CN105080617A - Preparation method and application of alumina carrier - Google Patents
Preparation method and application of alumina carrier Download PDFInfo
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- CN105080617A CN105080617A CN201410193211.1A CN201410193211A CN105080617A CN 105080617 A CN105080617 A CN 105080617A CN 201410193211 A CN201410193211 A CN 201410193211A CN 105080617 A CN105080617 A CN 105080617A
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Abstract
The invention relates to a method for preparing an alumina carrier. The method comprises the following steps: (I) preparing a mixture including alpha-Al2O3 trihydrate, pseudo-Al2O3 monohydrate and auxiliaries; (II) adding an adhesive into the mixture obtained in the step (I); (III) uniformly kneading the mixture obtained in the step (II), extruding and molding; (IV) drying the product obtained in the step (III), and roasting for the first time to obtain a carrier semi-finished product; (V) soaking the product obtained in the step (IV) with an auxiliary solvent, and drying; (VI) roasting the product obtained in the step (V) for the second time. The invention further relates to the alumina carrier prepared by the method, a silver catalyst prepared by the carrier and application of the silver catalyst. The silver catalyst is used for producing ethylene oxide by ethylene oxidation, and has excellent activity and stability.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof of alumina support, be specifically related to a kind of silver catalyst produced oxirane (EO) preparation method of the alumina support of silver catalyst for ethylene and obtained by this carrier, and described catalyst produces the application in oxirane at ethylene.
Background technology
Under silver catalyst effect, ethylene mainly generates oxirane, and side reaction occurs simultaneously and generates carbon dioxide and water etc., wherein active, selective and stability is the main performance index of silver catalyst.So-called activity refers to the reaction temperature that process for ethylene oxide production reaches required when necessarily reacting load.Reaction temperature is lower, and the activity of catalyst is higher.What is called is selective refers to that in reaction, ethylene conversion becomes the ratio of the molal quantity of oxirane and the overall reaction molal quantity of ethene.So-called stability is then expressed as the fall off rate of activity and selectivity, and the stability of fall off rate more small catalyst is better.Produce at ethylene in the process of oxirane and use high activity, high selectivity and the silver catalyst that has good stability greatly to increase economic efficiency, the silver catalyst therefore manufacturing high activity, high selectivity and good stability is the Main way of silver catalyst research.The performance of silver catalyst is except having important relationship with the composition of catalyst and preparation method, and performance and the preparation method of the carrier also used with catalyst have important relationship.
The preparation method of silver catalyst mainly comprise the preparation and administration to active component of porous carrier (as aluminium oxide) and auxiliary agent to as described in this two processes on carrier.What its carrier was generally selected is the Alpha-alumina that specific area is less.Aluminium oxide (Al
2o
3) be a kind of catalyst carrier of having many uses, its kind is very many, crystal structure, and surface catalysis performance is also very complicated, directly affects the performance of silver catalyst.
The primary raw material preparing alumina support is the hydrate of aluminium oxide (being aluminium hydroxide again), hydrated alumina dehydration can produce Louis (L) Acid and basic sites, and these L acid sites are easy to water suction and change proton (B) Acid and basic sites into.The crystal formation kind of aluminium oxide is a lot, and impurity and moisture impact more or less in addition, causes the surface physics of aluminium oxide, chemical property all very complicated.For the α-Al that silver catalyst is selected
2o
3although its surface only has the Acid and basic sites of seldom amount, they and active component acting in conjunction, impel ethylene conversion to be oxirane.
Carrier needs to provide certain area load active component, well that active component is thereon dispersed, and this just proposes very high requirement to the pore structure of carrier.The hole of alumina support can be divided into three types: 1) primary particle intercrystalline hole, the mainly dewatering hole of alumina raw material crystal grain, be substantially 1 ~ 2nm size parallel-plate face between gap; 2) hole between alumina raw material offspring, changing with the effusion of moisture and crystalline phase change in calcining, is the hole of tens of more than nm; 3) pore creating material and carrier shaping time produce defective hole and macropore.Therefore, the alumina raw material proportioning of variety classes and particle diameter, the consumption of pore creating material and molding mode and calcinating system etc. all can impact the pore structure of silver catalyst carrier and physical property, and then affect the performance of catalyst.
In general, the main method preparing silver catalyst carrier is, select various different alumina powder raw material (and/or) add pore creating material, binding agent and various additives etc., even through batch mixing and kneading, then extrusion molding is difform base substrate (Raschig ring, spheric granules, porous cylindrical, the shape of a saddle etc.), the last alpha-alumina supports product making porous heat-resistant at 1200 ~ 1700 DEG C of sintering, as described in patent US5063195, US5703001, US5801259 etc.
Auxiliary agent is added, in order to improve the performance of carrier toward contact in the preparation process of silver catalyst carrier.The silver catalyst carrier that the compound proposing to add heavy alkaline-earth metal in alumina powder raw material as patent CN02160081 is made, then load active component makes silver catalyst, it is active, selective is all improved.The mullite that patent CN102099109A proposes to add a kind of stability enhancing amount is in the carrier the stability that auxiliary agent can improve high-selectivity catalyst, extending catalyst service life, and " mullite " that use refers to that one has and SiO
2be integrated as the A1 of solid solution
2o
3the alumina silicate mineral of composition.Patent US5100859A proposes in alumina support, add alkaline-earth metal, SiO
2and zirconia can improve the performance etc. of silver catalyst.
