CN105080617B - A kind of preparation method and applications of alumina support - Google Patents
A kind of preparation method and applications of alumina support Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of alumina support, including：I) prepare to have and include three water α A12O3, one water A1 of vacation2O3With the mixture of auxiliary agent；II) to I) binding agent is added in obtained mixture；III) by II) in obtained mixture mediate uniformly and extrusion molding；IV) dry III) in obtained product, then carry out first time roasting, obtain carrier semi-finished product；V) used additives solution immersion IV) in obtained product and drying；VI) by V) in obtained product carry out second and be calcined.The invention further relates to the alumina support that methods described is prepared, and the application of silver catalyst and the silver catalyst as made from the carrier.The silver catalyst is used for ethylene production oxirane, there is good activity and stability.
Description
Technical field
The present invention relates to a kind of preparation method and applications of alumina support, and in particular to one kind is used for ethylene oxy metaplasia
Preparation method of the oxirane (EO) with the alumina support of silver catalyst and the silver catalyst as made from the carrier are produced, and
Application of the catalyst in ethylene produces oxirane.
Background technology
Silver catalyst effect under ethylene mainly generate oxirane, while occur side reaction generation carbon dioxide and
Water etc., wherein activity, selectivity and stability are the main performance index of silver catalyst.So-called activity refers to ethylene oxide production
Process reaches reaction temperature required during certain reaction load.Reaction temperature is lower, and the activity of catalyst is higher.So-called selectivity
Refer to that ethene changes into the ratio between the molal quantity of oxirane and the overall reaction molal quantity of ethene in reaction.So-called stability then represents
It is better for the fall off rate of activity and selectivity, the stability of fall off rate more small catalyst.Epoxy second is produced in ethylene
Economic benefit can be greatly improved using high activity, high selectivity and the silver catalyst that has good stability during alkane, therefore
The silver catalyst of manufacture high activity, high selectivity and good stability is the Main way of silver catalyst research.Silver catalyst
Performance with the composition of catalyst and preparation method in addition to having important relationship, the performance of the carrier also used with catalyst and preparation side
Method has important relationship.
The preparation method of silver catalyst mainly including porous carrier (such as aluminum oxide) preparation and apply active component and
Auxiliary agent is to the two processes on the carrier.What its carrier was typically selected is the less Alpha-alumina of specific surface area.Aluminum oxide
(Al2O3) it is a kind of catalyst carrier having many uses, its species is very more, crystal structure, and surface catalysis performance is also very multiple
It is miscellaneous, directly affect the performance of silver catalyst.
The primary raw material for preparing alumina support is the hydrate of aluminum oxide (being called aluminium hydroxide), and hydrated alumina takes off
Water can produce Louis (L) Acid and basic sites, and these L acid sites are easy to absorb water and be changed into proton (B) Acid and basic sites.Oxidation
The crystal formation species of aluminium is a lot, in addition impurity and the more or less influence of moisture, causes the surface physics of aluminum oxide, chemical property all
It is extremely complex.α-the Al selected for silver catalyst2O3For, although its surface only has minimal amount of Acid and basic sites, they
With active component collective effect, ethene is promoted to be converted into oxirane.
Carrier needs to provide certain area load active component, is well dispersed in active component thereon, this
Very high requirement just is proposed to the pore structure of carrier.The hole of alumina support can be divided into three types：1) primary particle crystal grain
Between hole, mainly alumina raw material crystal grain dewatering hole, gap between the parallel plate face of substantially 1~2nm sizes；2) aluminum oxide is former
Hole between material offspring, change in calcining with the effusion of moisture and crystalline phase and change, be tens of more than nm hole；3) pore creating material
With carrier shaping caused by defective hole and macropore.Therefore, the alumina raw material of variety classes and particle diameter matches, pore creating material
Dosage and molding mode and calcinating system etc. can all impact to the pore structure and physical property of silver catalyst carrier, and then
Influence the performance of catalyst.
In general, preparing the main method of silver catalyst carrier is, from a variety of alumina powder raw materials (and/
Or) pore creating material, binding agent and various additives etc. are added, through batch mixing and mediate uniformly, then extrusion molding is of different shapes
Base substrate (Raschig ring, spheric granules, porous cylindrical, shape of a saddle etc.), porous heat-resistant finally is made in 1200~1700 DEG C of sintering
Alpha-alumina supports product, as described in patent US5063195, US5703001, US5801259 etc..
Toward contact addition auxiliary agent in the preparation process of silver catalyst carrier, to improve the performance of carrier.Such as patent
CN02160081 proposes to add silver catalyst carrier made of the compound of weight alkaline-earth metal in alumina powder raw material, then loads
Silver catalyst is made in active component, and its activity, selectivity are improved.Patent CN102099109A proposes to add in the carrier
Add a kind of mullite of stability enhancing amount to improve the stability of high-selectivity catalyst for auxiliary agent, extend catalyst and use
Life-span, used " mullite " refer to that one kind has and SiO2It is integrated as the A1 of solid solution2O3The alumina silicate mineral of composition.
Patent US5100859A proposes to add alkaline-earth metal, SiO in alumina support2And zirconium oxide can improve silver catalyst
Performance etc..
The common methods that surface carries out pretreatment and carrier is prepared and handled are carried out to carrier.Such as：Washing, pickling, alkali
Wash and carrier surface is modified and modified with various auxiliary agents immersion etc..
These above-mentioned new methods are no longer only from adjustment alumina powder raw material, pore creating material, binding agent and various additives etc.
Or start with from shaping with sintering process, and more pay attention to surface modification or the pretreatment carried out to carrier, by adjusting and improving
Carrier and the active component bonding state of load improve the performance of epoxyethane catalyst.But these methods to carrier property and
The improvement that the activity and selectivity of catalyst is brought is also very limited, therefore this area still needs the manufacture method progress to carrier
Improve, in favor of producing the more preferable silver catalyst of performance.
