CN106607035B - A kind of modified alpha-alumina supports and its preparation and application - Google Patents
A kind of modified alpha-alumina supports and its preparation and application Download PDFInfo
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- CN106607035B CN106607035B CN201510686188.4A CN201510686188A CN106607035B CN 106607035 B CN106607035 B CN 106607035B CN 201510686188 A CN201510686188 A CN 201510686188A CN 106607035 B CN106607035 B CN 106607035B
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Abstract
The present invention relates to a kind of modified alpha-alumina supports and preparation method thereof.The modification alpha-alumina supports are prepared by the way that cobalt element is added in carrier preparation process and carries out acid processing to molding alpha-alumina supports.The invention further relates to using the modification Alpha-alumina as the preparation method of the silver catalyst of carrier and silver catalyst.The silver catalyst loaded with modification alpha-alumina supports of the invention shows good activity and selectivity in ethylene production ethylene oxide.The raw material that the present invention prepares modified alpha-alumina supports is easy to obtain, and preparation method step is simple.Modified alpha-alumina supports provided by the present invention and silver catalyst have wide application prospect.
Description
Technical field
The invention belongs to catalyst carriers and catalyst preparation technical field, and in particular to a kind of modified alpha-alumina supports
And its it prepares and applies.
Background technique
Ethylene mainly generates ethylene oxide under silver catalyst effect, while side reaction also occurs and generates carbon dioxide
With water etc., wherein activity, selectivity and stability are the main performance index of silver catalyst.So-called activity refers to that ethylene oxide is raw
Production process reaches reaction temperature required when certain reaction load；Reaction temperature is lower, and the activity of catalyst is higher.So-called selection
Property refer to reaction in ethylene be converted to the ratio between the molal quantity of ethylene oxide and the overall reaction molal quantity of ethylene.So-called stability then table
It is shown as the fall off rate of activity and selectivity, the stability of fall off rate more small catalyst is better.
It is catalyzed during ethylene produces ethylene oxide using high activity, silver that is highly selective and having good stability
Agent can greatly improve economic benefit, therefore manufacture high activity, highly selective and good stability silver catalyst are silver-colored catalysis
The Main way of agent research.The performance of silver catalyst in addition to having important relationship with the composition of catalyst and preparation method, also with urge
The performance for the carrier that agent uses and its it is prepared with important relationship.
Currently, silver catalyst or selectivity in the market is good, but activity is not so good；Activity is good, and selectivity is less
It is good.Therefore, it in view of the needs in market, needs to research and develop a kind of activity, stability that silver catalyst not only can be improved at present, but also can
Improve the processing technique of the carrier of silver catalyst selectivity, and the silver catalyst and its application method that are made from it.
Summary of the invention
The technical problem to be solved by the present invention is to solve the above shortcomings of the prior art and to provide a kind of modified Alpha-aluminas
Carrier, carrier specific surface area with higher and intensity, and have more macropore.With modified alpha-alumina supports system described in this
At silver catalyst, be conducive to the dispersion of chain carrier, and be conducive to the desorption of product.Therefore, by the modified alpha-oxygen
Change alumina supporter and be applied to ethylene production reacting ethylene oxide process, improves its activity and selectivity, especially obviously mention
High selectivity.
For this purpose, first aspect present invention provides a kind of modified alpha-alumina supports, passed through by alpha-alumina supports containing cobalt
Acid solution processing is crossed to be made.
In the present invention, the alpha-alumina supports containing cobalt are formed by the precursor mixture of alpha-alumina supports containing cobalt, are dried
It is made with roasting, wherein the precursor mixture of alpha-alumina supports containing cobalt includes:
Component a, three water A12O3；
Component b, one water A1 of vacation2O3；
Component d, mineralizer；
Component e, cobalt simple substance and/or cobalt compound；
Component f, binder；
Component g, water；And optional
Component c, weight alkaline earth metal compound.
In the present invention, the precursor mixture of alpha-alumina supports containing cobalt presses the composition of solid component a-e total weight
It is as follows:
Component g, the water of surplus.
Preferably, the precursor mixture of alpha-alumina supports containing cobalt is as follows by the composition of solid component a-e total weight:
Component g, the water of surplus.
In some embodiments of the invention, the mineralizer is fluoride.
In other embodiments of the invention, the cobalt compound includes cobalt oxide, cobalt carbonate, cobalt nitrate, chlorination
At least one of cobalt and cobaltous sulfate.It is preferred that the cobalt compound is cobalt oxide and/or cobalt nitrate.
Second aspect of the present invention provides a kind of preparation of modification alpha-alumina supports as described in the first aspect of the invention
Method comprising:
Step A mixes component a-g, and the precursor mixture of alpha-alumina supports containing cobalt is made；
Step B will contain the molding of cobalt alpha-alumina supports precursor mixture, and dry, roasting, Alpha-alumina containing cobalt is made and carries
Body；
Step C will contain cobalt alpha-alumina supports and carry out the obtained modified alpha-alumina support precursor of acid solution processing；
Step D is washed, dried and is roasted to modified alpha-alumina support precursor, and modified alpha-alumina supports are made；
Wherein, in step C, acid solution processing is carried out to alpha-alumina supports containing cobalt using the aqueous solution of acid compound.
