CN106607098A - Modified alpha-alumina supporter and preparation and application thereof - Google Patents
Modified alpha-alumina supporter and preparation and application thereof Download PDFInfo
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- CN106607098A CN106607098A CN201510685691.8A CN201510685691A CN106607098A CN 106607098 A CN106607098 A CN 106607098A CN 201510685691 A CN201510685691 A CN 201510685691A CN 106607098 A CN106607098 A CN 106607098A
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Abstract
The invention relates to a modified alpha-alumina supporter and a preparation method thereof. The modified alpha-alumina supporter is prepared by adding the nickel element during a supporter preparation process and performing acid treatment on a formed alpha-alumina supporter. The invention further relates to a silver catalyst which takes the modified alpha-alumina as the supporter and a preparation method for the silver catalyst. The silver catalyst which takes the modified alpha-alumina as the supporter shows good activity and selectivity in producing ethylene oxide through ethylene oxidation. Raw materials for preparing the modified alpha-alumina supporter are easily available, and the preparation method is simple in procedure. The modified alpha-alumina supporter and the silver catalyst have a wide application prospect.
Description
Technical field
The invention belongs to catalyst carrier and catalyst preparation technical field, and in particular to a kind of modified Alpha-alumina
Carrier and its preparation and application.
Background technology
Ethylene mainly generates oxirane under silver catalyst effect, while side reaction also occurs generates two
Carbonoxide and water etc., wherein activity, selectivity and stability are the main performance index of silver catalyst.It is so-called
Activity refers to that process for ethylene oxide production reaches reaction temperature required during certain reaction load；Reaction temperature is got over
Low, the activity of catalyst is higher.So-called selectivity refers to that ethene changes into the molal quantity of oxirane in reaction
With the ratio of the overall reaction molal quantity of ethene.So-called stability is then expressed as the fall off rate of activity and selectivity, under
The stability of reduction of speed rate more small catalyst is better.
Using high activity, high selectivity and have good stability during ethylene produces oxirane
Silver catalyst can greatly improve economic benefit, therefore manufacture high activity, high selectivity and good stability
Silver catalyst is the Main way of silver catalyst research.The performance of silver catalyst is except the composition and system with catalyst
Preparation Method has outside important relationship, and the performance of the carrier for also using with catalyst and its preparation have important relationship.
At present, or the silver catalyst on market is selective good, but activity is not so good；Activity is good, selects
Property is not so good.Therefore, in view of the needs in market, need that research and development are a kind of can both to have improved silver catalyst at present
Activity, stability, can improve the treatment technology of the selective carrier of silver catalyst again, and the silver being made from it is urged
Agent and its application process.
The content of the invention
The technical problem to be solved is for above-mentioned the deficiencies in the prior art, there is provided a kind of modified alpha-oxygen
Change alumina supporter, the carrier has higher specific surface area and intensity, and has more macropore.To be modified this described
Silver catalyst made by alpha-alumina supports, is conducive to the dispersion of chain carrier, and is conducive to product
Desorption.Therefore, the modified alpha-alumina supports are applied to into ethylene production reacting ethylene oxide process, are carried
High its activity and selectivity, especially significantly improves selectivity.
For this purpose, first aspect present invention provides a kind of modified alpha-alumina supports, it is carried by nickeliferous Alpha-alumina
Body is obtained through acid solution process.
In the present invention, the nickeliferous alpha-alumina supports are molded by nickeliferous alpha-alumina supports precursor mixture Jing,
It is dried and roasting is obtained, wherein, the nickeliferous alpha-alumina supports precursor mixture is included：
Component a, three water A12O3；
Component b, false water A12O3；
Component d, mineralizer；
Component e, nickel simple substance and/or nickel compound containing；
Component f, binding agent；
Component g, water；And it is optional
Component c, weight alkaline earth metal compound.
In the present invention, the nickeliferous alpha-alumina supports precursor mixture is by solid constituent a-e gross weight meter
Composition is as follows：
Preferably, the nickeliferous alpha-alumina supports precursor mixture presses the composition of solid constituent a-e gross weight meter
It is as follows：
In some embodiments of the invention, the mineralizer is fluoride.
The present invention other embodiments in, the nickel compound containing include nickel oxide, nickelous carbonate, nickel nitrate,
At least one in nickel chloride and nickel sulfate.It is preferred that the nickel compound containing is nickel oxide and/or nickel nitrate.
Second aspect present invention provides a kind of modified alpha-alumina supports as described in the first aspect of the invention
Preparation method, it includes：
Step A, by the mixing of component a-g, is obtained nickeliferous alpha-alumina supports precursor mixture；
Step B, nickeliferous alpha-alumina supports precursor mixture is molded, and dry, roasting, and prepared nickeliferous α-
Alumina support；
Nickeliferous alpha-alumina supports are carried out acid solution and process prepared modified alpha-alumina support precursor by step C；
Step D, is washed to modified alpha-alumina support precursor, is dried and roasting, and modified alpha-oxidation is obtained
Alumina supporter；
Wherein, in step C, acid solution is carried out to nickeliferous alpha-alumina supports using the aqueous solution of acid compound
Process.
