CN104437665B - Silver catalyst alpha-alumina carrier preparation method - Google Patents
Silver catalyst alpha-alumina carrier preparation method Download PDFInfo
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Abstract
The present invention relates to a preparation method for a silver catalyst alpha-alumina carrier for producing ethylene oxide through ethylene oxidation, wherein the surface of the carrier obtained through the method contains the cobalt compound. The present invention further relates to the alpha-alumina carrier prepared through the preparation method and the corresponding silver catalyst. With the application of the silver catalyst prepared from the carrier of the present invention in the ethylene oxide production through the ethylene oxidation, the good catalyst stability is provided.
Description
Technical field
The present invention relates to a kind of ethylene epoxidizing produces the preparation side of the alpha-alumina supports of oxirane silver catalyst
Method, and the silver catalyst thus prepared.
Background technology
Oxirane (eo) is a kind of important petrochemical industry and organic synthesis intermediate, be widely used in production antifreezing agent,
The products such as monoethanolamine, ethoxylated surfactant.At present, mainly adopt the ethene of carried silver catalyst catalysis and molecule oxygen-
Solid-phase selective oxidation reaction produces, and main side reaction is the complete oxidation generating carbon dioxide and water.
For improving the effective rate of utilization of argent and improving active, selectivity and the stability of catalyst, industrial universal
Using the reaction atmosphere of the higher reaction pressure of 1.0-2.2mpa and chloride organic hydrocarbon gas auxiliary agent, and add alkali metal etc. to help to urge
Agent (as patent us4010115 and us4356312).The interpolation of auxiliary agent can improve catalytic active component silver dispersion situation,
Change the Acidity of Aikalinity of carrier surface, in addition can also modulation metal silver surface electronics situation and reaction species adsorption and desorption,
Thus improving the catalytic performance of catalyst.
In addition to reaction process condition and auxiliary agent, carrier and its surface nature are also apparent from affecting silver catalyst performance.
Suitably the silver catalyst carrier of industrial use not only should have higher intensity, also should be able to provide suitable ratio table
Face and pore structure.Additionally, carrier surface should be also that the deep reaction to oxirane is inert.For improving silver catalyst preparation
The catalytic performance of oxirane, people have made substantial amounts of research work in terms of carrier composition adjustment, carrier hole structure control.
Cn1044416 reports a kind of method by dipping and applies the nothing being covered with 0.03-20 weight % in carrier channel surfaces
Sizing silica, drying and 700-1500 DEG C of high-temperature roasting, obtain silicon oxide surface modified support afterwards, this carrier loaded work
Property component silver and auxiliary agent after, under inert atmosphere in 400-950 DEG C be heat-treated, it is said that gained catalyst has higher selection
Property, active and lasting service life.According to the open cn1080211 of an other Chinese patent application of the said firm, with no
The mixture coated carrier hole surface of sizing silica and aluminum oxide is it is also possible to improving the active, selectivity of silver catalyst and prolonging
Long life.
Wo97/46316 describes a kind of area load to be had the silver catalyst carrier of titanium dioxide and is prepared by this carrier
Silver catalyst.Wherein titanium dioxide is the titanium-containing compound solution by water soluble or organic solvent or sol impregnation load
Body, more fired method makes.It is understood by the inventors that the titanium dioxide of carrier surface, preferably in 400-700 DEG C of roasting, makes two
Titanium oxide is existed with Detitanium-ore-type.Through with tio2The carrier processing can improve the physical property of carrier, such as intensity and wear rate, makes
Carrier is fine and close.Concrete grammar is: after carrier calcination, soaks tio2, sinter 6 hours at 500 DEG C.In an embodiment, treated
The silver catalyst activity and selectivity that carrier is made is above untreated sample, wherein selectively high by 0.8%.
But ethylene produces the oxirane catalyst activity in silver catalyst field, selectivity and catalyst stability
It need to improve further.