In the preparation method of modification alpha-alumina supports of the invention, the hydrogen ion of the aqueous solution of the acid compound
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 modification alpha-alumina supports of the invention, in step C, the alpha-alumina supports containing cobalt
Weight ratio with the aqueous solution of the acid compound is 1:(1-150).It is preferred that the alpha-alumina supports containing cobalt and the acid
Property compound aqueous solution weight ratio be 1:(20-60).
In the preparation method of modification alpha-alumina supports of the invention, 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；The Acidic inorganic salts packet
Include ammonium nitrate and/or ammonium chloride.
In the preparation method of modification alpha-alumina supports of the invention, in step C, the temperature of the acid solution processing is
20-200℃.It is preferred that the temperature of the acid solution processing is 40-100 DEG C.The time of the acid solution processing is 0.2-3h.It is preferred that described
The time of acid solution processing is 0.5-1.5h.
Third aspect present invention provides a kind of silver catalyst, includes modification alpha-oxidation as described in the first aspect of the invention
Modification alpha-alumina supports and be carried on the modified alpha-oxygen prepared by alumina supporter or as described in respect of the second aspect of the invention method
Change the silver-colored simple substance on alumina supporter.
Fourth aspect present invention provides a kind of preparation method of silver catalyst as described in the third aspect of the present invention, packet
It includes:
Step M: modification alpha-alumina supports or second party of the present invention described in maceration extract dipping first aspect present invention
The modification alpha-alumina supports of face the method preparation；
Step N: it is separated by solid-liquid separation and removes maceration extract.
In the preparation method of silver catalyst of the invention, the composition of the maceration extract by weight is as follows:
The water of surplus.
Preferably, the composition of the maceration extract by weight is as follows:
The water of surplus.
Fifth aspect present invention provides a kind of modification alpha-alumina supports as described in the first aspect of the invention, such as this hair
Modification alpha-alumina supports, silver catalyst as described in the third aspect of the present invention or such as sheet of bright second aspect the method preparation
Application of the silver catalyst of invention fourth aspect the method preparation during ethylene produces ethylene oxide.
Specific embodiment
To keep the present invention easier to understand, below in conjunction with embodiment, the present invention will be described in detail, these embodiments are only
Serve illustrative, it is not limited to application range of the invention.
Existing alumina support macropore is few, and specific surface area is small.It needs to research and develop one kind at present and catalyst both can be improved
Activity, stability, and the processing technique of the carrier of silver catalyst selectivity can be improved, and the silver catalyst that is made from it and its
Application method.
Therefore, first aspect present invention is related to a kind of modified alpha-alumina supports, is passed through by alpha-alumina supports containing cobalt
Acid solution processing is made.
In the present invention, the alpha-alumina supports containing cobalt are formed by the precursor mixture of alpha-alumina supports containing cobalt, are dried
It is made with roasting, wherein the precursor mixture of alpha-alumina supports containing cobalt includes:
Component a, three water A12O3；
Component b, one water A1 of vacation2O3；
Component c, weight alkaline earth metal compound (optional)；
Component d, mineralizer；
Component e, cobalt simple substance and/or cobalt compound；
Component f, binder；And
Component g, water.
In the present invention, the modified alpha-alumina supports are a kind of porous Alpha-alumina containing cobalt loads handled by acid solution
Body, and the cobalt element as contained in alpha-alumina supports containing cobalt is in its preparation process to mix jointly with other compositions
What mode was added, therefore the cobalt element in alpha-alumina supports containing cobalt and modified alpha-alumina supports containing cobalt is uniformly distributed
's.
In the present invention, component a is three water A12O3, and be three water α-A1 of graininess2O3, granularity is 50 mesh -500
Mesh.Three water A12O3Presence can increase the duct of carrier, to form porous α-A12O3Carrier.
In the present invention, component b is one water A1 of vacation2O3, granularity is preferably greater than to be equal to 200 mesh.
In the present invention, component c attaches most importance to alkaline earth metal compound, can improve the performance of carrier.It is of the present invention
Weight alkaline earth metal compound is the compound of strontium and/or barium, preferably include the oxide of strontium and/or barium, sulfate, acetate,
At least one of nitrate, carbonate and oxalates.The particularly preferred heavy alkaline earth metal compound is barium monoxide, sulfuric acid
At least one of barium, barium nitrate and barium carbonate.
In the present invention, it is preferred to which component d mineralizer is fluoride-mineralization agent.Fluoride-mineralization agent of the present invention adds
Entering is transformation of crystal for accelerated oxidation aluminium.It is preferred that fluoride of the present invention is inorganic fluoride, including hydrogen fluoride, fluorine
Change one of ammonium, aluminum fluoride, magnesium fluoride and ice crystal or a variety of.The particularly preferred fluoride is ammonium fluoride.
In the present invention, component f binder can be with one water A1 of component b vacation2O3Aluminum sol is generated, each component is bonded in
Together, become extrudable molding paste.Binder preferably used is acid in the present invention, including nitric acid, formic acid, acetic acid,
At least one of propionic acid and hydrochloric acid.When using acid as binder, preferred nitric acid, and it is hybridly prepared into nitric acid with water
Aqueous solution.
