CN104069894B - Method of preparing alpha-alumina carrier used for silver catalyst, the carrier and the catalyst - Google Patents
Method of preparing alpha-alumina carrier used for silver catalyst, the carrier and the catalyst Download PDFInfo
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Abstract
A method of preparing an alpha-alumina carrier used for a silver catalyst is disclosed. The preparing method includes: a step (I) of preparing a mixture comprising hydrated alumina, pseudo aluminum monohydrate, a fluoride mineralizer and a chromium compound, and mixing the mixture with an acid solution; and a step (II) of kneading the material obtained in the step (I), extruding, shaping, drying and calcinating to obtain the alpha-alumina carrier, wherein, based on the total weight of the mixture, the content of the hydrated alumina is 4.5-90 wt%, the content of the pseudo aluminum monohydrate is 5-95 wt%, the content of the fluoride mineralizer is 0.01-3.0 wt%, the content of the chromium compound is 0.001-2.000 wt%, and alumina sol can be adopted to replace a part of or all of the acid solution and the pseudo aluminum monohydrate. The silver catalyst prepared from the chromium-containing alpha-alumina carrier is used for ethylene oxide production process by ethylene oxidization, can significantly improve the reaction selectivity, and has a wide application prospect.
Description
Technical field
The present invention relates to a kind of method preparing the carrier for silver catalyst, it is more particularly related to a kind of
The method preparing the alumina support producing oxirane silver catalyst for oxidation of ethylene.The invention still further relates to above-mentioned preparation
Alumina support and the silver catalyst being obtained using above-mentioned carrier that method obtains.
Background technology
Silver catalyst effect under oxidation of ethylene mainly generate oxirane, simultaneously occur side reaction generate carbon dioxide and
Water, wherein activity, selectivity and stability are the main performance index of silver catalyst.Activity refers to that process for ethylene oxide production reaches
To required reaction temperature during certain reaction load；Reaction temperature is lower, and the activity of catalyst is higher.Selectivity refers in reaction
Ethylene changes into the molal quantity of oxirane and the ratio of the overall reaction molal quantity of ethylene.Stability is then expressed as activity and selectivity
Fall off rate, the stability of fall off rate more small catalyst is better.Use during oxidation of ethylene produces oxirane
High activity, high selectivity and the silver catalyst having good stability can greatly improve economic benefit, therefore manufacture high activity, Gao Xuan
The silver catalyst of selecting property and good stability is the Main way of silver catalyst research.The performance of silver catalyst is removed and catalyst
Composition and preparation method have outside important relationship, and the performance of the carrier also using with catalyst and its preparation have important relationship.
In prior art, the preparation method of silver catalyst includes porous carrier（As aluminium oxide）Preparation and supported active group
Divide and auxiliary agent this two processes on described carrier.
Add other components in alumina support to improve carrier is important grinding to improve the performance of silver catalyst
Study carefully direction, including interpolation alkaline earth oxide or other salt compounds.EP0150238（US4428863）High-purity,
Using a small amount of barium aluminate or barium silicate binding agent in the manufacture process of low surface oxidation alumina supporter, claim to improve the anti-of carrier
Broken intensity and wear resistance, the specific surface of prepared carrier is less than 0.3m2/ g, the activity and selectivity of prepared catalyst is all
Than relatively low.US5384302 claims by pretreatment α-Al2O3Can improve to reduce Na, K, Ca, Al ion concentration in carrier
The crushing strength of carrier and abrasion resistance properties.US5739075 by being previously deposited the rare earth of amount of auxiliary in alumina carrier surface
Metal and the slaine of another kind of amount of auxiliary（Alkaline-earth metal or VIII transition metal）, then carry out calcination processing,
The carrier handled well at last makes silver catalyst, and evaluation result shows, this selectivity of catalyst fall off rate is pre- less than not doing
The catalyst sample of deposition processes.
Fluoride, as a kind of mineralizer, has a wide range of applications in the preparation process of alumina support.
