperature for stating roasting is 1200-1600 DEG C；The time of the roasting is 5-25h.
Third aspect present invention provides a kind of alkene epoxidation silver catalyst, its gross weight based on catalyst
Meter includes following component：
Component l, alpha-alumina supports or square as described in respect of the second aspect of the invention as described in the first aspect of the invention
Alpha-alumina supports prepared by method；
Fourth aspect present invention provides a kind of preparation method of silver catalyst as described in third aspect present invention,
It is by alpha-alumina supports as described in the first aspect of the invention or as described in respect of the second aspect of the invention method system
Standby alpha-alumina supports are immersed in the solution of Ag-containing compound and auxiliary agent, are heat-treated and are made by overactivation.
The auxiliary agent includes the coassist agent of alkali metal promoter, base earth metal promoter, rhenium auxiliary agent and optional rhenium.
Fifth aspect present invention provides a kind of method that alkene epoxidation produces oxirane, and the alkene is at this
Silver catalyst prepared by silver catalyst described in the invention third aspect or fourth aspect present invention methods described is deposited
In lower carry out epoxidation reaction, the alkene includes one kind in styrene, propylene, ethene and 1,3-butadiene
Or it is a variety of.
Embodiment
To make the present invention easier to understand, the present invention is described in detail below in conjunction with embodiment, these implementations
Example only serves illustrative, it is not limited to application of the invention.
In view of existing silver catalyst carrier can not have good specific surface area and pore volume concurrently simultaneously, it is of the invention
The alpha-alumina supports that inventor produces silver catalyst used by oxirane to alkene epoxidation have been carried out further
Research, finds simultaneously using gibbsite and surge aluminium standby alpha-alumina supports made of stones, and control their addition weight
Amount ratio is in suitable scope, and the specific surface area and pore volume for the alpha-alumina supports prepared are all higher, and
Thus when the silver catalyst that prepared by carrier is used for ethylene epoxidizing production oxirane, catalyst activity and selectivity
It can be improved simultaneously.The present invention is based on what above-mentioned discovery was made.
Alkene epoxidation involved by first aspect present invention is by containing weight with the alpha-alumina supports of silver catalyst
Amount is than being (1-8):The alpha-alumina supports precursor mixture of 1 gibbsite and surge aluminium stone is through shaping, dry and roasting
Fire, wherein the weight content of Alpha-alumina is more than 90% (weight).The alpha-alumina supports it is anti-
Compressive Strength is 50-350N/；Specific surface area is 0.5-3.0m2/g；Pore volume is 0.4-1.2ml/g；Water absorption rate >=30%.
In some embodiments of the invention, preferably described gibbsite and the weight ratio of surge aluminium stone are (1.5-6):1.
According to certain specific embodiments of the invention, involved by second aspect present invention such as first party of the present invention
The preparation method of alpha-alumina supports involved by face comprises the following steps：
(1) prepare with the solid mixture constituted as follows：
Component a, accounts for the gibbsite that solid mixture gross weight is 5.0%-90.0% (weight)；
Component b, accounts for the boehmite that solid mixture gross weight is 5.0%-85.0% (weight)；
Component c, accounts for the heavy alkaline earth metal compound that solid mixture gross weight is 0.1%-8.0% (weight)；
Component d, accounts for the fluorine compounds that solid mixture gross weight is 0.1%-10.0% (weight)；
(2) component e binding agents are added in gained solid mixture into step (1) and Alpha-alumina is made in water
Support precursor mixture；
(3) the alpha-alumina supports precursor mixture for obtaining step (2) mediated, be molded, being dried,
Roasting, obtains alpha-alumina supports.
In the preparation method of above-mentioned carrier, in the solid mixture described in step (1), except above-mentioned a-d, this is several
Outside component, thermal decomposition burnout materials and lubricant can also be included；The thermal decomposition burnout materials include poly-
One or more in ethene, polypropylene, petroleum coke, carbon dust and graphite；The preferred vaseline of lubricant.
In the preparation method of above-mentioned carrier, preferably described gibbsite accounts for solid mixture gross weight
40.0%-80.0% (weight)；It is preferred that the boehmite accounts for the 15.0%-50.0% of solid mixture gross weight
(weight)；It is preferred that the heavy alkaline earth metal compound accounts for the 0.1%-4.0% (weight) of solid mixture gross weight；
It is preferred that the fluorine compounds account for the 0.2%-6.0% (weight) of solid mixture gross weight.