In some embodiments of the invention, preferably the weight ratio of nitric acid and water is 1:(1.25-10).More preferably,
The weight ratio of nitric acid and water is 1:(2-4).
In the present invention, it is also possible to which Aluminum sol partly or entirely replaces the binder of component f and one water of vacation of component b
A12O3。
In the present invention, the precursor mixture of alpha-alumina supports containing cobalt presses the composition of solid component a-e total weight
It is as follows:
Component g, the water of surplus.
Preferably, the precursor mixture of alpha-alumina supports containing cobalt is as follows by the composition of solid component a-e total weight:
Component g, the water of surplus.
In some embodiments of the invention, the cobalt compound includes cobalt oxide, cobalt carbonate, cobalt nitrate, cobalt chloride
At least one of with cobaltous sulfate.It is preferred that the cobalt compound is cobalt oxide and/or cobalt nitrate.
Second aspect of the present invention provides a kind of preparation of modification alpha-alumina supports as described in the first aspect of the invention
Method comprising:
Step A mixes component a-g, and the precursor mixture of alpha-alumina supports containing cobalt is made；
Step B will contain the molding of cobalt alpha-alumina supports precursor mixture, and dry, roasting, Alpha-alumina containing cobalt is made and carries
Body；
Step C will contain cobalt alpha-alumina supports and carry out the obtained modified alpha-alumina support precursor of acid solution processing；
Step D is washed, dried and is roasted to modified alpha-alumina support precursor, and modified alpha-alumina supports are made；
Wherein, in step C, acid solution processing is carried out to alpha-alumina supports containing cobalt using the aqueous solution of acid compound.
According to the method for the present invention, the composition of the precursor mixture of alpha-alumina supports containing cobalt is as follows:
Component a, three water Al of -500 purpose of 50 mesh2O3；
Component b, more than or equal to the one water Al of vacation of 200 mesh2O3；
Component c, Zhan Zufen a-e total weight is the heavy alkaline earth metal compound of 0-2% (weight)；
Component d, fluoride-mineralization agent；
Component e accounts for component a-e total weight for the cobalt simple substance of 0.001%-5% and/or containing cobalt with the poidometer of cobalt element
Close object；
Component f, binder；And
Component g, the water of surplus.
In the preparation method of modification alpha-alumina supports of the invention, the hydrogen ion of the aqueous solution of the acid compound
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 modification alpha-alumina supports of the invention, in step C, the alpha-alumina supports containing cobalt
Weight ratio with the aqueous solution of the acid compound is 1:(1-150).It is preferred that the alpha-alumina supports containing cobalt and the acid
Property compound aqueous solution weight ratio be 1:(20-60).
In the preparation method of modification alpha-alumina supports of the invention, 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；The Acidic inorganic salts packet
Include ammonium nitrate and/or ammonium chloride.
In the present invention, after the mixture in step A being mediated uniformly, paste is generally yielded.It is advantageous to the present invention
Be, usually first by component a-e (if all if use) after mixing, be transferred in kneader, then be added component f and g carry out
It mediates, is uniformly kneaded into paste, is especially kneaded into extrudable molding paste；Formed body is obtained after paste molding,
The formed body can be dried to aqueous 10% (weight) hereinafter, drying temperature is 80-120 DEG C, and drying time is according to moisture content control
System was at 1-24 hours.The shape of gained formed body can be annular, spherical shape, cylindricality, porous column shape or other arbitrary shapes.
Some specific embodiments according to the present invention, in stepb, usually at 1000-1500 DEG C, preferably in 1000-
It is roasted at a temperature of 1400 DEG C.Calcining time is no less than 1 hour.Calcining time is usually 2-24 hours.It is preferred that when roasting
Between be 2-8 hours.Aluminium oxide is set to be completely converted into α-A1 substantially by roasting2O3, such as 90% or more be converted into α-A12O3, obtain
To alpha-alumina supports.
In the present invention, it is preferred to which the acid solution processing carries out under agitation.
In the present invention, it is preferred to which the acid solution processing carries out under certain temperature (can such as pass through heating), according to of the invention
Inventor the study found that be performed under heating conditions acid solution processing can better dealuminzation, increase the specific surface area of carrier, and increase
Increase hole.
According to the method for the present invention, in step C, the temperature of the acid solution processing is 20-200 DEG C.It is preferred that at the acid solution
The temperature of reason is 40-100 DEG C.
According to the method for the present invention, in step C, the time of the acid solution processing is 0.2-3h.It is preferred that the acid solution processing
Time be 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 preferred that described
The temperature of 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 invention, in step D, the time of the roasting is at least 1 hour.It is preferred that described
The time of roasting is 2-24 hours.More preferably, the time of the roasting is 4-10 hours.
In some other embodiments of the invention, in step D, it is preferable to use deionized water washs modified alpha-oxidation
Modified alpha-alumina support precursor is washed to filtrate and is in neutrality by deionized water, is then dried again by alumina supporter precursor
Processing.The temperature of the drying is 60-180 DEG C.It is preferred that the temperature of the drying is 80-120 DEG C.