CN1034678A by granularity, three water Alpha-aluminas of ratio appropriate mix and a false water Alpha-alumina and carbonaceous material, flux
Agent, fluoride, binding agent and water mixing, kneaded and formed, alpha-alumina supports are made in drying roasting.The specific surface of this carrier is
0.2～2m2/ g, the hole that pore radius is more than 30 μm accounts for total pore volume below 25%；The impregnated silver compound of this carrier and promoter are simultaneously
After activation is dried, for oxidation of ethylene epoxy ethane, selectivity up to 83～84%.CN101007287A is by certain particle size
Three water Alpha-aluminas, a false water Alpha-alumina, a certain amount of can after-flame carbonaceous material, flux, fluoride, optional heavy alkaline earth
The compound phase mixing of metal, adds binding agent and water after mix homogeneously, mediates uniformly, extrusion molding, and drying roasting is made
Alpha-alumina supports；The specific surface of described carrier is 0.2～2.0m2/ g, pore volume is 0.35～0.85ml/g, water absorption rate >=30%,
Crushing strength 30～120N/ grain.This carrier argent-amine complex, alkali metal compound, the solution impregnation of alkaline earth metal compound,
Silver catalyst is obtained after activation is dried and is used for ethylene epoxidizing epoxy ethane.CN1634652A, in carrier preparation, does not use
Pore creating material, but directly three water Alpha-aluminas are mutually mixed with a false water aluminium oxide, flux, fluoride with certain proportion, mix
Close and uniformly add binding agent and water afterwards, mediate uniformly, extrusion molding, drying roasting, make alpha-alumina supports.This invention system
The carrier specific surface becoming is 0.2～2.0m2/ g, pore volume is 0.35～0.85ml/g, water absorption rate >=30%, crushing strength 20～
90N/ grain.The solution impregnation of this carrier argent-amine complex, alkali metal compound and alkaline earth metal compound, makes after activation is dried
Obtain silver catalyst and be used for ethylene epoxidizing epoxy ethane.
Although above-mentioned patent documentation is respectively adopted interpolation alkaline earth metal compound or fluoride etc. in alumina raw material
Method, to improve alumina support, brings different degrees of improvement to the activity and selectivity of catalyst, but with middle high selection
Property silver catalyst heavy industrialization application, the requirement to alumina support performance for this area also improve constantly.
Content of the invention
In view of the situation of above-mentioned prior art, the present inventor is carried out in silver catalyst and its alumina support field
Deep experimental study, it is found that preparing alumina support by adding compound containing Cr in support material, use
Silver catalyst made by this carrier, its selectivity is improved significantly.
According to an aspect of the present invention, provide a kind of method preparing silver catalyst alpha-alumina supports, including such as
Lower step：
Step I, preparation comprises hydrated alumina, the mixture of Alumina gel, fluoride-mineralization agent and chromium compound, wherein base
In the gross weight of mixture, the content of hydrated alumina is 4.5～90wt%, and the content of Alumina gel is 5～95wt%, fluoride ore deposit
The content of agent is 0.01～3.0wt%, and the content of chromium compound is 0.001～2.000wt%；Then mixture is mixed with acid solution
Close；A wherein false water aluminium oxide and acid solution can completely or partially be replaced with Alumina gel.
Step II, after the material obtaining in step I kneading, extrusion molding, drying and roasting obtain described alpha-oxidation
Alumina supporter.
In the above-mentioned methods, the gross weight based on mixture, the content of hydrated alumina is 23～80wt%, a false water oxygen
The content changing aluminum is 18～75wt%, and the content of fluoride-mineralization agent is 0.1～2.5wt%, the content of chromium compound is 0.005～
1.500wt%.It is preferably based on the gross weight of mixture, the content of hydrated alumina is 68～80wt%, and the content of Alumina gel is
18～30wt%, the content of fluoride-mineralization agent is 1.2～2.0wt%, and the content of chromium compound is 0.01～1.00wt%.
In the above-mentioned methods, the addition of described fluoride-mineralization thing can be with the transformation of crystal of accelerated oxidation aluminum.
