CN104549544B - Silver catalyst carrier preparation method, thus obtained silver catalyst carrier, silver catalyst and its application - Google Patents
Silver catalyst carrier preparation method, thus obtained silver catalyst carrier, silver catalyst and its application Download PDFInfo
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Abstract
A kind of preparation method of silver catalyst carrier, including：I) provide solid mixture, the solid mixture in terms of 100 parts by weight including：The water α Al of 50~500 purpose of granularity three2O320~90 parts by weight, granularity can pass through the water Al of vacation one of 200 mesh sieves2O35~70 parts by weight, the parts by weight of fluoride-mineralization agent 0.05~7.0, the parts by weight of alkaline earth metal compound 0.01~1.45 and the parts by weight of silicon-containing compound 0.01~1.0；II) in step I) solid mixture in add the parts by weight of titaniferous auxiliary compound 0~3.5；III) to step II) mixture in add 0.01~5.0 parts by weight lubriation material；IV) to step III) mixture in add binding agent mediated, extruded moulding；V) silver catalyst carrier is made in the product drying obtained in step IV) and roasting.Present invention also offers the silver catalyst carrier that a kind of methods described obtains, and the silver catalyst as made from the silver catalyst carrier, and application of the silver catalyst in ethylene epoxidizing produces oxirane.
Description
Technical field
The present invention relates to ethylene epoxidizing production oxirane silver catalyst field, and in particular to a kind of silver catalyst carries
The preparation method of body, the silver catalyst carrier obtained by the preparation method and by the silver catalyst comprising the silver catalyst carrier
And its application.
Background technology
Ethylene epoxidizing mainly generates oxirane under silver catalyst effect（EO）, while side reaction generation dioxy occurs
Change carbon and water, wherein activity, selectivity and stability are the main performance index of silver catalyst.Activity refers to ethylene oxide production
Process reaches reaction temperature required during certain reaction load, and reaction temperature is lower, and the activity of catalyst is higher；Selectivity refers to
Ethene changes into the ratio between the molal quantity of oxirane and the overall reaction molal quantity of ethene in reaction；Stability be then expressed as activity and
The fall off rate of selectivity, the stability of fall off rate more small catalyst are better.
Silver catalyst has three kinds at present：First, high activity silver catalyst, this kind of catalyst activity is high, stability is good, initially
Selectivity 80~82%, service life is in 2-5, suitable for all ethylene oxide/ethylene glycols（EO/EG）Process units；Second,
High selectivity silver catalyst, this kind of catalyst is just selective up to more than 88%, but requires CO in Reactor inlet reaction gas2Concentration
Below 1.0%, suitable for the relatively low EO/EG process units of newly-built, space-time yield；Third, intermediate selectivity silver catalysis
Agent（Silver catalyst of the activity and selectivity between the former two）, the selectivity of this kind of catalyst can reach 83~85%,
Seek CO in the reaction gas of Reactor inlet2Concentration is below 3%.The selectivity of different type catalyst can be according to CO in reaction gas2
Concentration and outlet EO concentration accordingly adjust, the silver catalyst extensive use of high selectivity silver catalyst and intermediate selectivity in recent years
In industrial production and it instead of original high activity silver catalyst.
The performance of silver catalyst also uses in addition to having important relationship with the composition of catalyst and preparation method with catalyst
Carrier property and preparation method have important relationship.For with α-Al2O3For the carrier of key component, carrier physical property includes anti-
Compressive Strength, porosity, than surface and pore size distribution etc., a good catalyst carrier has outstanding compression strength, porosity and
Specific surface area.Higher porosity can reduce reactant and product gas diffusional resistance at reaction conditions；Have than surface requirements
One minimum, to ensure that catalyst component can be impregnated on carrier；Compression strength is weigh carrier physical integrity one
Parameter, it is subjected to operating condition for catalyst, ensures that longer service life is necessary.Study and found that new pore creating material is same
Binding agent has a major impact to the physical property specification of control vector together.Carrier has preferably than surface and porosity, pressure resistance
Degree may reduce；Opposite compression strength is high, can reduce than surface and porosity.Balance between different physical property is for carrier
It is very important.
United States Patent (USP) US5512530 passes through blend alpha-Al2O3, pore creating material and titanium dioxide prepare carrier, carrier have compared with
There is good compression strength while good porosity and catalytic performance；US5929259 elaborates a kind of titania modified
Carrier, first by least one Al2O3, vitrified bonding and liquid medium be molded and carrier be made through high temperature sintering, then with by two
Titanium oxide sol and the mixing liquid of titanium-containing compound solution composition are dipped through the carrier of high temperature sintering, the load after dipping
Finished product is made through 450~700 DEG C of calcinings again in body, and titanium dioxide is dispersed in the carrier, improves the structure of carrier；It is Chinese special
Sharp CN102553589A is using a kind of compound titanium solution that titanium dioxide can be converted into roasting or sol impregnation through roasting
α-Al after burning2O3Carrier, carrier finished product then is made through dry and 900-1380 DEG C of roasting, thus catalyst made of carrier
Show good activity and selectivity；United States Patent (USP) US6603028 and US8124798 are respectively described in carrier containing titanium
Propylene ring oxidation reaction of the catalyst in the presence of hydrogen and oxygen.
In addition, United States Patent (USP) US2013006002A1 elaborates a kind of low surface area α phases Al2O3The preparation method of carrier, its
Middle α phases Al2O3Content is more than 90wt%, and silicone content is less than 6wt%, by α phases Al2O3And/or transitional face Al2O3, binding agent and solid
Pore creating material, water-soluble titanium compound, add water extrusion molding, drying and 1150~1600 DEG C of roastings after dry blended and carrier be made,
Carrier pore volume 0.2~0.8ml/g, it is preferably in 0.25~0.6ml/g；It is 0.4~4.0m than surface2/ g, preferably 0.6~
1.5ml/g；Crushing strength is more than 8 pounds, preferably more than 10 pounds；United States Patent (USP) US4200552 is elaborated by α-Al2O3Extremely
A kind of few compound, such as SiO2、TiO2、ZrO2At least one of with MgO etc., prepare Al as sintering aid2O3Carrier, always
0.05~0.50ml/g of pore volume, 0.05~5.0 μm of average pore size, than 3~60m of surface2/g；United States Patent (USP) US6908879 is introduced
It is a kind of in acid α-Al2O3Carrier, first aluminum contained compound, silicon-containing compound and titanium-containing compound are mixed and add binding agent
And water, calcined through mediating, being molded after at 1000-2000 DEG C, alundum (Al2O3) in carrier finished product, silica and titanium dioxide
More than the 99% of carrier gross weight is accounted for, the silica and titanium dioxide after calcining exist with amorphous state；United States Patent (USP)
US7060651B2, a kind of high silicon carrier is described, the content of silica is more than 70%, than surface 0.5-30m2/ g, with platinum,
At least one of metal components such as palladium, silver, molybdenum, titanium, zirconium and copper or its oxide are active component, its content in terms of metal not
More than 2%, active component impregnates and is supported on carrier at 40-200 DEG C in the form of a solution, then thermally treated obtained catalyst can
For ethene or propylene ring oxidation reaction.
The content of the invention
The present inventor has carried out research extensively and profoundly in silver catalyst carrier preparation field, finds with three water
Al2O3With a water Al2O3It is raw material in carrier preparation process, addition silicon additive can make to increase than surface；Addition titanium auxiliary agent can make
Carrier porosity increases；Two kinds of auxiliary agents add the carrier after high temperature sintering simultaneously, are keeping the premise of advantages of higher compressive strength
Under, porosity increase, it is increased slightly than surface, less than 0.5 μm hole accounts for the ratio increase of total pore volume, the catalysis that thus prepared by carrier
When agent is used for ethylene epoxidizing epoxy ethane, catalyst activity and selectivity is significantly improved.
The present invention provides a kind of preparation method of silver catalyst carrier, including：
I) provide solid mixture, the solid mixture in terms of 100 parts by weight including：
II) in step I) solid mixture in add obtained the first intermediate product of titaniferous auxiliary compound, the titanium
Auxiliary compound 0~3.5 parts by weight in terms of titanium elements, preferably 0.1~3.5 parts by weight；
III) to step II) 0.01~5.0 parts by weight lubriation material is added in obtained the first intermediate product obtains second
Intermediate product；
IV) to step III) add that binding agent is mediated, extruded moulding obtains the 3rd in obtained the second intermediate product
The dosage of intermediate product, wherein binding agent is 25~60 parts by weight；
V) silver catalyst carrier is made in the 3rd intermediate product obtained in step IV) drying and roasting.
In a preferred embodiment of the preparation method of above-mentioned silver catalyst carrier of the invention, the three water α-
Al2O3Dosage be 50~80 parts by weight.
In a preferred embodiment of the preparation method of above-mentioned silver catalyst carrier of the invention, a false water
Al2O3Dosage be 15~45 parts by weight.
In a preferred embodiment of the preparation method of above-mentioned silver catalyst carrier of the invention, the fluoride
Mineralizer is selected from least one of following compound：Hydrogen fluoride, aluminum fluoride, ammonium fluoride, magnesium fluoride and ice crystal.The fluorination
The effect of thing mineralizer is to accelerate Al2O3Transformation of crystal, and reduce by less than 0.5 μm of pore, its addition preferably 0.1~
6.0wt%。
In a preferred embodiment of the preparation method of above-mentioned silver catalyst carrier of the invention, the alkaline earth gold
Belong to compound be selected from alkaline-earth metal oxide, sulfate, acetate, nitrate and oxalates, preferably strontium compound and/or
Barium compound.Its role is to be improved to carrier property, addition is preferably 0.2~0.9%.
In a preferred embodiment of the preparation method of above-mentioned silver catalyst carrier of the invention, the silicide-comprising
Compound is selected from silicate and/or silica.The effect of the silicon compound is increasing in it can make carrier less than 0.5 μm of hole,
Carrier is set to keep higher ratio surface, its addition is preferably 0.1~0.5%.
In a preferred embodiment of the preparation method of above-mentioned silver catalyst carrier of the invention, the titaniferous helps
Immunomodulator compounds are selected from least one of titanium dioxide, titanium tetrachloride and organic titanate.The effect of the titanium auxiliary compound
It is the porosity for increasing carrier, its addition is preferably 0.2~2.5%.
The silicon-containing compound of addition is solid silicate or silica, between temperature rise and organic titanium auxiliary agent
Interact very little, and the mainly interaction between silicon-containing compound and aluminum oxide and titanium-containing compound and aluminum oxide is siliceous
Compound can make to increase less than 0.5 μm of hole, and titanium-containing compound can increase the macropore in carrier, control the ratio of silicon and titanium and can make
Carrier reaches suitable pore size distribution, so that catalyst performance reaches optimal.
In a preferred embodiment of the preparation method of above-mentioned silver catalyst carrier of the invention, the lubrication material
Material is selected from least one of petroleum coke, carbon dust, graphite and vaseline.The lubriation material be preferably can after-flame lubrication material
Material, it is added to make the material after kneading be easy to be molded and be granulated, while oxidation reaction occurs in material roasting process,
Gas effusion is generated, is not introduced when carrier is made or introduces other impurities as few as possible, so as to not influence the property of catalyst
Energy.According to the present invention can after-flame lubriation material can be powdered, paste, its dosage is preferably 0.05~4.0wt%.
In the preparation method of above-mentioned carrier, the three water α-Al2O3Dehydration turns brilliant into α-Al in high-temperature calcination process2O3,
One water Al of vacation2O3With acid reaction in acid adding kneading process, colloidal sol is changed into, plays binding agent, in high-temperature calcination process
Change into stable α-Al2O3, turn into α-Al2O3A part for carrier.Three water α-Al2O3Addition be preferably 50~80 weight
Part；One water Al of vacation2O3Addition be preferably 15~45 parts by weight.
In the preparation method of above-mentioned carrier, the water Al of vacation one in addition binding agent and mixture2O3Alumina gel is generated, each
Component is bonded together, and turns into the paste of extrudable shaping.Binding agent used includes acid, such as nitric acid, formic acid, acetic acid, third
Acid and hydrochloric acid etc..When using acid be used as binding agent, the preferably aqueous solution of nitric acid, wherein the weight ratio of nitric acid and water are 1:
1.25~10.
In the preparation method of above-mentioned carrier, the binding agent and one water Al of vacation2O3Alumina gel all or part generation can be used
Replace.In the present invention, because binding agent is acid, Alumina gel is generated with a false water oxygen reactive aluminum, with ready-made quite concentration
Alumina gel should belong to same material, therefore can be by binding agent and one water Al of vacation2O3Replaced with Alumina gel.
In the preparation method of above-mentioned carrier, the solid mixture is mediated to obtain a kind of paste with binding agent, so
It can be dried after paste extrusion molding afterwards to aqueous below 10 weight %, support shapes can be annular, spherical, cylindricality or porous
Cylindricality.Drying temperature is 80~120 DEG C, and drying time is controlled at 1~24 hour according to moisture.
In the preparation method of above-mentioned carrier, the roasting time in the step V) is 1~20 hour, and preferably 2~15 is small
When, roasting makes Al2O3It is completely converted into α-Al2O3.The sintering temperature of the roasting is preferably 1100-1450 DEG C.
The present invention provides a kind of α-Al of ethylene epoxidizing silver catalyst2O3Carrier, the carrier include α-Al2O3, its
In, hole of the carrier pore size distribution mesopore footpath less than 0.5 μm accounts for the 4~15% of total pore volume, contains titanium and silicon member in the carrier
Element, and the mass ratio of titanium elements and element silicon is 0~10, preferably 0.5~4.5.
In above-mentioned carrier, the α-Al2O3Mass content is more than 90%.
The crushing strength of the carrier is 60~210N/ grains, preferably 80~150N/ grains；It is 0.80~2.0m than surface2/
G, preferably 0.9~1.8m2/g；Porosity is more than 60%；0.4~0.75ml/g of pore volume, preferably 0.45~0.6ml/g.
In the present invention, the side crush intensity of carrier uses the type intelligence detector for strength of particles of DL II, chooses carrier sample
Product, average to obtain after determining radial direction crushing strength；Specific surface area is determined using nitrogen physisorption BET methods；Porosity,
Pore volume and pore size distribution$ are using pressure mercury method measure.
Present invention also offers a kind of ethylene epoxidizing silver catalyst, including：
a）α-the Al of the present invention2O3Carrier；
b）Silver compound；
c）Alkali metal promoter；
d）Base earth metal promoter；
E) rhenium auxiliary agent and its coassist agent.
The silver catalyst of the present invention can be prepared in the usual way, be helped by using a kind of Ag-containing compound, organic amine, alkali metal
The solution of agent, base earth metal promoter and rhenium-containing auxiliary agent and its optional coassist agent composition impregnates above-mentioned Al2O3It is prepared by carrier.Should
Organic amine compound can be any organic amine compound suitable for preparing ethylene oxide silver catalyst, as long as this is organic
Amines can form argent-amine complex with silver compound, such as pyridine, butylamine, ethylenediamine, 1,3- propane diamine, monoethanolamine
Or the mixture of its mixture, preferably ethylenediamine and monoethanolamine.
The silver compound also has no particular limits, as long as can form argent-amine complex with the organic amine compound
, preferably silver oxalate and/or silver nitrate.
The alkali metal promoter can be at least one of compound of lithium, sodium, potassium, rubidium or caesium, such as their nitric acid
Salt, sulfate or hydroxide, or any combination of two or more of aforesaid compound, preferably sulfuric acid caesium and/or
Cesium nitrate.
The base earth metal promoter can be at least one of compound of magnesium, calcium, strontium or barium, such as their oxidation
Thing, oxalates, sulfate, acetate or nitrate, or any combination of two or more of aforesaid compound, preferably
The compound of barium or strontium, more preferably barium acetate and/or strontium acetate.The base earth metal promoter can before immersion silver while or
It is applied on carrier, can also be immersed in after silver compound is reduced on carrier afterwards.
The rhenium auxiliary agent can be the oxide, perrhenic acid, perrhenate of rhenium, or its mixture, preferably perrhenic acid and height
Rhenate, such as perrhenic acid, perrhenic acid caesium and ammonium perrhenate etc.；The coassist agent can be any transition gold in the periodic table of elements
The compound of category, or the mixture of several transistion metal compounds, the metal in the coassist agent are preferably selected from group vib and VIIB
Race's element, the coassist agent can include the oxyacid and its salt of group vib and VIIB races element, such as wolframic acid, wolframic acid caesium, molybdenum
The salt of acid, ammonium molybdate etc. or rare earth element (such as cerous sulfate).Rhenium auxiliary agent and its coassist agent can before immersion silver,
Simultaneously or after be applied on carrier, can also be immersed in after silver compound is reduced on carrier.By adding rhenium auxiliary agent
And its coassist agent can further improve the stability of the gained activity of silver catalyst, selectivity and activity and selectivity.
In above-mentioned silver catalyst, include by 100 weight %, the catalyst of the gross weight of the catalyst：
Silver catalyst preparation method comprises the following steps in specific embodiment：
1) with the silver compound containing sufficient amount, organic amine, alkali metal promoter, base earth metal promoter, rhenium-containing auxiliary agent and its altogether
The solution of auxiliary agent impregnates above-mentioned porous α-Al2O3Carrier；
2) maceration extract is filtered off, dries impregnated carrier；With
3) step 2) resulting vehicle is activated in containing oxygen gas mixture, the silver catalyst is made.
In the preparation of silver catalyst of the present invention, silver-colored amine is made with ethylenediamine and aqueous ethanolamine dissolving silver oxalate first
Solution, add above-mentioned auxiliary agent and be made into maceration extract；Then above-mentioned α-Al are soaked with the maceration extract prepared2O3Carrier, drain, in sky
Air-flow or oxygen content are not more than 21%（Such as oxygen-containing 8.0%）Nitrogen oxygen atmosphere in 180~700 DEG C preferably 200~500 DEG C of temperature
Kept in the range of degree 0.5~120 minute, carry out thermal decomposition and finished product silver catalyst is made within preferably 1~60 minute.
Present invention also offers a kind of application of described silver catalyst in ethylene epoxidizing produces oxirane.In second
In alkene epoxidation production oxirane, the ethene is subjected to epoxy in reaction unit in the presence of above-mentioned silver catalyst
Change reaction, the reaction unit import CO2Concentration is less than 3mol%.The reaction unit can carry out epoxy to be any
Change the device of reaction.
Beneficial effects of the present invention：
The carrier of the present invention adds titaniferous auxiliary compound and siliceous auxiliary compound in preparation process, is roasted by high temperature
After burning obtained carrier have more preferably porosity, than surface and pore structure, wherein the hole less than 0.5 μm accounts for total pore volume
4~15%（By volume）, compared with the prior art, silver catalyst is applied to instead according to made of carrier provided by the invention
Answer device import CO2Concentration is the epoxidation reaction less than 3mol%, especially suitable for the anti-of ethylene production oxirane
Should, it is active and selectivity it is high the advantages of.
Embodiment
The present invention is described further with reference to embodiment, but the scope of the present invention is not limited to these embodiments.
It is primality that the various silver catalysts of the present invention with laboratory reactor (following letter " micro- anti-") evaluating apparatus test its
Energy and stability.The reactor that micro anti-evaluation device uses is internal diameter 4mm stainless steel tube, and reactor is placed in heating mantle.Urge
The admission space of agent is 1ml, and inert filler is arranged at bottom, beds is located at the flat-temperature zone of heating mantle.
The condition determination for the activity and selectivity that the present invention uses is as follows：
The gas composition (mol%) of Reactor inlet：Ethene (C2H4), 28.0 ± 1.0；Oxygen (O2), 7.4 ± 0.2；Titanium dioxide
Carbon (CO2), ＜ 3.0；Cause steady gas (N2), surplus；Inhibitor dichloroethanes（In right amount）, oxirane（EO）Concentration, 2.50%.Reaction
Pressure, 2.1MPa；Air speed, 7000/h；Space-time yield, 344gEO/mlCat./h.
METHOD FOR CONTINUOUS DETERMINATION reactor enters after above-mentioned reaction condition is stably reached, exit gas forms.Measurement result carries out body
Product calculates selectivity as follows after shrinking correction：
Wherein, EO is to work off one's feeling vent one's spleen poor with inlet gas ethylene oxide concentration, takes the average conduct of more than 10 groups test datas
The result of the test on the same day.
Embodiment 1
The preparation of carrier
By the water α-Al of 50~500 purpose three2O34800g, pass through the water Al of vacation one of 200 mesh sieves2O31200g, NH4F150g, nitre
Sour barium 21g and silica 9.8g are put into blender and are well mixed, and are transferred in kneader, add 42g vaseline and 2100ml
Dust technology (nitric acid：Water=1：3, weight ratio), it is kneaded into the paste of extrudable shaping.Extrusion molding is external diameter 8.0mm, length
6.0mm, internal diameter 1.0mm five hole columns, dried more than 2 hours at 80~120 DEG C, free water content is reduced to 10%
Below.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, 1280 DEG C were increased to from room temperature through 33 hours, in 1280 DEG C of bars
Calcined 10 hours under part, obtain white silver catalyst carrier.The carrier physical property and pore size distribution$ data measured is respectively such as table 1 below
It is shown.
The preparation of catalyst
980g ethylenediamines and 255g monoethanolamines are dissolved in 1500g deionized waters, are under agitation slowly added to silver oxalate
In mixed liquor, temperature is maintained at less than 40 DEG C, silver oxalate is all dissolved, and the addition of silver oxalate is with silver dollar in silver catalyst
The silver content of element meter is 13%（Weight）, add 9.0g cesium nitrates, 7.8g calcium acetates, 4.4g perrhenic acid, 1.0g cerous sulfates and go
Ionized water makes solution gross mass reach 5000g, and it is stand-by to be configured to maceration extract.
Support samples 2500g is taken, is put into the container that can be vacuumized, is evacuated to more than 10mmHg, introduces above-mentioned dipping
Liquid, keeps 30min, and unnecessary solution is removed in leaching.Carrier after dipping heats 3min in 450 DEG C of air stream, cooling, that is, makes
Into silver catalyst.
The activity and selectivity of catalyst sample is determined under the conditions of previous process using microreactor evaluating apparatus, it is micro-
Anti- evaluation result is listed in table 2.
Comparative example 1
With embodiment 1, difference is to be added without silica the preparation method of carrier, obtained carrier physical property and hole
Structure distribution data difference is as shown in table 1 below；The preparation of catalyst the results are shown in Table 2 with embodiment 1, the micro anti-evaluation of catalyst.
Embodiment 2
By the water α-Al of 50~500 purpose three2O34800g, pass through the water Al of vacation one of 200 mesh sieves2O31200g, NH4F150g,
Barium nitrate 21g and silica 9.8g is put into blender and is well mixed, and is transferred in kneader, addition 22.3g butyl titanates,
42g vaseline and 2100ml dust technology (nitric acid：Water=1：3, weight ratio), it is kneaded into the paste of extrudable shaping.Extrusion molding
For external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm five hole columns, dried more than 2 hours at 80~120 DEG C, make free contain
Water is reduced to less than 10%.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, be increased to 1280 from room temperature through 33 hours
DEG C, calcined 10 hours under the conditions of 1280 DEG C, obtain white silver catalyst carrier.The carrier physical property and pore size distribution$ number measured
According to as shown in table 1 below respectively.
Embodiment 3
With embodiment 1, difference is to add 42.7g butyl titanates the preparation method of carrier, obtained silver catalysis
Physical property and pore size distribution$ the data difference of agent carrier are as shown in table 1 below；The preparation of catalyst with embodiment 1, catalyst it is micro-
Anti- evaluation result is shown in Table 2.
Embodiment 4
With embodiment 1, difference is to add 85.6g butyl titanates the preparation method of carrier, obtained silver catalysis
Physical property and pore size distribution$ the data difference of agent carrier are as shown in table 1 below；The preparation of catalyst with embodiment 1, catalyst it is micro-
Anti- evaluation result is shown in Table 2.
Embodiment 5
The preparation of carrier is with embodiment 1, and difference is to add 128.8g butyl titanates, and obtained silver catalyst carries
Physical property and pore size distribution$ the data difference of body are as shown in table 1 below；With embodiment 1, the micro- of catalyst counter comments for the preparation of catalyst
Valency the results are shown in Table 2.
Comparative example 2
With embodiment 1, difference is to add 128.8g butyl titanates but is added without silica for the preparation of carrier,
Physical property and pore size distribution$ the data difference of obtained silver catalyst carrier are as shown in table 1 below；Catalyst prepares same embodiment
1, the micro anti-evaluation of catalyst the results are shown in Table 2.
Embodiment 6
The preparation of carrier is with embodiment 1, and difference is to add 213.8g butyl titanates, and obtained silver catalyst carries
Physical property and pore size distribution$ the data difference of body are as shown in table 1 below；With embodiment 1, the micro- of catalyst counter comments for the preparation of catalyst
Valency the results are shown in Table 2.
As can be seen from Table 1, porosity, pore volume and the specific surface area for the catalyst carrier that the present invention obtains, which have, is better than contrast
The catalyst carrier that example provides, particularly in pore size distribution structure, aperture is the 0-0.5 μm and 0.5-1.5 μm ratio for accounting for total pore volume
It is important more much higher than the carrier provided in comparative example, illustrate the average pore size for the catalyst carrier that the preparation method of the present invention obtains
The average pore size of the carrier provided relative to comparative example is much smaller.
In addition, the catalytic effect of the silver catalyst prepared using the carrier of the present invention is as shown in table 2, it is suitable in selectivity
Under the conditions of, the reaction temperature using the silver catalyst of the present invention is lower very than the reaction temperature of the silver catalyst using comparative example
It is more, illustrate higher than the activity for the silver catalyst that comparative example provides using the silver catalyst of the method for the present invention.
The physical property and pore size distribution$ data of the carrier of table 1
The performance of the catalyst of table 2
Claims (14)
1. a kind of preparation method of silver catalyst carrier, including：
I) provide solid mixture, the solid mixture in terms of 100 parts by weight including：
II) in step I) solid mixture in add obtained the first intermediate product of titaniferous auxiliary compound, the titanium auxiliary agent
Compound 0.1~3.5 parts by weight in terms of titanium elements；
III) to step II) 0.01~5.0 parts by weight lubriation material is added in obtained the first intermediate product obtains among second
Product；
IV) to step III) add that binding agent is mediated, extruded moulding is obtained among the 3rd in obtained the second intermediate product
The dosage of product, wherein binding agent is 25~60 parts by weight；
V) silver catalyst carrier is made in the 3rd intermediate product obtained in step IV) drying and roasting；
The mass ratio of titanium elements and element silicon is 1.36-4.5 in the carrier.
2. preparation method according to claim 1, it is characterised in that the three water α-A12O3Dosage be 50~80 weight
Part；The false water A12O3Dosage be 15~45 parts by weight；The fluoride-mineralization agent in following compound at least
It is a kind of：Hydrogen fluoride, aluminum fluoride, ammonium fluoride, magnesium fluoride and ice crystal；The alkaline earth metal compound be selected from strontium compound and/or
Barium compound.
3. preparation method according to claim 1 or 2, it is characterised in that the silicon-containing compound be selected from silicate and/or
Silica.
4. preparation method according to claim 1 or 2, it is characterised in that the titaniferous auxiliary compound is selected from titanium dioxide
At least one of titanium, titanium tetrachloride and organic titanate.
5. the silver catalyst carrier that a kind of preparation method including according to any one of claim 1-4 obtains, the load
Body includes α-A12O3, wherein, hole of the carrier pore size distribution mesopore footpath less than 0.5 μm accounts for the 4~15% of total pore volume.
6. silver catalyst carrier according to claim 5, it is characterised in that the crushing strength of the carrier be 60~
210N/ grains；It is 0.80~2.0m than surface2/g；Porosity is more than 60%；Pore volume is 0.4~0.75ml/g.
7. silver catalyst carrier according to claim 6, it is characterised in that the crushing strength of the carrier be 80~
150N/ grains；It is 0.9~1.8m than surface2/g；Pore volume is 0.45~0.6ml/g.
8. a kind of silver catalyst, including：
A) carrier in claim 5~7 described in any one；
B) silver compound；
C) alkali metal promoter；
D) base earth metal promoter；
E) rhenium auxiliary agent and its coassist agent.
9. silver catalyst according to claim 8, it is characterised in that the silver compound is selected from silver oxalate and/or nitric acid
Silver；The alkali metal promoter is selected from least one of compound of lithium, sodium, potassium, rubidium or caesium；The base earth metal promoter is selected from
Magnesium, calcium, at least one of the compound of strontium or barium；In the oxide of the rhenium auxiliary agent selected from rhenium, perrhenic acid and perrhenate
At least one；The coassist agent is selected from least one of wolframic acid, wolframic acid caesium, molybdic acid, ammonium molybdate and cerous sulfate.
10. silver catalyst according to claim 9, it is characterised in that the alkali metal promoter is selected from cesium sulfate and/or nitre
Sour caesium；The base earth metal promoter is selected from the compound of barium and/or strontium；The rhenium auxiliary agent is selected from perrhenic acid caesium and/or perrhenic acid
Ammonium.
11. silver catalyst according to claim 10, it is characterised in that the base earth metal promoter be selected from barium acetate and/
Or strontium acetate.
12. silver catalyst according to claim 8 or claim 9, it is characterised in that using the gross weight of catalyst as 100 weight %
Part meter, the catalyst include：
13. silver catalyst according to claim 12, it is characterised in that using the gross weight of catalyst as 100 weight % parts
Meter, the catalyst include：
14. a kind of silver catalyst according to any one of claim 8-13 is produced in ethylene epoxidizing in oxirane
Using.
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| CN106955692B (en) * | 2016-01-08 | 2019-09-27 | 中国石油化工股份有限公司 | A kind of alpha-alumina supports, silver catalyst prepared therefrom and its application |
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| CN103357442A (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 as well as preparation method and application thereof |
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| CN103357442A (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 as well as preparation method and application thereof |
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