Content of the invention
In view of the situation of above-mentioned prior art, the present inventor enters in silver catalyst and its alpha-alumina supports field
The research gone extensively and profoundly, it was found that when alpha-alumina supports channel surfaces contain a small amount of cobalt, can be obviously improved by
The stability of the performance of the silver catalyst that this carrier is made, especially silver catalyst.
Specifically, the present invention provides a kind of ethylene epoxidizing to produce the alpha-alumina supports of oxirane silver catalyst
Preparation method, comprises the steps:
1) molded and after roasting alpha-alumina supports be impregnated in cobalt compound solution, after drying is impregnated
Alpha-alumina supports；
2) by step 1) resulting vehicle at 800～1200 DEG C, preferably 900～1100 DEG C roasting at least 1 hour, preferably roast
Burn 3-24 hour, described alpha-alumina supports finished product is obtained.
It is preferable that first passing through the following methods comprising the steps of to prepare the institute in step 1) in such scheme
State the alpha-alumina supports after molded and roasting, a) form the mixture comprising following component: i) three water Alpha-aluminas, transition
Phase alumina or its mixture, ii) a false water aluminum oxide, iii) optionally, carbonaceous material, iv can be burnt out) optionally, mineralising
Agent, v) optionally, flux, vi) optionally, shaping assistant；And vii) binding agent；With step b) by step a) gained mixture
Shaping, drying and roasting obtain described alpha-alumina supports.It is prepared into using three water Alpha-aluminas in preferred version of the present invention
Combine to alpha-alumina supports with dipping cobalt compound in the alpha-alumina supports after molded and roasting, it contains cobalt
The catalytic performance difference of the corresponding silver catalyst of carrier before and after compound dipping becomes apparent from it is shown that in preferred embodiment of the present invention
" preparations of the alpha-alumina supports after shaping and roasting " and the good association of " preparation of alpha-alumina supports finished product " this two step
Same-action.The silver catalyst alpha-alumina supports optimum of commercial Application is to prepare under above-mentioned combination.
In the support preparation method of the present invention, as alpha-oxidation silicon source, need using three water Alpha-aluminas, transitional face oxygen
Change aluminium or its mixture, i.e. component i).Component i) is in generally solidapowder form.For the purpose of the present invention, the granularity of component i) is excellent
Elect 50-500 mesh as.Based on the gross weight of all solids component in the mixture of preparation in step a), the consumption of component i) is usual
For 5-90 weight %, preferably 15-80 weight %, more preferably 35-80 weight %, particularly preferably 50-80 weight %.
In the support preparation method of the present invention, also need to using a false water aluminum oxide, i.e. component as alumina component
ii).Component ii) it is in generally solidapowder form.For the purpose of the present invention, component ii) granularity be preferably less than be equal to 200 mesh,
I.e. this false water aluminum oxide passes through the sieve of 200 mesh.Gross weight based on all solids component of the mixture of preparation in step a)
Amount, component ii) consumption be usually 5-50 weight %, preferably 10-40 weight %, more preferably 15-40 weight %, particularly preferably
15-35 weight %.
In the support preparation method of the present invention, as component iii) burnt out carbonaceous material be non-to have to use for group
Point, but preferably use.Carbonaceous material can be burnt out is added to manufacture macropore, so that carrier has suitable pore structure
And specific surface.Described carbonaceous material includes one of petroleum coke, carbon dust, graphite, polyethylene, polypropylene, rosin, vaseline etc.
Or multiple mixtures, preferably petroleum coke, graphite or vaseline or its mixture.Carbonaceous material aoxidizes in roasting process, raw
Become gas effusion, form macropore in the carrier.The addition that carbonaceous material can be burnt out is 0-30 weight %, preferably 0.01-20 weight
Amount %, more preferably 0.1-10 weight %, based on component i) and ii) gross weight.