In the preparation method of the modified alpha-alumina supports of the present invention, the hydrogen of the aqueous solution of the acid compound
Ion concentration is 0.01-4mol/L.It is preferred that the hydrogen ion concentration of the aqueous solution of the acid compound is
0.05-1.5mol/L。
In the preparation method of the modified alpha-alumina supports of the present invention, in step C, the nickeliferous alpha-oxidation
Alumina supporter is 1 with the weight ratio of the aqueous solution of the acid compound:(1-150).It is preferred that the nickeliferous α-oxygen
It is 1 to change alumina supporter with the weight ratio of the aqueous solution of the acid compound:(20-60).
The present invention modified alpha-alumina supports preparation method in, the acid compound include inorganic acid and
/ or Acidic inorganic salts, wherein the inorganic acid includes at least one of sulfuric acid, nitric acid, hydrochloric acid and oxalic acid；It is described
Acidic inorganic salts include ammonium nitrate and/or ammonium chloride.
In the preparation method of the modified alpha-alumina supports of the present invention, in step C, what the acid solution was processed
Temperature is 20-200 DEG C.It is preferred that the temperature that the acid solution is processed is 40-100 DEG C.The time that the acid solution is processed is
0.2-3h.It is preferred that the time that the acid solution is processed is 0.5-1.5h.
Third aspect present invention provide a kind of silver catalyst, comprising modified alpha as described in the first aspect of the invention-
Modified alpha-alumina supports and be carried on prepared by alumina support or as described in respect of the second aspect of the invention method
Silver-colored simple substance in the modified alpha-alumina supports.
Fourth aspect present invention provides a kind of preparation method of the silver catalyst as described in third aspect present invention,
Including：
Step M：The modified alpha-alumina supports or the present invention the described in first aspect present invention are impregnated with maceration extract
Modified alpha-alumina supports prepared by two aspect methods describeds；
Step N：Separation of solid and liquid removes maceration extract.
In the preparation method of the silver catalyst of the present invention, maceration extract composition by weight is as follows：
Preferably, maceration extract composition by weight is as follows：
Fifth aspect present invention provides a kind of modified alpha-alumina supports as described in the first aspect of the invention, such as
Modified alpha-alumina supports, the silver as described in third aspect present invention prepared by second aspect present invention methods described
Catalyst or the silver catalyst such as the preparation of fourth aspect present invention methods described produce oxirane in ethylene
During application.
Specific embodiment
To make the present invention easier to understand, below in conjunction with embodiment the present invention is described in detail, these enforcements
Example only plays illustrative effect, it is not limited to the range of application of the present invention.
Existing alumina support macropore is few, and specific surface area is little.Need research and development one kind both can improve at present to urge
The activity of agent, stability, can improve the treatment technology of the selective carrier of silver catalyst again, and be made from it
Silver catalyst and its application process.
Therefore, first aspect present invention is related to a kind of modified alpha-alumina supports, and it is by nickeliferous alpha-alumina supports
It is obtained through acid solution process.
In the present invention, the nickeliferous alpha-alumina supports are molded by nickeliferous alpha-alumina supports precursor mixture Jing,
It is dried and roasting is obtained, wherein, the nickeliferous alpha-alumina supports precursor mixture is included：
Component a, three water A12O3；
Component b, false water A12O3；
Component c, weight alkaline earth metal compound (optional)；
Component d, mineralizer；
Component e, nickel simple substance and/or nickel compound containing；
Component f, binding agent；And
Component g, water.
In the present invention, the modified alpha-alumina supports are a kind of nickeliferous Alpha-aluminas of porous through acid solution process
Carrier, and due to nickel element contained in nickeliferous alpha-alumina supports be in its preparation process with other compositions
What the mode of common mixing was added, therefore in nickeliferous alpha-alumina supports and modified nickeliferous alpha-alumina supports
Nickel element is equally distributed.
In the present invention, component a is three water A12O3, and be the water α-A1 of graininess three2O3, its granularity is
The mesh of 50 mesh -500.Three water A12O3Presence can increase the duct of carrier, so as to form porous α-A12O3Carrier.
In the present invention, component b is false water A12O3, its granularity is preferably greater than equal to 200 mesh.
In the present invention, component c is attached most importance to alkaline earth metal compound, and it can improve the performance of carrier.The present invention
Described heavy alkaline earth metal compound is the compound of strontium and/or barium.Preferably include strontium and/or barium oxide,
At least one in sulfate, acetate, nitrate, carbonate and oxalates.The particularly preferred heavy alkaline earth
Metallic compound is at least one in barium monoxide, barium sulfate, barium nitrate and brium carbonate.
In the present invention, it is preferred to component d mineralizer is fluoride-mineralization agent.Fluoride-mineralization of the present invention
The transformation of crystal for being added to accelerated oxidation aluminium of agent.It is preferred that fluoride of the present invention is inorganic fluoriding
One or more in thing, including hydrogen fluoride, ammonium fluoride, aluminum fluoride, magnesium fluoride and ice crystal.Particularly preferably
The fluoride is ammonium fluoride.
In the present invention, component f binding agent can be with component b one water A1 of vacation2O3Alumina gel is generated, by each group
Divide and be bonded together, become the paste of extrudable shaping.Binding agent preferably used is acid, bag in the present invention
Include at least one in nitric acid, formic acid, acetic acid, propionic acid and hydrochloric acid.When using acid as binding agent, preferably
Nitric acid, and it is hybridly prepared into into aqueous solution of nitric acid with water.
In some embodiments of the invention, preferred nitric acid and the weight ratio of water are 1:(1.25-10).It is more excellent
Choosing, nitric acid is 1 with the weight ratio of water:(2-4).
