CN106955744B - The alpha-alumina supports and its preparation and application of alkene epoxidation silver catalyst - Google Patents
The alpha-alumina supports and its preparation and application of alkene epoxidation silver catalyst Download PDFInfo
- Publication number
- CN106955744B CN106955744B CN201610010169.4A CN201610010169A CN106955744B CN 106955744 B CN106955744 B CN 106955744B CN 201610010169 A CN201610010169 A CN 201610010169A CN 106955744 B CN106955744 B CN 106955744B
- Authority
- CN
- China
- Prior art keywords
- alpha
- alumina supports
- component
- preparation
- silver catalyst
- 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.)
- Active
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 and preparation method thereof of alkene epoxidation silver catalyst, alpha-alumina supports specific surface area with higher and pore volume as made from the gibbsite and surge aluminium stone of Suitable weight ratio are added in the preparation process of carrier.The invention further relates to the silver catalyst made of the alpha-alumina supports and its applications in ethylene epoxidizing production ethylene oxide, and the silver catalyst is for having both higher activity and selectivity in ethylene epoxidizing production ethylene oxide.
Description
Technical field
The invention belongs to catalyst carriers and catalyst preparation technical field, and in particular to a kind of alkene epoxidation is urged with silver
The alpha-alumina supports and its preparation and application of agent.
Background technique
In alkene epoxidation production epoxide reaction, under certain reaction condition, containing alkene and oxygen
Reaction mixture gas reacts the production by-products such as epoxide and a small amount of carbon dioxide, water under the effect of the catalyst.Wherein
Activity, selectivity and stability are the main performance index of silver catalyst.Activity refers to that process for ethylene oxide production reaches certain
Reaction temperature required when load is reacted, reaction temperature is lower, and the activity of catalyst is higher；Selectivity refers to that ethylene turns in reaction
It is melted into the ratio between molal quantity and the overall reaction molal quantity of ethylene of ethylene oxide；Stability is then expressed as the decline of activity and selectivity
The stability of rate, fall off rate more small catalyst is better.
Ethylene oxide can be made as one of epoxide under the action of silver catalyst with ethylene and oxygen
It is obtained for reaction gas.So far, silver catalyst is still uniquely having for industrial ethylene epoxidizing production ethylene oxide (EO)
Catalyst is imitated, silver catalyst carrier is usually made of Alpha-alumina resistant to high temperature.
The material for preparing the alpha-alumina supports of silver catalyst generally comprises: alpha-alumina powder and/or its presoma；It is viscous
Agent is tied, for shortening the sintering time for being bonded together particle；Thermal decomposition burnout materials form material for serving as duct
Material；Lubricant is conducive to carrier molding；Auxiliary agent, for improving the performance of alpha-alumina supports and/or silver catalyst.It is general next
It says, the method for preparing alpha-alumina supports is that these raw materials are carried out to mixing, are mediated, then according to molding blank of different shapes
Finally alpha-alumina supports are made by high temperature sintering in molding.Alpha-alumina supports have very important work to silver catalyst
With such as: improving the dispersibility of active component；The dosage for reducing active component, reduces cost；Increase effective specific surface area, mentions
For suitable pore volume；Improve the thermal stability of catalyst.The especially specific surface area and pore volume of alpha-alumina supports, due to
It is strong exothermal reaction that ethylene epoxidizing, which produces reacting ethylene oxide, they play particularly important work to the performance of silver catalyst
With.Specific surface area such as alpha-alumina supports is too low, then it is evenly dispersed on carrier to be unfavorable for active component；Such as Alpha-alumina
The pore volume of carrier is too low, then is unfavorable for catalytic reaction process reactant or the timely adsorption desorption of product, and also result in
The heat that reaction generates cannot be taken away in time, and local temperature is excessively high, and silver catalyst reduced performance is caused even to inactivate.
The prior art largely improved by thermal decomposition burnout materials, auxiliary agent alpha-alumina supports specific surface area and
Pore volume, but its specific surface area can be improved simultaneously and the prior art of pore volume is less.Therefore, it is badly in need of research and development at present
A kind of alpha-alumina supports of the alkene epoxidation silver catalyst with good specific surface area and pore volume.