In order to improve the intensity of alpha-alumina supports, the present invention adds weight during alpha-alumina supports are prepared
Alkaline earth metal compound, the heavy alkaline earth metal compound is the compound of strontium and/or barium；The strontium and/or barium
Compound include the corresponding salt of the oxide and strontium and/or barium of strontium and/or barium in one or more；The strontium
And/or the corresponding salt of barium include one kind in sulfate, carbonate, nitrate and the oxalates of strontium and/or barium or
It is a variety of.
In the preparation method of above-mentioned carrier, hydrated alumina (gibbsite, boehmite) is heated de-
Water changes into transition aluminas, and when reaching certain sintering temperature, transition aluminas changes to Alpha-alumina.
In the preparation method of above-mentioned carrier, the addition of fluorine compounds can promote alumina crystalline phase transition process, disappear
Except unnecessary micropore, the pore of less than 0.1 μm of reduction improves the selectivity of silver catalyst.It is of the present invention
Fluorine compounds include hydrogen fluoride, aluminum fluoride, ammonium fluoride, magnesium fluoride and ice crystal in one or more.
In the preparation method of above-mentioned carrier, it is molten that binding agent can generate aluminium with the boehmite in solid mixture
Glue, is bonded together each component, the paste as extrudable shaping.According to the present invention, the binding agent
Weight ratio with water is 1:(1-10)；It is preferred that the binding agent includes citric acid, nitric acid, formic acid, acetic acid, third
One or more in acid and hydrochloric acid.
The consumption of binding agent is had no particular limits in the present invention, its consumption with can with solid mixture
The paste that boehmite generation Alumina gel to form extrudable shaping so as to be glued together with each component is defined.
Term " water " of the present invention unless otherwise specified, refers both to deionized water.
It need not be added in order between solid mixture and the addition of binder solution in the present invention, for example solid
Fluoride in mixture can be just added in solid mixture together with binder solution finally.
In order to which mixture is well mixed, the present invention is mediated mixture, is mediated and is carried out in kneader,
Kneading time is 5-90min.After mixture is mediated fully, carrier can be made to definite shape, including ball
Shape, block shape, cylinder, Round Porous cylindricality, Raschig ring shape, cloverleaf pattern, honeycombed etc., described shaping
Carried out in forming machine.For the ease of extrusion molding thing, shaping assistant can be added in solid mixture, into
Type auxiliary agent includes the one or more in vaseline, graphite, paraffin, vegetable oil.Then article shaped is dried,
The drying is carried out at 60-120 DEG C, by water content control in article shaped below 10%.In order to be had
Dried article shaped is calcined by the alpha-alumina supports of proper characteristics, the present invention, and the temperature of the roasting is
1200-1600℃；The time of the roasting is 5-25h.
Alkene epoxidation involved by third aspect present invention is to be based on first aspect present invention institute with silver catalyst
Alpha-alumina supports system prepared by the alpha-alumina supports being related to or the method as involved by second aspect present invention
, in addition to the alpha-alumina supports, silver element, alkali metal, alkali are also contained in the silver catalyst
Metallic element in the coassist agent of earth metal element, rhenium element and optional rhenium.
In above-mentioned silver catalyst, at least one of the alkali metal in lithium, sodium, potassium, rubidium and caesium；It is described
At least one of the alkaline-earth metal in calcium, magnesium, strontium and barium.
According to some embodiments of the present invention, the gross weight meter based on catalyst, silver element in the silver catalyst
Content be 10%-40% (weight)；The content of alkali metal is 5-2000ppm (weight)；Alkaline earth gold
The content for belonging to element is 5-20000ppm (weight)；The content of rhenium element is 50-10000ppm (weight)；
Content≤2000ppm (weight) of metallic element in the coassist agent of rhenium.
Term " optionally " of the present invention refers to contain or not contain, and also refers to add or is added without.
The component of scope is limited in the present invention with "≤", refers to the component of optional or selective addition.
For example, " metallic element≤2000ppm (weight) in the coassist agent of rhenium " represents the coassist agent of rhenium optionally to add
Enter component, and its addition is metallic element≤2000ppm (weight) in the coassist agent of 0≤rhenium.
Term " coassist agent of rhenium " of the present invention is also referred to as " coassist agent of rhenium auxiliary agent ".