Obtained modification alpha-alumina supports prepared according to the methods of the invention, are by the alpha-alumina supports containing cobalt through peracid
It is made after processing, is also referred to as modified alpha-alumina supports containing cobalt or contains cobalt improved alpha-alumina supports.It is provided by the present invention
Alpha-alumina supports have the feature that specific surface area is 0.2-2.0m2/ g, Kong Rongwei 0.35-0.85mL/g, water absorption rate >=
30%, crushing strength is 20-140N/.
In the present invention, cobalt element is added in the preparation process of carrier, therefore, is equally evenly distributed in and is changed
In property alpha-alumina supports.The addition of cobalt element is conducive to the specific surface area and intensity that improve carrier, and the place of acid compound
Reason, further improves duct and the specific surface area of carrier.
The present invention has carried out sour processing to the alpha-alumina supports containing cobalt, can play in this way cobalt element effect and
Play the effect of acid processing.After peracid treatment, alumina wafer can become smaller the alpha-alumina supports containing cobalt, and surface occurs more
Fold, increase the specific surface area of carrier, improve the activity of silver catalyst；Macropore increases, and increases the de- of ethylene oxide
It is attached, improve the selectivity of silver catalyst.After peracid treatment, cobalt element is still uniformly distributed in the carrier.
Third aspect present invention is related to a kind of silver catalyst, includes modification Alpha-alumina as described in the first aspect of the invention
Modification alpha-alumina supports and be carried on the modified alpha-oxidation prepared by carrier or as described in respect of the second aspect of the invention method
Silver-colored simple substance on alumina supporter, wherein the content of the silver-colored simple substance loaded in the modified alpha-alumina supports is about 16.1% (weight
Amount).
Fourth aspect present invention is related to a kind of preparation method of silver catalyst described in third aspect present invention, comprising:
Step M: modification alpha-alumina supports or second party of the present invention described in maceration extract dipping first aspect present invention
The modification alpha-alumina supports of face the method preparation；
Step N: it is separated by solid-liquid separation and removes maceration extract.
In the preparation method of silver catalyst of the invention, the composition of the maceration extract by weight is as follows:
The water of surplus.
Preferably, the composition of the maceration extract by weight is as follows:
The water of surplus.
In the present invention, the preferably described silver compound is at least one of silver oxide, silver nitrate and silver oxalate.
In the present invention, the preferably described alkali metal promoter is one of compound of lithium, sodium, potassium, rubidium and caesium or a variety of.More
Preferably, the alkali metal promoter is one of cesium sulfate, cesium nitrate, lithium nitrate and potassium hydroxide or a variety of.Most preferably,
The alkali metal promoter is cesium sulfate.
In the present invention, the preferably described base earth metal promoter is one of compound of magnesium, calcium, strontium and barium or a variety of.More
Preferably, the base earth metal promoter is in oxide, oxalates, sulfate, acetate and the nitrate of magnesium, calcium, strontium and barium
It is one or more.
In the present invention, the preferably described rhenium auxiliary agent is one of oxide, perrhenic acid, perrhenic acid caesium and the ammonium perrhenate of rhenium
Or it is a variety of.It is furthermore preferred that the rhenium auxiliary agent is ammonium perrhenate.
In the present invention, the preferably described organic amine is one of pyridine, butylamine, ethylenediamine, 1,3- propane diamine and ethanol amine
Or it is a variety of.It is furthermore preferred that the organic amine is ethylenediamine and/or ethanol amine.It is highly preferred, the organic amine be ethylenediamine and
Ethanolamine mixtures.
It in some embodiments of the invention, further include the coassist agent of rhenium auxiliary agent in the maceration extract, to be further improved
Activity, selectivity and the stability of gained silver catalyst.The coassist agent of the rhenium auxiliary agent includes any mistake in the periodic table of elements
Cross the compound of metal or the mixture of several transistion metal compounds.It is preferred that the coassist agent of the rhenium auxiliary agent be group vib and
The oxyacid and its salt of VIIB race element, including wolframic acid, sodium tungstate, potassium tungstate, ammonium tungstate, wolframic acid caesium, molybdic acid, ammonium molybdate and partially
One of ammonium tungstate is a variety of.Its dosage is 0-1000wt ppm.It is preferred that its dosage is 0-500wt ppm.
In the present invention, the dipping process can carry out under subatmospheric pressure conditions.It is preferred that being less than 10mmHg in vacuum degree
Under conditions of carry out.Dip time is preferably 10-60min.
In the present invention, the preferably described solid is separated into leaching.
In the present invention, the silver compound is major catalyst, the alkali metal promoter, base earth metal promoter, rhenium auxiliary agent etc.
For catalyst promoter.
In some embodiments of the invention, the modification alpha-alumina supports of above method preparation can be according to need before use
It is activated.Activation can carry out in the nitrogen oxygen atmosphere of air or oxygen content no more than 21v%.Its activation temperature is 180-
700℃.It is preferred that activation temperature is 200-500 DEG C.Its activation time is 1-120min.It is preferred that activation time is 2-60min.