In the support preparation method of the present invention, as component iv) mineralizer be non-have to use for component, but excellent
Choosing uses.The transformation of crystal being added to accelerated oxidation aluminium of mineralizer, and reduce pore.Present invention preferably uses fluoride
Mineralizer, more preferably inorganic fluoride, including hydrogen fluoride, ammonium fluoride, aluminum fluoride, magnesium fluoride, ice crystal etc., are preferably selected from
One or more of hydrogen fluoride, aluminum fluoride, ammonium fluoride, magnesium fluoride and ice crystal, particularly preferably ammonium fluoride.To the present invention
Speech, based on the gross weight of all solids component of the mixture of preparation in step a), the addition of mineralizer is usually 0.01-
3.0 weight %, preferably 0.1-2.5 weight %, particularly preferred 0.5-2.0 weight %.
In the support preparation method of the present invention, as component v) flux be non-have to use for component, but excellent
Choosing uses.Being added to of flux makes carrier have good intensity under low sintering temperature.The example of flux includes
Magnesium compound, is selected from one or more of magnesia, magnesium sulfate, magnesium nitrate and magnesium carbonate.For the purpose of the present invention, it is based on
The gross weight of all solids component of mixture of preparation in step a), the addition of flux is usually 0.01-3.0 weight %,
Preferably 0.1-2.5 weight %, particularly preferred 0.3-2.0 weight %.
In the support preparation method of the present invention, as component vi) shaping assistant be non-have to use for component, but
Preferably use.Being added to of shaping assistant is easy to be molded, for example, be easy to extrusion molding.As shaping assistant, can select
Vaseline, graphite, atoleine, vegetable oil or its mixture etc..
In addition it is also necessary to use binding agent in the support preparation method of the present invention, i.e. component vii).Add bonding agent, it and
Vacation one water aluminum oxide in mixture generates Alumina gel, and each component is bonded together, become can extrusion molding paste.Institute
Bonding agent includes acid, such as nitric acid, formic acid, acetic acid, propionic acid and/or hydrochloric acid etc., preferably nitric acid, acetic acid or its mixture.Or
Person can partly or entirely replace a sour and false water aluminum oxide with Alumina gel.When being used acid as bonding agent, most preferably
Aqueous solution of nitric acid.The consumption of binding agent is conventional, as long as can be bonded together each component.Typically, binding agent
With, if use if, total consumption of water is 10-40 weight %, and preferably 15-35 weight %, based on component i) to vi) gross weight
Amount.
After each component mixing in step a), generally yield paste.Gained paste is molded, is preferably extruded into
Type, obtains formed body, i.e. carrier blank.This formed body can be dried to below aqueous 10 weight %, and baking temperature is 60-200 DEG C,
Drying time controls in 0.1-24 hour according to moisture.The shape of gained formed body can be annular, spherical, cylindricality or many
Hole post shape, or other shapes.
The generally roasting at 1200-1600 DEG C, preferred 1200-1500 DEG C of dried formed body, roasting time is usually
2-8 hour.Aluminum oxide is made substantially to be completely converted into α-a1 by roasting2o3, such as more than 90% is converted into α-a12o3.Thus
To semi-finished product alpha-alumina supports.
In the present invention, preferably described cobalt compound solution is the aqueous solution or the alcoholic solution of cobalt compound, preferably cobalt nitrate
The aqueous solution or alcoholic solution.
After obtaining alpha-alumina supports, used cobalt compound solution impregnation, the cobalt in solution is in subsequent roasting
Cobalt oxide can be converted in burning.It will therefore be appreciated that any suitable cobalt compound can use, if it with
Form or resolve into cobalt oxide in high-temperature calcination process afterwards and do not leave residue or the residue that stays do not disturb by
The performance of the catalyst that resulting vehicle is made.
Form volatile products when therefore, containing impregnated in roasting alpha-alumina supports and leave the cobalt of cobalt oxide
The aqueous solution of complex compound or alcoholic solution are suitable.Herein, for preparing the alcohol of cobalt compound alcoholic solution, can be first
The small molecule alcohols such as alcohol, ethanol, propyl alcohol, ethylene glycol, preferred alcohol.