In the present invention, it is also possible to which Alumina gel partly or entirely replaces the vacation one of the binding agent of component f and component b
Water A12O3。
In the present invention, the nickeliferous alpha-alumina supports precursor mixture is by solid constituent a-e gross weight meter
Composition is as follows：
Preferably, the nickeliferous alpha-alumina supports precursor mixture presses the composition of solid constituent a-e gross weight meter
It is as follows：
In some embodiments of the invention, the nickel compound containing include nickel oxide, nickelous carbonate, nickel nitrate,
At least one in nickel chloride and nickel sulfate.It is preferred that the nickel compound containing is nickel oxide and/or nickel nitrate.
Second aspect present invention provides a kind of modified alpha-alumina supports as described in the first aspect of the invention
Preparation method, it includes：
Step A, by the mixing of component a-g, is obtained nickeliferous alpha-alumina supports precursor mixture；
Step B, nickeliferous alpha-alumina supports precursor mixture is molded, and dry, roasting, and prepared nickeliferous α-
Alumina support；
Nickeliferous alpha-alumina supports are carried out acid solution and process prepared modified alpha-alumina support precursor by step C；
Step D, is washed to modified alpha-alumina support precursor, is dried and roasting, and modified alpha-oxidation is obtained
Alumina supporter；
Wherein, in step C, acid solution is carried out to nickeliferous alpha-alumina supports using the aqueous solution of acid compound
Process.
According to the inventive method, the composition of the nickeliferous alpha-alumina supports precursor mixture is as follows：
Component a, the water Al of -500 purpose of 50 mesh three2O3；
Component b, more than or equal to the water Al of vacation one of 200 mesh2O3；
Component c, accounts for the heavy alkaline earth metal compound that component a-e gross weight is 0-2% (weight)；
Component d, fluoride-mineralization agent；
Component e, is counted with the weight of nickel element and accounts for nickel simple substance of the component a-e gross weight as 0.001%-5% and/or contain
Nickel compound；
Component f, binding agent；And
Component g, the water of surplus.
In the preparation method of the modified alpha-alumina supports of the present invention, the hydrogen of the aqueous solution of the acid compound
Ion concentration is 0.01-4mol/L.It is preferred that the hydrogen ion concentration of the aqueous solution of the acid compound is
0.05-1.5mol/L。
In the preparation method of the modified alpha-alumina supports of the present invention, in step C, the nickeliferous alpha-oxidation
Alumina supporter is 1 with the weight ratio of the aqueous solution of the acid compound:(1-150).It is preferred that the nickeliferous α-oxygen
It is 1 to change alumina supporter with the weight ratio of the aqueous solution of the acid compound:(20-60).
The present invention modified alpha-alumina supports preparation method in, the acid compound include inorganic acid and
/ or Acidic inorganic salts, wherein the inorganic acid includes at least one of sulfuric acid, nitric acid, hydrochloric acid and oxalic acid；It is described
Acidic inorganic salts include ammonium nitrate and/or ammonium chloride.
In the present invention, after is mediated uniformly the mixture in step A, paste is generally yielded.To the present invention
Advantageously, after generally first component a-e (if all if use) is well mixed, in proceeding to kneader, so
Add component f and g to be mediated afterwards, be uniformly kneaded into paste, be especially kneaded into the cream of extrudable shaping
Shape thing；Formed body is obtained after paste shaping, the formed body can be dried to aqueous 10% (weight) below, done
Dry temperature is 80-120 DEG C, and drying time is controlled in 1-24 hours according to moisture.The shape of gained formed body
Can be annular, spherical, cylindricality, porous column shape or other arbitrary shapes.
Some specific embodiments of the invention, in stepb, generally at 1000-1500 DEG C, preferably
Roasting is carried out at a temperature of 1000-1400 DEG C.Roasting time is no less than 1 hour.Roasting time is usually 2-24
Hour.It is preferred that roasting time is 2-8 hours.Aluminum oxide is set to be completely converted into α-A1 substantially by roasting2O3,
Such as more than 90% is converted into α-A12O3, obtain alpha-alumina supports.
In the present invention, it is preferred to the acid solution is processed carry out under agitation.
In the present invention, it is preferred to the acid solution is processed carry out under uniform temperature (such as by heating), according to this
Inventor's research of invention finds, carry out in a heated condition acid solution process can more preferable dealuminzation, increase carrier
Specific surface area, and increase macropore.
According to the inventive method, in step C, the temperature that the acid solution is processed is 20-200 DEG C.It is preferred that described
The temperature of acid solution process is 40-100 DEG C.
According to the inventive method, in step C, the time that the acid solution is processed is 0.2-3h.It is preferred that the acid
The time of liquid process is 0.5-1.5h.
In some embodiments of the invention, in step D, the temperature of the roasting is 400-1000 DEG C.It is excellent
The temperature for selecting the roasting is 500-800 DEG C.It is furthermore preferred that the temperature of the roasting is 540 DEG C.
In other embodiments of the present invention, in step D, the time of the roasting is at least 1 hour.
It is preferred that the time of the roasting is 2-24 hours.It is more highly preferred to, the time of the roasting is 4-10 hours.