In the above-mentioned methods, described hydrated alumina is selected from three water Alpha-aluminas and β-gibbsite；Described fluoride
Mineralizer is selected from fluohydric acid gas, aluminium fluoride, ammonium fluoride, Afluon (Asta) and cryolite, preferred fluorinated ammonium；Described chromium compound is selected from chromium
Oxide, chromate, halogenide, hydroxide, nitrate and bichromate, are preferably selected from chromium oxide, chromic nitrate and dichromic acid
Potassium.
In the above-mentioned methods, described acid solution can form Alumina gel with a false water oxygen reactive aluminum, thus as binding agent
Use.In a specific embodiment, when a false water aluminium oxide and acid solution can all be replaced with Alumina gel, described comprise water
Close Alumina gel in aluminium oxide, Alumina gel, fluoride-mineralization agent and chromium compound and the mixture of weight alkaline earth metal compound
Content accounts for 18～75wt%.
In the above-mentioned methods, the consumption of described acid solution is 5～50wt% based on said mixture gross weight.Have at one
In the embodiment of body, described acid solution is aqueous solution of nitric acid, and in described aqueous solution of nitric acid, nitric acid and the volume ratio of water are 1:1.25～
10, preferably 1:2～4.
In a specific embodiment of said method, in described mixture, comprise weight alkaline earth metal compound, described heavy
Alkaline earth metal compound is selected from oxide, sulfate, acetate, nitrate and the oxalates of strontium and barium, be preferably selected from Barium monoxide,
Barium sulfate, barium nitrate and brium carbonate.Based on the gross weight of mixture, the content of described heavy alkaline earth metal compound is 0.001～
2.0wt%, preferably 0.001～1.0wt%, most preferably 0.1～0.5wt%.
In the above-mentioned methods, the sintering temperature in described step II is 800～1800 DEG C, preferably 1100～1500 DEG C.Logical
Crossing roasting makes aluminium oxide substantially be completely converted into α-A12O3, such as more than 90% is converted into α-A12O3, obtain α-A12O3Carrier.
According to a further aspect in the invention, there is provided a kind of alpha-alumina supports of utilization said method preparation, chromaking is closed
The amount of thing is calculated as 0.001～3.000wt% of vehicle weight with chromium, and the amount of weight alkaline earth metal compound is calculated as carrying with alkaline-earth metal
0～3.0wt% of body weight.
In above-mentioned carrier, the specific surface area of described carrier is 0.2～3.0m2/ g, water absorption rate is not less than 30%.
According to a further aspect in the invention, one kind is provided to produce oxirane silver catalyst, described silver by oxidation of ethylene
Catalyst is in above-mentioned α-Al2O3On carrier, dipping includes the auxiliary agent of silver compound and obtains.Described auxiliary agent also can comprise otherization
Compound, such as alkali metal promoter, rhenium auxiliary agent.Described silver catalyst can be prepared by conventional methods.
The silver catalyst of the alpha-alumina supports preparation containing chromium being provided according to the present invention, prepares ring for ethylene epoxidizing
Oxidative ethane, can significantly improve the selectivity of reaction, can obviously reduce the discharge of carbon dioxide by-product, improve ethylene raw
Utilization rate, has the prospects for commercial application of broadness.
Specific embodiment
The present invention is described further with reference to following embodiments, but the scope of the present invention is not limited to these embodiments.
The mensure of catalyst performance：
The various silver catalyst laboratory microreactor evaluating apparatus of the present invention test its activity and selectivity.Miniature
Used in reactor evaluations device, reactor is the stainless steel reaction pipe of internal diameter 4mm, and reaction tube is placed in heating mantle.Catalyst
Admission space be 1ml, there is inert filler bottom, makes beds be located at the flat-temperature zone of heating mantle.