Summary of the invention
The technical problem to be solved by the present invention is to solve the above shortcomings of the prior art and to provide a kind of alkene epoxidation use
The alpha-alumina supports of silver catalyst, the alpha-alumina supports have both good specific surface area and pore volume.The present invention also provides
A kind of preparation method of above-mentioned alpha-alumina supports, this method add Suitable weight ratio simultaneously in carrier preparation process
Gibbsite and surge aluminium stone, the specific surface area and pore volume of prepared alpha-alumina supports are all higher.It will be by above-mentioned alpha-oxidation
The silver catalyst of alumina supporter preparation produces ethylene oxide for ethylene epoxidizing, and catalyst activity and selectivity can obtain simultaneously
Improve.
For this purpose, first aspect present invention provides a kind of alpha-alumina supports of alkene epoxidation silver catalyst, it is
Alpha-alumina supports precursor mixture is made through molding, drying and roasting, and the alpha-alumina supports precursor mixture includes:
Component a, three water α-Al2O3；
Component b, boehmite；
Component c, weight alkaline earth metal compound；
Component d, fluorine compounds；
Component e, binder；And
Water；
Wherein, the gibbsite includes gibbsite and surge aluminium stone；The weight ratio of the gibbsite and surge aluminium stone
For (1-8): 1.
According to the present invention, the alpha-alumina supports precursor mixture is as follows by the composition of solid component a-d total weight:
In some embodiments of the invention, the alpha-alumina supports precursor mixture presses solid component a-d total weight
The composition of meter is as follows:
According to the present invention, the heavy alkaline earth metal compound include the weight oxide of alkaline-earth metal, sulfate, carbonate,
One or more of 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, magnesium fluoride and
One of ice crystal is a variety of.
In other embodiments of the invention, the weight ratio of the binder and water is 1:(1-10)；The binder
Including one of citric acid, nitric acid, formic acid, acetic acid, propionic acid and hydrochloric acid or a variety of.
According to the present invention, the compression strength of the carrier is 50-350N/；Specific surface area is 0.5-3.0m2/g；Kong Rong
For 0.4-1.2ml/g；Water absorption rate >=30%.
Second aspect of the present invention provides a kind of preparation method of alpha-alumina supports as described in the first aspect of the invention,
Comprising:
Component a-d is mixed to form solid mixture by step S1；
Step S2 mixes component e and water with solid mixture, and alpha-alumina supports precursor mixture is made；
Step S3 forms alpha-alumina supports precursor mixture, and dry, roasting, and alpha-alumina supports are made.
In some embodiments of the invention, in step s3, the temperature of the drying is 60-120 DEG C；The roasting
Temperature 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, the total weight packet based on catalyst
Containing following component:
Component l, 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；
Fourth aspect present invention provides a kind of preparation method of silver catalyst as described in the third aspect of the present invention, 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 preparation Alpha-alumina
Carrier impregnation is heat-treated by overactivation and is made in the solution of Ag-containing compound and auxiliary agent.The auxiliary agent includes that alkali metal helps
Agent, base earth metal promoter, rhenium auxiliary agent and optional rhenium coassist agent.
Fifth aspect present invention provides a kind of method of alkene epoxidation production ethylene oxide, and the alkene is in the present invention
Epoxy is carried out in the presence of silver catalyst described in the third aspect or the silver catalyst of fourth aspect present invention the method preparation
Change reaction, the alkene includes one of styrene, propylene, ethylene and 1,3-butadiene or a variety of.
Specific embodiment
To keep the present invention easier to understand, below in conjunction with embodiment, the present invention will be described in detail, these embodiments are only
Serve illustrative, it is not limited to application range of the invention.
Good specific surface area and pore volume, invention of the invention cannot be had both simultaneously in view of existing silver catalyst carrier
People makes further research the alpha-alumina supports of silver catalyst used in alkene epoxidation production ethylene oxide, and discovery is simultaneously
Using gibbsite and surge aluminium standby alpha-alumina supports made of stones, and control their addition weight ratio within the appropriate range,
The specific surface area and pore volume for the alpha-alumina supports prepared are all higher, and thus the silver catalyst of carrier preparation is used for ethylene
When epoxidation produces ethylene oxide, catalyst activity and selectivity can be improved simultaneously.The present invention is based on above-mentioned hair
Now make.