In some other embodiment of the present invention, in step D, deionized water washing is preferably used modified
Alpha-alumina supports precursor, is washed modified alpha-alumina support precursor to filtrate in neutrality by deionized water,
Then process is dried again.The temperature of the drying is 60-180 DEG C.It is preferred that the temperature of the drying is
80-120℃。
The modified alpha-alumina supports for obtaining prepared according to the methods of the invention, are by nickeliferous alpha-alumina supports Jing
It is obtained after peracid treatment, be also referred to as modified nickeliferous alpha-alumina supports or nickeliferous modified alpha-alumina supports.This
The there is provided alpha-alumina supports of invention have following characteristics：Specific surface area is 0.2-2.0m2/ g, pore volume is
0.35-0.85mL/g, water absorption rate >=30%, crushing strength is 20-140N/ grains.
In the present invention, nickel element is added in carrier preparation process, therefore, it is equally evenly distributed
In modified alpha-alumina supports.The addition of nickel element, is conducive to improving the specific surface area and intensity of carrier, and
The process of acid compound, further increases duct and the specific surface area of carrier.
The present invention has carried out acid treatment to nickeliferous alpha-alumina supports, can so play the effect of nickel element,
The effect of acid treatment can be played again.After acid treatment, alumina wafer can diminish the nickeliferous alpha-alumina supports,
There are more folds in surface, increases the specific surface area of carrier, improves the activity of silver catalyst；Macropore increases
It is many, the desorption of oxirane is increased, improve the selectivity of silver catalyst.After acid treatment, nickel element
Still it is uniformly distributed in the carrier.
Third aspect present invention is related to a kind of silver catalyst, comprising modified alpha-oxygen as described in the first aspect of the invention
Change alumina supporter or the as described in respect of the second aspect of the invention modified alpha-alumina supports of method preparation and be carried on institute
The silver-colored simple substance in modified alpha-alumina supports is stated, wherein, the silver-colored simple substance loaded in the modified alpha-alumina supports
Content be about 16.1% (weight).
Fourth aspect present invention is related to a kind of preparation method of silver catalyst described in third aspect present invention, including：
Step M：The modified alpha-alumina supports or the present invention the described in first aspect present invention are impregnated with maceration extract
Modified alpha-alumina supports prepared by two aspect methods describeds；
Step N：Separation of solid and liquid removes maceration extract.
In the preparation method of the silver catalyst of the present invention, maceration extract composition by weight is as follows：
Preferably, maceration extract composition by weight is as follows：
In the present invention, preferably the silver compound is at least one in silver oxide, silver nitrate and silver oxalate.
In the present invention, preferably the alkali metal promoter for the one kind in the compound of lithium, sodium, potassium, rubidium and caesium or
It is various.It is furthermore preferred that the alkali metal promoter is in cesium sulfate, cesium nitrate, lithium nitrate and potassium hydroxide
Plant or various.Most preferably, the alkali metal promoter is cesium sulfate.
In the present invention, preferably the base earth metal promoter is the one kind or many in the compound of magnesium, calcium, strontium and barium
Kind.It is furthermore preferred that the base earth metal promoter be the oxide of magnesium, calcium, strontium and barium, oxalates, sulfate,
One or more in acetate and nitrate.
In the present invention, preferably the rhenium auxiliary agent is in oxide, perrhenic acid, perrhenic acid caesium and the ammonium perrhenate of rhenium
One or more.It is furthermore preferred that the rhenium auxiliary agent is ammonium perrhenate.
In the present invention, preferably the organic amine is in pyridine, butylamine, ethylenediamine, 1,3- propane diamine and monoethanolamine
One or more.It is furthermore preferred that the organic amine is ethylenediamine and/or monoethanolamine；It is highly preferred, it is described
Organic amine is ethylenediamine and ethanolamine mixtures.
In some embodiments of the invention, also including the coassist agent of rhenium auxiliary agent in the maceration extract, with further
Improve gained the active of silver catalyst, selectivity and stability.The coassist agent of the rhenium auxiliary agent includes element week
The compound of arbitrary transition metal in phase table, or the mixture of several transistion metal compounds.It is preferred that the rhenium is helped
The coassist agent of agent is group vib and the oxyacid and its salt of VIIB races element, including wolframic acid, sodium tungstate, wolframic acid
One or more in potassium, ammonium tungstate, wolframic acid caesium, molybdic acid, ammonium molybdate and ammonium metatungstate.Its consumption is 0-1000wt
ppm.It is preferred that its consumption is 0-500wt ppm.
In the present invention, the dipping process can be carried out under subatmospheric pressure conditions.It is preferred that being less than in vacuum
Carry out under conditions of 10mmHg.Dip time is preferably 10-60min.
In the present invention, the preferably solid is separated into leaching.
In the present invention, the silver compound be major catalyst, the alkali metal promoter, base earth metal promoter, rhenium
Auxiliary agent etc. is catalyst promoter.
In some embodiments of the invention, the modified alpha-alumina supports that prepared by said method are can root using before
Activated according to needs.Activation can be carried out in air or oxygen content are not more than the nitrogen oxygen atmosphere of 21v%.Its
Activation temperature is 180-700 DEG C.It is preferred that activation temperature is 200-500 DEG C.Its soak time is 1-120min.It is excellent
Soak time is selected to be 2-60min.
Fifth aspect present invention provides modified alpha-alumina supports as described in the first aspect of the invention, such as this
Modified alpha-alumina supports prepared by bright second aspect methods described, the silver catalysis as described in third aspect present invention
Agent or the silver catalyst such as the preparation of fourth aspect present invention methods described produce oxirane process in ethylene
In application.