Surface is carried out to carrier and carries out the common methods that pretreatment is also carrier preparation and process.As: washing, pickling, alkali cleaning and modification and modification etc. are carried out to carrier surface with various auxiliary agent immersions etc.
These new methods above-mentioned are no longer only from adjusting alumina powder raw material, pore creating material, binding agent and various additives etc. or starting with sintering process from shaping, and more pay attention to finishing that carrier is carried out or pretreatment, the performance of epoxyethane catalyst is improved by the active component bonding state regulated and improve carrier and load.But the improvement that the activity and selectivity of these methods to carrier property and catalyst brings is also very limited, and therefore this area still needs to improve the manufacture method of carrier, is beneficial to produce the better silver catalyst of performance.
Summary of the invention
In view of the situation of above-mentioned prior art, the present inventor has carried out research extensively and profoundly in silver catalyst field, found that, adopt alumina support prepared by following methods, through the solution that is mixed with of dipping silver compound, organic amine and specific adjuvant, the prepared activity and selectivity of silver catalyst in ethylene oxidation reactions is all improved after containing heat treatment in oxygen gas mixture.Concrete grammar is: the method adopting after baking, and at support greenware after first time, roasting completed, used additives solution (as alkaline including earth metal, silicon, zirconium and fluorine-containing solution etc.) soaks semi-finished product, then makes carrier finished product through second time roasting.The temperature of after baking controls to meet: if higher temperature is selected in first time roasting, then after baking can select lower temperature; Otherwise if lower temperature is selected in first time roasting, then after baking can select higher temperature.
Therefore, the object of this invention is to provide a kind of novel oxidized alumina supporter, described carrier has good crushing strength and lower wear rate.
Another object of the present invention is to provide a kind of preparation method of above-mentioned carrier.
An also 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 the application of above-mentioned silver catalyst in ethylene production oxirane, and described silver catalyst demonstrates good activity and selectivity.
One aspect of the present invention provides a kind of preparation method of alumina support, and described carrier is porous alpha-alumina supports, produces oxirane silver catalyst for the preparation of ethylene.Described method comprises the steps:
I) preparation has the mixture of following composition:
A) based on mixture total weight amount be 50 order ~ 500 order three water α-A1 of 50 ~ 90% weight
2o
3;
B) granularity being 5 ~ 50% weight based on mixture total weight amount is greater than the false water A1 of 200 objects
2o
3; And
C) based on mixture total weight amount be the auxiliary agent of 0 ~ 5% weight;
II) to I) gross weight added in the mixture that obtains based on described mixture is the binding agent of 15 ~ 60% weight;
III) by II) in the mixture that obtains mediate evenly and extrusion molding;
IV) dry III) in the product that obtains, then carry out first time roasting, obtain carrier semi-finished product;
V) used additives solution soaks IV) in the product that obtains, and the product that drying so obtains;
VI) by V) in the product that obtains carry out second time roasting, obtain alumina support of the present invention.
In step I) amount of component b) in, described auxiliary agent be selected from silicon, siliceous compound, zirconium and zirconium-containing compound one or more, the preferred silica of described siliceous compound and/or silicate; Described zirconium-containing compound preferential oxidation zirconium; The effect of these auxiliary agents is to improve carrier.
Step V) in compounding agent solution be selected from the siliceous aqueous solution and/or containing the aqueous solution of zirconium, the preferred teos solution of the described siliceous aqueous solution, the preferred zirconium oxychloride of the aqueous solution containing zirconium and/or zirconyl nitrate solution.
Further, the present invention is in step I) amount of component b) in, described auxiliary agent also comprises alkaline earth metal compound and/or fluoride, one or more preferably in the oxide of beryllium, magnesium, calcium, strontium and/or barium, sulfate, acetate, nitrate and oxalates of described alkaline earth metal compound, one or more more preferably in the oxide of strontium and/or barium, sulfate, acetate, nitrate and oxalates; Described fluoride is preferably from hydrogen fluoride, ammonium fluoride, aluminum fluoride and ice crystal or its mixture, more preferably aluminum fluoride and/or ammonium fluoride, and effect is the transformation of crystal of accelerated oxidation aluminium, and reduces by the pore of less than 0.1 μm.
It should be noted that step V) in compounding agent solution used and step I) in amount of component b) can be identical, also can be different.Difference is step I) in amount of component b) auxiliary agent that uses can be insoluble matter, and step V) auxiliary agent used in compounding agent solution must be water miscible.In step I) in can not add any auxiliary agent, and in step V) in add the compounding agent solution of q.s; Also can in step I) add part of auxiliary, and in step V) in add the compounding agent solution of remaining q.s; Finally make the adjuvant component containing q.s in finished product carrier.
The present invention in carrier preparation process by adding the vacation one water A1 in binding agent and mixture
2o
3generate Alumina gel, each component is bonded together, becoming can the paste of extrusion molding, also can add appropriate water while adding binding agent.Binding agent used comprises acid, as the aqueous solution of nitric acid, formic acid, acetic acid, propionic acid and hydrochloric acid etc.When using acid as binding agent, preferably aqueous solution of nitric acid, wherein the weight ratio of nitric acid and water is 1:1.25 ~ 10.Can in step I) and/or Step II) in, by a false water A1
2o
3replace with acid Alumina gel.Namely, by step I) in components b) replace with Alumina gel and cancellation step II) and in binding agent, or cancellation step I) in components b) and by Step II) in binding agent replace with Alumina gel, or by step I) in components b) and Step II) in binding agent all replace with Alumina gel.