The alpha-alumina supports of the silver catalyst of alkene epoxidation involved in first aspect present invention are by containing weight ratio
For (1-8): 1 gibbsite and the alpha-alumina supports precursor mixture of surge aluminium stone are made through molding, drying and roasting, wherein
The weight content of Alpha-alumina is 90% (weight) or more.The compression strength of the alpha-alumina supports is 50-350N/；Than
Surface area is 0.5-3.0m2/g；Kong Rongwei 0.4-1.2ml/g；Water absorption rate >=30%.
In some embodiments of the invention, the weight ratio of the preferably described gibbsite and surge aluminium stone is (1.5-6): 1.
Some specific embodiments according to the present invention, second aspect of the present invention are related such as first aspect present invention institute
The preparation methods of the alpha-alumina supports being related to the following steps are included:
(1) preparation has the solid mixture formed as follows:
Component a accounts for the gibbsite that solid mixture total weight is 5.0%-90.0% (weight)；
Component b accounts for the boehmite that solid mixture total weight is 5.0%-85.0% (weight)；
Component c accounts for the heavy alkaline earth metal compound that solid mixture total weight is 0.1%-8.0% (weight)；
Component d accounts for the fluorine compounds that solid mixture total weight is 0.1%-10.0% (weight)；
(2) component e binder is added in obtained solid mixture in step (1) and alpha-alumina supports precursor is made in water
Mixture；
(3) the alpha-alumina supports precursor mixture that step (2) obtains mediated, formed, dried, roasted, obtained
Alpha-alumina supports.
In the preparation method of above-mentioned carrier, in solid mixture described in step (1), exceptionally except above-mentioned a-d these types group,
It can also include thermal decomposition burnout materials and lubricant；The thermal decomposition burnout materials include polyethylene, polypropylene, petroleum
One of burnt, carbon dust and graphite are a variety of；The preferred vaseline of lubricant.
In the preparation method of above-mentioned carrier, the preferably described gibbsite accounts for the 40.0%- of solid mixture total weight
80.0% (weight)；It is preferred that the boehmite accounts for the 15.0%-50.0% (weight) of solid mixture total weight；It is preferred that institute
State the 0.1%-4.0% (weight) that weight alkaline earth metal compound accounts for solid mixture total weight；It is preferred that the fluorine compounds account for admittedly
The 0.2%-6.0% (weight) of body total weight of the mixture.
In order to improve the intensity of alpha-alumina supports, the present invention joined weight alkaline earth during preparing alpha-alumina supports
Metallic compound, the heavy alkaline earth metal compound are the compound of strontium and/or barium；The compound of the strontium and/or barium includes
One of oxide and strontium and/or the corresponding salt of barium of strontium and/or barium are a variety of；The strontium and/or the corresponding salt of barium include
One of the sulfate of strontium and/or barium, carbonate, nitrate and oxalates are a variety of.
In the preparation method of above-mentioned carrier, the conversion of hydrated alumina (gibbsite, boehmite) thermal dehydration
At transition aluminas, when reaching certain maturing 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, eliminate not
Necessary micropore reduces by 0.1 μm of pore below, improves the selectivity of silver catalyst.Fluorine compounds of the present invention include
One of hydrogen fluoride, aluminum fluoride, ammonium fluoride, magnesium fluoride and ice crystal are a variety of.
In the preparation method of above-mentioned carrier, binder can generate Aluminum sol with the boehmite in solid mixture,
Each component is bonded together, extrudable molding paste is become.According to the present invention, the weight ratio of the binder and water is
1:(1-10)；It is preferred that the binder includes one of citric acid, nitric acid, formic acid, acetic acid, propionic acid and hydrochloric acid or a variety of.
The dosage of binder is not particularly limited in the present invention, dosage is with can be thin with intending in solid mixture
Diaspore generates Aluminum sol to be glued together to be formed subject to extrudable molding paste with each component.
Term " water " of the present invention unless otherwise specified, refers both to deionized water.