Fifth aspect present invention provides modification alpha-alumina supports as described in the first aspect of the invention, such as present invention the
Modification alpha-alumina supports, silver catalyst as described in the third aspect of the present invention or such as present invention of two aspect the methods preparation
Application of the silver catalyst of fourth aspect the method preparation during ethylene produces ethylene oxide.
Silver catalyst made from the method is used in epoxidation of ethylene according to the present invention, the epoxidation reaction condition
For common reaction condition in the art, such as reaction temperature can be 200-275 DEG C.
" water " word used in the present invention refers to deionized water in the case where not specifying.
Term " optionally " of the present invention, which refers to, to be contained or not contain, and is also referred to be added or is added without.
The specific surface area of carrier is measured according to international test standards ISO-9277 using nitrogen physisorption BET method.Example
Such as, the specific surface area of U.S. Kang Ta company NOVA2000e type nitrogen physisorption instrument measurement carrier can be used.
The Kong Rong of carrier is measured using mercury injection method.It is, for example, possible to use Merck & Co., Inc, U.S. AutoPore9510 types to press mercury
The Kong Rong of instrument measurement carrier.
The amount of alkaline earth metal compound can be obtained by calculation in carrier.
The side pressure strength of carrier is surveyed for example, can produce II type intelligence granule strength of DL using Dalian Chemical Research &. Design Inst.
Determine instrument, randomly select 30 support samples, is averaged to obtain after measuring radial crushing strength.
Term " water absorption rate " used refers to the volume of the carrier saturation absorption water of unit mass in the present invention, and unit is mL/
g.Measuring method is as follows: weighing a certain amount of carrier first (it is assumed that its quality is m1), carrier taking-up is erected after 1h is boiled in boiling water
It stands and removes the extra moisture of carrier surface on the moderate wet gauze of water content, the quality of the carrier after finally weighing absorption water
(it is assumed that m2), the water absorption rate of carrier is calculated as follows.
Water absorption rate=(m2-m1)/m1/ρWater
Wherein ρWaterIt is the density that measuring temperature, atmospheric pressure are lauched.
The measurement of catalyst performance: laboratory microreactor (the following letter of various silver catalysts involved in the present invention
Claiming " micro- anti-") evaluating apparatus tests its initial activity and selectivity.Reactor used in micro anti-evaluation device is internal diameter 4mm
Stainless steel tube, reaction tube are placed in heating mantle.The admission space of catalyst is 1mL, and there is inert filler in lower part, makes catalyst bed
Positioned at the flat-temperature zone of heating mantle.The determination condition for the catalyst activity and selectivity that the present invention uses such as table 1:
The determination condition of 1 catalyst activity and selectivity of table
METHOD FOR CONTINUOUS DETERMINATION reactor enters after stably reaching above-mentioned reaction condition, exit gas forms.Measurement result carries out body
Product calculates selectivity S after shrinking correction as follows:
Wherein Δ EO is reactor outlet gas and inlet gas ethylene oxide concentration difference, Δ CO2Reactor outlet gas with
Gas concentration lwevel is poor in inlet gas, takes test result of the average of 10 groups or more test datas as the same day.
Modified alpha-alumina supports provided by the present invention and its silver catalyst of load have the advantage that
(1) modified alpha-alumina supports provided by the invention, by adding cobalt element and right in carrier preparation process
Molding alpha-alumina supports carry out the processing of acid compound, and specific surface area and the crushing for improving alpha-alumina supports are strong
Degree, active component after being conducive to it is evenly dispersed；And being uniformly distributed for cobalt element is helpful to catalyst activity is improved, and has
Conducive to the reservation of aperture, increase carrier specific surface area；The surface of alpha-alumina supports containing cobalt is in alkalescent, and it is de- to be conducive to ethylene oxide
It is attached, improve selectivity.
(2) modified alpha-alumina supports macropore provided by the invention is more, and water absorption rate is high, is conducive to ethylene oxide desorption, has
It is selective conducive to improving.
(3) silver catalyst provided by the invention made of modification alpha-alumina supports of the invention, in ethylene oxy metaplasia
During producing ethylene oxide, 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 is simple.
(5) modified alpha-alumina supports provided by the invention and silver catalyst have wide application prospect.
Embodiment
Comparative example 1
By three water α-A1 of -500 purpose of 200 mesh2O3The one water A1 of vacation of 372g, -400 mesh of 200 mesh2O3112g、MgF23g and Ba
(NO3)2The solid mixture of 0.5g is put into blender and is uniformly mixed, and is then transferred to kneader, be added dust technology (nitric acid: water=
1:3, weight ratio) 90mL, it is kneaded into extrudable molding paste, extrusion molding is outer diameter 8.0mm, long 6.0mm, internal diameter
The five hole columns of 1.0mm.The five holes column is dried into 10h at 80-120 DEG C, free water content is made to be reduced to 10% (weight
Amount) hereinafter, molding alpha-alumina supports precursor is made.Then the precursor is put into electric furnace, is increased to 1400 from room temperature through 30h
DEG C, constant temperature 2h, is made white α-A1 later2O3Carrier.By obtained white α-A12O3Carrier is named as Z-1, and measures it
Crushing strength, water absorption rate and specific surface area, the results are shown in Table 2.
