CN104069894A - 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 of the carrier for the preparation of silver catalyst, more particularly, the present invention relates to a kind of method of using the alumina support of silver catalyst for the preparation of ethylene production oxirane.The invention still further relates to the alumina support that above-mentioned preparation method obtains and the silver catalyst that uses above-mentioned carrier to obtain.
Background technology
Under silver catalyst effect, ethylene mainly generates oxirane, side reaction occurs simultaneously and generate carbon dioxide and water, and wherein active, selective and stability is the main performance index of silver catalyst.Activity refers to reaction temperature required when process for ethylene oxide production reaches certain reaction load; Reaction temperature is lower, and the activity of catalyst is higher.Selectively refer to that ethene in reaction changes into the ratio of the molal quantity of oxirane and the overall reaction molal quantity of ethene.Stability is expressed as the fall off rate of activity and selectivity, and the fall off rate more stability of small catalyst is better.The silver catalyst that uses high activity, high selectivity and have good stability in the process of ethylene production oxirane can be increased economic efficiency greatly, and the silver catalyst of therefore manufacturing high activity, high selectivity and good stability is the main direction of silver catalyst research.The performance of silver catalyst has important relationship except the composition with catalyst and preparation method, the performance of the carrier also using with catalyst and be prepared with important relationship.
In prior art the preparation method of silver catalyst comprise the preparation of porous carrier (as aluminium oxide) and load active component and auxiliary agent to as described in this two processes on carrier.
In alumina support, adding other component improvement carrier is an important research direction to improve the performance of silver catalyst, comprising adding alkaline earth oxide or other salt compounds.EP0150238(US4428863) in the manufacture process of high-purity, low surface oxidation alumina supporter, use a small amount of barium aluminate or barium silicate binding agent, claim crushing strength and the wear resistance that can improve carrier, the specific surface of prepared carrier is less than 0.3m
2/ g, the activity and selectivity of prepared catalyst is all lower.US5384302 claims by pretreatment α-Al
2o
3reduce crushing strength and abrasion resistance properties that Na, K, Ca, Al ion concentration in carrier can improve carrier.US5739075 is by the alumina carrier surface rare earth metal of deposition aid amount and the slaine of another kind of amount of auxiliary (alkaline-earth metal or VIII group 4 transition metal) in advance, then carry out calcination processing, the carrier of handling well the most at last is made silver catalyst, evaluation result shows, the selective fall off rate of this catalyst is less than does not do the catalyst sample that pre-deposition is processed.
Fluoride, as a kind of mineralizer, has a wide range of applications in the preparation process of alumina support.CN1034678A is by three water Alpha-aluminas of granularity, ratio appropriate mix and a false water Alpha-alumina and carbonaceous material, flux, fluoride, binding agent and water mixing, and kneaded and formed, alpha-alumina supports is made in drying roasting.The specific surface of this carrier is 0.2～2m
2/ g, the hole that pore radius is greater than 30 μ m accounts for total pore volume below 25%; This carrier is after dipping silver compound and co-catalyst dry activation, for ethylene epoxy ethane, selectively up to 83～84%.CN101007287A by three water Alpha-aluminas of certain particle size, a false water Alpha-alumina, a certain amount of can after-flame carbonaceous material, the Compound Phase of flux, fluoride, optional heavy alkaline-earth metal mixes, after mixing, add binding agent and water, mediate evenly, extrusion modling, drying roasting, makes alpha-alumina supports; The specific surface of described carrier is 0.2～2.0m
2/ g, pore volume is 0.35～0.85ml/g, water absorption rate>=30%, crushing strength 30～120N/ grain.The solution impregnation of this argent-amine complex, alkali metal compound, alkaline earth metal compound for carrier, makes silver catalyst for ethylene epoxidizing epoxy ethane after dry activation.CN1634652A, in carrier preparation, is not used pore creating material, but directly three water Alpha-aluminas is mixed with a false water aluminium oxide, flux, fluoride mutually with certain proportion, after mixing, add binding agent and water, mediate evenly extrusion modling, drying roasting, makes alpha-alumina supports.The carrier specific surface that this invention is made is 0.2～2.0m
2/ g, pore volume is 0.35～0.85ml/g, water absorption rate>=30%, crushing strength 20～90N/ grain.The solution impregnation of this argent-amine complex, alkali metal compound and alkaline earth metal compound for carrier, makes silver catalyst for ethylene epoxidizing epoxy ethane after dry activation.
Although above-mentioned patent documentation adopts respectively methods such as adding alkaline earth metal compound or fluoride in alumina raw material to improve alumina support, the activity and selectivity of catalyst is brought to improvement in various degree, but along with the heavy industrialization application of middle high selectivity silver catalyst, this area is also improving constantly the requirement of alumina support performance.