Silver catalyst is used in epoxidation of ethylene according to obtained in the method for the invention, the epoxidation reaction
Condition is conventional reaction condition in the art, and such as the reaction temperature can be 200-275 DEG C.
" water " one word used in the present invention, in the case where not specifying, refers to deionized water.
Term " optional " of the present invention refers to and contains or not contain, also refers to add or be added without.
The specific surface area of carrier is surveyed according to international test standards ISO-9277 using nitrogen physisorption BET method
It is fixed.It is, for example possible to use U.S. Kang Ta companies NOVA2000e type nitrogen physisorptions instrument determines the ratio of carrier
Surface area.
The pore volume of carrier is determined using mercury injection method.It is, for example possible to use Merck ＆ Co., Inc of U.S. AutoPore9510 types
Mercury injection apparatus determines the pore volume of carrier.
The amount of alkaline earth metal compound can be by being calculated in carrier.
The side pressure strength of carrier, it is for instance possible to use Dalian Chemical Research ＆. Design Inst. produces the types of DL II intelligence particle
Intensity measuring device, randomly selects 30 support samples, averages after measure radial direction crushing strength and obtains.
Term " water absorption rate " used refers to that the carrier saturation of unit mass adsorbs the volume of water, unit in the present invention
It is mL/g.Assay method is as follows：A certain amount of carrier is weighed first (it is assumed that its quality is m1), in boiling water
Boil to take out to be erected on the moderate wet gauze of water content by carrier after 1h and remove the unnecessary moisture of carrier surface, most
The quality of the carrier after absorption water is weighed afterwards (it is assumed that m2), the water absorption rate of carrier is calculated as follows.
Water absorption rate=(m2-m1)/m1/ρWater
Wherein ρWaterIt is the density of water under temperature of the measurement, atmospheric pressure.
The measure of catalyst performance：Be related in the present invention various silver catalyst laboratories microreactor (with
Lower abbreviation " micro- anti-") evaluating apparatus test its initial activity and selectivity.The reaction that micro anti-evaluation device is used
Device is the stainless steel tube of internal diameter 4mm, and reaction tube is placed in heating mantle.The admission space of catalyst is 1mL,
Inert filler is arranged at bottom, makes beds be located at the flat-temperature zone of heating mantle.The catalyst activity that the present invention is adopted
With selective condition determination such as table 1：
The condition determination of the catalyst activity and selectivity of table 1
METHOD FOR CONTINUOUS DETERMINATION reactor enters after above-mentioned reaction condition is stably reached, exit gas is constituted.Measurement result is entered
Calculate selectivity S after the correction of row volume contraction as follows：
Wherein Δ EO is reactor outlet gas and inlet gas ethylene oxide concentration difference；ΔCO2It is reactor outlet
Gas is poor with gas concentration lwevel in inlet gas, takes the test of the average as the same day of more than 10 groups test datas
As a result.
Modified alpha-alumina supports provided by the present invention and its silver catalyst of load have advantages below：
(1) the modified alpha-alumina supports that the present invention is provided, by adding nickel element in carrier preparation process
And the alpha-alumina supports to being molded carry out the process of acid compound, improve the ratio table of alpha-alumina supports
Area and crushing strength, the active component after being conducive to it is dispersed；And nickel element is uniformly distributed to carrying
High catalyst activity is helpful, is conducive to the reservation of aperture, increases carrier specific surface area；Nickeliferous Alpha-alumina is carried
Body surface face is in alkalescent, is conducive to oxirane to be desorbed, and improves selective.
(2) the modified alpha-alumina supports macropore that the present invention is provided is more, and water absorption rate is high, is conducive to oxirane
Desorption, is conducive to improving selective.
(3) silver catalyst by made by the modified alpha-alumina supports of the present invention that the present invention is provided, in ethene
During oxidation production oxirane, good selectivity and activity are unexpectedly shown.
(4) present invention is easy to obtain to the raw material that alpha-alumina supports are modified, and preparation method step
Simply.
(5) the modified alpha-alumina supports and silver catalyst that the present invention is provided have broad application prospect.
Embodiment
Comparative example 1
By the water α-A1 of -500 purpose of 200 mesh three2O3The water A1 of vacation one of 372g, the mesh of 200 mesh -4002O3112g、
MgF23g and Ba (NO3)2The solid mixture of 0.5g is put in blender and is well mixed, and then proceeds to kneader,
Add dust technology (nitric acid:Water=1:3, weight ratio) 90mL, the paste of extrudable shaping is kneaded into, extrude
It is shaped to the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm.By the five holes column in
10h is dried at 80-120 DEG C, makes free water content be reduced to 10% (weight) below, shaping alpha-oxidation is obtained
Alumina supporter precursor.Then the precursor is put in electric furnace, Jing 30h are increased to 1400 DEG C from room temperature, afterwards constant temperature
2h, is obtained white α-A12O3Carrier.By obtained white α-A12O3Carrier is named as Z-1, and determines
Its crushing strength, water absorption rate and specific surface area, the results are shown in Table 2.
Comparative example 2
Being put in the raw material of blender mixing also includes Ni (NO3)2.6H2O1.49g, remaining is identical with comparative example 1.
By obtained white nickeliferous α-A12O3Carrier is named as Z-2, and determines its crushing strength, water absorption rate and ratio
Surface area, the results are shown in Table 2.