Comparative example 2
Being put into the raw material of blender mixing further includes Co (NO3)2.6H2O 1.48g, remaining is identical as comparative example 1.By institute
White α containing cobalt-A1 obtained2O3Carrier is named as Z-2, and measures its crushing strength, water absorption rate and specific surface area, the results are shown in Table
2。
Comparative example 3
It is that 1:20 prepares 400g 0.5mol/L's by alpha-alumina supports and the weight ratio of the aqueous solution of acid compound
HNO3Solution, and by HNO3Solution is heated to 80 DEG C, weighs 20g Z-1 carrier and is put into HNO3Solution, after stirring 0.5h, acid solution
Alpha-alumina supports precursor takes out, and is cleaned with deionized water, until filtrate pH value is 7 or so；Then acid solution alpha-alumina supports
Precursor is put into baking oven in 100 DEG C of dry 10h, after dry acid solution alpha-alumina supports precursor be put into Muffle furnace roasted in 540 DEG C
It burns 4 hours, modified alpha-alumina supports is made.Obtained modification alpha-alumina supports are named as Z-3, and measure its crushing
Intensity, water absorption rate and specific surface area, the results are shown in Table 2.
Embodiment 1
It is that 1:20 prepares 400g 0.5mol/L's by alpha-alumina supports and the weight ratio of the aqueous solution of acid compound
HNO3Solution, and by HNO3Solution is heated to 80 DEG C, weighs 20g Z-2 carrier and is put into HNO3Solution, after stirring 0.5h, acid solution
Alpha-alumina supports precursor takes out, and is cleaned with deionized water, until filtrate pH value is 7 or so.Then acid solution alpha-alumina supports
Precursor is put into baking oven in 100 DEG C of dry 10h, after dry acid solution alpha-alumina supports precursor be put into Muffle furnace roasted in 540 DEG C
It burns 4 hours, modified alpha-alumina supports is made.Obtained modification alpha-alumina supports are named as Z-4, and measure its crushing
Intensity, water absorption rate and specific surface area, the results are shown in Table 2.
Embodiment 2
It is that 1:20 prepares 400g 0.01mol/L's by alpha-alumina supports and the weight ratio of the aqueous solution of acid compound
HNO3Solution, and by HNO3Solution is heated to 80 DEG C, weighs 20g Z-2 carrier and is put into HNO3Solution, after stirring 0.5h, acid solution
Alpha-alumina supports precursor takes out, and is cleaned with deionized water, until filtrate pH value is 7 or so.Then acid solution alpha-alumina supports
Precursor is put into baking oven in 100 DEG C of dry 10h, after dry acid solution alpha-alumina supports precursor be put into Muffle furnace roasted in 540 DEG C
It burns 4 hours, modified alpha-alumina supports is made.Obtained modification alpha-alumina supports are named as Z-5, and measure its crushing
Intensity, water absorption rate and specific surface area, the results are shown in Table 2.
Embodiment 3
It is that 1:20 prepares 400g 1.5mol/L's by alpha-alumina supports and the weight ratio of the aqueous solution of acid compound
HNO3Solution, and by HNO3Solution is heated to 80 DEG C, weighs 20g Z-2 carrier and is put into HNO3Solution, after stirring 0.5h, acid solution
Alpha-alumina supports precursor takes out, and is cleaned with deionized water, until filtrate pH value is 7 or so.Then acid solution alpha-alumina supports
Precursor is put into baking oven in 100 DEG C of dry 10h, after dry acid solution alpha-alumina supports precursor be put into Muffle furnace roasted in 540 DEG C
It burns 4 hours, modified alpha-alumina supports is made.Obtained modification alpha-alumina supports are named as Z-6, and measure its crushing
Intensity, water absorption rate and specific surface area, the results are shown in Table 2.
Embodiment 4
It is that 1:60 prepares 1200g 0.5mol/L's by alpha-alumina supports and the weight ratio of the aqueous solution of acid compound
HNO3Solution, and by HNO3Solution is heated to 80 DEG C, weighs 20g Z-2 carrier and is put into HNO3Solution, after stirring 0.5h, acid solution
Alpha-alumina supports precursor takes out, and is cleaned with deionized water, until filtrate pH value is 7 or so.Then acid solution alpha-alumina supports
Precursor is put into baking oven in 100 DEG C of dry 10h, after dry acid solution alpha-alumina supports precursor be put into Muffle furnace roasted in 540 DEG C
It burns 4 hours, modified alpha-alumina supports is made.Obtained modification alpha-alumina supports are named as Z-7, and measure its crushing
Intensity, water absorption rate and specific surface area, the results are shown in Table 2.
Embodiment 5
It is that 1:20 prepares 400g 0.5mol/L's by alpha-alumina supports and the weight ratio of the aqueous solution of acid compound
HNO3Solution, and by HNO3Solution is heated to 40 DEG C, weighs 20g Z-2 carrier and is put into HNO3Solution, after stirring 0.5h, acid solution
Alpha-alumina supports precursor takes out, and is cleaned with deionized water, until filtrate pH value is 7 or so.Then acid solution alpha-alumina supports
Precursor is put into baking oven in 100 DEG C of dry 10h, after dry acid solution alpha-alumina supports precursor be put into Muffle furnace roasted in 540 DEG C
It burns 4 hours, modified alpha-alumina supports is made.Obtained modification alpha-alumina supports are named as Z-8, and measure its crushing
Intensity, water absorption rate and specific surface area, the results are shown in Table 2.