In the step using the solution impregnation of cobalt compound, for ensureing all even abundant of semi-finished product alpha-alumina supports
Load, carrier preferably vacuumizes in advance.And, the consumption of the solution of cobalt compound generally should be at least equal to alpha-alumina supports
Total pore volume, preferably excessively.This dipping is by being added to the solution of cobalt compound or colloidal sol in semi-finished product alpha-alumina supports
Carry out.It is advantageous that carrier is stood a period of time, such as 5-120 minute after charging finishes.In the solution with cobalt compound
After dipping, impregnated alpha-alumina supports are dried, this is generally carried out in 60-200 DEG C, the time is usually 1-48 hour,
Roasting afterwards.
Although the compound of the cobalts such as document report cobalt nitrate just can be analyzed to cobalt oxide more than 300 DEG C, in order that cobalt
Have higher combination with carrier surface, carrier containing cobalt should be processed through 800 DEG C of high temperature above before immersion silver, with ensure cobalt with
Stable cobalt compound form is present in carrier surface.Therefore, support preparation method step 2 of the present invention) in roasting generally exist
800-1200 DEG C, carry out at preferred 900-1100 DEG C.Roasting at such high temperatures, generation cobalt compound or cobalt are come to the surface with aluminium
Compound, these cobalt compounds are located at the channel surfaces of alpha-alumina supports.
Support according to the present invention preparation method, is obtained a kind of surface-modified alpha-alumina supports, the hole of this carrier
Compound containing cobalt in road.This alumina support can be in the common form in this area, for example annular, spherical, cylindricality or many
Hole post shape, preferably external diameter are 6-9mm, and hole diameter is the cellular cylindrical particle of seven apertures in the human head of 1-2mm, or external diameter is 6-9mm, interior
Footpath is the circular particle of single hole of 2-6mm.
Therefore, according to a further aspect in the invention, the present invention also provides a kind of ethylene epoxidizing to produce oxirane silver
The alumina support of catalyst, on the channel surfaces of this carrier, deposition has and is calculated as 0.02-0.4 weight % with cobalt element, preferably
The cobalt compound of 0.04-0.2 weight %.The specific surface area that the alpha-alumina supports that the present invention obtains have is not higher than 2.0m2/ g,
It is preferably 0.5-2.0m2/ g, and total pore volume is 0.3-0.7ml/g, preferably 0.4-0.7ml/g.
The present invention also provides a kind of ethylene epoxidizing to produce oxirane silver catalyst, comprise in described silver catalyst as
Go up described alpha-alumina supports and be deposited on the silver in this alpha-alumina supports.And silver element in preferably described silver catalyst
Content is 10-35 weight %, more preferably 10-30 weight %.
In the present invention, the preparation method of silver catalyst is, for example: first with the silver compound containing q.s, organic amine, optional
The solution impregnation of the collaborative auxiliary agent of alkali metal promoter, optional base earth metal promoter and optional rhenium auxiliary agent and optional rhenium this
Bright alpha-alumina supports；Leaching maceration extract；With in air or inert gas, resulting vehicle is activated, make described silver
Catalyst.
Specific embodiment
The specific surface area of carrier adopts nitrogen physisorption bet method to measure.Pore volume is measured using pressure mercury method.
The mensure of catalyst performance: the various silver catalysts of the present invention are (hereinafter referred to as " micro- with laboratory microreactor
Instead ") evaluate initial performance and stability.The reactor that micro anti-evaluation device uses is the stainless steel reaction pipe of internal diameter 4mm, reaction
Pipe is placed in heating mantle.Catalyst packing volume 1ml(catalyst particle size 12-18 mesh), inert filler is arranged at bottom, makes catalyst bed
Layer is located at the flat-temperature zone of heating mantle.(actual is anti-as follows for the catalysis activity of present invention employing and selective standard appreciation condition
Condition is answered to see each embodiment explanation): reacting gas composition, ethene (c2h4) it is 30.0 ± 1.5mol%, oxygen (o2) for 7.1 ±
0.3mol%, carbon dioxide (co2) it is ＜ 4.0mol%, cause steady gas (n2) it is surplus；Inhibitor dichloroethanes is 0.02-3ppmv,
Reaction pressure is 1.8mpa, and air speed is 7000h-1, reactor outlet eo concentration is 2.5mol%.