Comparative example 3
It is 1 by the weight ratio of alpha-alumina supports and the aqueous solution of acid compound:20 prepare 400g 0.5mol/L
HNO3Solution, and by HNO3Solution is heated to 80 DEG C, weighs 20g Z-1 carriers and is put into HNO3Solution,
After stirring 0.5h, acid solution alpha-alumina supports precursor is taken out, deionized water cleaning is to filtrate pH value
7 or so.Then acid solution alpha-alumina supports precursor is put into baking oven and is dried 10h in 100 DEG C, after dry acid
Liquid alpha-alumina supports precursor is put into Muffle furnace in 540 DEG C of roastings 4 hours, and modified alpha-alumina supports are obtained.
Obtained modified alpha-alumina supports are named as into Z-3, and determine its crushing strength, water absorption rate and specific surface
Product, the results are shown in Table 2.
Embodiment 1
It is 1 by the weight ratio of alpha-alumina supports and the aqueous solution of acid compound:20 prepare 400g 0.5mol/L
HNO3Solution, and by HNO3Solution is heated to 80 DEG C, weighs 20g Z-2 carriers and is put into HNO3Solution,
After stirring 0.5h, acid solution alpha-alumina supports precursor is taken out, deionized water cleaning is to filtrate pH value
7 or so.Then acid solution alpha-alumina supports precursor is put into baking oven and is dried 10h in 100 DEG C, after dry acid
Liquid alpha-alumina supports precursor is put into Muffle furnace in 540 DEG C of roastings 4 hours, and modified alpha-alumina supports are obtained.
Obtained modified alpha-alumina supports are named as into Z-4, and determine its crushing strength, water absorption rate and specific surface
Product, the results are shown in Table 2.
Embodiment 2
It is 1 by the weight ratio of alpha-alumina supports and the aqueous solution of acid compound:20 prepare 400g 0.01mol/L
HNO3Solution, and by HNO3Solution is heated to 80 DEG C, weighs 20g Z-2 carriers and is put into HNO3Solution,
After stirring 0.5h, acid solution alpha-alumina supports precursor is taken out, deionized water cleaning is to filtrate pH value
7 or so.Then acid solution alpha-alumina supports precursor is put into baking oven and is dried 10h in 100 DEG C, after dry acid
Liquid alpha-alumina supports precursor is put into Muffle furnace in 540 DEG C of roastings 4 hours, and modified alpha-alumina supports are obtained.
Obtained modified alpha-alumina supports are named as into Z-5, and determine its crushing strength, water absorption rate and specific surface
Product, the results are shown in Table 2.
Embodiment 3
It is 1 by the weight ratio of alpha-alumina supports and the aqueous solution of acid compound:20 prepare 400g 1.5mol/L
HNO3Solution, and by HNO3Solution is heated to 80 DEG C, weighs 20g Z-2 carriers and is put into HNO3Solution,
After stirring 0.5h, acid solution alpha-alumina supports precursor is taken out, deionized water cleaning is to filtrate pH value
7 or so.Then acid solution alpha-alumina supports precursor is put into baking oven and is dried 10h in 100 DEG C, after dry acid
Liquid alpha-alumina supports precursor is put into Muffle furnace in 540 DEG C of roastings 4 hours, and modified alpha-alumina supports are obtained.
Obtained modified alpha-alumina supports are named as into Z-6, and determine its crushing strength, water absorption rate and specific surface
Product, the results are shown in Table 2.
Embodiment 4
It is 1 by the weight ratio of alpha-alumina supports and the aqueous solution of acid compound:60 prepare 1200g 0.5mol/L
HNO3Solution, and by HNO3Solution is heated to 80 DEG C, weighs 20g Z-2 carriers and is put into HNO3Solution,
After stirring 0.5h, acid solution alpha-alumina supports precursor is taken out, deionized water cleaning is to filtrate pH value
7 or so.Then acid solution alpha-alumina supports precursor is put into baking oven and is dried 10h in 100 DEG C, after dry acid
Liquid alpha-alumina supports precursor is put into Muffle furnace in 540 DEG C of roastings 4 hours, and modified alpha-alumina supports are obtained.
Obtained modified alpha-alumina supports are named as into Z-7, and determine its crushing strength, water absorption rate and specific surface
Product, the results are shown in Table 2.
Embodiment 5
It is 1 by the weight ratio of alpha-alumina supports and the aqueous solution of acid compound:20 prepare 400g 0.5mol/L
HNO3Solution, and by HNO3Solution is heated to 40 DEG C, weighs 20g Z-2 carriers and is put into HNO3Solution,
After stirring 0.5h, acid solution alpha-alumina supports precursor is taken out, deionized water cleaning is to filtrate pH value
7 or so.Then acid solution alpha-alumina supports precursor is put into baking oven and is dried 10h in 100 DEG C, after dry acid
Liquid alpha-alumina supports precursor is put into Muffle furnace in 540 DEG C of roastings 4 hours, and modified alpha-alumina supports are obtained.
Obtained modified alpha-alumina supports are named as into Z-8, and determine its crushing strength, water absorption rate and specific surface
Product, the results are shown in Table 2.
Embodiment 6
It is 1 by the weight ratio of alpha-alumina supports and the aqueous solution of acid compound:20 prepare 400g 0.5mol/L
HNO3Solution, and by HNO3Solution is heated to 80 DEG C, weighs 20g Z-2 carriers and is put into HNO3Solution,
After stirring 1h, acid solution alpha-alumina supports precursor is taken out, deionized water cleaning is 7 to filtrate pH value
Left and right.Then acid solution alpha-alumina supports precursor is put into baking oven and is dried 10h in 100 DEG C, after dry acid
Liquid alpha-alumina supports precursor is put into Muffle furnace in 540 DEG C of roastings 4 hours, and modified alpha-alumina supports are obtained.