Embodiment 6
It is that 1:20 prepares 400g 0.5mol/L's by alpha-alumina supports and the weight ratio of the aqueous solution of acid compound
HNO3Solution, and by HNO3Solution is heated to 80 DEG C, weighs 20g Z-2 carrier and is put into HNO3Solution, after stirring 1h, acid solution α-
Alumina support precursor takes out, and is cleaned with deionized water, until filtrate pH value is 7 or so.Then before acid solution alpha-alumina supports
Body is put into baking oven in 100 DEG C of dry 10h, after dry acid solution alpha-alumina supports precursor be put into Muffle furnace roast 4 in 540 DEG C
Hour, modified alpha-alumina supports are made.Obtained modification alpha-alumina supports are named as Z-9, and it is strong to measure its crushing
Degree, water absorption rate and specific surface area, the results are shown in Table 2.
The physical parameter of 2 carrier of table
| Carrier source | Support samples | Crushing strength (N/) | Water absorption rate (%) | Specific surface area (m2/g) |
| Comparative example 1 | Z-1 | 48 | 51.14 | 0.752 |
| Comparative example 2 | Z-2 | 59 | 52.46 | 1.065 |
| Comparative example 3 | Z-3 | 41 | 50.93 | 1.187 |
| Embodiment 1 | Z-4 | 53 | 52.19 | 1.356 |
| Embodiment 2 | Z-5 | 57 | 52.32 | 1.169 |
| Embodiment 3 | Z-6 | 50 | 51.56 | 1.621 |
| Embodiment 4 | Z-7 | 52 | 52.06 | 1.402 |
| Embodiment 5 | Z-8 | 56 | 52.27 | 1.178 |
| Embodiment 6 | Z-9 | 51 | 52.02 | 1.411 |
By above-mentioned comparative example 2, embodiment 1-6 as can be seen that in carrier preparation process compared with comparative example 1 and comparative example 3
After middle addition cobalt element, the intensity and specific surface area of carrier are improved；And after carrying out sour processing, specific surface area further increases,
But intensity is declined again.Especially comparative example 3, intensity is substantially reduced, this is because not adding in the carrier preparation process
Cobalt element is added directly to carry out sour processing.
The preparation of corresponding silver catalyst in comparative example 1-3 and embodiment 1-6
700g silver nitrate is dissolved in 750mL deionized water, silver nitrate solution is made；325g ammonium oxalate is dissolved in 250mL
Ammonium oxalate solution is made in 50 DEG C of deionized water；Silver nitrate solution is uniformly mixed with ammonium oxalate solution with vigorous stirring,
Generate white silver oxalate precipitate；After silver oxalate precipitate aging 1h, filtering, and filter cake is washed with deionized up to nothing in filtrate
Paste silver oxalate filter cake is made in nitrate ion, contains metallic silver about 60% (weight) in filter cake obtained, and aqueous about 15%
(weight).
300g ethylenediamine, 110g ethanol amine and 375g deionized water are added in the glass flask with stirring, is 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, makes oxalic acid
Silver-colored all dissolutions, are then added 2.2g cesium sulfate and 1.4g strontium acetate, then plus deionized water so that solution gross mass is reached 2000g,
Acquired solution is uniformly mixed, silver catalyst maceration extract is obtained, the silver content of silver compound maceration extract obtained is 22% (weight
Amount).
Each 15g of support samples obtained in comparative example 1-3 and embodiment 1-6 is taken, is respectively placed in the container of vacuum-pumping,
Vacuum degree is evacuated to lower than 10mmHg, above-mentioned silver catalyst maceration extract is added thereto, submerges carrier, keeps 30min.Later
Leaching removes extra silver catalyst maceration extract, and the carrier after dipping is heated 5min in 350 DEG C of air stream, cooling, point
Comparative example 1-3 and the corresponding silver catalyst of embodiment 1-6 are not prepared.Obtained silver catalyst is named as CZ-1 extremely
CZ-9 analyzes, CZ-1 to CZ- the content of silver and auxiliary agent in obtained silver catalyst (wherein content is in terms of metal)
The content of silver and auxiliary agent (caesium and strontium) in 9 is essentially identical, and wherein the content of silver element is about 16.1% (weight).And using micro-
Type reactor evaluations device measures its activity and selectivity, and the temperature and selective data when reaction proceeds to the 8th day are listed in table 3
In.