The selective condition determination such as table 1 that the present invention adopts：
The reaction assay condition of table 1 catalyst
After stablizing and reach above-mentioned reaction condition, METHOD FOR CONTINUOUS DETERMINATION reactor inlet and exit gas form.Measurement result
Selectivity is calculated as follows after carrying out volume contraction correction：
Selectivity
Wherein Δ EO is reactor outlet gas and inlet gas ethylene oxide concentration difference, Δ CO2Reactor outlet gas with
In inlet gas, gas concentration lwevel is poor, takes the result of the test as the same day for the average of more than 10 groups test datas.
Embodiment 1
By 7990g β-gibbsite, 1640g vacation one water A12O3Put into mix homogeneously in blender；By 160g ammonium fluoride
With 20g potassium dichromate in 2.6 liters of dilute nitric acid solution（Nitric acid：Water=1：3, volume ratio）In be completely dissolved after pour in kneader,
Be kneaded into can extrusion molding paste.Paste placed in banded extruder, extrusion molding is external diameter 8.0mm, the post of long 6.0mm
Shape thing, dries more than 2 hours so as to free water content is reduced to below 10wt% at 80～120 DEG C.By dried column
Thing is put in natural gas kiln, is increased to 1350 DEG C through 18 hours from room temperature, then constant temperature 5 hours, obtains α-A12O3Carrier, its
Related physical performance data is shown in Table 2.
Embodiment 2
With embodiment 1, difference is, the amount of the potassium dichromate of addition is 40g, the α-A1 obtaining2O3The correlation of carrier
Physical performance data is shown in Table 2.
Embodiment 3
With embodiment 1, difference is, by 7900g tri- water Alpha-alumina, 1730g vacation one water A12O3With 20g barium sulfate
Put into mix homogeneously in blender；Add the dilute nitric acid solution of 160g ammonium fluoride and 54.5g nine water chromic nitrate and 2.0 liters；Described
Column was increased to 1340 DEG C through 18 hours from room temperature, then constant temperature 4 hours, obtained α-A12O3Carrier, its related physical performance
Data is shown in Table 2.
The physical data of table 2 carrier
| Bearer number | Intensity（N/ grain） | Water absorption rate（%） | Specific surface（m2/g） |
| Embodiment 1 | 92 | 57.57 | 1.585 |
| Embodiment 2 | 100 | 57.95 | 1.66 |
| Embodiment 3 | 58 | 48.82 | 0.893 |
From table 2 it can be seen that α-the A1 being provided according to the present invention2O3Carrier, its have higher mechanical strength with suitable
Specific surface area, the commercial Application that can preferably meet EO silver catalyst requires.
Comparative example 1
With embodiment 1, difference is not add potassium dichromate.
Catalyst preparation
Add 48.2g ethylenediamine, 16.3g ethanolamine and 115.1g deionized water in the glass beaker with stirring, mixed
Close liquid；Continuously stirred lower 108.3g silver oxalate is slowly added in mixed liquor, temperature is maintained at less than 40 DEG C, makes silver oxalate whole
Dissolving；Then add 4.77ml cesium nitrate aqueous solution successively（Concentration is 0.0503g/ml, in terms of Cs atom weight）, the high rhenium of 7.41ml
Sour aqueous ammonium（Concentration is 0.0162g/ml, in terms of rhenium atom weight）, it is stand-by that mix homogeneously makes dipping solution.
Take 20g to be derived from above-described embodiment 1～3 and the carrier of comparative example 1 preparation respectively, put it into the glass of energy evacuation
In container；It is evacuated to below 10mmHg, pours above-mentioned dipping solution into, be totally submerged carrier, keep about 15 minutes, then leaching
Remove unnecessary solution.Finally impregnated support samples are placed in 260 DEG C of air stream and heat 3 minutes, cooling, obtain
Silver catalyst.
The corresponding silver catalyst that carrier in embodiment 1～3 and comparative example 1 is obtained is existed using microreactor evaluating apparatus
The performance of catalyst sample is measured, the data result that reaction starts latter 10th day is shown in Table 3 under the conditions of previous process.