Carry out drying after the extrusion molding of gained paste, preferred baking temperature is 80 ~ 120 DEG C, and drying time controls, at 1 hour ~ 24 hours, water content to be down to less than 10% after drying according to moisture.
First dried paste carries out first time roasting, and is incubated 2 ~ 24 hours, obtains carrier semi-finished product.
Then carrier semi-finished product are put into compounding agent solution to soak, its object is to carry out modification and modification to carrier surface.Step V) in compounding agent solution can also comprise the aqueous solution of alkaline earth metal compound and/or fluorine-containing solution, the preferred self-contained strontium of the aqueous solution of described alkaline earth metal compound and/or the aqueous solution of barium, fluorine-containing solution is preferably from ammonium fluoride solution.Carrier semi-finished product once can be soaked the aqueous solution containing multiple auxiliary agent, also successively can repeatedly soak various compounding agent solution, solution concentration can regulate within the scope of 0.01 ~ 10wt%, finally to make the adjuvant component containing q.s in carrier finished product suitable.Amount of solution is soaked one times of carrier semi-finished product weight to ten times, is excellent not have carrier surface of semi-finished.Soak time controls at 10 minutes ~ 2 hours, and then filter and drying, preferred baking temperature is 80 ~ 120 DEG C, and drying time controls at 1 hour ~ 24 hours according to moisture.
Afterwards second time roasting is carried out to the carrier semi-finished product through above-mentioned process, and be incubated 2 ~ 24 hours, obtain final α-A1
2o
3carrier finished product.Support shapes can be annular, spherical, cylindricality or porous column shape.
It should be noted that the temperature of after baking need meet specific requirement, because the too high activity and selectivity that can affect the catalyst made of temperature, the too low then support strength of sintering temperature is poor.Specifically, the temperature of after baking will select a higher temperature and lower temperature collocation, if that is: higher temperature is selected in first time roasting, then after baking can select lower temperature; Otherwise if lower temperature is selected in first time roasting, then after baking can select higher temperature.Wherein higher temperature T
hcan select carry out within the scope of 1000 ~ 1500 DEG C and be incubated 2 ~ 24 hours, within the scope of being preferably 1000 ~ 1200 DEG C; Lower temperature T
lt can be selected
h1/4 ~ 3/4 scope in carry out and be incubated 2 ~ 24 hours, preferred T
lfor T
h40% ~ 60%, more preferably T
lbe in the scope of 400 ~ 700 DEG C.
If twice roasting all at a lower temperature, carrier cannot transfer α-phase to.And select all to use for twice higher temperature obviously can consume the more energy, there is no need.So the present invention have selected a higher temperature and lower temperature collocation, roasting makes carrier complete a turn crystalline substance at relatively high temperatures, and carrier now can use but poor-performing.But arrange once the process of roasting at a lower temperature at relatively high temperatures before and after roasting, carrier property can be made to have greatly improved.
In one particular embodiment of the present invention, by precursor carrier first roasting at 1200 DEG C also dry for extrusion molding, the crushing strength of carrier is now low, poor-performing.Then soaked by the carrier used additives of first time roasting, then carry out roasting at 600 DEG C, the carrier obtained has good crushing strength, the stable performance of the silver catalyst prepared by this carrier, and has higher activity.
In another specific embodiment of the present invention, precursor carrier first roasting at 600 DEG C, carrier is now transitional face, and poor-performing cannot be used for silver catalyst.Then used additives soaks roasting at 1200 DEG C again, and result can with it quite or better.
The temperature that usual aluminium oxide changes α phase into is 1200 DEG C, and therefore the highest sintering temperature of prior art is not less than 1200 DEG C usually, otherwise the transformation of final carrier is not thorough, causes carrier property significantly to reduce.And the present invention does not add any pore creating material in support material, and the fluoride added in carrier can reduce and turns a brilliant temperature, and carrying out bakes to burn the article at lower than 1200 DEG C just can make most aluminium oxide transfer α phase to.But roasting can cause intensity to decrease at lower than 1200 DEG C, and can the intensity of lifting carrier further by the roasting at another lower temperature, after first low temperature high temperature condition under roasting effect particularly evident.Therefore the higher sintering temperature of carrier of the present invention can also lower than 1200 DEG C, and keep the performance change of final carrier little.And used additives soaks the performance that significantly can improve carrier with second time roasting, not only save the consumption of the energy in roasting process like this, also make the strength enhancing of carrier, the performance of final catalyst have also been obtained raising.
Carrying alumina shape of the present invention is external diameter is 7-9mm, and honeycomb aperture is the cellular cylindrical α-A1 in the seven apertures in the human head of 1-3mm, five holes or three holes
2o
3particle, or external diameter be 7-9mm, internal diameter is the circular α of the single hole-A1 of 3-6mm
2o
3particle.
The present invention provides a kind of porous alpha-alumina supports obtained as stated above on the other hand, wherein A1
2o
3content is more than 90 % by weight, preferably more than 95 % by weight; The auxiliary elements such as all the other alkaline-earth metal, silicon, zirconium and fluorine add up to 0.01 ~ 5% of vehicle weight with element, and have following feature: crushing strength >20N, preferably 40 ~ 200N; Specific surface is 0.5 ~ 4.0m
2/ g, preferably 1.0 ~ 2.0m
2/ g; Water absorption rate is not less than 30%, is preferably not less than 45%; Pore volume is 0.35 ~ 0.85ml/g, preferably 0.40 ~ 0.80ml/g.