The content of the invention
In view of the situation of above-mentioned prior art, the present inventor has carried out grinding extensively and profoundly in silver catalyst field
Study carefully, as a result find, the alumina support prepared using following methods, prepared through impregnating silver compound, organic amine and specific adjuvant
Into solution, activity and selection of the prepared silver catalyst in ethylene oxidation reactions after being heat-treated in containing oxygen gas mixture
Property is improved.Specific method is：Using the method for after baking, after the completion of support greenware is calcined through first time, use
Compounding agent solution (such as alkaline including earth metal, silicon, zirconium and fluorine-containing solution) soaks semi-finished product, then by second roasting be made carrier into
Product.The temperature control of after baking will meet：If for the first time roasting select higher temperature, after baking can select compared with
Low temperature；, whereas if relatively low temperature is selected in roasting for the first time, then after baking can select higher temperature.
It is therefore an object of the present invention to provide a kind of novel oxidized alumina supporter, the carrier has good crushing strength
With relatively low wear rate.
It is a further object of the present invention to provide a kind of preparation method of above-mentioned carrier.
The a further object of the present invention is to provide a kind of silver catalyst prepared by above-mentioned carrier.
Another object of the present invention is to provide application of the above-mentioned silver catalyst in ethylene produces oxirane, described
Silver catalyst shows good activity and selectivity.
One aspect of the present invention provides a kind of preparation method of alumina support, and the carrier carries for porous Alpha-alumina
Body, for preparing ethylene production oxirane silver catalyst.Methods described comprises the following steps：
I) prepare with the mixture formed as follows：
A) based on the water α-A1 of 50 mesh~500 mesh three that total weight of the mixture is 50~90% weight2O3；
B) it is more than the water A1 of vacation one of 200 mesh for the granularity of 5~50% weight based on total weight of the mixture2O3；And
C) based on the auxiliary agent that total weight of the mixture is 0~5% weight；
II) to I) bonding that the gross weight based on the mixture is 15~60% weight is added in obtained mixture
Agent；
III) by II) in obtained mixture mediate uniformly and extrusion molding；
IV) dry III) in obtained product, then carry out first time roasting, obtain carrier semi-finished product；
V) used additives solution immersion IV) in obtained product, and dry so obtained product；
VI) by V) in obtained product carry out second and be calcined, obtain alumina support of the present invention.
In step I) component c) in, the one kind of the auxiliary agent in silicon, siliceous compound, zirconium and zirconium-containing compound
Or a variety of, the preferred silica of the siliceous compound and/or silicate；The preferred zirconium oxide of zirconium-containing compound；These
The effect of auxiliary agent is to be improved carrier.
Step V) in compounding agent solution be selected from the siliceous aqueous solution and/or the aqueous solution containing zirconium, the siliceous aqueous solution
It is preferred that teos solution, the preferred zirconium oxychloride of the aqueous solution and/or zirconyl nitrate solution containing zirconium.
Further, the present invention in step I) component c) in, the auxiliary agent also includes alkaline earth metal compound and/or fluorine
Compound, the alkaline earth metal compound preferably are selected from oxide, sulfate, acetate, the nitrate of beryllium, magnesium, calcium, strontium and/or barium
And the one or more in oxalates, more preferably from the oxide of strontium and/or barium, sulfate, acetate, nitrate and grass
One or more in hydrochlorate；The fluoride preferably is selected from hydrogen fluoride, ammonium fluoride, aluminum fluoride and ice crystal or its mixture,
More preferably aluminum fluoride and/or ammonium fluoride, effect is the transformation of crystal of accelerated oxidation aluminium, and reduces by less than 0.1 μm of pore.
It should be noted that step V) in used compounding agent solution and step I) in component c) can be with identical, can also not
Together.Difference is step I) in the auxiliary agents that use of component c) can be insoluble matter, and step V) helping used in compounding agent solution
Agent must be water miscible.In step I) in can be added without any auxiliary agent, and in step V) in add sufficient amount auxiliary agent it is molten
Liquid；Can also be in step I) add part of auxiliary, and in step V) in add the compounding agent solution of remaining sufficient amount；Finally make finished product
Adjuvant component containing sufficient amount in carrier.
The present invention is in carrier preparation process by adding binding agent and the water A1 of vacation one in mixture2O3Generate Alumina gel,
Each component is bonded together, turns into the paste of extrudable shaping, can also be added while binding agent is added in right amount
Water.Binding agent used includes acid, such as aqueous solution of nitric acid, formic acid, acetic acid, propionic acid and hydrochloric acid.Bonded when using acid to be used as
During agent, preferably aqueous solution of nitric acid, wherein the weight ratio of nitric acid and water are 1:1.25~10.Can be in step I) and/or step
Rapid II) in, by one water A1 of vacation2O3Replaced with acid with Alumina gel.That is, by step I) in component b) replace with Alumina gel and cancel
Step II) in binding agent, or cancellation step I) in component b) and by step II) in binding agent replace with Alumina gel,
Or by step I) in component b) and step II) in binding agent replace with Alumina gel.
It is dried after gained paste extrusion molding, preferably drying temperature is 80~120 DEG C, and drying time is according to moisture
Content is controlled at 1 hour~24 hours, water content can be down into less than 10% after drying.
Dried paste carries out first time roasting first, and is incubated 2~24 hours, obtains carrier semi-finished product.