The performance measurement result of table 3 catalyst
| Catalyst is numbered | Selectivity % |
| Comparative example 1 | 82.35 |
| Embodiment 1 | 83.14 |
| Embodiment 2 | 83.55 |
| Embodiment 3 | 83.67 |
As seen from Table 3, compared with the comparative example 1 of silver catalyst obtained by the carrier being not added with Cr compound, according to this
Bright, prepare silver catalyst obtained by the alumina support containing Cr under the same conditions and be respectively provided with higher selectivity.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute any to the present invention
Limit.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive
With explanatory vocabulary, rather than limited vocabulary.Within the scope of the claims the present invention can be made by regulation
Modification, and in without departing substantially from scope and spirit of the present invention, the present invention is revised.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, this
Bright can be extended to other all methods and applications with identical function.
Claims (19)
1. a kind of method preparing silver catalyst alpha-alumina supports, comprises the steps：
Step I, preparation comprises hydrated alumina, the mixture of a false water aluminium oxide, fluoride-mineralization agent and chromium compound, wherein
Based on the gross weight of mixture, the content of hydrated alumina is 4.5～90wt%, the content of a false water aluminium oxide is 5～
95wt%, the content of fluoride-mineralization agent is 0.01～3.0wt%, and the content of chromium compound is 0.001～2.000wt%；So
Afterwards mixture is mixed with acid solution；A wherein false water aluminium oxide and acid solution can completely or partially be replaced with Alumina gel；
Step II, after the material obtaining in step I kneading, extrusion molding, drying and roasting obtain described Alpha-alumina and carry
Body,
Described hydrated alumina is selected from β-gibbsite.
2. method according to claim 1 is it is characterised in that gross weight based on mixture, the content of hydrated alumina
For 23～80wt%, the content of a false water aluminium oxide is 18～75wt%, and the content of fluoride-mineralization agent is 0.1～2.5wt%,
The content of chromium compound is 0.005～1.500wt%.
3. method according to claim 2 is it is characterised in that gross weight based on mixture, the content of hydrated alumina
For 68～80wt%, the content of a false water aluminium oxide is 18～30wt%, and the content of fluoride-mineralization agent is 1.2～2.0wt%,
The content of chromium compound is 0.01～1.00wt%.
4. the method according to any one in claims 1 to 3 is it is characterised in that described fluoride-mineralization agent is selected from fluorine
Change hydrogen, aluminium fluoride, ammonium fluoride, Afluon (Asta) and cryolite；Described chromium compound is selected from the oxide of chromium, chromate, halogenide, hydrogen
Oxide, nitrate and bichromate.
5. method according to claim 4 is it is characterised in that described fluoride-mineralization agent is ammonium fluoride.
6. method according to claim 4 is it is characterised in that described chromium compound is selected from chromium oxide, chromic nitrate and weight chromium
Sour potassium.
7. the method according to any one in claims 1 to 3 is it is characterised in that the consumption of described acid solution accounts for described mixing
5～50wt% of compound gross weight.
8. the method according to any one in claims 1 to 3 it is characterised in that described acid solution be aqueous solution of nitric acid, institute
Stating nitric acid and the volume ratio of water in aqueous solution of nitric acid is 1:1.25～10.
9. the method according to any one in claims 1 to 3 it is characterised in that described acid solution be aqueous solution of nitric acid, institute
Stating nitric acid and the volume ratio of water in aqueous solution of nitric acid is 1:2～4.
10. the method according to any one in claims 1 to 3 is it is characterised in that comprise weight alkaline earth in described mixture
Metallic compound, described heavy alkaline earth metal compound is selected from oxide, sulfate, acetate, nitrate and the oxalic acid of strontium and barium
Salt.
11. methods according to claim 10 it is characterised in that comprise in described mixture weight alkaline earth metal compound,
Described heavy alkaline earth metal compound is selected from Barium monoxide, barium sulfate, barium nitrate and brium carbonate.
12. methods according to claim 10 are it is characterised in that gross weight based on described mixture, described heavy alkaline earth
The content of metallic compound is 0.001～2.0wt%.