The preparation method of silver catalyst involved by fourth aspect present invention be using usual manner prepare, i.e., by α-
Alumina support is made by the solution dipping of Ag-containing compound and auxiliary agent by activation heat treatment.The auxiliary agent
Include the coassist agent of alkali metal promoter, base earth metal promoter, rhenium auxiliary agent and optional rhenium.
Auxiliary agent of the present invention can be applied on carrier prior to, concurrently with, or after immersion silver, can also be in silver
Compound is immersed on carrier after being reduced.Auxiliary agent of the present invention is used for improving the catalytic of silver catalyst
Energy.
The present invention can prepare the silver catalyst with relatively high silver content by using the method repeatedly impregnated.
In the preparation method of above-mentioned catalyst, the rhenium auxiliary agent is in perrhenic acid, perrhenic acid caesium and ammonium perrhenate
At least one；The coassist agent of the rhenium in wolframic acid, wolframic acid caesium, molybdic acid, ammonium molybdate and cerous sulfate extremely
Few one kind.
The method of alkene epoxidation production oxirane involved by fifth aspect present invention includes alkene being placed in
In reaction unit epoxidation is carried out in the presence of silver catalyst prepared by above-mentioned silver catalyst or the above method
Reaction, the reaction unit can carry out the device of epoxidation reaction to be any；The alkene includes benzene second
One or more in alkene, propylene, ethene and 1,3- butadiene.
The detection method of the physical property of alpha-alumina supports and the performance of silver catalyst is as follows in the present invention：
The specific surface area of carrier is surveyed according to international test standards ISO-9277 using nitrogen physisorption BET methods
It is fixed.It is, for example, possible to use U.S. Kang Ta companies NOVA2000e type nitrogen physisorptions instrument determines the ratio of carrier
Surface area.
Porosity, pore volume and the pore size distribution$ of carrier are determined using mercury injection method.It is, for example, possible to use american wheat
Gram company AutoPore9510 types mercury injection apparatus determines the pore volume of carrier.
The side pressure strength of carrier, it is for instance possible to use the intelligent particle of Dalian Chemical Research ＆. Design Inst.'s production DL II types
Intensity measuring device, randomly selects 30 support samples, determines to average after radial direction crushing strength and obtains.
Term " water absorption rate " used refers to that the carrier saturation of unit mass adsorbs the volume of water, unit in the present invention
It is mL/g.Assay method is as follows：A certain amount of carrier is weighed first (it is assumed that its quality is m1), in boiling water
Boil to take out to be erected on the moderate wet gauze of water content by carrier after 1h and remove the unnecessary moisture of carrier surface, most
The quality of the carrier after absorption water is weighed afterwards (it is assumed that m2), the water absorption rate of carrier is calculated as follows.
Water absorption rate=(m2-m1)/m1/ρWater
Wherein ρWaterIt is the density of water under temperature of the measurement, atmospheric pressure.
The measure of catalyst performance：Be related in the present invention various silver catalyst laboratories microreactor (with
Lower abbreviation " micro- anti-") evaluating apparatus tests its initial activity and selectivity.What is used in micro anti-evaluation device is anti-
The stainless steel tube that device is internal diameter 4mm is answered, reaction tube is placed in heating mantle.The admission space of catalyst is 1mL,
Inert filler is arranged at bottom, beds is located at the flat-temperature zone of heating mantle.
The condition determination for the catalyst activity and selectivity that the present invention is used such as table 1：
The condition determination of the catalyst activity and selectivity of table 1
METHOD FOR CONTINUOUS DETERMINATION reactor enters after above-mentioned reaction condition is stably reached, exit gas is constituted.Measurement result is entered
Selectivity S is calculated as follows after the correction of row volume contraction：
Wherein, Δ EO is reactor outlet gas and inlet gas ethylene oxide concentration difference, Δ CO2It is that reactor goes out
Implication and gas concentration lwevel in inlet gas are poor, take the average of more than 10 groups test datas as the examination on the same day
Test result.
According to the present invention, the gibbsite and surge aluminium of Suitable weight ratio are added simultaneously in carrier preparation process
Stone, obtained carrier has ideal specific surface area and pore volume concurrently simultaneously after high-temperature roasting.With it is existing
Technology is compared, and the silver catalyst that the carrier provided using the present invention is made produces oxirane to ethylene epoxidizing
Reaction has the active high and good advantage of selectivity concurrently.