It does not need to be added in order between solid mixture and the addition of binder solution in the present invention, such as solid mixing
Fluoride in object can just be added in solid mixture together with binder solution finally.
In order to which mixture to be uniformly mixed, the present invention is mediated mixture, and kneading carries out in kneader, is mediated
Time is 5-90min.After mixture is mediated sufficiently, carrier can be made to certain shapes, including spherical shape, block shape, cylinder,
Round Porous cylindricality, Rasching ring, cloverleaf pattern, honeycombed etc., described being molded in molding machine carry out.For the ease of being extruded into
Type object, can be added shaping assistant in solid mixture, and shaping assistant includes vaseline, graphite, paraffin, one in vegetable oil
Kind is a variety of.Then molding is dry, the drying carries out at 60-120 DEG C, by water content control in molding 10%
Below.There are the alpha-alumina supports of proper characteristics in order to obtain, the present invention roasts the molding after drying, the roasting
Temperature is 1200-1600 DEG C；The time of the roasting is 5-25h.
Alkene epoxidation involved in third aspect present invention is based on involved by first aspect present invention with silver catalyst
Alpha-alumina supports or the method as involved in second aspect of the present invention preparation alpha-alumina supports made from, in addition to the α-
Carrying alumina is external, and silver element, alkali metal element, alkali earth metal, rhenium element are also contained in the silver catalyst and is appointed
Metallic element in the coassist agent of the rhenium of choosing.
In above-mentioned silver catalyst, the alkali metal is selected from least one of lithium, sodium, potassium, rubidium and caesium；The alkaline-earth metal
Selected from least one of calcium, magnesium, strontium and barium.
According to some embodiments of the present invention, based on the total weight of catalyst, silver element contains in the silver catalyst
Amount is 10%-40% (weight)；The content of alkali metal element is 5-2000ppm (weight)；The content of alkali earth metal is 5-
20000ppm (weight)；The content of rhenium element is 50-10000ppm (weight)；The content of metallic element in the coassist agent of rhenium≤
2000ppm (weight).
Term " optionally " of the present invention, which refers to, to be contained or not contain, and is also referred to be added or is added without.
The component for limiting range 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 " indicates that the coassist agent of rhenium is to be optionally added component, and it adds
Enter metallic element≤2000ppm (weight) in the coassist agent that amount is 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 in fourth aspect present invention is to be prepared using usual manner, i.e., by alpha-oxidation
Alumina supporter is made by the solution of Ag-containing compound and auxiliary agent dipping by activation heat treatment.The auxiliary agent includes that alkali metal helps
Agent, base earth metal promoter, rhenium auxiliary agent and optional rhenium coassist agent.
Auxiliary agent of the present invention can be applied on carrier prior to, concurrently with, or after immersion silver, can also be closed in patina
Object is immersed on carrier after being reduced.Auxiliary agent of the present invention is used to improve the catalytic performance of silver catalyst.
The present invention can have the silver catalyst of relatively high silver content by using the method preparation repeatedly impregnated.
In the preparation method of above-mentioned catalyst, the rhenium auxiliary agent in perrhenic acid, perrhenic acid caesium and ammonium perrhenate extremely
Few one kind；The coassist agent of the rhenium is selected from least one of wolframic acid, wolframic acid caesium, molybdic acid, ammonium molybdate and cerous sulfate.
The method that alkene epoxidation involved in fifth aspect present invention produces ethylene oxide includes that alkene is placed in reaction
Epoxidation reaction, the reaction are carried out in the presence of silver catalyst prepared by above-mentioned silver catalyst or the above method in device
Device can be any device that can carry out epoxidation reaction；The alkene includes styrene, propylene, ethylene and 1,3- fourth two
One of alkene is a variety of.
The detection method of the performance of the physical property and silver catalyst of alpha-alumina supports is as follows in the present invention:
The specific surface area of carrier is measured according to international test standards ISO-9277 using nitrogen physisorption BET method.Example
Such as, the specific surface area of U.S. Kang Ta company NOVA2000e type nitrogen physisorption instrument measurement carrier can be used.
Porosity, Kong Rong and the pore size distribution$ of carrier are measured using mercury injection method.It is, for example, possible to use Merck & Co., Inc, the U.S.