Then carrier semi-finished product are put into compounding agent solution and soaked, its object is to carrier surface is modified and repaiied
Decorations.Step V) in compounding agent solution can also include the aqueous solution of alkaline earth metal compound and/or fluorine-containing solution, alkaline earth gold
The aqueous solution of category compound preferably is selected from the aqueous solution containing strontium and/or barium, and fluorine-containing solution preferably is selected from ammonium fluoride solution.Can be by carrier
Semi-finished product once soak the aqueous solution containing a variety of auxiliary agents, successively can also repeatedly soak various compounding agent solutions, and solution concentration can be with
Adjusted in the range of 0.01~10wt%, finally to make the adjuvant component containing sufficient amount in carrier finished product suitable.Amount of solution is
By one times to ten times of immersion carrier semi-finished product weight, not cross carrier surface of semi-finished to be excellent.Soak time is controlled at 10 points
Clock~2 hour, then filter and dry, preferably drying temperature is 80~120 DEG C, and drying time is controlled 1 according to moisture
Hour~24 hours.
Second is carried out to the carrier semi-finished product Jing Guo above-mentioned processing afterwards to be calcined, and be incubated 2~24 hours, obtain final
α-A12O3Carrier finished product.Support shapes can be annular, spherical, cylindricality or porous column shape.
It should be noted that the temperature of after baking need to meet specific requirement, because temperature is too high to influence manufactured urge
The activity and selectivity of agent, the too low then support strength of sintering temperature are poor.Specifically, the temperature of after baking will select one
Higher temperature and lower temperature collocation, i.e.,：If for the first time roasting select higher temperature, after baking can select compared with
Low temperature；, whereas if relatively low temperature is selected in roasting for the first time, then after baking can select higher temperature.Wherein
Higher temperature ThIt may be selected to carry out in the range of 1000~1500 DEG C and be incubated 2~24 hours, preferably 1000~1200 DEG C of scopes
It is interior；Lower temperature TlT may be selectedh1/4~3/4 in the range of carry out and be incubated 2~24 hours, preferably TlFor Th40%~
60%, more preferably TlIn the range of 400~700 DEG C.
If be all calcined at a lower temperature twice, carrier can not switch to α-phase.And select all to use higher temperature twice
Obviously the more energy can be consumed, it is not necessary that.So the present invention have selected a higher temperature and a lower temperature collocation, compared with
Roasting makes carrier complete to turn crystalline substance under high-temperature, and carrier now can use but poor-performing.But before being calcined at relatively high temperatures
The process being once calcined at a lower temperature is arranged afterwards, carrier property can be made to have greatly improved.
In one particular embodiment of the present invention, the precursor carrier of extrusion molding and drying is first roasted at 1200 DEG C
Burn, the crushing strength of carrier now is low, poor-performing.Then the carrier used additives by first time roasting soak, then 600
It is calcined at DEG C, obtained carrier has preferable crushing strength, the stable performance of the silver catalyst prepared by the carrier, and
With higher activity.
In another specific embodiment of the present invention, precursor carrier is first calcined at 600 DEG C, and carrier now is transition
Phase, poor-performing, it is not used to silver catalyst.Then used additives immersion be calcined again at 1200 DEG C, as a result can therewith quite or
More preferably.
The temperature that usual aluminum oxide is changed into α phases is 1200 DEG C, therefore the highest sintering temperature of prior art is not generally low
In 1200 DEG C, otherwise the transformation of final carrier is not thorough, causes carrier property to be greatly reduced.And the present invention in support material not
Add any pore creating material, and the fluoride added in carrier can reduce and turn brilliant temperature, be once calcined at less than 1200 DEG C
Just most aluminum oxide can be made to switch to α phases.But at less than 1200 DEG C roasting intensity can be caused to decrease, and by
The roasting of another lower temperature can further lifting carrier intensity, roasting effect is particularly under conditions of high temperature after first low temperature
Substantially.Therefore the higher sintering temperature of the carrier of the present invention may also be below 1200 DEG C, and keep the performance change of final carrier
Less.And used additives immersion and second of roasting can greatly improve the performance of carrier, so not only save energy in roasting process
The consumption in source, also makes the strength enhancing of carrier, and the performance of final catalyst is also improved.
It is 7-9mm that the alumina support of the present invention, which is shaped as external diameter, and honeycomb aperture is 1-3mm seven apertures in the human head, five holes or three holes
Cellular cylindrical α-A12O3Particle, or the single hole annular shape α-A1 that external diameter is 7-9mm, internal diameter is 3-6mm2O3Particle.
Another aspect of the present invention provides a kind of porous alpha-alumina supports obtained as stated above, wherein A12O3Content
For more than 90 weight %, preferably more than 95 weight %；The auxiliary elements such as remaining alkaline-earth metal, silicon, zirconium and fluorine are added up to element
For the 0.01~5% of vehicle weight, and there is following feature：Crushing strength>20N, preferably 40~200N；Than surface be 0.5~
4.0m2/ g, preferably 1.0~2.0m2/g；Water absorption rate is not less than 30%, preferably not less than 45%；Pore volume is 0.35~0.85ml/g,
It is preferred that 0.40~0.80ml/g.
Further aspect of the present invention provides a kind of silver catalyst for ethene catalytic gas phase oxidation production oxirane, bag
Include：
1) catalyst carrier provided by the invention；
2) silver of deposition on the carrier；
3) alkali metal and/or alkaline-earth metal or the compound based on alkali metal and/or alkaline-earth metal；
4) rhenium metal and/or the compound based on rhenium；
It is preferred that the collaboration auxiliary agent of rhenium is additionally added in the silver catalyst, its one kind or more in chromium, molybdenum, tungsten and boron
Kind element and/or compound.
The silver catalyst of the present invention can be prepared in the usual way, such as by using a kind of Ag-containing compound, organic amine, alkali gold
Category auxiliary agent and/or base earth metal promoter, rhenium metal and/or the compound based on rhenium, and the collaboration auxiliary agent of optional rhenium are molten
It is prepared by the alumina support that liquid impregnates the invention described above offer.