Further aspect of the present invention provides a kind of silver catalyst producing oxirane for ethene catalytic gas phase oxidation, comprising:
1) catalyst carrier provided by the invention;
2) deposition silver 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;
In described silver catalyst, preferably also add the collaborative auxiliary agent of rhenium, it is selected from one or more elements in chromium, molybdenum, tungsten and boron and/or compound.
Silver catalyst of the present invention can be prepared in the usual way, such as pass through with a kind of Ag-containing compound, organic amine, alkali metal promoter and/or base earth metal promoter, rhenium metal and/or the compound based on rhenium, and prepared by the alumina support that solution impregnation the invention described above of the collaborative auxiliary agent of optional rhenium provides.
In one particular embodiment of the present invention, described silver catalyst is prepared by the following method:
1) with containing the Ag-containing compound of q.s, organic amine, alkali metal promoter and/or base earth metal promoter, rhenium metal and/or the compound based on rhenium, and the alumina support that solution impregnation the invention described above of the collaborative auxiliary agent of optional rhenium provides;
2) elimination maceration extract, dry impregnated carrier; With
3) containing in oxygen gas mixture to step 2) gained carrier activates, and makes described silver catalyst.
The present invention also relates in one aspect to the application of described silver catalyst in ethylene production oxirane.
In the preparation of silver catalyst of the present invention, first the aqueous solution of silver nitrate and ammonium oxalate or oxalic acid aqueous solution is made to react, separate out silver oxalate precipitate, after filtration, spend deionized water, until without nitrate ion, then silver oxalate is dissolved in organic amine as pyridine, butylamine, ethylenediamine, 1, in the aqueous solution of 3-propane diamine, monoethanolamine or its mixture, add auxiliary agent, be made into dipping solution.Then above-mentioned alumina support is flooded with gained dipping solution, drain, be not more than at air stream or oxygen content in the nitrogen oxygen atmosphere of 21% (as containing oxygen 8.0%) in 180 ~ 700 DEG C, keep 30 seconds ~ 120 minutes in the temperature range of preferred 200-500 DEG C, preferably 1 minute ~ 60 minutes, to carry out thermal decomposition.Also can replace silver nitrate with silver oxide, silver oxalate also can not analyse filter, direct and organic amine complexing, then impregnated carrier.The amount of the silver compound used in dipping process of the present invention should be enough to make argentiferous 1 ~ 30% weight, preferably 5 ~ 26% weight in finally prepd silver catalyst, with silver catalyst total weight.
Alkali metal promoter in the present invention can be the compound of lithium, sodium, potassium, rubidium or caesium, as oxide, oxalates, sulfate, acetate or nitrate etc. or its mixture, in final silver catalyst, alkali-metal content is 5 ~ 2000ppm, preferably 10 ~ 1500ppm.Alkali metal promoter can before dipping silver, also can be immersed on carrier after silver compound is reduced simultaneously or be applied to afterwards on carrier.
Base earth metal promoter in the present invention can be the compound of magnesium, calcium, strontium or barium, as oxide, oxalates, sulfate, acetate or nitrate etc. or its mixture, in final silver catalyst, the content (not comprising the alkaline-earth metal added in carrier preparation process) of alkaline-earth metal is 5 ~ 2000ppm, preferably 10 ~ 1200ppm.Base earth metal promoter can before dipping silver, also can be immersed on carrier after silver compound is reduced simultaneously or be applied to afterwards on carrier.
Except alkali metal promoter above-mentioned and base earth metal promoter, other auxiliary agents can also be added, such as rhenium compound (other compounds or its mixture as ammonium perrhenate, rhenium) and coassist agent (compound or its mixture as chromium, molybdenum, tungsten, boron etc.), to improve the activity of gained silver catalyst, the stability of selective and activity and selectivity further.In final silver catalyst, the content of rhenium is 5 ~ 1500ppm, preferably 10 ~ 1000ppm; The content of coassist agent is 5ppm ~ 1000ppm, and preferred 10ppm ~ 500ppm, based on the gross weight of described silver catalyst.These other auxiliary agents can before dipping silver, also can be immersed on carrier after silver compound is reduced simultaneously or be applied to afterwards on carrier.
The present invention compared to the prior art, have selected a higher temperature and a lower temperature collocation roasting is carried out to carrier, roasting makes carrier crystallization at relatively high temperatures, and carrier now can use but poor-performing.But arrange once the process of roasting at a lower temperature at relatively high temperatures before and after roasting, carrier property can be made to make moderate progress.The higher sintering temperature of carrier of the present invention can also lower than 1200 DEG C, and keep the performance change of final carrier little.And used additives soaks the performance that significantly can improve carrier with second time roasting, not only saves the energy that roasting process consumes like this, also makes the strength enhancing of carrier, and the performance of final catalyst have also been obtained raising.The porous alumina carrier stable performance of silver catalyst of making made in accordance with the present invention, and there is higher activity, be specially adapted to the reaction that ethylene produces oxirane.