The Kong Rong of AutoPore9510 type mercury injection apparatus measurement carrier.
The side pressure strength of carrier is surveyed for example, can produce II type intelligence granule strength of DL using Dalian Chemical Research &. Design Inst.
Determine instrument, randomly select 30 support samples, is averaged to obtain after measuring radial crushing strength.
Term " water absorption rate " used refers to the volume of the carrier saturation absorption water of unit mass in the present invention, and unit is mL/
g.Measuring method is as follows: weighing a certain amount of carrier first (it is assumed that its quality is m1), carrier taking-up is erected after 1h is boiled in boiling water
It stands and removes the extra moisture of carrier surface on the moderate wet gauze of water content, the quality of the carrier after finally weighing absorption water
(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 that measuring temperature, atmospheric pressure are lauched.
The measurement of catalyst performance: laboratory microreactor (the following letter of various silver catalysts involved in the present invention
Claiming " micro- anti-") evaluating apparatus tests its initial activity and selectivity.Reactor used in micro anti-evaluation device is internal diameter 4mm
Stainless steel tube, reaction tube are placed in heating mantle.The admission space of catalyst is 1mL, and there is inert filler in lower part, makes catalyst bed
Positioned at the flat-temperature zone of heating mantle.
The determination condition for the catalyst activity and selectivity that the present invention uses such as table 1:
The determination condition of 1 catalyst activity and selectivity of table
METHOD FOR CONTINUOUS DETERMINATION reactor enters after stably reaching above-mentioned reaction condition, exit gas forms.Measurement result carries out body
Product calculates selectivity S after shrinking correction as follows:
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.
According to the present invention, the gibbsite and surge aluminium stone of Suitable weight ratio, warp is added simultaneously in carrier preparation process
It crosses carrier obtained after high-temperature roasting while having both ideal specific surface area and pore volume.Compared with prior art, it uses
Silver catalyst made of carrier provided by the invention has both active high and choosing to the reaction of ethylene epoxidizing production ethylene oxide
The good advantage of selecting property.
Embodiment
Embodiment 1:
(1) the surge aluminium stone of 427.0g gibbsite, 71.0g, 102.0g boehmite, 10.0g fluorine the preparation of carrier: are weighed
Change ammonium, 4.0g barium sulfate, is put into blender and is uniformly mixed, be transferred in kneader, addition dust technology (nitric acid: water=1:3,
Weight ratio, the density of nitric acid are 1.07g/cm3) until be kneaded into extrudable molding paste, paste placed into banded extruder
In, it is extruded into five hole columns, is dried at 60-120 DEG C more than for 24 hours, free water content is made to be reduced to 10% hereinafter, then will do
Dry five good hole columns are put into natural gas kiln kiln roasting, and maturing 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) 60.0g ethylenediamine, 22.0g ethanol amine, 75.0g the preparation of catalyst: are added in the glass flask with stirring
Deionized water, silver oxalate keep mixed solution temperature at -5 to 10 DEG C, dissolve silver oxalate all, control the addition of silver oxalate
Amount, makes silver content 24wt% in mixed liquor, and 0.6g cesium nitrate, 0.5g strontium acetate, 0.8g high rhenium then is added to mixed solution
Sour ammonium, adding deionized water makes solution gross mass reach 400g, is uniformly mixed that dipping solution is made is stand-by.Take above-mentioned preparation
Carrier 20g is put it into the glass container that can be vacuumized, and pours into the dipping solution prepared, is totally submerged carrier, is taken out true
It is empty to be extremely lower than 10mmHg, about 15min is kept, then extra solution is removed in leaching.Finally impregnated support samples are placed
3min is heated in 320 DEG C of air, it is cooling, that is, silver catalyst is made.
(3) it catalyst performance evaluation: is urged made of being measured under the conditions of previous process using microreactor evaluating apparatus
The catalytic performance of agent sample, reaction start rear 10th day test result and are listed in table 3.
Embodiment 2:
(1) the surge aluminium stone of 398.0g gibbsite, 100.0g, 102.0g boehmite, 10.0g the preparation of carrier: are weighed
Ammonium fluoride, 7.0g barium sulfate are put into blender and are uniformly mixed, be transferred in kneader, addition dust technology (nitric acid: water=1:
3, weight ratio, the density of nitric acid is 1.07g/cm3) until be kneaded into extrudable molding paste, paste placed into extrusion
In machine, it is extruded into five hole columns, is dried at 60-120 DEG C more than for 24 hours, free water content is made to be reduced to 10% hereinafter, then will
Five dried hole columns are put into natural gas kiln kiln roasting, and maturing temperature is 1350 DEG C, and constant temperature calcining 10h is finally cooled down
To room temperature, alpha-alumina supports are obtained.The related physical performance data of the embodiment alpha-alumina supports is shown in Table 2.
(2) preparation of catalyst is the same as embodiment 1.
(3) performance evaluation of catalyst is listed in table 3 with embodiment 1, micro anti-evaluation result.
Embodiment 3:
(1) the surge aluminium stone of 356.0g gibbsite, 142.0g, 102.0g boehmite, 15.0g the preparation of carrier: are weighed
Ammonium fluoride, 7.0g barium sulfate are put into blender and are uniformly mixed, be transferred in kneader, addition dust technology (nitric acid: water=1:
3, weight ratio, the density of nitric acid is 1.07g/cm3) until be kneaded into extrudable molding paste, paste placed into extrusion
In machine, it is extruded into five hole columns, is dried at 60-120 DEG C more than for 24 hours, free water content is made to be reduced to 10% hereinafter, then will
Five dried hole columns are put into natural gas kiln kiln roasting, and maturing temperature is 1250 DEG C, and constant temperature calcining 10h is finally cooled down
To room temperature, alpha-alumina supports are obtained.The related physical performance data of the embodiment alpha-alumina supports is shown in Table 2.
(2) preparation of catalyst is the same as embodiment 1.
(3) performance evaluation of catalyst is listed in table 3 with embodiment 1, micro anti-evaluation result.
Embodiment 4:
(1) the surge aluminium stone of 299.0g gibbsite, 199.0g, 102.0g boehmite, 10.0g the preparation of carrier: are weighed
Ammonium fluoride, 3.5g barium sulfate are put into blender and are uniformly mixed, be transferred in kneader, addition dust technology (nitric acid: water=1:
3, weight ratio, the density of nitric acid is 1.07g/cm3) until be kneaded into extrudable molding paste, paste placed into extrusion
In machine, it is extruded into five hole columns, is dried at 60-120 DEG C more than for 24 hours, free water content is made to be reduced to 10% hereinafter, then will
Five dried hole columns are put into natural gas kiln kiln roasting, and maturing temperature is 1250 DEG C, and constant temperature calcining 10h is finally cooled down
To room temperature, alpha-alumina supports are obtained.The related physical performance data of the embodiment alpha-alumina supports is shown in Table 2.
(2) preparation of catalyst is the same as embodiment 1.
(3) performance evaluation of catalyst is listed in table 3 with embodiment 1, micro anti-evaluation result.
Comparative example 1:
(1) 498.0g gibbsite, 102.0g boehmite, 10.0g ammonium fluoride, 4.0g sulphur the preparation of carrier: are weighed
Sour barium is put into blender and is uniformly mixed, is transferred in kneader, and dust technology (nitric acid: water=1:3, weight ratio, nitric acid is added
Density be 1.07g/cm3) until be kneaded into extrudable molding paste, it pastes placed into banded extruder, is extruded into five holes
Column is dried at 60-120 DEG C more than for 24 hours, and free water content is made to be reduced to 10% hereinafter, then by five dried holes
Column is put into natural gas kiln kiln roasting, and maturing temperature is 1300 DEG C, and constant temperature calcining 10h is finally cooled to room temperature, obtains α-
Alumina support.The related physical performance data of the comparative example alpha-alumina supports is shown in Table 2.
(2) preparation of catalyst is the same as embodiment 1.
(3) performance evaluation of catalyst is listed in table 3 with embodiment 1, micro anti-evaluation result.
Comparative example 2:
(1) the surge aluminium stone of 166.0g gibbsite, 332.0g, 102.0g boehmite, 10.0g the preparation of carrier: are weighed
Ammonium fluoride, 4.0g barium sulfate are put into blender and are uniformly mixed, be transferred in kneader, addition dust technology (nitric acid: water=1:
3, weight ratio, the density of nitric acid is 1.07g/cm3) until be kneaded into extrudable molding paste, paste placed into extrusion
In machine, it is extruded into five hole columns, is dried at 60-120 DEG C more than for 24 hours, free water content is made to be reduced to 10% hereinafter, then will
Five dried hole columns are put into natural gas kiln kiln roasting, and maturing temperature is 1300 DEG C, and constant temperature calcining 10h is finally cooled down
To room temperature, alpha-alumina supports are obtained.The related physical performance data of the comparative example alpha-alumina supports is shown in Table 2.
(2) preparation of catalyst is the same as embodiment 1.
(3) performance evaluation of catalyst is listed in table 3 with embodiment 1, micro anti-evaluation result.
The physical property of 2 carrier of table
| Carrier source | Specific surface area (m2/g) | Kong Rong (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 3 catalyst of table
It can be seen that the gibbsite that Suitable weight ratio is added by contrast table 2,3 data of table and surge aluminium be made of stones standby
Alpha-alumina supports while specific surface area with higher and pore volume, and the silver catalyst that thus prepared by carrier is in ethylene ring
Activity and selectivity with higher in oxidation production reacting ethylene oxide.
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 (10)
1. a kind of alpha-alumina supports of alkene epoxidation silver catalyst, be alpha-alumina supports precursor mixture through at
Type, drying and roasting are made, and the alpha-alumina supports precursor mixture includes:
Component a, three water α-Al2O3；
Component b, boehmite；
Component c, weight alkaline earth metal compound；
Component d, fluorine compounds；
Component e, binder；And
Water；
Wherein, the three water α-Al2O3For gibbsite and surge aluminium stone；The weight ratio of the gibbsite and surge aluminium stone is (1.5-
6):1；
The alpha-alumina supports precursor mixture is as follows by the composition of solid component a-d total weight:
Component e, binder；And
The water of surplus.
2. alpha-alumina supports according to claim 1, which is characterized in that the alpha-alumina supports precursor mixture is pressed
The composition of solid component a-d total weight is as follows:
Component e, binder；And
The water of surplus.
3. alpha-alumina supports according to claim 1 or 2, which is characterized in that
In oxide, sulfate, carbonate, nitrate and oxalates of the heavy alkaline earth metal compound selected from weight alkaline-earth metal
It is one or more；
The fluorine compounds are selected from one of hydrogen fluoride, aluminum fluoride, ammonium fluoride, magnesium fluoride and ice crystal or a variety of；
The weight ratio of the binder and water is 1:(1-10)；The binder is selected from citric acid, nitric acid, formic acid, acetic acid, propionic acid
With one of hydrochloric acid or a variety of.
4. alpha-alumina supports according to claim 3, which is characterized in that the heavy alkaline-earth metal is strontium and/or barium.
5. alpha-alumina supports according to claim 1 or 2, which is characterized in that the compression strength of the carrier is 50-
350N/；Specific surface area is 0.5-3.0m2/g；Kong Rongwei 0.4-1.2ml/g；Water absorption rate >=30%.
6. a kind of preparation method of the alpha-alumina supports as described in any one of claim 1-5 comprising:
Component a-d is mixed to form solid mixture by step S1；
Step S2 mixes component e and water with solid mixture, and alpha-alumina supports precursor mixture is made；
Step S3 forms alpha-alumina supports precursor mixture, and dry, roasting, and alpha-alumina supports are made.
7. preparation method according to claim 6, which is characterized in that in step s3, the temperature of the drying is 60-
120℃；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, the total weight based on catalyst includes following component:
Component l, alpha-alumina supports as described in any one of claim 1-5 or as claimed in claims 6 or 7 method system
Standby alpha-alumina supports；
9. a kind of preparation method of silver catalyst as claimed in claim 8, for will be such as any one of claim 1-5 institute
The alpha-alumina supports stated or the as claimed in claims 6 or 7 alpha-alumina supports of method preparation be immersed in Ag-containing compound and
In the solution of auxiliary agent, it is made by activation heat treatment；The auxiliary agent be selected from alkali metal promoter, base earth metal promoter, rhenium auxiliary agent and
The coassist agent of optional rhenium.
10. a kind of method of alkene epoxidation production ethylene oxide, the alkene is in silver catalyst according to any one of claims 8 or power
Carry out epoxidation reaction in the presence of the silver catalyst that benefit requires 9 the methods to prepare, the alkene be selected from styrene, propylene,
One of ethylene and 1,3- butadiene are a variety of.
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 CN106955744A (en) | 2017-07-18 |
| CN106955744B true 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) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN112007625B (en) * | 2019-05-28 | 2023-05-30 | 中国石油化工股份有限公司 | Alpha-alumina carrier, preparation method, silver catalyst and application |
| CN112439399B (en) * | 2019-08-29 | 2023-05-09 | 中国石油化工股份有限公司 | Alpha-alumina carrier, preparation method, 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 |
| 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 |
Citations (7)
| 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 |
| US7825062B2 (en) * | 2005-06-07 | 2010-11-02 | Saint-Gobain Ceramics & Plastics, Inc. | Catalyst carrier and a process for preparing the catalyst carrier |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8791280B2 (en) * | 2005-08-10 | 2014-07-29 | Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg | Process for preparation of catalyst carrier and its use in catalyst preparation |
-
2016
- 2016-01-08 CN CN201610010169.4A patent/CN106955744B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7825062B2 (en) * | 2005-06-07 | 2010-11-02 | Saint-Gobain Ceramics & Plastics, Inc. | Catalyst carrier and a process for preparing the catalyst carrier |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106955744A (en) | 2017-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106955744B (en) | The alpha-alumina supports and its preparation and application of alkene epoxidation silver catalyst | |
| CN103372466B (en) | Preparation method of silver catalyst carrier for production of ethylene oxide and application thereof | |
| CN101007287A (en) | Carrier of ethylene oxide silver catalyst, and its preparation method and application | |
| CN102145285A (en) | Carrier of silver catalyst for producing epoxy ethane, preparation method and application of carrier of silver catalyst | |
| CN104549543B (en) | Alumina support, the silver catalyst being made from it and its application | |
| KR20120046706A (en) | An alumina support, a preparation method for the same, and a silver catalyst prepared from the same, and use thereof | |
| CN109499558A (en) | A kind of alpha-alumina supports, silver catalyst and olefin epoxidation process | |
| CN105080617A (en) | Preparation method and application of alumina carrier | |
| CN108855237A (en) | Porous alumina carrier and preparation method thereof and silver catalyst and application | |
| CN103357436B (en) | The preparations and applicatio of the silver catalyst of alumina support alkali treatment modifying, its load | |
| CN103357441B (en) | Silver catalyst carrier, its preparation method, the catalyst be made up of it and application | |
| CN109499560A (en) | A kind of alpha-alumina supports, ethylene epoxidizing silver catalyst and ethylene method | |
| CN104549544B (en) | Silver catalyst carrier preparation method, thus obtained silver catalyst carrier, silver catalyst and its application | |
| CN105080618B (en) | A kind of preparation method of alpha-aluminium oxide carrier for silver catalyst | |
| CN108855238A (en) | Porous alumina carrier and preparation method thereof and silver catalyst and application | |
| CN108855239A (en) | Porous alumina carrier and preparation method thereof and silver catalyst and application | |
| CN106955692A (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 | |
| CN107413389A (en) | Alpha-aluminium oxide carrier for silver catalyst and preparation method and application | |
| CN112007625B (en) | Alpha-alumina carrier, preparation method, silver catalyst and application | |
| CN109499559B (en) | Alpha-alumina carrier, silver catalyst for ethylene epoxidation and ethylene oxidation method | |
| CN109201027B (en) | Alpha-alumina carrier and preparation method and application thereof | |
| CN108607533A (en) | Alumina support, catalyst and application | |
| CN108607617A (en) | A kind of method and silver catalyst preparing the alumina support for silver catalyst | |
| CN106607035B (en) | A kind of modified alpha-alumina supports and its preparation 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 |