In one particular embodiment of the present invention, the silver catalyst is prepared via a method which：
1) with the Ag-containing compound containing sufficient amount, organic amine, alkali metal promoter and/or base earth metal promoter, rhenium metal and/
Or the compound based on rhenium, and the collaboration auxiliary agent of optional rhenium solution impregnate the invention described above offer alumina support；
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.
Further aspect of the present invention is related to application of the silver catalyst in ethylene produces oxirane.
In the preparation of silver catalyst of the present invention, make the aqueous solution of silver nitrate and ammonium oxalate or oxalic acid aqueous solution anti-first
Should, silver oxalate precipitate is separated out, after filtering, is washed with deionized, until without nitrate ion, then silver oxalate is dissolved in organic
In the amine such as aqueous solution of pyridine, butylamine, ethylenediamine, 1,3- propane diamine, monoethanolamine or its mixture, auxiliary agent is added, is made into dipping
Solution.Then use gained dipping solution to impregnate above-mentioned alumina support, drain, in air stream or oxygen content no more than 21% (such as
30 seconds~120 points are kept in oxygen-containing nitrogen oxygen atmosphere 8.0%) within the temperature range of 180~700 DEG C, preferably 200-500 DEG C
Clock, preferably 1 minute~60 minutes, to be thermally decomposed.Also silver nitrate can be replaced with silver oxide, silver oxalate can not also analyse filter, directly
Connect and be complexed with organic amine, then impregnated carrier.The amount of the silver compound used in the dipping process of the present invention should be enough to make finally
The weight of argentiferous 1~30% in the silver catalyst of preparation, preferably 5~26% weight, with silver catalyst gross weight meter.
Alkali metal promoter in the present invention can be the compound of lithium, sodium, potassium, rubidium or caesium, such as oxide, oxalates, sulphur
Hydrochlorate, acetate or nitrate etc. or its mixture, the content of alkali metal is 5~2000ppm, preferably 10 in final silver catalyst
~1500ppm.Alkali metal promoter can be applied on carrier prior to, concurrently with, or after immersion silver, can also be in silver compound quilt
It is immersed in after reduction on carrier.
Base earth metal promoter in the present invention can be the compound of magnesium, calcium, strontium or barium, such as oxide, oxalates, sulfuric acid
Salt, acetate or nitrate etc. or its mixture, the content of alkaline-earth metal is not (including carrier preparation process in final silver catalyst
The alkaline-earth metal of middle addition) it is 5~2000ppm, preferably 10~1200ppm.Base earth metal promoter can before immersion silver, simultaneously
Or be applied to afterwards on carrier, it can also be immersed in after silver compound is reduced on carrier.
In addition to alkali metal promoter above-mentioned and base earth metal promoter, other auxiliary agents, such as rhenium can also be added
Compound (other compounds or its mixture of such as ammonium perrhenate, rhenium) and coassist agent (such as chromium, molybdenum, tungsten, boron compound or
Its mixture), further to improve the activity of gained silver catalyst, selectivity and the stability of activity and selectivity.Finally
The content of rhenium is 5~1500ppm, preferably 10~1000ppm in silver catalyst；The content of coassist agent is 5ppm~1000ppm, excellent
10ppm~500ppm is selected, the gross weight based on the silver catalyst.These other auxiliary agents can before immersion silver while or
It is applied on carrier, can also be immersed in after silver compound is reduced on carrier afterwards.
Compared to the prior art the present invention, have selected a higher temperature and lower temperature collocation is calcined to carrier,
Roasting makes carrier crystallization at relatively high temperatures, and carrier now can use but poor-performing.But before being calcined at relatively high temperatures
The process being once calcined at a lower temperature is arranged afterwards, carrier property can be made to make moderate progress.The higher roasting of the carrier of the present invention
Burn temperature and may also be below 1200 DEG C, and keep the performance change of final carrier little.And used additives immersion and second of roasting
The performance of carrier can be greatly improved, so not only saves the energy of roasting process consumption, also makes the strength enhancing of carrier, and
And the performance of final catalyst is also improved.Silver catalyst made of porous alumina carrier made in accordance with the present invention
Stable performance, and there is higher activity, the reaction especially suitable for ethylene production oxirane.
Embodiment
The present invention is described further with reference to embodiment, but the scope of the present invention is not limited to these embodiments.
The measure of catalyst performance
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 measure of initial activity, selectivity
The condition determination for the activity and selectivity that the present invention uses is as follows：
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：
Selectivity
Wherein Δ 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.
Carrier comparative example 1
By the α-three water A1 of 50~500 mesh2O3390g, the water A1 of vacation one more than 200 mesh2O3110g、NH4F7g、
SiO20.5g、ZrO21.0g and BaSO41.0g is put into blender and is well mixed, and is transferred in kneader, adds dust technology (nitric acid：
Water=1：3, weight ratio) 90 milliliters, it is kneaded into the paste of extrudable shaping.Extrusion molding be external diameter 8.0mm, long 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 less than 10%.
Then green compact are put into electric furnace, through 30 hours or so between room temperature is increased to 1350 DEG C~1550 DEG C, constant temperature 2 hours, obtained
To white α-A12O3Support samples.
Carrier comparative example 2
By the α-three water A1 of 50~500 mesh2O3390g, the water A1 of vacation one more than 200 mesh2O3110g、NH4F7g、
SiO20.5g、ZrO21.0g and BaSO41.0g is put into blender and is well mixed, and is transferred in kneader, adds dust technology (nitric acid：
Water=1：3, weight ratio) 90 milliliters, it is kneaded into the paste of extrudable shaping.Extrusion molding is external diameter 8.0mm, long 6.0mm, interior
Footpath 1.0mm five hole columns, dried more than 2 hours at 80~120 DEG C, free water content is reduced to less than 10%.So
Green compact are put into electric furnace afterwards, 700 DEG C was increased to from room temperature through 30 hours or so, constant temperature 2 hours, obtains white support sample.