Detailed description of the invention
The present invention is described further below in conjunction with embodiment, but scope of the present invention is not limited to these embodiments.
the mensuration of catalyst performance
Various silver catalyst laboratory reaction device of the present invention (following letter " micro-anti-") evaluating apparatus tests its initial performance and stability.The reactor that micro anti-evaluation device uses is the stainless steel tube of internal diameter 4mm, and reactor is placed in heating jacket.The admission space of catalyst is 1ml, and inert filler is arranged at bottom, makes beds be positioned at the flat-temperature zone of heating jacket.
initial activity, optionally to measure
The condition determination of the activity and selectivity that the present invention uses is as follows:
When stable reach above-mentioned reaction condition after METHOD FOR CONTINUOUS DETERMINATION reactor enter, exit gas composition.Measurement result calculates selective as follows after carrying out volume contraction correction:
Selective
Wherein Δ EO works off one's feeling vent one's spleen poor with inlet gas ethylene oxide concentration, gets the result of the test of average as the same day of more than 10 groups test datas.
carrier comparative example 1
By 50 ~ 500 object α-three water A1
2o
3390g, be greater than the false water A1 of 200 objects
2o
3110g, NH
4f7g, SiO
20.5
g, ZrO
21.0g and BaSO
41.0g puts into blender and mixes, and proceeds in kneader, adds dust technology (nitric acid: water=1:3, weight ratio) 90 milliliters, and being kneaded into can the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, dries more than 2 hours, make free water content be reduced to less than 10% at 80 ~ 120 DEG C.Then green compact are put into electric furnace, be elevated between 1350 DEG C ~ 1550 DEG C through 30 hours from room temperature, constant temperature 2 hours, obtain white α-A1
2o
3support samples.
carrier comparative example 2
By 50 ~ 500 object α-three water A1
2o
3390g, be greater than the false water A1 of 200 objects
2o
3110g, NH
4f7g, SiO
20.5g, ZrO
21.0g and BaSO
41.0g puts into blender and mixes, and proceeds in kneader, adds dust technology (nitric acid: water=1:3, weight ratio) 90 milliliters, and being kneaded into can the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, dries more than 2 hours, make free water content be reduced to less than 10% at 80 ~ 120 DEG C.Then green compact are put into electric furnace, be elevated to 700 DEG C through 30 hours from room temperature, constant temperature 2 hours, obtains white support sample.
carrier comparative example 3
By 50 ~ 500 object α-three water A1
2o
3390g, be greater than the false water A1 of 200 objects
2o
3110g, NH
4f7g, SiO
20.5g, ZrO
21.0g and BaSO
41.0g puts into blender and mixes, and proceeds in kneader, adds dust technology (nitric acid: water=1:3, weight ratio) 90 milliliters, and being kneaded into can the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, dries more than 2 hours, make free water content be reduced to less than 10% at 80 ~ 120 DEG C.Then green compact are put into electric furnace, be elevated to 1050 DEG C through 30 hours from room temperature, constant temperature 2 hours, obtain white α-A1
2o
3support samples.
carrier embodiment 1
By 50 ~ 500 object α-three water A1
2o
3390g, be greater than the false water A1 of 200 objects
2o
3110g, NH
4f7g puts into blender and mixes, and proceeds in kneader, adds dust technology (nitric acid: water=1:3, weight ratio) 90 milliliters, and being kneaded into can the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, dries more than 2 hours, make free water content be reduced to less than 10% at 80 ~ 120 DEG C.Then green compact are put into electric furnace, be elevated to 1200 DEG C through 20 hours from room temperature, constant temperature 2 hours, obtains white A1
2o
3carrier semi-finished product.Then, first soak half an hour with the barium acetate aqueous solution 500g containing 0.5wt%, filter and dry at 80 ~ 120 DEG C after 2 hours, half an hour is soaked again with the ethyl orthosilicate aqueous solution 500g of 0.3wt%, filter and dry at 80 ~ 120 DEG C after 2 hours, finally soaking above-mentioned A1 with the mixed aqueous solution 500g containing 3.5wt% ammonium fluoride and 0.5wt% zirconyl nitrate
2o
3carrier semi-finished product half an hour, filter and also dry after more than 2 hours at 80 ~ 120 DEG C, put into electric furnace, be elevated to 600 DEG C through 10 hours from room temperature, constant temperature 2 hours, obtain white α-A1
2o
3support samples.
carrier embodiment 2
By 50 ~ 500 object α-three water A1
2o
3390g, be greater than the false water A1 of 200 objects
2o
3110g, NH
4f7g puts into blender and mixes, and proceeds in kneader, adds dust technology (nitric acid: water=1:3, weight ratio) 90 milliliters, and being kneaded into can the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, dries more than 2 hours, make free water content be reduced to less than 10% at 80 ~ 120 DEG C.Then green compact are put into electric furnace, be elevated to 600 DEG C through 10 hours from room temperature, constant temperature 2 hours, obtains white A1
2o
3carrier semi-finished product.Then, first soak half an hour with the barium acetate aqueous solution 500g containing 0.5wt%, filter and dry at 80 ~ 120 DEG C after 2 hours, half an hour is soaked again with the ethyl orthosilicate aqueous solution 500g of 0.3wt%, filter and dry at 80 ~ 120 DEG C after 2 hours, finally soaking above-mentioned A1 with the mixed aqueous solution 500g containing 3.5wt% ammonium fluoride and 0.5wt% zirconyl nitrate
2o
3carrier semi-finished product half an hour, filter and also dry after more than 2 hours at 80 ~ 120 DEG C, put into electric furnace, be elevated to 1200 DEG C through 20 hours from room temperature, constant temperature 2 hours, obtain white α-A1
2o
3support samples.