Summary of the invention
Situation in view of above-mentioned prior art, the present inventor has carried out deep experimental study at silver catalyst and alumina support field thereof, found that by adding containing Cr compound and prepare alumina support in support material, use the made silver catalyst of this carrier, it is selectively improved significantly.
According to an aspect of the present invention, provide a kind of method of alpha-alumina supports for silver catalyst of preparing, comprise the steps:
Step I, the mixture that preparation comprises hydrated alumina, aluminium colloidal sol, fluoride-mineralization agent and chromium compound, the gross weight based on mixture wherein, the content of hydrated alumina is 4.5～90wt%, the content of aluminium colloidal sol 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%; Then mixture is mixed with acid solution; Wherein a false water aluminium oxide and acid solution can all or part ofly replace with aluminium colloidal sol.
Step II, by after the material kneading obtaining in step I, extrusion molding, drying and roasting obtain described alpha-alumina supports.
In said method, the gross weight based on mixture, the content of hydrated alumina is 23～80wt%, and the content of a false water aluminium oxide is 18～75wt%, and the content of fluoride-mineralization agent is 0.1～2.5wt%, and the content of chromium compound is 0.005～1.500wt%.Preferably, the gross weight based on mixture, the content of hydrated alumina is 68～80wt%, and the content of aluminium colloidal sol is 18～30wt%, and the content of fluoride-mineralization agent is 1.2～2.0wt%, and the content of chromium compound is 0.01～1.00wt%.
In said method, described fluoride-mineralization thing add can accelerated oxidation aluminium transformation of crystal.
In said method, described hydrated alumina is selected from three water Alpha-alumina and β-gibbsites; Described fluoride-mineralization agent is selected from hydrogen fluoride, aluminum fluoride, ammonium fluoride, magnesium fluoride and ice crystal, preferred fluorinated ammonium; Described chromium compound is selected from oxide, chromate, halide, hydroxide, nitrate and the bichromate of chromium, is preferably selected from chromium oxide, chromic nitrate and potassium bichromate.
In said method, described acid solution can be reacted with a false water aluminium oxide and be formed aluminium colloidal sol, thereby uses as binding agent.In a specific embodiment, when a false water aluminium oxide and acid solution can all replace with aluminium colloidal sol, described in comprise hydrated alumina, aluminium colloidal sol, fluoride-mineralization agent and chromium compound and heavy alkaline earth metal compound mixture in the content of aluminium colloidal sol account for 18～75wt%.
In said method, the consumption of described acid solution is 5～50wt% based on said mixture gross weight.In a specific embodiment, described acid solution is aqueous solution of nitric acid, and in described aqueous solution of nitric acid, the volume ratio of nitric acid and water is 1:1.25～10, preferably 1:2～4.
In a specific embodiment of said method, in described mixture, comprise heavy alkaline earth metal compound, described heavy alkaline earth metal compound is selected from oxide, sulfate, acetate, nitrate and the oxalates of strontium and barium, is preferably selected from barium monoxide, barium sulfate, barium nitrate and brium carbonate.Gross weight based on 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 said method, the sintering temperature in described step II is 800～1800 ℃, preferably 1100～1500 ℃.By roasting, make aluminium oxide substantially all be converted into α-A1
2o
3, for example, more than 90% be converted into α-A1
2o
3, obtain α-A1
2o
3carrier.
According to a further aspect in the invention, a kind of alpha-alumina supports of utilizing said method to prepare is provided, the amount of chromium compound is counted 0.001～3.000wt% of vehicle weight with chromium, the amount of heavy alkaline earth metal compound is counted 0～3.0wt% of vehicle weight with alkaline-earth metal.
In above-mentioned carrier, the specific area of described carrier is 0.2～3.0m
2/ g, water absorption rate is not less than 30%.
According to a further aspect in the invention, provide a kind of and produce oxirane silver catalyst by ethylene, described silver catalyst is at above-mentioned α-Al
2o
3on carrier, dipping comprises the auxiliary agent of silver compound and obtains.Described auxiliary agent also can comprise other compound, as alkali metal promoter, rhenium auxiliary agent.Can prepare by conventional methods described silver catalyst.
According to the silver catalyst of preparing containing the alpha-alumina supports of chromium provided by the invention, for ethylene epoxidizing, prepare oxirane, can significantly improve the selective of reaction, can obviously reduce the discharge of carbon dioxide by-product, the utilization rate that improves ethylene raw, has broad prospects for commercial application.