Under certain operation space velocities, when stable reaction is got off, and after reaching above-mentioned reaction condition, METHOD FOR CONTINUOUS DETERMINATION is reacted
Device entrance and exit gas forms.Measurement result calculates selectively (s) after carrying out volume contraction correction as follows:
Wherein δ eo is that reactor entry and exit ethylene oxide concentration is poor, δ co2It is reactor outlet and entrance carbon dioxide
Concentration difference, takes the experimental result as the same day for the average of more than ten groups experimental datas.
Comparative example 1
By 50-500 purpose three water Alpha-alumina 485g, granularity be less than 200 mesh vacation one water aluminum oxide 120g, 10.0g fluorine
Change ammonium and 9.0g magnesium nitrate is placed in blender and mixes, then proceed to kneader, add the aqueous solution of nitric acid of 18wt%
136g, be kneaded into can extrusion molding paste, extrusion molding be external diameter 8.3mm, internal diameter 2.7mm, long 7.0-8.0mm draw west
Ring.This Raschig ring shape thing is dried 12 hours in 90 DEG C, in high temperature jar kiln, is warmed up to 1300- in 40 hours
1400 DEG C, constant temperature 3h afterwards, obtain white alpha-alumina supports a, its physical data is shown in Table 1.
Embodiment 1
The preparation of carrier: weigh 0.7352g cabaltous nitrate hexahydrate, add suitable quantity of water, obtain the solution of cobalt content 0.20%.
40.2g carrier a is taken to be placed in the glass container of vacuum-pumping, being evacuated to vacuum is 700mmhg, adds obtained above containing
Cobalt liquor, submergence carrier, drain redundant solution after dipping 40min, at 120 DEG C, 24h is dried.Afterwards, by such acquisition
The impregnation product being dried, in 1000 DEG C of roasting 3h, prepares the carrier b that cobalt content is 0.09wt%, the physical parameter of this carrier
It is shown in Table 1.
Embodiment 2
The preparation of carrier: with embodiment 1, but prepare the solution 100g of cobalt content 0.30% with cobalt nitrate for cobalt source, soaked with it
Stain 51g carrier a.After leaching removes redundant solution, 24h is dried at 120 DEG C, afterwards, the dipping of such drying obtaining is produced
Thing, in 1000 DEG C of roasting 4h, prepares the carrier c that cobalt content is 0.14wt%, and the physical parameter of this carrier see table 1.
Embodiment 3
The preparation of carrier: with embodiment 1, prepare the solution 100g of cobalt content 0.80% with cobalt nitrate for cobalt source, impregnated with it
51g carrier a.After leaching removes redundant solution, 24h is dried at 120 DEG C, afterwards, by the impregnation product of such drying obtaining
In 1000 DEG C of roasting 4h, prepare the carrier d that cobalt content is 0.38wt%, the physical parameter of this carrier see table 1.
Comparative example 2
A kind of preparation of carrier: Raschig ring shape alpha-oxidation adopting outsourcing, being prepared with boehmite for primary raw material
Alumina supporter e(external diameter 8.0mm, internal diameter 2.5mm, long 7.0mm).Its specific surface area 1.25m2/ g, pore volume 0.48ml/g, x- ray is glimmering
Photoelement analysis is consisting of: aluminium 52.7wt%, oxygen 47.17wt%, iron 0.01wt%, silicon 0.10wt%, gallium 0.020wt%.
Embodiment 4
The preparation of carrier: the carrier e in comparative example 2 is impregnated using method same as Example 2, prepares cobalt content
Carrier f for 0.13wt%, this carrier specific surface area 1.1m after measured2/ g, pore volume 0.47ml/g.