carrier embodiment 3
By 50 ~ 500 object α-three water A1
2o
3390g, be greater than the false water A1 of 200 objects
2o
3110g puts into blender and mixes, and proceeds in kneader, adds dust technology (nitric acid: water=1:3, weight ratio) 90 milliliters, and being kneaded into can the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, dries more than 2 hours, make free water content be reduced to less than 10% at 80 ~ 120 DEG C.Then green compact are put into electric furnace, be elevated to 600 DEG C through 10 hours from room temperature, constant temperature 2 hours, obtains white A1
2o
3carrier semi-finished product.Then above-mentioned A1 is soaked with the ethyl orthosilicate aqueous solution 500g containing 0.3wt%
2o
3carrier semi-finished product half an hour, filter and also dry after more than 2 hours at 80 ~ 120 DEG C, put into electric furnace, be elevated to 1200 DEG C through 20 hours from room temperature, constant temperature 2 hours, obtain white α-A1
2o
3support samples.
carrier embodiment 4
By 50 ~ 500 object α-three water A1
2o
3390g, be greater than the false water A1 of 200 objects
2o
3110g, ZrO
21.0g puts into blender and mixes, and proceeds in kneader, adds dust technology (nitric acid: water=1:3, weight ratio) 90 milliliters, and being kneaded into can the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, dries more than 2 hours, make free water content be reduced to less than 10% at 80 ~ 120 DEG C.Then green compact are put into electric furnace, be elevated to 1200 DEG C through 20 hours from room temperature, constant temperature 2 hours, obtains white A1
2o
3carrier semi-finished product.And then put into electric furnace, be elevated to 600 DEG C through 10 hours from room temperature, constant temperature 2 hours, obtain white α-A1
2o
3support samples.
carrier embodiment 5
By 50 ~ 500 object α-three water A1
2o
3390g, be greater than the false water A1 of 200 objects
2o
3110g, NH
4f7g puts into blender and mixes, and proceeds in kneader, adds dust technology (nitric acid: water=1:3, weight ratio) 90 milliliters, and being kneaded into can the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, dries more than 2 hours, make free water content be reduced to less than 10% at 80 ~ 120 DEG C.Then green compact are put into electric furnace, be elevated to 450 DEG C through 10 hours from room temperature, constant temperature 2 hours, obtains white A1
2o
3carrier semi-finished product.Then, first soak half an hour with the barium acetate aqueous solution 500g containing 0.5wt%, filter and dry at 80 ~ 120 DEG C after 2 hours, half an hour is soaked again with the ethyl orthosilicate aqueous solution 500g of 0.3wt%, filter and dry at 80 ~ 120 DEG C after 2 hours, finally soaking above-mentioned A1 with the mixed aqueous solution 500g containing 3.5wt% ammonium fluoride and 0.5wt% zirconyl nitrate
2o
3carrier semi-finished product half an hour, filter and also dry after more than 2 hours at 80 ~ 120 DEG C, put into electric furnace, be elevated to 1050 DEG C through 20 hours from room temperature, constant temperature 2 hours, obtain white α-A1
2o
3support samples.
carrier embodiment 6
By 50 ~ 500 object α-three water A1
2o
3390g, be greater than the false water A1 of 200 objects
2o
3110g, NH
4f7g puts into blender and mixes, and proceeds in kneader, adds dust technology (nitric acid: water=1:3, weight ratio) 90 milliliters, and being kneaded into can the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, dries more than 2 hours, make free water content be reduced to less than 10% at 80 ~ 120 DEG C.Then green compact are put into electric furnace, be elevated to 1050 DEG C through 20 hours from room temperature, constant temperature 2 hours, obtains white A1
2o
3carrier semi-finished product.Then, first soak half an hour with the barium acetate aqueous solution 500g containing 0.5wt%, filter and dry at 80 ~ 120 DEG C after 2 hours, half an hour is soaked again with the ethyl orthosilicate aqueous solution 500g of 0.3wt%, filter and dry at 80 ~ 120 DEG C after 2 hours, finally soaking above-mentioned A1 with the mixed aqueous solution 500g containing 3.5wt% ammonium fluoride and 0.5wt% zirconyl nitrate
2o
3carrier semi-finished product half an hour, filter and also dry after more than 2 hours at 80 ~ 120 DEG C, put into electric furnace, be elevated to 450 DEG C through 10 hours from room temperature, constant temperature 2 hours, obtain white α-A1
2o
3support samples.
carrier embodiment 7
By 50 ~ 500 object α-three water A1
2o
3390g, be greater than the false water A1 of 200 objects
2o
3110g, NH
4f7g, BaSO
41g, SiO
20.5g, ZrO
21g puts into blender and mixes, and proceeds in kneader, adds dust technology (nitric acid: water=1:3, weight ratio) 90 milliliters, and being kneaded into can the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, dries more than 2 hours, make free water content be reduced to less than 10% at 80 ~ 120 DEG C.Then green compact are put into electric furnace, be elevated to 1450 DEG C through 30 hours from room temperature, constant temperature 2 hours, obtains white A1
2o
3carrier semi-finished product.And then put into electric furnace, be elevated to 700 DEG C through 10 hours from room temperature, constant temperature 2 hours, obtain white α-A1
2o
3support samples.
carrier embodiment 8
By 50 ~ 500 object α-three water A1
2o
3390g, be greater than the false water A1 of 200 objects
2o
3110g puts into blender and mixes, and proceeds in kneader, adds dust technology (nitric acid: water=1:3, weight ratio) 90 milliliters, and being kneaded into can the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, dries more than 2 hours, make free water content be reduced to less than 10% at 80 ~ 120 DEG C.Then green compact are put into electric furnace, be elevated to 700 DEG C through 10 hours from room temperature, constant temperature 2 hours, obtains white A1
2o
3carrier semi-finished product.Then, first soak half an hour with the barium acetate aqueous solution 500g containing 0.5wt%, filter and dry at 80 ~ 120 DEG C after 2 hours, half an hour is soaked again with the ethyl orthosilicate aqueous solution 500g of 0.3wt%, filter and dry at 80 ~ 120 DEG C after 2 hours, finally soaking above-mentioned A1 with the mixed aqueous solution 500g containing 3.5wt% ammonium fluoride and 0.5wt% zirconyl nitrate
2o
3carrier semi-finished product half an hour, filter and also dry after more than 2 hours at 80 ~ 120 DEG C, put into electric furnace, be elevated to 1450 DEG C through 10 hours from room temperature, constant temperature 2 hours, obtain white α-A1
2o
3support samples.
carrier embodiment 9
By 50 ~ 500 object α-three water A1
2o
3390g, be greater than the false water A1 of 200 objects
2o
3110g, NH
4f7g puts into blender and mixes, and proceeds in kneader, adds dust technology (nitric acid: water=1:3, weight ratio) 90 milliliters, and being kneaded into can the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, dries more than 2 hours, make free water content be reduced to less than 10% at 80 ~ 120 DEG C.Then green compact are put into electric furnace, be elevated to 600 DEG C through 10 hours from room temperature, constant temperature 2 hours, obtains white A1
2o
3carrier semi-finished product.Then, soak half an hour with the ethyl orthosilicate aqueous solution 500g of 0.3wt%, filter and dry after 2 hours at 80 ~ 120 DEG C, finally putting into electric furnace, be elevated to 1200 DEG C through 20 hours from room temperature, constant temperature 2 hours, obtain white α-A1
2o
3support samples.
carrier embodiment 10
By 50 ~ 500 object α-three water A1
2o
3390g, be greater than the false water A1 of 200 objects
2o
3110g puts into blender and mixes, and proceeds in kneader, adds dust technology (nitric acid: water=1:3, weight ratio) 90 milliliters, and being kneaded into can the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, dries more than 2 hours, make free water content be reduced to less than 10% at 80 ~ 120 DEG C.Then green compact are put into electric furnace, be elevated to 600 DEG C through 20 hours from room temperature, constant temperature 2 hours, obtains white A1
2o
3carrier semi-finished product.Then, first soak half an hour with the ethyl orthosilicate aqueous solution 500g of 0.3wt%, filter and dry after 2 hours at 80 ~ 120 DEG C, then soaking above-mentioned A1 with the mixed aqueous solution 500g of 0.5wt% zirconyl nitrate
2o
3carrier semi-finished product half an hour, finally again put into electric furnace, be elevated to 1200 DEG C through 10 hours from room temperature, constant temperature 2 hours, obtain white α-A1
2o
3support samples.
The carrier of above-mentioned comparative example 1,2,3 and embodiment 1-10 is measured its crushing strength, water absorption rate, specific surface, pore volume etc. respectively, performance data is listed in table 1.
The physical data of table 1 comparative example 1,2,3 and embodiment 1-10 carrier
As known from Table 1, the crushing strength of embodiment 1-10 carrier is apparently higher than comparative example 1-3.
cOMPARATIVE CATALYST EXAMPLE 1,2,3 and embodiment 1-10
Get 700g silver nitrate to be dissolved in 750ml deionized water.Get 325g ammonium oxalate to be dissolved in the deionized water of 250ml50 DEG C.Mix two kinds of solution with vigorous stirring, generate white silver oxalate precipitate.Aging more than 30 minutes, filter, spend deionized water and be precipitated to without nitrate ion.Filter cake argentiferous about 60% (weight), moisture about 15% (weight).
300g ethylenediamine, 110g monoethanolamine and 375g deionized water is added in the glass flask that band stirs.Under stirring, obtained silver oxalate paste is slowly added in mixed liquor, temperature remains on less than 40 DEG C, and silver oxalate is all dissolved, and the addition of silver oxalate makes the maceration extract argentiferous 23 ~ 25% (weight) obtained.Add 2.2g cesium sulfate, 1.0g ammonium perrhenate, then add deionized water and make solution gross mass reach 2000g, make solution for later use.
Get the sample of 50g carrier comparative example 1,2,3 and carrier embodiment 1-9 respectively, put into the container that can vacuumize.Be evacuated to more than 10mmHg, every part of carrier puts into the maceration extract 100g of above-mentioned preparation, and submergence carrier also keeps 30 minutes.Unnecessary solution is removed in leaching.Carrier after dipping heats 5 minutes in the air stream of 250 DEG C, and cooling, namely makes silver catalyst for ethylene oxide.
Analyze the silver of the catalyst made and auxiliary agent content, wherein content is in metal; Use microreactor evaluating apparatus under previous process condition, measure the activity and selectivity of catalyst sample, result of the test lists in table 2.
The result of the test of the catalyst oxidation ethylene production oxirane of table 2 comparative example 1,2,3 and embodiment 1-10
* note: selectively get accumulative EO output and reach 400T/M
3mean value during catalyst.
As known from Table 2, because carrier comparative example 2 is in transition state A1
2o
3, do not form α-A1
2o
3, therefore can not be applicable to EO completely and produce, therefore there is no evaluating data, although carrier comparative example 3 defines α-A1
2o
3but thorough not due to phase in version, so selective lower.In sum, after carrier is made catalyst, embodiment selective at least higher than comparative example 1%, this is improvement clearly in silver catalyst field.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.
Claims (10)
1. a preparation method for alumina support, is made up of following steps:
I) preparation has the mixture of following composition:
A) based on mixture total weight amount be 50 order ~ 500 order three water α-A1 of 50 ~ 90% weight
2o
3;
B) granularity being 5 ~ 50% weight based on mixture total weight amount is greater than the false water A1 of 200 objects
2o
3; And
C) based on mixture total weight amount be the auxiliary agent of 0 ~ 5% weight;
II) to I) gross weight added in the mixture that obtains based on described mixture is the binding agent of 15 ~ 60% weight;
III) by II) in the mixture that obtains mediate evenly and extrusion molding;
IV) dry III) in the product that obtains, then carry out first time roasting, obtain carrier semi-finished product;
V) used additives solution soaks IV) in the product that obtains dry;
VI) by V) in the product that obtains carry out second time roasting, obtain described alumina support;
In step I) amount of component b) in, described auxiliary agent be selected from silicon, siliceous compound, zirconium and zirconium-containing compound one or more, the preferred silica of described siliceous compound and/or silicate; Described zirconium-containing compound preferential oxidation zirconium;
Step V) in compounding agent solution be selected from the siliceous aqueous solution and/or containing the aqueous solution of zirconium, the preferred teos solution of the described siliceous aqueous solution, the preferred zirconium oxychloride of the aqueous solution containing zirconium and/or zirconyl nitrate solution.
2. method according to claim 1, it is characterized in that, in step I) amount of component b) in, described auxiliary agent also comprises alkaline earth metal compound and/or fluoride, one or more preferably in the oxide of beryllium, magnesium, calcium, strontium and/or barium, sulfate, acetate, nitrate and oxalates of described alkaline earth metal compound, one or more more preferably in the oxide of strontium and/or barium, sulfate, acetate, nitrate and oxalates; Described fluoride is preferably from hydrogen fluoride, ammonium fluoride, aluminum fluoride and ice crystal or its mixture, more preferably aluminum fluoride and/or ammonium fluoride.
3. method according to claim 1, it is characterized in that, in Step II) in, described binding agent is selected from nitric acid, formic acid, acetic acid, propionic acid and/or salt aqueous acid, preferred nitre aqueous acid, more preferably the weight ratio of nitric acid and water is 1:1.25 ~ 10.
4. method according to claim 3, is characterized in that, in step I) and/or Step II) in, replace a false water A1 with Alumina gel
2o
3and binding agent.
5. method according to claim 1, it is characterized in that, step V) in compounding agent solution also comprise the aqueous solution of alkaline earth metal compound and/or fluorine-containing solution, the preferred self-contained strontium of the aqueous solution of described alkaline earth metal compound and/or the aqueous solution of barium, fluorine-containing solution is preferably from ammonium fluoride solution, the concentration of preferred described compounding agent solution is 0.01 ~ 10wt%, amount of solution is one times of carrier semi-finished product weight to ten times, soak time is 10 minutes ~ 2 hours, baking temperature is 80 ~ 120 DEG C, and drying time is 1 hour ~ 24 hours.
6. method according to claim 1, is characterized in that, step IV) with VI) described in the temperature of roasting different.
7. method according to claim 6, is characterized in that, step IV) and VI) middle employing one higher temperature and lower temperature collocation, higher temperature T
hbe 1000 ~ 1500 DEG C carry out and be incubated 2 ~ 24 hours, be preferably 1000 ~ 1200 DEG C; Lower temperature T
lfor T
h1/4 ~ 3/4 and be incubated 2 ~ 24 hours, preferred T
lfor T
h40% ~ 60%, more preferably T
lit is 400 ~ 700 DEG C.
8. alumina support prepared by the method according to any one of claim 1 ~ 7, wherein A1
2o
3content is more than 90 % by weight, preferably more than 95 % by weight; Auxiliary element adds up to 0.01 ~ 5% of vehicle weight with element, the crushing strength >20N of described carrier, preferably 40 ~ 200N; Specific surface is 0.5 ~ 4.0m
2/ g, preferably 1.0 ~ 2.0m
2/ g; Water absorption rate is not less than 30%, is preferably not less than 45%; Pore volume is 0.35 ~ 0.85ml/g, preferably 0.40 ~ 0.80ml/g.
9. a silver catalyst, comprising:
1) catalyst carrier prepared by the method as described in claim 1-7 or catalyst carrier as claimed in claim 8;
2) deposition silver 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;
In described silver catalyst, preferably add the collaborative auxiliary agent of rhenium, it is selected from one or more elements in chromium, molybdenum, tungsten and boron and/or compound.
10. the application in oxirane produced by silver catalyst as claimed in claim 9 at ethylene.
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| CN106955692A (en) * | 2016-01-08 | 2017-07-18 | 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 |
| CN107812542A (en) * | 2016-09-14 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of alpha-aluminium oxide carrier and preparation method and application |
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| CN114433042A (en) * | 2020-11-05 | 2022-05-06 | 中国石油化工股份有限公司 | Alumina carrier and preparation method thereof |
| CN114433043A (en) * | 2020-11-05 | 2022-05-06 | 中国石油化工股份有限公司 | Alumina carrier and preparation method thereof, silver catalyst and application |
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| 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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