The specific embodiment
The present invention is described further in conjunction with following embodiment, but scope of the present invention is not limited to these embodiment.
The mensuration of catalyst performance:
Various silver catalyst of the present invention is tested its activity and selectivity with laboratory microreactor evaluating apparatus.The reactor using in microreactor evaluating apparatus is the stainless steel reaction pipe of internal diameter 4mm, and reaction tube is placed in heating jacket.The admission space of catalyst is 1ml, and inert filler is arranged at bottom, makes beds be positioned at the flat-temperature zone of heating jacket.
The optionally condition determination that the present invention adopts is as table 1:
The reaction assay condition of table 1 catalyst
When stablizing and reaching after above-mentioned reaction condition, METHOD FOR CONTINUOUS DETERMINATION reactor inlet and exit gas form.Measurement result carries out calculating as follows selectively after volume contraction correction:
Selectively
Wherein Δ EO is that in reactor outlet gas and inlet gas, ethylene oxide concentration is poor, Δ CO
2be that in reactor outlet gas and inlet gas, gas concentration lwevel is poor, get the result of the test of the average of 10 groups of above test datas as the same day.
Embodiment 1
By 7990g β-gibbsite, the false water A1 of 1640g
2o
3putting into blender mixes; After 160g ammonium fluoride and 20g potassium bichromate are dissolved completely in the dilute nitric acid solution (nitric acid: water=1:3, volume ratio) of 2.6 liters, pour in kneader, be kneaded into can extrusion molding paste.Paste is put into banded extruder, and extrusion molding is the column of external diameter 8.0mm, long 6.0mm, at 80～120 ℃, dries more than 2 hours, and its free water content is reduced to below 10wt%.Dried column is put into natural gas kiln, through 18 hours, from room temperature, be elevated to 1350 ℃, then constant temperature is 5 hours, obtains α-A1
2o
3carrier, its related physical performance data is in Table 2.
Embodiment 2
With embodiment 1, difference is, the amount of the potassium bichromate adding is 40g, the α-A1 obtaining
2o
3the related physical performance data of carrier is in Table 2.
Embodiment 3
With embodiment 1, difference is, by 7900g tri-water Alpha-aluminas, and the false water A1 of 1730g
2o
3putting into blender with 20g barium sulfate mixes; The dilute nitric acid solution that adds 160g ammonium fluoride and 54.5g nine water chromic nitrates and 2.0 liters; Described column was elevated to 1340 ℃ through 18 hours from room temperature, and then constant temperature is 4 hours, obtains α-A1
2o
3carrier, its related physical performance data is in Table 2.
The physical data of table 2 carrier
| Bearer number | Intensity (N/ grain) | Water absorption rate (%) | Specific surface (m 2/g） |
| Embodiment 1 | 92 | 57.57 | 1.585 |
| Embodiment 2 | 100 | 57.95 | 1.66 |
| Embodiment 3 | 58 | 48.82 | 0.893 |
As can be seen from Table 2, according to α-A1 provided by the invention
2o
3carrier, it has higher mechanical strength and suitable specific area, can meet preferably the commercial Application requirement of EO silver catalyst.
Comparative example 1
With embodiment 1, difference is not add potassium bichromate.
Catalyst preparation
In the glass beaker stirring at band, add 48.2g ethylenediamine, 16.3g monoethanolamine and 115.1g deionized water, obtain mixed liquor; Under continuing to stir, 108.3g silver oxalate is slowly added in mixed liquor, temperature remains on below 40 ℃, and silver oxalate is all dissolved; Then add successively the 4.77ml cesium nitrate aqueous solution (concentration is 0.0503g/ml, take caesium atomic wts), the 7.41ml ammonium perrhenate aqueous solution (concentration is 0.0162g/ml, with rhenium atom weighing scale), mix that to make dipping solution stand-by.
Get respectively 20g from the carrier of above-described embodiment 1～3 and comparative example 1 preparation, put it in the glass container that can vacuumize; Be evacuated to below 10mmHg, pour above-mentioned dipping solution into, submergence carrier, keeps approximately 15 minutes completely, and then unnecessary solution is removed in leaching.Finally impregnated support samples is placed in the air stream of 260 ℃ and heats 3 minutes, cooling, obtain silver catalyst.
The corresponding silver catalyst that carrier in embodiment 1～3 and comparative example 1 is obtained is used microreactor evaluating apparatus under aforementioned process conditions, to measure the performance of catalyst sample, and after reaction starts, the data result of the 10th day is in Table 3.