Table 1
The preparation of corresponding catalyst in comparative example 1～2 and embodiment 1～4: take 70g silver nitrate to be dissolved in 75ml deionized water
In, take 32g ammonium oxalate to be dissolved in 260ml50 DEG C of deionized water.Mix two kinds of solution of gained with vigorous stirring, generate white
Color silver oxalate precipitate.Aging more than 30 minutes afterwards, filter, be washed with deionized and be precipitated to no nitrate ion.Final institute
Obtaining filter cake is silver oxalate paste, argentiferous 60 weight %, aqueous about 15 weight %.30g second is added in the glass flask with stirring
Diamines, 11g monoethanolamine and 56g deionized water, obtain mixed solution.Under stirring, the silver oxalate paste being obtained is slowly added into mixed
Close in liquid, temperature is maintained at 0-20 DEG C, so that silver oxalate is all dissolved, add 0.30g cesium sulfate and 0.20g barium acetate afterwards, then
Plus deionized water makes solution gross mass reach 200g, resulting solution is mixed, obtain argentiferous maceration extract, stand-by.Take carrier a
The each 20g of～f, is respectively placed in the container of vacuum-pumping, and being evacuated to vacuum is 700mmhg, is added thereto to above argentiferous
Maceration extract, submergence carrier, impregnate 30 minutes.Leaching afterwards removes unnecessary maceration extract, then heats in 270 DEG C of air stream
5 minutes, cooling, prepare comparative example silver catalyst a and e and embodiment silver catalyst b, c, d and f respectively.By above-mentioned preparation
The silver catalyst a-f obtaining carries out catalytic performance test under reaction condition mentioned above, and acquired results are shown in Table 2.
Table 2
From table 2, no matter being prepared through cobalt improved before using three water Alpha-aluminas or using boehmite
Alpha-alumina supports, through cobalt surface modification alpha-alumina supports preparation silver catalyst b, c, d, f urge with the silver without cobalt
Agent a, e is compared, and the stability of its catalyst is all substantially improved.Specifically, catalyst runs initial stage (the 3rd day) embodiment reaction
Activity and selectivity with comparative example in reactivity and selectively close, but through after a while (to the 21st day) operating
Afterwards, quickly, and the activity decrease of the silver catalyst in embodiment is slow for the activity decrease of the silver catalyst in comparative example, and it shows
Significantly superior different catalyst stability.In addition, knowable to the comparison with embodiment 4 for the comparative example 2, being prepared into using boehmite
To under the conditions of alpha-alumina supports, the reaction temperature change of corresponding silver catalyst is respectively 2.6 DEG C and 0.5 DEG C, differs 2.1 DEG C；
And accordingly knowable to the comparison of comparative example 1 and embodiment 2, the three water Alpha-aluminas using preferred embodiment in the present invention prepare
Under the conditions of alpha-alumina supports, the reaction temperature change of corresponding silver catalyst is respectively 3.0 DEG C and 0.2 DEG C, differs 2.8 DEG C；This
" preparing alpha-alumina supports with three water Alpha-aluminas " and " impregnating cobalt in alpha-alumina supports " this two steps are described
There is good collaborative facilitation effect.
Claims (19)
1. a kind of ethylene epoxidizing produces the preparation method of the alpha-alumina supports of oxirane silver catalyst, walks including following
Rapid:
1) molded and after roasting alpha-alumina supports be impregnated in cobalt compound solution, the α-oxygen after drying is impregnated
Change alumina supporter；
2) by step 1) resulting vehicle roasting at least 1 hour at 800～1200 DEG C, described alpha-alumina supports finished product is obtained；
The cobalt compound being calculated as 0.02-0.4 weight % with cobalt element is contained in described alpha-alumina supports.
2. method according to claim 1 is it is characterised in that in step 2) in, by step 1) resulting vehicle 900～
Roasting 3～24h at 1100 DEG C, is obtained described alpha-alumina supports finished product.