Obtained modified alpha-alumina supports are named as into Z-9, and determine its crushing strength, water absorption rate and specific surface
Product, the results are shown in Table 2.
The physical parameter of the carrier of table 2
| Carrier is originated | Support samples | Crushing strength (N/ grains) | Water absorption rate (%) | Specific surface area (m2/g) |
| Comparative example 1 | Z-1 | 48 | 51.14 | 0.752 |
| Comparative example 2 | Z-2 | 65 | 51.48 | 1.439 |
| Comparative example 3 | Z-3 | 41 | 50.93 | 1.187 |
| Embodiment 1 | Z-4 | 57 | 51.03 | 1.657 |
| Embodiment 2 | Z-5 | 62 | 51.23 | 1.496 |
| Embodiment 3 | Z-6 | 48 | 50.39 | 1.798 |
| Embodiment 4 | Z-7 | 54 | 50.98 | 1.689 |
| Embodiment 5 | Z-8 | 61 | 51.20 | 1.521 |
| Embodiment 6 | Z-9 | 55 | 50.99 | 1.673 |
Above-mentioned comparative example 2, embodiment 1-6 is compared as can be seen that in carrier with comparative example 1 with comparative example 3
Add after nickel element in preparation process, the intensity and specific surface area of carrier are improved；And carry out after acid treatment, than
Surface area further increases, but intensity has declined again.Especially comparative example 3, its intensity is substantially reduced, this
It is because that not adding nickel element in the carrier preparation process has directly carried out acid treatment.
The preparation of corresponding silver catalyst in comparative example 1-3 and embodiment 1-6
700g silver nitrates are dissolved in 750mL deionized waters silver nitrate solution is obtained；325g ammonium oxalate is dissolved in
Ammonium oxalate solution is obtained in 250mL50 DEG C of deionized water；With vigorous stirring by silver nitrate solution and ammonium oxalate
Solution uniformly mixes, and generates white silver oxalate precipitate；After the aging 1h of silver oxalate precipitate, filter, and spend
Ion water washing filter cake is until without nitrate ion in filtrate, be obtained paste silver oxalate filter cake, the filter cake for being obtained
In contain argent about 60% (weight), aqueous about 15% (weight).
300g ethylenediamines, 110g monoethanolamines and 375g deionized waters are added in the glass flask of band stirring, is obtained
To mixed solution.Obtained silver oxalate paste is slowly added in mixed liquor under stirring, temperature is maintained at -5 DEG C
To 10 DEG C, silver oxalate is all dissolved, be subsequently adding 2.2g cesium sulfates and 1.4g strontium acetates, then add deionization
Water makes solution gross mass reach 2000g, and resulting solution is well mixed, and obtains silver catalyst maceration extract, is obtained
The silver content of the silver compound maceration extract for obtaining is 22% (weight).
The each 15g of obtained support samples in comparative example 1-3 and embodiment 1-6 is taken, the appearance of vacuum-pumping is respectively placed in
In device, vacuum being evacuated to less than 10mmHg, being added thereto to above-mentioned silver catalyst maceration extract, submergence is carried
Body, keeps 30min.Leaching afterwards removes unnecessary silver catalyst maceration extract, by the carrier after dipping at 350 DEG C
Air stream in heat 5min, cool down, comparative example 1-3 is prepared respectively and the corresponding silver of embodiment 1-6 is urged
Agent.Obtained silver catalyst is named as into CZ-1 to CZ-9, to the silver in obtained silver catalyst and helping
The content (wherein content is in terms of metal) of agent is analyzed, in CZ-1 to CZ-9 silver and auxiliary agent (caesium and
Strontium) content it is essentially identical, the content of wherein silver element is about 16.1% (weight).And use minisize reaction
Device evaluating apparatus determine its activity and selectivity, and the temperature and selective data when reaction proceeds to the 8th day is listed in
In table 3.
The physical parameter of the catalyst of table 3
| Catalyst source | Catalyst | Initial reaction temperature (DEG C) | EO (mol%) | Selective (%) |
| Comparative example 1 | CZ-1 | 227 | 2.51 | 83.02 |
| Comparative example 2 | CZ-2 | 222.4 | 2.50 | 83.87 |
| Comparative example 3 | CZ-3 | 228.1 | 2.50 | 83.23 |
| Embodiment 1 | CZ-4 | 223.1 | 2.49 | 84.21 |
| Embodiment 2 | CZ-5 | 222.6 | 2.49 | 83.92 |
| Embodiment 3 | CZ-6 | 225.5 | 2.50 | 84.82 |
| Embodiment 4 | CZ-7 | 223.5 | 2.51 | 84.40 |
| Embodiment 5 | CZ-8 | 222.9 | 2.51 | 84.05 |
| Embodiment 6 | CZ-9 | 223.7 | 2.50 | 84.38 |
By data in table 3 it is known that its load according to made by the modified alpha-alumina supports of present invention offer
Silver catalyst, be applied to ethylene production reacting ethylene oxide during, be conducive to chain carrier
Catalyst (CZ-1 prepared by the carrier (without nickel element) in dispersion, with comparative example 1 and comparative example 3
With CZ-3) to compare, the selectivity of catalyst and activity are significantly improved；(contain nickel element with the carrier of comparative example 2
But without acid compound process) prepare catalyst (CZ-2) compare, its selectivity is improved significantly.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to the present invention's
Any restriction.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein used
Word is descriptive and explanatory vocabulary, rather than limited vocabulary.Can be by regulation in the claims in the present invention
In the range of the present invention is modified, and the present invention is carried out in without departing substantially from scope and spirit of the present invention
Revision.Although the present invention described in it is related to specific method, material and embodiment, it is not intended that
The present invention is limited to wherein disclosed particular case, conversely, the present invention to can be extended to other all with identical function
Methods and applications.