Carrier comparative example 3
By the α-three water A1 of 50~500 mesh2O3390g, the water A1 of vacation one more than 200 mesh2O3110g、NH4F7g、
SiO20.5g、ZrO21.0g and BaSO41.0g is put into blender and is well mixed, and is transferred in kneader, adds dust technology (nitric acid：
Water=1：3, weight ratio) 90 milliliters, it is kneaded into the paste of extrudable shaping.Extrusion molding is external diameter 8.0mm, long 6.0mm, interior
Footpath 1.0mm five hole columns, dried more than 2 hours at 80~120 DEG C, free water content is reduced to less than 10%.So
Green compact are put into electric furnace afterwards, 1050 DEG C was increased to from room temperature through 30 hours or so, constant temperature 2 hours, obtains white α-A12O3Carry
Body sample.
Carrier embodiment 1
By the α-three water A1 of 50~500 mesh2O3390g, the water A1 of vacation one more than 200 mesh2O3110g、NH4F7g is put into batch mixing
It is well mixed, is transferred in kneader in device, adds dust technology (nitric acid：Water=1：3, weight ratio) 90 milliliters, it is kneaded into extrudable
The paste of shaping.Extrusion molding is external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm five hole columns, at 80~120 DEG C
Drying more than 2 hours, free water content is set to be reduced to less than 10%.Then green compact are put into electric furnace, through 20 hours or so from
Room temperature is increased to 1200 DEG C, constant temperature 2 hours, obtains white A12O3Carrier semi-finished product.Then, first with the acetic acid containing 0.5wt%
Barium aqueous solution 500g soaks half an hour, after filtering and being dried 2 hours at 80~120 DEG C, then the tetraethyl orthosilicate with 0.3wt%
Aqueous solution 500g soaks half an hour, filters and after dry 2 hours at 80~120 DEG C, finally with ammonium fluoride containing 3.5wt% with
The mixed aqueous solution 500g of 0.5wt% zirconyl nitrates soaks above-mentioned A12O3Carrier semi-finished product half an hour, filter and at 80~120 DEG C
After lower drying more than 2 hours, it is put into electric furnace, was increased to 600 DEG C from room temperature through 10 hours or so, constant temperature 2 hours, obtains white
α-A12O3Support samples.
Carrier embodiment 2
By the α-three water A1 of 50~500 mesh2O3390g, the water A1 of vacation one more than 200 mesh2O3110g、NH4F7g is put into batch mixing
It is well mixed, is transferred in kneader in device, adds dust technology (nitric acid：Water=1：3, weight ratio) 90 milliliters, it is kneaded into extrudable
The paste of shaping.Extrusion molding is external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm five hole columns, at 80~120 DEG C
Drying more than 2 hours, free water content is set to be reduced to less than 10%.Then green compact are put into electric furnace, through 10 hours or so from
Room temperature is increased to 600 DEG C, constant temperature 2 hours, obtains white A12O3Carrier semi-finished product.Then, first with the barium acetate containing 0.5wt%
Aqueous solution 500g soaks half an hour, after filtering and being dried 2 hours at 80~120 DEG C, then the tetraethyl orthosilicate water with 0.3wt%
Solution 500g soaks half an hour, filters and after dry 2 hours at 80~120 DEG C, finally with ammonium fluoride containing 3.5wt% with
The mixed aqueous solution 500g of 0.5wt% zirconyl nitrates soaks above-mentioned A12O3Carrier semi-finished product half an hour, filter and at 80~120 DEG C
After lower drying more than 2 hours, it is put into electric furnace, was increased to 1200 DEG C from room temperature through 20 hours or so, constant temperature 2 hours, obtains white
Color α-A12O3Support samples.
Carrier embodiment 3
By the α-three water A1 of 50~500 mesh2O3390g, the water A1 of vacation one more than 200 mesh2O3110g is put into blender and mixed
Close uniformly, be transferred in kneader, add dust technology (nitric acid：Water=1：3, weight ratio) 90 milliliters, it is kneaded into extrudable shaping
Paste.Extrusion molding is external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm five hole columns, and it is small that 2 are dried at 80~120 DEG C
When more than, free water content is reduced to less than 10%.Then green compact are put into electric furnace, raised through 10 hours or so from room temperature
To 600 DEG C, constant temperature 2 hours, white A1 is obtained2O3Carrier semi-finished product.Then with the tetraethyl orthosilicate aqueous solution containing 0.3wt%
500g soaks above-mentioned A12O3Carrier semi-finished product half an hour, after filtering and being dried more than 2 hours at 80~120 DEG C, it is put into electric furnace
In, 1200 DEG C were increased to from room temperature through 20 hours or so, constant temperature 2 hours, obtains white α-A12O3Support samples.
Carrier embodiment 4
By the α-three water A1 of 50~500 mesh2O3390g, the water A1 of vacation one more than 200 mesh2O3110g、ZrO21.0g is put into mixed
It is well mixed, is transferred in kneader in glassware, adds dust technology (nitric acid：Water=1：3, weight ratio) 90 milliliters, being kneaded into squeeze
Go out the paste of shaping.Extrusion molding is external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm five hole columns, at 80~120 DEG C
Lower drying more than 2 hours, free water content is set to be reduced to less than 10%.Then green compact are put into electric furnace, through 20 hours or so
1200 DEG C are increased to from room temperature, constant temperature 2 hours, obtains white A12O3Carrier semi-finished product.Then it is placed again into electric furnace, it is small through 10
When or so be increased to 600 DEG C from room temperature, constant temperature 2 hours, obtain white α-A12O3Support samples.