13. methods according to claim 10 are it is characterised in that gross weight based on described mixture, described heavy alkaline earth
The content of metallic compound is 0.001～1.0wt%.
14. methods according to claim 10 are it is characterised in that gross weight based on described mixture, described heavy alkaline earth
The content of metallic compound is 0.1～0.5wt%.
15. methods according to any one in claims 1 to 3 are it is characterised in that sintering temperature in described step II
For 800～1800 DEG C.
16. methods according to any one in claims 1 to 3 are it is characterised in that sintering temperature in described step II
For 1100～1500 DEG C.
A kind of 17. alpha-alumina supports of methods according to claim 10 preparation are it is characterised in that the amount of chromium compound
It is calculated as 0.001～3.000wt% of vehicle weight with chromium, the amount of weight alkaline earth metal compound is calculated as vehicle weight with alkaline-earth metal
More than 0 to less than or equal to 3.0wt%.
18. alpha-alumina supports according to claim 17 are it is characterised in that the specific surface of described alpha-alumina supports is
0.2～3.0m2/ g, water absorption rate is not less than 30%.
19. one kind produce oxirane silver catalyst by oxidation of ethylene, and described silver catalyst is included in claim 1～16
α-the Al that any one methods described produces2O3α-Al described in carrier or claim 17 or 182O3Immersion silver on carrier and obtain
Arrive.
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| CN110354841A (en) * | 2018-03-26 | 2019-10-22 | 中国石油化工股份有限公司 | Silver catalyst alpha-alumina supports and preparation method thereof and ethylene epoxidizing silver catalyst and application |
| CN112125869B (en) * | 2019-06-25 | 2022-08-19 | 中国石油化工股份有限公司 | Method for preparing ethylene oxide by ethylene epoxidation |
| CN114426527B (en) * | 2020-10-15 | 2023-11-10 | 中国石油化工股份有限公司 | Silver catalyst carrier for ethylene oxide, preparation method and silver catalyst and application |
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| CN87107194A (en) * | 1986-10-31 | 1988-07-27 | 国际壳牌研究有限公司 | The catalytic production method of epoxyethane catalyst and oxyethane |
| CN1634652A (en) * | 2003-12-31 | 2005-07-06 | 中国石油化工股份有限公司北京燕山分公司研究院 | Silver catalyst carrier for epoxyethane production, preparation method and application thereof |
| CN101618313A (en) * | 2008-06-30 | 2010-01-06 | 中国石油化工股份有限公司 | Desulfurization adsorbent, preparation method and application thereof |
| CN102553589A (en) * | 2010-12-29 | 2012-07-11 | 中国石油化工股份有限公司 | Alumina support, preparation method of alumina support, silver catalyst prepared by alumina support, and use of silver catalyst |
| CN102688784A (en) * | 2011-03-21 | 2012-09-26 | 中国石油化工股份有限公司 | Alumina supporter for silver catalyst and silver catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8791280B2 (en) * | 2005-08-10 | 2014-07-29 | Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg | Process for preparation of catalyst carrier and its use in catalyst preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87107194A (en) * | 1986-10-31 | 1988-07-27 | 国际壳牌研究有限公司 | The catalytic production method of epoxyethane catalyst and oxyethane |
| CN1634652A (en) * | 2003-12-31 | 2005-07-06 | 中国石油化工股份有限公司北京燕山分公司研究院 | Silver catalyst carrier for epoxyethane production, preparation method and application thereof |
| CN101618313A (en) * | 2008-06-30 | 2010-01-06 | 中国石油化工股份有限公司 | Desulfurization adsorbent, preparation method and application thereof |
| CN102553589A (en) * | 2010-12-29 | 2012-07-11 | 中国石油化工股份有限公司 | Alumina support, preparation method of alumina support, silver catalyst prepared by alumina support, and use of silver catalyst |
| CN102688784A (en) * | 2011-03-21 | 2012-09-26 | 中国石油化工股份有限公司 | Alumina supporter for silver catalyst and silver catalyst |
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