The physical parameter of 3 catalyst of table
| Catalyst source | Catalyst | Initial reaction temperature (DEG C) | EO (mol%) | Selectivity (%) |
| Comparative example 1 | CZ-1 | 227 | 2.51 | 83.02 |
| Comparative example 2 | CZ-2 | 222.5 | 2.50 | 84.07 |
| Comparative example 3 | CZ-3 | 228.1 | 2.50 | 83.23 |
| Embodiment 1 | CZ-4 | 223.8 | 2.50 | 84.77 |
| Embodiment 2 | CZ-5 | 223.0 | 2.51 | 84.19 |
| Embodiment 3 | CZ-6 | 225.9 | 2.51 | 85.10 |
| Embodiment 4 | CZ-7 | 223.9 | 2.49 | 84.89 |
| Embodiment 5 | CZ-8 | 223.2 | 2.50 | 84.24 |
| Embodiment 6 | CZ-9 | 224 | 2.51 | 84.88 |
Data in table 3 it is known that the silver that it is loaded made of the modification alpha-alumina supports provided according to the present invention
Catalyst is applied to during ethylene production reacting ethylene oxide, is conducive to the dispersion of chain carrier, with comparative example
1 with the catalyst of carrier (the be free of cobalt element) preparation in comparative example 3 (CZ-1 is compared with CZ-3), the selectivity of catalyst and
Activity significantly improves；With the catalyst (CZ-2) of carrier (containing cobalt element but without acid compound processing) preparation of comparative example 2
It compares, selectivity is improved significantly.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (14)
1. a kind of modified alpha-alumina supports are made by alpha-alumina supports containing cobalt by acid solution processing, the α containing cobalt-oxygen
Change alumina supporter and be made by the precursor mixture of alpha-alumina supports containing cobalt through molding, drying and roasting, wherein the alpha-oxidation containing cobalt
Alumina supporter precursor mixture is as follows by the composition of solid component a-e total weight:
2. modified alpha-alumina supports according to claim 1, which is characterized in that the precursor of alpha-alumina supports containing cobalt
Mixture is as follows by the composition of solid component a-e total weight:
3. modified alpha-alumina supports according to claim 1 or 2, which is characterized in that
The mineralizer is fluoride；
The cobalt compound includes at least one of cobalt oxide, cobalt carbonate, cobalt nitrate, cobalt chloride and cobaltous sulfate.
4. modified alpha-alumina supports according to claim 3, which is characterized in that the cobalt compound is cobalt oxide
And/or cobalt nitrate.
5. a kind of preparation method of the modification alpha-alumina supports as described in any one of claim 1-4 comprising:
Step A mixes component a-g, and the precursor mixture of alpha-alumina supports containing cobalt is made；
Step B will contain the molding of cobalt alpha-alumina supports precursor mixture, and dry, roasting, alpha-alumina supports containing cobalt are made；
Step C will contain cobalt alpha-alumina supports and carry out the obtained modified alpha-alumina support precursor of acid solution processing；
Step D is washed, dried and is roasted to modified alpha-alumina support precursor, and modified alpha-alumina supports are made；
Wherein, in step C, acid solution processing is carried out to alpha-alumina supports containing cobalt using the aqueous solution of acid compound.
6. preparation method according to claim 5, which is characterized in that the hydrogen ion of the aqueous solution of the acid compound is dense
Degree is 0.01-4mol/L.
7. preparation method according to claim 6, which is characterized in that the hydrogen ion of the aqueous solution of the acid compound is dense
Degree is 0.05-1.5mol/L.
8. preparation method according to claim 5, which is characterized in that in step C, the alpha-alumina supports containing cobalt with
The weight ratio of the aqueous solution of the acid compound is 1:(1-150).
9. preparation method according to claim 8, which is characterized in that in step C, the alpha-alumina supports containing cobalt with
The weight ratio of the aqueous solution of the acid compound is 1:(20-60).
10. preparation method according to claim 5, which is characterized in that the acid compound includes inorganic acid and/or acid
Property inorganic salts, wherein the inorganic acid includes at least one of sulfuric acid, nitric acid, hydrochloric acid and oxalic acid；The Acidic inorganic salts include
Ammonium nitrate and/or ammonium chloride.
11. preparation method according to claim 5, which is characterized in that in step C, the temperature of the acid solution processing is
The time of the 20-200 DEG C of acid solution processing is 0.2-3h.
12. preparation method according to claim 11, which is characterized in that the temperature of the acid solution processing is 40-100 DEG C,
The time of the acid solution processing is 0.5-1.5h.
13. a kind of silver catalyst, comprising the modification alpha-alumina supports as described in any one of claim 1-4 or such as right
It is required that any one of 5-12 the method preparation modification alpha-alumina supports and be carried on the modified alpha-carrying alumina
Silver-colored simple substance on body.
14. modification alpha-alumina supports, any one of such as claim 5-12 as described in any one of claim 1-4
The modification alpha-alumina supports of the method preparation or silver catalyst as claimed in claim 13 are in ethylene production epoxy
Application during ethane.
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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 |
| CN102441435A (en) * | 2010-09-30 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing alumina carrier for silver catalyst, carrier prepared by using method and application thereof |
| CN104437665A (en) * | 2013-09-16 | 2015-03-25 | 中国石油化工股份有限公司 | Silver catalyst alpha-alumina carrier preparation method |
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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 |
| CN102441435A (en) * | 2010-09-30 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing alumina carrier for silver catalyst, carrier prepared by using method and application thereof |
| CN104437665A (en) * | 2013-09-16 | 2015-03-25 | 中国石油化工股份有限公司 | Silver catalyst alpha-alumina carrier preparation method |
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