Carrier embodiment 5
By the α-three water A1 of 50~500 mesh2O3390g, the water A1 of vacation one more than 200 mesh2O3110g、NH4F7g is put into batch mixing
It is well mixed, is transferred in kneader in device, adds dust technology (nitric acid：Water=1：3, weight ratio) 90 milliliters, it is kneaded into extrudable
The paste of shaping.Extrusion molding is external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm five hole columns, at 80~120 DEG C
Drying more than 2 hours, free water content is set to be reduced to less than 10%.Then green compact are put into electric furnace, through 10 hours or so from
Room temperature is increased to 450 DEG C, constant temperature 2 hours, obtains white A12O3Carrier semi-finished product.Then, first with the barium acetate containing 0.5wt%
Aqueous solution 500g soaks half an hour, after filtering and being dried 2 hours at 80~120 DEG C, then the tetraethyl orthosilicate water with 0.3wt%
Solution 500g soaks half an hour, filters and after dry 2 hours at 80~120 DEG C, finally with ammonium fluoride containing 3.5wt% with
The mixed aqueous solution 500g of 0.5wt% zirconyl nitrates soaks above-mentioned A12O3Carrier semi-finished product half an hour, filter and at 80~120 DEG C
After lower drying more than 2 hours, it is put into electric furnace, was increased to 1050 DEG C from room temperature through 20 hours or so, constant temperature 2 hours, obtains white
Color α-A12O3Support samples.
Carrier embodiment 6
By the α-three water A1 of 50~500 mesh2O3390g, the water A1 of vacation one more than 200 mesh2O3110g、NH4F7g is put into batch mixing
It is well mixed, is transferred in kneader in device, adds dust technology (nitric acid：Water=1：3, weight ratio) 90 milliliters, it is kneaded into extrudable
The paste of shaping.Extrusion molding is external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm five hole columns, at 80~120 DEG C
Drying more than 2 hours, free water content is set to be reduced to less than 10%.Then green compact are put into electric furnace, through 20 hours or so from
Room temperature is increased to 1050 DEG C, constant temperature 2 hours, obtains white A12O3Carrier semi-finished product.Then, first with the acetic acid containing 0.5wt%
Barium aqueous solution 500g soaks half an hour, after filtering and being dried 2 hours at 80~120 DEG C, then the tetraethyl orthosilicate with 0.3wt%
Aqueous solution 500g soaks half an hour, filters and after dry 2 hours at 80~120 DEG C, finally with ammonium fluoride containing 3.5wt% with
The mixed aqueous solution 500g of 0.5wt% zirconyl nitrates soaks above-mentioned A12O3Carrier semi-finished product half an hour, filter and at 80~120 DEG C
After lower drying more than 2 hours, it is put into electric furnace, was increased to 450 DEG C from room temperature through 10 hours or so, constant temperature 2 hours, obtains white
α-A12O3Support samples.
Carrier embodiment 7
By the α-three water A1 of 50~500 mesh2O3390g, the water A1 of vacation one more than 200 mesh2O3110g、NH4F7g、BaSO41g、
SiO20.5g、ZrO21g is put into blender and is well mixed, and is transferred in kneader, adds dust technology (nitric acid：Water=1：3, weight
Than) 90 milliliters, it is kneaded into the paste of extrudable shaping.Extrusion molding is external diameter 8.0mm, long 6.0mm, the five of internal diameter 1.0mm
Hole column, dried more than 2 hours at 80~120 DEG C, free water content is reduced to less than 10%.Then green compact are put into
In electric furnace, 1450 DEG C were increased to from room temperature through 30 hours or so, constant temperature 2 hours, obtains white A12O3Carrier semi-finished product.Then again
It is secondary to be put into electric furnace, 700 DEG C were increased to from room temperature through 10 hours or so, constant temperature 2 hours, obtains white α-A12O3Support samples.
Carrier embodiment 8
By the α-three water A1 of 50~500 mesh2O3390g, the water A1 of vacation one more than 200 mesh2O3110g is put into blender and mixed
Close uniformly, be transferred in kneader, add dust technology (nitric acid：Water=1：3, weight ratio) 90 milliliters, it is kneaded into extrudable shaping
Paste.Extrusion molding is external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm five hole columns, and it is small that 2 are dried at 80~120 DEG C
When more than, free water content is reduced to less than 10%.Then green compact are put into electric furnace, raised through 10 hours or so from room temperature
To 700 DEG C, constant temperature 2 hours, white A1 is obtained2O3Carrier semi-finished product.Then, first with the barium acetate aqueous solution containing 0.5wt%
500g soaks half an hour, after filtering and being dried 2 hours at 80~120 DEG C, then the tetraethyl orthosilicate aqueous solution with 0.3wt%
500g soaks half an hour, after filtering and being dried 2 hours at 80~120 DEG C, finally uses ammonium fluoride containing 3.5wt% and 0.5wt%
The mixed aqueous solution 500g of zirconyl nitrate soaks above-mentioned A12O3Carrier semi-finished product half an hour, filter and dry 2 at 80~120 DEG C
After more than hour, it is put into electric furnace, was increased to 1450 DEG C from room temperature through 10 hours or so, constant temperature 2 hours, obtains white α-A12O3
Support samples.