Embodiment
Embodiment 1：
(1) preparation of carrier：Weigh the surge aluminium stone of 427.0g gibbsites, 71.0g, 102.0g boehmites,
10.0g ammonium fluorides, 4.0g barium sulfate, are put into blender and are well mixed, be transferred in kneader, add dilute
Nitric acid (nitric acid:Water=1:3, weight ratio, the density of nitric acid is 1.07g/cm3) until being kneaded into extrudable shaping
Paste, is pasted placed into banded extruder, is extruded into five hole columns, and more than 24h is dried at 60-120 DEG C,
Free water content is reduced to less than 10%, then five dried hole columns are put into natural gas kiln and roasted
Burn, sintering temperature is 1300 DEG C, and constant temperature calcining 10h is finally cooled to room temperature, obtains alpha-alumina supports.
The related physical performance data of the embodiment alpha-alumina supports is shown in Table 2.
(2) preparation of catalyst：60.0g ethylenediamines, 22.0g ethanol are added in the glass flask with stirring
Amine, 75.0g deionized waters, silver oxalate, keep mixed solution temperature at -5 to 10 DEG C, make silver oxalate all molten
Solution, controls the addition of silver oxalate, and it is 24wt% to make silver content in mixed liquor, then adds 0.6g to mixed solution
Cesium nitrate, 0.5g strontium acetates, 0.8g ammonium perrhenates, adding deionized water makes solution gross mass reach 400g,
It is well mixed that dipping solution is made is stand-by.The carrier 20g of above-mentioned preparation is taken, the glass that can be vacuumized is put it into
In container, the dipping solution prepared is poured into, carrier is totally submerged, be evacuated to less than 10mmHg, protect
About 15min is held, unnecessary solution is removed in then leaching.Impregnated support samples are finally placed on 320 DEG C
Air in heat 3min, cool down, that is, silver catalyst is made.
(3) catalyst performance evaluation：System is determined under the conditions of previous process using microreactor evaluating apparatus
Into catalyst sample catalytic performance, reaction starts the result of the test of latter 10th day and is listed in table 3.
Embodiment 2：
(1) preparation of carrier：Weigh the surge aluminium stone of 398.0g gibbsites, 100.0g, 102.0g and intend thin water aluminium
Stone, 10.0g ammonium fluorides, 7.0g barium sulfate, are put into blender and are well mixed, be transferred in kneader, plus
Enter dust technology (nitric acid:Water=1:3, weight ratio, the density of nitric acid is 1.07g/cm3) until be kneaded into it is extrudable into
The paste of type, is pasted placed into banded extruder, is extruded into five hole columns, 24h is dried at 60-120 DEG C
More than, free water content is reduced to less than 10%, five dried hole columns are then put into natural gas kiln
Kiln roasting, sintering temperature is 1350 DEG C, and constant temperature calcining 10h is finally cooled to room temperature, obtains Alpha-alumina
Carrier.The related physical performance data of the embodiment alpha-alumina supports is shown in Table 2.
(2) the preparation be the same as Example 1 of catalyst.
(3) the performance evaluation be the same as Example 1 of catalyst, micro anti-evaluation result is listed in table 3.
Embodiment 3：
(1) preparation of carrier：Weigh the surge aluminium stone of 356.0g gibbsites, 142.0g, 102.0g and intend thin water aluminium
Stone, 15.0g ammonium fluorides, 7.0g barium sulfate, are put into blender and are well mixed, be transferred in kneader, plus
Enter dust technology (nitric acid:Water=1:3, weight ratio, the density of nitric acid is 1.07g/cm3) until be kneaded into it is extrudable into
The paste of type, is pasted placed into banded extruder, is extruded into five hole columns, 24h is dried at 60-120 DEG C
More than, free water content is reduced to less than 10%, five dried hole columns are then put into natural gas kiln
Kiln roasting, sintering temperature is 1250 DEG C, and constant temperature calcining 10h is finally cooled to room temperature, obtains Alpha-alumina
Carrier.The related physical performance data of the embodiment alpha-alumina supports is shown in Table 2.
(2) the preparation be the same as Example 1 of catalyst.
(3) the performance evaluation be the same as Example 1 of catalyst, micro anti-evaluation result is listed in table 3.