The performance measurement result of table 3 catalyst
| Catalyst numbering | Selective % |
| Comparative example 1 | 82.35 |
| Embodiment 1 | 83.14 |
| Embodiment 2 | 83.55 |
| Embodiment 3 | 83.67 |
As seen from Table 3, compare with the comparative example 1 of not adding the obtained silver catalyst of carrier of Cr compound, according to the present invention, preparation under the same conditions all has higher selective containing the obtained silver catalyst of alumina support of Cr.
It should be noted in the discussion above that above-described embodiment, only for explaining the present invention, does not form any limitation of the invention.By with reference to exemplary embodiments, invention has been described, but should be understood to word wherein used, be descriptive and explanatory vocabulary, rather than limited vocabulary.Can in the scope of the claims in the present invention, to the present invention, modify in accordance with regulations, and within not deviating from scope and spirit of the present invention, the present invention be revised.Although the present invention who wherein describes relates to specific method, material and embodiment, and does not mean that the present invention is limited to wherein disclosed particular case, on the contrary, the present invention can extend to other all methods and applications with identical function.
Claims (12)
1. prepare a method for alpha-alumina supports for silver catalyst, comprise the steps:
Step I, the mixture that preparation comprises hydrated alumina, a false water aluminium oxide, fluoride-mineralization agent and chromium compound, the gross weight based on mixture wherein, 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%; Then mixture is mixed with acid solution; Wherein a false water aluminium oxide and acid solution can all or part ofly replace with aluminium colloidal sol;
Step II, by after the material kneading obtaining in step I, extrusion molding, drying and roasting obtain described alpha-alumina supports.
2. method according to claim 1, is characterized in that, the gross weight based on mixture, the content of hydrated alumina is 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%, and the content of chromium compound is 0.005～1.500wt%.
3. method according to claim 2, is characterized in that, the gross weight based on mixture, the content of hydrated alumina is 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%, and the content of chromium compound is 0.01～1.00wt%.
4. according to the method described in any one in claim 1～3, it is characterized in that, described hydrated alumina is selected from three water Alpha-alumina and β-gibbsites; Described fluoride-mineralization agent is selected from hydrogen fluoride, aluminum fluoride, ammonium fluoride, magnesium fluoride and ice crystal, preferred fluorinated ammonium; Described chromium compound is selected from oxide, chromate, halide, hydroxide, nitrate and the bichromate of chromium, is preferably selected from chromium oxide, chromic nitrate and potassium bichromate.
5. according to the method described in any one in claim 1～4, it is characterized in that, the consumption of described acid solution accounts for 5～50wt% of described mixture total weight amount.
6. according to the method described in any one in claim 1～5, it is characterized in that, described acid solution is aqueous solution of nitric acid, and in described aqueous solution of nitric acid, the volume ratio of nitric acid and water is 1:1.25～10, preferably 1:2～4.
7. according to the method described in any one in claim 1～6, it is characterized in that, in described mixture, comprise heavy alkaline earth metal compound, described heavy alkaline earth metal compound is selected from oxide, sulfate, acetate, nitrate and the oxalates of strontium and barium, is preferably selected from barium monoxide, barium sulfate, barium nitrate and brium carbonate.
8. according to the method described in any one in claim 1～7, it is characterized in that, the gross weight based on described 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%.
9. according to the method described in any one in claim 1～8, it is characterized in that, the sintering temperature in described step II is 800～1800 ℃, preferably 1100～1500 ℃.
10. an alpha-alumina supports of preparing according to the method described in any one in claim 1～9, the amount of chromium compound is counted 0.001～3.000wt% of vehicle weight with chromium, the amount of heavy alkaline earth metal compound is counted 0～3.0wt% of vehicle weight with alkaline-earth metal.
11. alpha-alumina supports according to claim 10, is characterized in that, the specific surface of described alpha-alumina supports is 0.2～3.0m
2/ g, water absorption rate is not less than 30%.
By ethylene, produce oxirane silver catalyst for 12. 1 kinds, described silver catalyst is included in α-Al that in claim 1～9, described in any one, method is produced
2o
3α-Al described in carrier or claim 10 or 11
2o
3on carrier, flood silver and obtain.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112125869A (en) * | 2019-06-25 | 2020-12-25 | 中国石油化工股份有限公司 | Method for preparing ethylene oxide by ethylene epoxidation |
| CN114426527A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Silver catalyst carrier for ethylene oxide, preparation method thereof, silver catalyst and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN112125869A (en) * | 2019-06-25 | 2020-12-25 | 中国石油化工股份有限公司 | Method for preparing ethylene oxide by ethylene epoxidation |
| 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 |
| CN114426527A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Silver catalyst carrier for ethylene oxide, preparation method thereof, silver catalyst and application |
| 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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