Carrier embodiment 9
By the α-three water A1 of 50~500 mesh2O3390g, the water A1 of vacation one more than 200 mesh2O3110g、NH4F7g is put into batch mixing
It is well mixed, is transferred in kneader in device, adds dust technology (nitric acid：Water=1：3, weight ratio) 90 milliliters, it is kneaded into extrudable
The paste of shaping.Extrusion molding is external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm five hole columns, at 80~120 DEG C
Drying more than 2 hours, free water content is set to be reduced to less than 10%.Then green compact are put into electric furnace, through 10 hours or so from
Room temperature is increased to 600 DEG C, constant temperature 2 hours, obtains white A12O3Carrier semi-finished product.Then, with 0.3wt% tetraethyl orthosilicate water
Solution 500g soaks half an hour, after filtering and being dried 2 hours at 80~120 DEG C, is finally putting into electric furnace, through 20 hours or so
1200 DEG C are increased to from room temperature, constant temperature 2 hours, obtains white α-A12O3Support samples.
Carrier embodiment 10
By the α-three water A1 of 50~500 mesh2O3390g, the water A1 of vacation one more than 200 mesh2O3110g is put into blender and mixed
Close uniformly, be transferred in kneader, add dust technology (nitric acid：Water=1：3, weight ratio) 90 milliliters, it is kneaded into extrudable shaping
Paste.Extrusion molding is external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm five hole columns, and it is small that 2 are dried at 80~120 DEG C
When more than, free water content is reduced to less than 10%.Then green compact are put into electric furnace, raised through 20 hours or so from room temperature
To 600 DEG C, constant temperature 2 hours, white A1 is obtained2O3Carrier semi-finished product.Then, first with the 0.3wt% tetraethyl orthosilicate aqueous solution
500g soaks half an hour, after filtering and being dried 2 hours at 80~120 DEG C, then the mixed aqueous solution with 0.5wt% zirconyl nitrates
500g soaks above-mentioned A12O3Carrier semi-finished product half an hour, finally it is placed again into electric furnace, was increased to through 10 hours or so from room temperature
1200 DEG C, constant temperature 2 hours, obtain white α-A12O3Support samples.
By the carrier of above-mentioned comparative example 1,2,3 and embodiment 1-10 determine respectively its crushing strength, water absorption rate, than surface,
Pore volume etc., performance data is listed in table 1.
The physical data of the comparative example 1,2,3 of table 1 and embodiment 1-10 carriers
As known from Table 1, the crushing strength of embodiment 1-10 carriers is apparently higher than comparative example 1-3.
COMPARATIVE CATALYST EXAMPLE 1,2,3 and embodiment 1-10
700g silver nitrates are taken to be dissolved in 750ml deionized waters.The deionized water for taking 325g ammonium oxalate to be dissolved in 250ml50 DEG C
In.Two kinds of solution are mixed with vigorous stirring, generate white silver oxalate precipitate.Aging more than 30 minutes, filtering, uses deionized water
Washing is precipitated to no nitrate ion.Filter cake argentiferous about 60% (weight), aqueous about 15% (weight).
Add 300g ethylenediamines, 110g monoethanolamines and 375g deionized waters in the glass flask with stirring.Lower system of stirring
The silver oxalate paste obtained is slowly added into mixed liquor, and temperature is maintained at less than 40 DEG C, silver oxalate is all dissolved, silver oxalate
Addition makes obtained maceration extract argentiferous 23~25% (weight).Add 2.2g cesium sulfates, 1.0g ammonium perrhenates, then add deionized water
Solution gross mass is reached 2000g, solution for later use is made.
50g carriers comparative example 1,2,3 and carrier embodiment 1-9 sample are taken respectively, are put into the container that can be vacuumized.Take out
For vacuum to more than 10mmHg, every part of carrier is put into the maceration extract 100g of above-mentioned preparation, submerges carrier and is kept for 30 minutes.Leaching is gone
Unnecessary solution.Carrier after dipping heats 5 minutes in 250 DEG C of air stream, cooling, that is, oxirane silver catalysis is made
Agent.
The silver and auxiliary agent content of manufactured catalyst are analyzed, wherein content is in terms of metal；Use microreactor
Evaluating apparatus determines the activity and selectivity of catalyst sample under the conditions of previous process, and result of the test is listed in table 2.
The comparative example 1,2,3 of table 2 and embodiment 1-10 catalyst ethylene oxide produce the result of the test of oxirane
* note：Selectivity takes accumulative EO yield to reach 400T/M3Average value during catalyst.
As known from Table 2, because carrier comparative example 2 is in transition state A12O3, α-A1 are not formed2O3, therefore completely not
EO productions are can be suitably used for, therefore do not have evaluating data, although carrier comparative example 3 forms α-A12O3, but due to phase in version not
It is enough thorough, so selectivity is relatively low.In summary, after carrier being made into catalyst, the selectivity of embodiment at least above contrasts
Example 1%, this is apparent improvement in silver catalyst field.
It should be noted that embodiment described above is only used for explaining the present invention, do not form to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used 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 wherein disclosed particular case, on the contrary, this hair
It is bright to can be extended to other all methods and applications with identical function.
Claims (15)
1. a kind of preparation method of alumina support, is comprised the steps of：
I) prepare with the mixture formed as follows：
A) based on the water α-A1 of 50 mesh~500 mesh three that total weight of the mixture is 50~90% weight2O3；
B) it is more than the water A1 of vacation one of 200 mesh for the granularity of 5~50% weight based on total weight of the mixture2O3；And
C) based on the auxiliary agent that total weight of the mixture is 0~5% weight；
II) to I) binding agent that the gross weight based on the mixture is 15~60% weight is added in obtained mixture；
III) by II) in obtained mixture mediate uniformly and extrusion molding；
IV) dry III) in obtained product, then carry out first time roasting, obtain carrier semi-finished product；
V) used additives solution immersion IV) in obtained product and drying；
VI) by V) in obtained product carry out second and be calcined, obtain described alumina support；
In step I) component c) in, the one kind or more of the auxiliary agent in silicon, siliceous compound, zirconium and zirconium-containing compound
Kind；
Step V) in compounding agent solution be selected from the siliceous aqueous solution and/or the aqueous solution containing zirconium, the siliceous aqueous solution are selected from
Teos solution, the aqueous solution containing zirconium are selected from zirconium oxychloride and/or zirconyl nitrate solution；
Wherein, higher temperature is selected in roasting for the first time, and relatively low temperature is selected in second of roasting；Higher temperature ThFor 1200~
1500 DEG C carry out and are incubated 2~24 hours；Lower temperature TlFor Th40%~60% and be incubated 2~24 hours.
In component c) 2. according to the method for claim 1, it is characterised in that in step I), the siliceous compound
For silica and/or silicate；The zirconium-containing compound is zirconium oxide.