Embodiment 4：
(1) preparation of carrier：Weigh the surge aluminium stone of 299.0g gibbsites, 199.0g, 102.0g and intend thin water aluminium
Stone, 10.0g ammonium fluorides, 3.5g barium sulfate, are put into blender and are well mixed, be transferred in kneader, plus
Enter dust technology (nitric acid:Water=1:3, weight ratio, the density of nitric acid is 1.07g/cm3) until be kneaded into it is extrudable into
The paste of type, is pasted placed into banded extruder, is extruded into five hole columns, 24h is dried at 60-120 DEG C
More than, free water content is reduced to less than 10%, five dried hole columns are then put into natural gas kiln
Kiln roasting, sintering temperature is 1250 DEG C, and constant temperature calcining 10h is finally cooled to room temperature, obtains Alpha-alumina
Carrier.The related physical performance data of the embodiment alpha-alumina supports is shown in Table 2.
(2) the preparation be the same as Example 1 of catalyst.
(3) the performance evaluation be the same as Example 1 of catalyst, micro anti-evaluation result is listed in table 3.
Comparative example 1：
(1) preparation of carrier：Weigh 498.0g gibbsites, 102.0g boehmites, 10.0g ammonium fluorides,
4.0g barium sulfate, is put into blender and is well mixed, be transferred in kneader, adds dust technology (nitric acid:Water=1:3,
Weight ratio, the density of nitric acid is 1.07g/cm3) until be kneaded into the paste of extrudable shaping, paste is put
Enter in banded extruder, be extruded into five hole columns, more than 24h is dried at 60-120 DEG C, make free water content reduction
To less than 10%, five dried hole columns are then put into natural gas kiln kiln roasting, sintering temperature is
1300 DEG C, constant temperature calcining 10h is finally cooled to room temperature, obtains alpha-alumina supports.The comparative example alpha-oxidation
The related physical performance data of alumina supporter is shown in Table 2.
(2) the preparation be the same as Example 1 of catalyst.
(3) the performance evaluation be the same as Example 1 of catalyst, micro anti-evaluation result is listed in table 3.
Comparative example 2：
(1) preparation of carrier：Weigh the surge aluminium stone of 166.0g gibbsites, 332.0g, 102.0g and intend thin water aluminium
Stone, 10.0g ammonium fluorides, 4.0g barium sulfate, are put into blender and are well mixed, be transferred in kneader, plus
Enter dust technology (nitric acid:Water=1:3, weight ratio, the density of nitric acid is 1.07g/cm3) until be kneaded into it is extrudable into
The paste of type, is pasted placed into banded extruder, is extruded into five hole columns, 24h is dried at 60-120 DEG C
More than, free water content is reduced to less than 10%, five dried hole columns are then put into natural gas kiln
Kiln roasting, sintering temperature is 1300 DEG C, and constant temperature calcining 10h is finally cooled to room temperature, obtains Alpha-alumina
Carrier.The related physical performance data of the comparative example alpha-alumina supports is shown in Table 2.
(2) the preparation be the same as Example 1 of catalyst.
(3) the performance evaluation be the same as Example 1 of catalyst, micro anti-evaluation result is listed in table 3.
The physical property of the carrier of table 2
| Carrier is originated | Specific surface area (m2/g) | Pore volume (ml/g) | Crushing strength (N/) | Water absorption rate (%) |
| Embodiment 1 | 1.69 | 0.54 | 257 | 56.1 |
| Embodiment 2 | 1.76 | 0.54 | 303 | 54.0 |
| Embodiment 3 | 1.96 | 0.57 | 271 | 56.4 |
| Embodiment 4 | 2.01 | 0.56 | 230 | 54.7 |
| Comparative example 1 | 1.21 | 0.47 | 119 | 53.4 |
| Comparative example 2 | 1.37 | 0.50 | 198 | 53.7 |
The performance of the catalyst of table 3
| Catalyst source | Reaction temperature (DEG C) | Selectivity (%) |
| Embodiment 1 | 84.2 | 225.0 |
| Embodiment 2 | 83.6 | 223.9 |
| Embodiment 3 | 85.3 | 232.6 |
| Embodiment 4 | 84.8 | 228.1 |
| Comparative example 1 | 82.2 | 233.8 |
| Comparative example 2 | 82.6 | 233.5 |
The gibbsite and surge aluminium stone for adding Suitable weight ratio are can be seen that by contrast table 2, the data of table 3
The alpha-alumina supports of preparation have higher specific surface area and pore volume, and the silver that thus prepared by carrier simultaneously
Catalyst has higher activity and selectivity in ethylene epoxidizing production reacting ethylene oxide.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to the present invention's
Any limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein used
Word is descriptive and explanatory vocabulary, rather than limited vocabulary.Can be by regulation in the claims in the present invention
In the range of the present invention is modified, and in without departing substantially from scope and spirit of the present invention to the present invention progress
Revision.Although the present invention described in it is related to specific method, material and embodiment, it is not intended that
The present invention is limited to wherein disclosed particular case, on the contrary, to can be extended to other all with identical function by the present invention
Methods and applications.