3. method prepares step it is characterised in that first passing through the following methods comprising the steps of according to claim 1
The alpha-alumina supports after described molded and roasting in rapid 1),
A) form the mixture comprising following component:
I) three water Alpha-aluminas, transition aluminas or its mixture,
Ii) false water an aluminum oxide,
Iii) optionally, carbonaceous material can be burnt out,
Iv) optionally, mineralizer,
V) optionally, flux,
Vi) optionally, shaping assistant；With
Vii) binding agent；
B) step a) gained mixture is molded, drying and roasting obtain described alpha-alumina supports.
4. method according to claim 3 it is characterised in that: the described carbonaceous material that burns out is selected from petroleum coke, graphite
One or more of with vaseline, described mineralizer is in hydrogen fluoride, aluminum fluoride, ammonium fluoride, magnesium fluoride and ice crystal
One or more, described flux is selected from one or more of magnesia, magnesium sulfate, magnesium nitrate and magnesium carbonate, described
Shaping assistant is vaseline, graphite, atoleine, vegetable oil or its mixture, and described binding agent is acid.
5. method according to claim 4 is it is characterised in that described binding agent is nitric acid, acetic acid or its mixture.
6. method according to claim 3 it is characterised in that: described three water Alpha-aluminas be step a) gained mixture in
5-90 weight % of all solids component, a described false water aluminum oxide is the 5- of all solids component in step a) gained mixture
50 weight %.
7. method according to claim 6 is it is characterised in that described three water Alpha-aluminas are in step a) gained mixture
50-80 weight % of all solids component, a described false water aluminum oxide is all solids component in step a) gained mixture
15-35 weight %.
8. method according to claim 3 it is characterised in that: described mineralizer be step a) gained mixture in all solid
0.01-3.0 weight % of body component, described flux is the 0.01-3.0 weight of all solids component in step a) gained mixture
Amount %.
9. method according to claim 8 is it is characterised in that described mineralizer is all solid in step a) gained mixture
0.5-2.0 weight % of body component, described flux is the 0.3-2.0 weight of all solids component in step a) gained mixture
Amount %.
10. method according to claim 3 it is characterised in that: partly or entirely replace a described false water using Alumina gel
Aluminum oxide and described binding agent.
11. methods according to any one in claim 1～10 it is characterised in that: described cobalt compound solution is
The aqueous solution of cobalt compound or alcoholic solution.
12. methods according to claim 11 are it is characterised in that described cobalt compound is the aqueous solution or the alcohol of cobalt nitrate
Solution.
A kind of 13. alpha-alumina supports being prepared according to any one methods described in claim 1～10, its feature exists
In containing the cobalt compound being calculated as 0.02-0.4 weight % with cobalt element in described alpha-alumina supports.
14. alpha-alumina supports according to claim 13 are it is characterised in that contain with cobalt in described alpha-alumina supports
Element is calculated as the cobalt compound of 0.04-0.2 weight %.
15. alpha-alumina supports according to claim 13 or 14 are not it is characterised in that the specific surface area of described carrier is high
In 2.0m2/ g, and total pore volume is 0.3-0.7ml/g.
16. alpha-alumina supports according to claim 15 are it is characterised in that the specific surface area of described carrier is 0.5-
2.0m2/ g, and total pore volume is 0.4-0.7ml/g.
A kind of 17. ethylene epoxidizings produce oxirane silver catalyst, comprise such as claim 1～12 in described silver catalyst
The alpha-alumina supports that middle any one method is obtained or the Alpha-alumina as described in any one in claim 13～16 carry
Body, and it is deposited on the silver in this alpha-alumina supports.
18. silver catalysts according to claim 17 it is characterised in that in described silver catalyst silver dollar cellulose content be 10-
35 weight %.
19. silver catalysts according to claim 18 it is characterised in that in described silver catalyst silver dollar cellulose content be 10-
30 weight %.
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| CN105294157B (en) * | 2015-11-06 | 2018-02-16 | 中国第一汽车股份有限公司 | The particulate filter carrier material preparation method of mixture of passive regeneration |
| CN114425336A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Silver catalyst for producing ethylene oxide by ethylene oxidation and preparation method and application thereof |
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