3. in component c) according to the method for claim 1, it is characterised in that in step I), the auxiliary agent also includes alkali
Earth metal compound and/or fluoride, the alkaline earth metal compound are selected from oxide, the sulfuric acid of beryllium, magnesium, calcium, strontium and/or barium
One or more in salt, acetate, nitrate and oxalates；The fluoride be selected from hydrogen fluoride, ammonium fluoride, aluminum fluoride with
And ice crystal or its mixture.
In component c) 4. according to the method for claim 3, it is characterised in that in step I), the alkaline-earth metal chemical combination
One or more in oxide of the thing selected from strontium and/or barium, sulfate, acetate, nitrate and oxalates；The fluorination
Thing is selected from aluminum fluoride and/or ammonium fluoride.
5. according to the method for claim 1, it is characterised in that in step II) in, the binding agent be selected from nitric acid, formic acid,
The aqueous solution of acetic acid, propionic acid and/or hydrochloric acid.
6. according to the method for claim 1, it is characterised in that in step II), the binding agent is water-soluble for nitric acid
Liquid.
7. according to the method for claim 6, it is characterised in that in step II) in, in the aqueous solution of the nitric acid nitric acid with
The weight ratio of water is 1:1.25~10.
8. the method according to claim 11, it is characterised in that in step I) and/or step II) in, replaced with Alumina gel
One water A1 of vacation2O3And binding agent.
9. compounding agent solution according to the method for claim 1, it is characterised in that step V) also includes alkaline-earth metal chemical combination
The aqueous solution of thing and/or fluorine-containing solution, the aqueous solution of the alkaline earth metal compound are selected from the aqueous solution containing strontium and/or barium, contained
Fluorine solution is selected from ammonium fluoride solution, and the concentration of the compounding agent solution is 0.01~10wt%, and amount of solution is carrier semi-finished product weight
One times to ten times, soak time be 10 minutes~2 hours, drying temperature be 80~120 DEG C, drying time be 1 hour~24
Hour.
10. according to the method for claim 1, it is characterised in that lower temperature TlFor 600~700 DEG C.
11. alumina support prepared by the method according to any one of claim 1~10, wherein A12O3Content is 90 weights
Measure more than %；Auxiliary element adds up to the 0.01~5% of vehicle weight, the crushing strength of the carrier with element>20N；Compare table
Face is 0.5~4.0m2/g；Water absorption rate is not less than 30%；Pore volume is 0.35~0.85ml/g.
12. alumina support prepared by the method according to any one of claim 1~10, wherein A12O3Content is 95 weights
Measure more than %；Auxiliary element adds up to the 0.01~5% of vehicle weight with element, the crushing strength of the carrier for 40~
200N；It is 1.0~2.0m than surface2/g；Water absorption rate is not less than 45%；Pore volume is 0.40~0.80ml/g.
13. a kind of silver catalyst, including：
1) catalyst carrier or the catalyst as described in claim 11-12 that prepared by the method as described in claim 1-10
Carrier；
2) silver of deposition on the carrier；
3) alkali metal and/or alkaline-earth metal or the compound based on alkali metal and/or alkaline-earth metal；
4) rhenium metal and/or the compound based on rhenium.
14. silver catalyst according to claim 13, it is characterised in that the collaboration that rhenium is added in the silver catalyst helps
Agent, its one or more element and/or compound in chromium, molybdenum, tungsten and boron.
15. application of the silver catalyst in ethylene produces oxirane as described in claim 13-14.
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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 |
| CN107812542B (en) * | 2016-09-14 | 2020-10-23 | 中国石油化工股份有限公司 | Alpha-alumina carrier and preparation method and application thereof |
| CN108283943B (en) * | 2017-01-10 | 2021-07-02 | 中国石油化工股份有限公司 | Alumina carrier and preparation method thereof, silver catalyst for ethylene epoxidation reaction and method for preparing ethylene oxide by ethylene epoxidation |
| CN109499621A (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 and preparation method thereof, ethylene epoxidizing silver catalyst |
| CN112295553B (en) * | 2019-08-02 | 2023-06-30 | 中国石油天然气股份有限公司 | Preparation method of modified alumina carrier |
| CN112295561B (en) * | 2019-08-02 | 2023-07-25 | 中国石油天然气股份有限公司 | Epoxidation catalyst and preparation method thereof |
| CN112300096A (en) * | 2019-08-02 | 2021-02-02 | 中国石油天然气股份有限公司 | Method for producing ethylene oxide by ethylene epoxidation |
| CN114433042B (en) * | 2020-11-05 | 2024-05-07 | 中国石油化工股份有限公司 | Alumina carrier and preparation method thereof |
| CN114433043B (en) * | 2020-11-05 | 2024-05-07 | 中国石油化工股份有限公司 | Alumina carrier, preparation method thereof, silver catalyst and application |
| CN115382526A (en) * | 2021-05-24 | 2022-11-25 | 中国石油化工股份有限公司 | Alumina carrier, preparation method and application thereof |
| CN115382525B (en) * | 2021-05-24 | 2024-05-10 | 中国石油化工股份有限公司 | Alpha-alumina carrier, preparation method thereof, silver catalyst and application |
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