Claims (10)
1. a kind of alpha-alumina supports of alkene epoxidation silver catalyst, it is mixed for alpha-alumina supports precursor
Compound is made through shaping, dry and roasting, and the alpha-alumina supports precursor mixture is included：
Component a, three water α-Al2O3；
Component b, boehmite；
Component c, weight alkaline earth metal compound；
Component d, fluorine compounds；
Component e, binding agent；And
Water；
Wherein, the three water α-Al2O3Including gibbsite and surge aluminium stone；The gibbsite and surge aluminium stone
Weight ratio is (1-8):1.
2. alpha-alumina supports according to claim 1, it is characterised in that the alpha-alumina supports
Precursor mixture is as follows by the composition of solid constituent a-d gross weight meters：
3. alpha-alumina supports according to claim 2, it is characterised in that the alpha-alumina supports
Precursor mixture is as follows by the composition of solid constituent a-d gross weight meters：
4. the alpha-alumina supports according to any one in claim 1-3, it is characterised in that
Oxide of the heavy alkaline earth metal compound including weight alkaline-earth metal, sulfate, carbonate, nitrate
With the one or more in oxalates；It is preferred that the heavy alkaline-earth metal is strontium and/or barium；
The fluorine compounds include one kind or many in hydrogen fluoride, aluminum fluoride, ammonium fluoride, magnesium fluoride and ice crystal
Kind；
The weight ratio of the binding agent and water is 1:(1-10)；The binding agent include citric acid, nitric acid, formic acid,
One or more in acetic acid, propionic acid and hydrochloric acid.
5. the alpha-alumina supports according to any one in claim 1-4, it is characterised in that the load
The compression strength of body is 50-350N/；Specific surface area is 0.5-3.0m2/g；Pore volume is 0.4-1.2ml/g；Water suction
Rate >=30%.
6. a kind of preparation method of the alpha-alumina supports in 1-5 such as claim as described in any one, it includes：
Step S1, solid mixture is mixed to form by component a-d；
Step S2, component e and water are mixed with solid mixture, and alpha-alumina supports precursor mixture is made；
Step S3, alpha-alumina supports precursor mixture is molded, and is dried, is calcined, and α-oxygen is made
Change alumina supporter.
7. preparation method according to claim 6, it is characterised in that in step s3, the drying
Temperature be 60-120 DEG C；The temperature of the roasting is 1200-1600 DEG C；The time of the roasting is 5-25h.
8. a kind of alkene epoxidation silver catalyst, its gross weight meter based on catalyst includes following component：
Component l, alpha-alumina supports or such as claim 6 or 7 as described in any one in claim 1-5
Alpha-alumina supports prepared by methods described；
9. a kind of preparation method of silver catalyst as claimed in claim 8, it is will be as in claim 1-5
Alpha-alumina supports prepared by alpha-alumina supports described in any one or as claimed in claims 6 or 7 method
In the solution for being immersed in Ag-containing compound and auxiliary agent, it is made by activation heat treatment；The auxiliary agent includes alkali metal
Auxiliary agent, base earth metal promoter, the coassist agent of rhenium auxiliary agent and optional rhenium.