Claims (12)
1. a kind of modified alpha-alumina supports, it is obtained by nickeliferous alpha-alumina supports through acid solution process.
2. modified alpha-alumina supports according to claim 1, it is characterised in that the nickeliferous α-oxygen
Change alumina supporter is molded by nickeliferous alpha-alumina supports precursor mixture Jing, dry and roasting is obtained, wherein, it is described
Nickeliferous alpha-alumina supports precursor mixture is included：
Component a, three water A12O3；
Component b, false water A12O3；
Component d, mineralizer；
Component e, nickel simple substance and/or nickel compound containing；
Component f, binding agent；
Component g, water；And it is optional
Component c, weight alkaline earth metal compound.
3. modified alpha-alumina supports according to claim 2, it is characterised in that the nickeliferous α-oxygen
The composition for changing alumina supporter precursor mixture by solid constituent a-e gross weight meter is as follows：
4. modified alpha-alumina supports according to claim 3, it is characterised in that the nickeliferous α-oxygen
The composition for changing alumina supporter precursor mixture by solid constituent a-e gross weight meter is as follows：
5. modified alpha-alumina supports according to any one in claim 2-4, it is characterised in that
The mineralizer is fluoride；
The nickel compound containing includes at least in nickel oxide, nickelous carbonate, nickel nitrate, nickel chloride and nickel sulfate
Kind；It is preferred that the nickel compound containing is nickel oxide and/or nickel nitrate.
6. a kind of preparation method of the modified alpha-alumina supports as described in any one in claim 1-5,
It includes：
Step A, by the mixing of component a-g, is obtained nickeliferous alpha-alumina supports precursor mixture；
Step B, nickeliferous alpha-alumina supports precursor mixture is molded, and dry, roasting, and prepared nickeliferous α-
Alumina support；
Nickeliferous alpha-alumina supports are carried out acid solution and process prepared modified alpha-alumina support precursor by step C；
Step D, is washed to modified alpha-alumina support precursor, is dried and roasting, and modified alpha-oxidation is obtained
Alumina supporter；
Wherein, in step C, acid solution is carried out to nickeliferous alpha-alumina supports using the aqueous solution of acid compound
Process.
7. preparation method according to claim 6, it is characterised in that the acid compound it is water-soluble
The hydrogen ion concentration of liquid is 0.01-4mol/L；It is preferred that the hydrogen ion concentration of the aqueous solution of the acid compound is
0.05-1.5mol/L。
8. preparation method according to claim 6, it is characterised in that in step C, the nickeliferous α-
Alumina support is 1 with the weight ratio of the aqueous solution of the acid compound:(1-150)；It is preferred that the nickeliferous α-
Alumina support is 1 with the weight ratio of the aqueous solution of the acid compound:(20-60).
9. the preparation method according to any one in claim 6-8, it is characterised in that the acidification
Compound includes inorganic acid and/or Acidic inorganic salts, wherein the inorganic acid includes sulfuric acid, nitric acid, hydrochloric acid and oxalic acid
At least one of；The Acidic inorganic salts include ammonium nitrate and/or ammonium chloride.
10. the preparation method according to any one in claim 6-9, it is characterised in that in step C
In, the temperature that the acid solution is processed is 20-200 DEG C；It is preferred that the temperature that the acid solution is processed is 40-100 DEG C；Institute
The time for stating acid solution process is 0.2-3h；It is preferred that the time that the acid solution is processed is 0.5-1.5h.
11. a kind of silver catalysts, comprising the modified alpha-carrying alumina as described in any one in claim 1-5
Modified alpha-alumina supports and be carried on that in body or such as claim 6-10 prepared by any one methods described
Silver-colored simple substance in the modified alpha-alumina supports.
12. modified alpha-alumina supports as described in any one in claim 1-5, such as claim 6-10
Modified alpha-alumina supports or silver catalyst as claimed in claim 11 prepared by middle any one methods described
Application during ethylene produces oxirane.
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|---|---|---|---|---|
| CN1511633A (en) * | 2002-12-31 | 2004-07-14 | 中国石油化工股份有限公司北京燕山分 | Carrier for producing silver catalyst for epoxy ethane production, its preparing method and use |
| CN104707665A (en) * | 2013-12-16 | 2015-06-17 | 中国石油化工股份有限公司 | Alumina carrier, preparation method and alumina carrier supported catalyst |
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|---|---|---|---|---|
| CN1511633A (en) * | 2002-12-31 | 2004-07-14 | 中国石油化工股份有限公司北京燕山分 | Carrier for producing silver catalyst for epoxy ethane production, its preparing method and use |
| CN104707665A (en) * | 2013-12-16 | 2015-06-17 | 中国石油化工股份有限公司 | Alumina carrier, preparation method and alumina carrier supported catalyst |
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