10. a kind of method that alkene epoxidation produces oxirane, the alkene is in the silver described in claim 8
Epoxidation reaction, the alkene are carried out in the presence of silver catalyst prepared by catalyst or claim 9 methods described
Hydrocarbon includes the one or more in styrene, propylene, ethene and 1,3- butadiene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610010169.4A CN106955744B (en) | 2016-01-08 | 2016-01-08 | The alpha-alumina supports and its preparation and application of alkene epoxidation silver catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610010169.4A CN106955744B (en) | 2016-01-08 | 2016-01-08 | The alpha-alumina supports and its preparation and application of alkene epoxidation silver catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106955744A true CN106955744A (en) | 2017-07-18 |
| CN106955744B CN106955744B (en) | 2019-09-27 |
Family
ID=59480444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610010169.4A Active CN106955744B (en) | 2016-01-08 | 2016-01-08 | The alpha-alumina supports and its preparation and application of alkene epoxidation silver catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106955744B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109499560A (en) * | 2017-09-15 | 2019-03-22 | 中国石油化工股份有限公司 | A kind of alpha-alumina supports, ethylene epoxidizing silver catalyst and ethylene method |
| CN111939884A (en) * | 2019-05-16 | 2020-11-17 | 中国石油化工股份有限公司 | Alpha-alumina carrier and preparation method thereof, silver catalyst and application |
| CN112007625A (en) * | 2019-05-28 | 2020-12-01 | 中国石油化工股份有限公司 | Alpha-alumina carrier, preparation method thereof, silver catalyst and application |
| CN112439399A (en) * | 2019-08-29 | 2021-03-05 | 中国石油化工股份有限公司 | Alpha-alumina carrier, preparation method thereof, silver catalyst and application |
| CN115475609A (en) * | 2021-06-15 | 2022-12-16 | 中国石油化工股份有限公司 | High-stability alpha-alumina carrier, silver catalyst and olefin epoxidation method |
| CN115475610A (en) * | 2021-06-15 | 2022-12-16 | 中国石油化工股份有限公司 | Alpha-alumina carrier and preparation method thereof, silver catalyst and olefin epoxidation method |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762579A (en) * | 2005-09-09 | 2006-04-26 | 清华大学 | Method for preparing large pore capacity, high specific surface area alumina |
| US20060281631A1 (en) * | 2005-06-07 | 2006-12-14 | Gerdes William H | Catalyst carrier and a process for preparing the catalyst carrier |
| US20070037991A1 (en) * | 2005-08-10 | 2007-02-15 | Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg | Process for preparation of catalyst carrier and its use in catalyst preparation |
| CN102133544A (en) * | 2010-01-25 | 2011-07-27 | 中国石油化工股份有限公司 | Alkaline-earth metal fluoride modified alumina supporter, preparation method thereof, and silver catalyst made from alumina supporter and application of silver catalyst in ethylene epoxide (EO) production |
| CN103357439A (en) * | 2012-03-28 | 2013-10-23 | 中国石油化工股份有限公司 | Carrier of silver catalyst for olefin epoxidation, preparation method and application |
| CN103816940A (en) * | 2012-11-19 | 2014-05-28 | 中国石油化工股份有限公司 | Aluminum oxide carrier and preparation method thereof |
| CN104275212A (en) * | 2013-07-02 | 2015-01-14 | 中国石油化工股份有限公司 | Alpha-aluminium oxide carrier for silver catalyst and preparation method thereof |
| CN104707592A (en) * | 2013-12-12 | 2015-06-17 | 中国石油化工股份有限公司 | Preparation method of alpha-alumina carrier for silver catalyst |
-
2016
- 2016-01-08 CN CN201610010169.4A patent/CN106955744B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060281631A1 (en) * | 2005-06-07 | 2006-12-14 | Gerdes William H | Catalyst carrier and a process for preparing the catalyst carrier |
| US7825062B2 (en) * | 2005-06-07 | 2010-11-02 | Saint-Gobain Ceramics & Plastics, Inc. | Catalyst carrier and a process for preparing the catalyst carrier |
| US20070037991A1 (en) * | 2005-08-10 | 2007-02-15 | Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg | Process for preparation of catalyst carrier and its use in catalyst preparation |
| CN1762579A (en) * | 2005-09-09 | 2006-04-26 | 清华大学 | Method for preparing large pore capacity, high specific surface area alumina |
| CN102133544A (en) * | 2010-01-25 | 2011-07-27 | 中国石油化工股份有限公司 | Alkaline-earth metal fluoride modified alumina supporter, preparation method thereof, and silver catalyst made from alumina supporter and application of silver catalyst in ethylene epoxide (EO) production |
| CN103357439A (en) * | 2012-03-28 | 2013-10-23 | 中国石油化工股份有限公司 | Carrier of silver catalyst for olefin epoxidation, preparation method and application |
| CN103816940A (en) * | 2012-11-19 | 2014-05-28 | 中国石油化工股份有限公司 | Aluminum oxide carrier and preparation method thereof |
| CN104275212A (en) * | 2013-07-02 | 2015-01-14 | 中国石油化工股份有限公司 | Alpha-aluminium oxide carrier for silver catalyst and preparation method thereof |
| CN104707592A (en) * | 2013-12-12 | 2015-06-17 | 中国石油化工股份有限公司 | Preparation method of alpha-alumina carrier for silver catalyst |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109499560A (en) * | 2017-09-15 | 2019-03-22 | 中国石油化工股份有限公司 | A kind of alpha-alumina supports, ethylene epoxidizing silver catalyst and ethylene method |
| CN109499560B (en) * | 2017-09-15 | 2021-04-09 | 中国石油化工股份有限公司 | Alpha-alumina carrier, silver catalyst for ethylene epoxidation and ethylene oxidation method |
| CN111939884A (en) * | 2019-05-16 | 2020-11-17 | 中国石油化工股份有限公司 | Alpha-alumina carrier and preparation method thereof, silver catalyst and application |
| CN111939884B (en) * | 2019-05-16 | 2023-05-09 | 中国石油化工股份有限公司 | Alpha-alumina carrier, preparation method thereof, silver catalyst and application |
| CN112007625A (en) * | 2019-05-28 | 2020-12-01 | 中国石油化工股份有限公司 | Alpha-alumina carrier, preparation method thereof, silver catalyst and application |
| CN112439399A (en) * | 2019-08-29 | 2021-03-05 | 中国石油化工股份有限公司 | Alpha-alumina carrier, preparation method thereof, silver catalyst and application |
| CN115475609A (en) * | 2021-06-15 | 2022-12-16 | 中国石油化工股份有限公司 | High-stability alpha-alumina carrier, silver catalyst and olefin epoxidation method |
| CN115475610A (en) * | 2021-06-15 | 2022-12-16 | 中国石油化工股份有限公司 | Alpha-alumina carrier and preparation method thereof, silver catalyst and olefin epoxidation method |
| CN115475610B (en) * | 2021-06-15 | 2024-03-29 | 中国石油化工股份有限公司 | Alpha-alumina carrier, preparation method thereof, silver catalyst and olefin epoxidation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106955744B (en) | 2019-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106955744A (en) | The alpha-alumina supports of alkene epoxidation silver catalyst and its preparation and application | |
| CN103372466B (en) | Preparation method of silver catalyst carrier for production of ethylene oxide and application thereof | |
| CN100577289C (en) | The carrier of ethylene oxide silver catalyst, its preparation method and application thereof | |
| CN102015095B (en) | Porous body precursors, shaped porous bodies, processes for making them, and end-use products based upon the same | |
| CN102145285A (en) | Carrier of silver catalyst for producing epoxy ethane, preparation method and application of carrier of silver catalyst | |
| CN106955693A (en) | The alpha-alumina supports of ethylene epoxidizing silver catalyst and its preparation and application | |
| CN106311353B (en) | A kind of alpha-alumina supports, corresponding silver catalyst and application | |
| CN109499558A (en) | A kind of alpha-alumina supports, silver catalyst and olefin epoxidation process | |
| CN103418380B (en) | A kind of preparation method of silver catalyst and producing in oxirane at ethylene applies | |
| CN103357441B (en) | Silver catalyst carrier, its preparation method, the catalyst be made up of it and application | |
| CN104275212B (en) | Alpha-aluminium oxide carrier for silver catalyst and preparation method thereof | |
| CN104549544B (en) | Silver catalyst carrier preparation method, thus obtained silver catalyst carrier, silver catalyst and its application | |
| CN102553651B (en) | The application of alumina support, its preparation method, the silver catalyst be made up of it and this silver catalyst | |
| CN105080618B (en) | A kind of preparation method of alpha-aluminium oxide carrier for silver catalyst | |
| CN106955692B (en) | A kind of alpha-alumina supports, silver catalyst prepared therefrom and its application | |
| CN104069893B (en) | Produce silver catalyst carrier, preparation method and application thereof for oxirane | |
| CN112007625B (en) | Alpha-alumina carrier, preparation method, silver catalyst and application | |
| CN106955694B (en) | A kind of alpha-alumina supports, silver catalyst prepared therefrom and its application | |
| CN107413389A (en) | Alpha-aluminium oxide carrier for silver catalyst and preparation method and application | |
| CN109201027B (en) | Alpha-alumina carrier and preparation method and application thereof | |
| CN104549545B (en) | For silver catalyst alpha-aluminium oxide carrier and preparation method thereof of alkene epoxidation | |
| CN107812542B (en) | Alpha-alumina carrier and preparation method and application thereof | |
| CN109499559B (en) | Alpha-alumina carrier, silver catalyst for ethylene epoxidation and ethylene oxidation method | |
| CN106955745A (en) | A kind of alpha-alumina supports, silver catalyst prepared therefrom and application | |
| CN111437888A (en) | α -alumina carrier, silver catalyst for ethylene epoxidation and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |