CN104549573A - Method for preparing regenerated epoxidation catalyst - Google Patents
Method for preparing regenerated epoxidation catalyst Download PDFInfo
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- CN104549573A CN104549573A CN201410621451.7A CN201410621451A CN104549573A CN 104549573 A CN104549573 A CN 104549573A CN 201410621451 A CN201410621451 A CN 201410621451A CN 104549573 A CN104549573 A CN 104549573A
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- epoxidation catalyst
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Abstract
The invention discloses a method for preparing a regenerated epoxidation catalyst. The method comprises the following steps: providing a proper amount of waste epoxidation catalyst, and depositing additive silver with the quantity more than or equal to 1wt% on the waste epoxidation catalyst based on the weight of the waste epoxidation catalyst by virtue of a deposition precipitation method; before depositing the additive silver on the waste epoxidation catalyst, washing the waste epoxidation catalyst by contacting the waste epoxidation catalyst with water-containing solvents for a period of time, and reducing the washed waste epoxidation catalyst at 120-180 DEG C for 4-6 hours in the presence of hydrogen, wherein the solvents are methanol, ethanol, propanol, isopropanol, tetrahydrofuran, glycol, glycol dimethyl ether, diglyme, acetone and methyl ethyl ketone, and the proportion of the solvents to water is (1 to 15)-(2 to 1). The regenerated epoxidation catalyst regenerated by virtue of a regeneration process has relatively high selectivity, and the yield is basically same as that of a fresh catalyst, so that the use value of the waste catalyst is greatly increased.
Description
Technical field
The present invention relates to a kind of method preparing the epoxidation catalyst of regeneration.
Background technology
Oxirane and other alkylene oxide are important industrial chemicals, and it is as the raw material preparing such as ethylene glycol, propane diols, glycol ether, ethylene carbonate, monoethanolamine and washing agent and so on chemicals.A kind of method of producing alkylene oxide is by alkene epoxidation, that is makes olefin catalytic partial oxidation obtain alkylene oxide with oxygen.The silver catalyst of the catalyst producing oxirane for ethene and molecular oxygen normally on carrier.This kind of catalyst adopts alkali metal as co-catalyst usually.At United States Patent (USP) U.S3,962,136 (mandate on June 8th, 1976) and U.S4, mention the effective co-catalyst adopting a small amount of alkali metal potassium, rubidium, caesium as the silver catalyst on carrier in 010,115 (mandates on March 1st, 1977).United States Patent (USP) U.S4,766,105 (mandate on August 23rd, 1988) and U.S4,808,738 (mandates on February 28th, 1989) disclose the application of other co-catalyst, as the mixture of rhenium or rhenium and sulphur, molybdenum, tungsten or chromium.United States Patent (USP) U.S4,908,343 (mandates on March 13 nineteen ninety) disclose a kind of containing the silver catalyst on the carrier of cesium salt mixture, and cesium salt mixture is made up of cesium salt and one or more alkali metal salts or alkali salt.
In epoxidation process, catalyst experience performance reduces, and this itself shows as catalyst activity and forms the selective loss of required alkylene oxide.In order to tackle loss of activity, epoxidation reaction temperature can be raised, so that the speed of production of alkylene oxide is maintained.The operation of commercial reactors is subject to the restriction of reaction temperature usually.When reaching adoptable temperature extremes, the speed of production of alkylene oxide reduces, or must interrupt the production of alkylene oxide, to replace existing epoxidation catalyst charging with fresh charging.
United States Patent (USP) U.S4,897,498 (mandates on January 30 nineteen ninety) disclose by the silver catalyst on broken metal promoted carrier without the application in the alkene epoxidation of allylic hydrogen.The application of porous ceramic catalyst carrier is existing in numerous patents to be described, such as U.S5,100,895 (mandates on March 31st, 1992), U.S5,055,442 (mandates on October 8th, 1991), U.S5,037,794 (mandate on August 6th, 1991) and U.S4,874,739 (mandates on October 17th, 1989).This kind of catalyst carrier has potential using value widely and is that the occasion of aluminium oxide (as alpha-type aluminum oxide) is particularly useful at ceramic monolith in catalytic field.Although alpha-type aluminum oxide is often as the ceramic monolith of the catalyst preferentially selected, other ceramic material (as silica, carborundum, silicon nitride, magnesia, titanium dioxide, spinelle, cordierite and other forms of aluminium oxide) can certainly use.In further discussing, take alpha-type aluminum oxide as the catalyst exemplarily example use of carrier, but be to be understood that the content told about has more general purposes herein.
European patent application 0 327 356 (issue on August 9th, 1989) discloses a kind of silver-containing catalyst preparation technology for the production of oxirane, and the carrier of this catalyst agent is made up of alumina material, the carbonaceous material having done meticulous collocation in granularity and relative scale two, flux, fluoride and bonding agent.Optional carbonaceous material is petroleum coke, carbon, graphite, polyethylene, rosin and their mixture.In fact petroleum coke and graphite is only illustrated.According to the content that this invention discloses, its effect is to provide the catalyst of some high selectivities.
CN96191744 discloses a kind of catalyst of oxirane, and its preparation method is as follows: (i) makes mixture, comprises in mixture: the granular alumina composition of (a) at least one; (b) by ceramic component total weight, the combustible substance of 0.5% to 50% organic synthesis, this combustible substance ash content will lower than 0.1%; (c) water, the water yield is enough to make said mixture extrusion molding; (ii) mixture is squeezed into the shape of requirement; (iii) with fire calcining, alumina particle is sintered into the porous carrier of alpha-type aluminum oxide system, its surface area of carrier is 0.4m
2/ g to 5.0m
2/ g, preferably between 0.4m
2/ g to 1.5m
2between/g, METAL EXTRACTION thing, lower than 2000ppm, is preferably lower than 1500ppm.Catalyst carrier can be made up of multiple aluminium oxide and can optional other ceramic raw material, the object selected is that these character comprise porosity, void volume, breaking strength etc. in order to contribute to some extent the catalytic property expected and (or) physical property.Two kinds of different alpha-type aluminum oxides combine often relatively good, and the composition that the composition that wherein a kind of particle is thicker is thinner with another kind of particle mixes, and both weight ratios are from 10: 90 to 90: 10.The object of such work makes the surface area of finished product between 0.4m
2/ g to 5m
2between/g.The alpha-type aluminum oxide system porous carrier being applicable to doing catalyst contains METAL EXTRACTION thing composition, and content is at below 2000ppm.Porosity and the stamped density of carrier and ceramic component all identical time, compared with the carrier made of routine or traditional non-organic polymer combustion material, carrier of the present invention demonstrates abrasion and at least reduces by 10%, good situation at least reduces by 20%, breaking strength at least improves 10%, and good situation at least improves 20%.The porosity of the carrier finished product after calcining is preferably at least 50%, and better between 60% to 75%, breaking strength is at least 5 pounds, and stable stamped density is at least 0.5 kilogram/liter, is at least preferably 0.6 kilogram/liter.Pass through the carrier assembled watch area of calcining preferably between 0.4m
2/ g to 5m
2between/g, between 0.6m
2/ g to 1.5m
2better between/g.
United States Patent (USP) 4529714 (" ' 714 " patent) describes the renovation process at the carried catalyst preparing the argentiferous used in oxirane.The method comprises the catalyst with the solution-treated inactivation containing potassium, rubidium or cesium compound and reducing agent.In the embodiment of ' 714 patents, after use about four years, epoxyethane catalyst is regenerated, between the operating period of described 4 years, " catalytic activity " (namely selective) is reduced to 76.7% (at 247 DEG C) from 81.5% initial (218 DEG C).4th hurdle of ' 714 patents, 11.16-18; Also see the table across 3-4 hurdle.Reflection " S% " maximum raising at any temperature is in the table only 3.2% (bringing up to 79.9 from 76.7).
Summary of the invention
The object of the invention is to propose a kind of method preparing the epoxidation catalyst of regeneration.
For reaching this object, the present invention by the following technical solutions:
Prepare a method for the epoxidation catalyst of regeneration, provide appropriate spent epoxidation catalyst, the silver that this spent epoxidation catalyst has comprised basic crack is more than or equal to 0.20kT/m with having
3the accumulation alkylene oxide output of spent epoxidation catalyst; With the weight based on spent epoxidation catalyst, the silver that the amount this spent epoxidation catalyst adopting deposition-precipitation method deposition be more than or equal to 1wt% is added; It is characterized in that, spent epoxidation catalyst is washed before spent epoxidation catalyst deposits additional silver, spent epoxidation catalyst is washed by making spent epoxidation catalyst contact the regular hour with aqueous solvent, subsequently the spent epoxidation catalyst after washing is reduced 4-6 hour under 120-180 DEG C of hydrogen atmosphere, described solvent methanol, ethanol, propyl alcohol, isopropyl alcohol, oxolane, ethylene glycol, glycol dimethyl ether, diethylene glycol dimethyl ether, acetone and MEK, the ratio of solvent and water is 1:15-2:1.
Wherein epoxidation catalyst comprises one or more the 11st race's metals.In one embodiment, described 11st race's metal can be selected from silver and gold.Preferably, described 11st race's metal comprises silver.Especially, described 11st race's metal amount of comprising is the silver metal of at least 90wt%, more especially at least 95wt%, such as at least 99wt% or at least 99.5wt%, with the total weight of the weight of silver metal relative to the 11st race's metal.By the 11st race's Metal Phase of nitric acid boiling and silver-colored titrimetry for the content of catalyst weight be at least 10g/kg time, epoxidation catalyst shows obvious catalytic activity.Preferably, based on the gross weight of epoxidation catalyst, catalyst comprises the 11st race's metal that content is 50-500g/kg, more preferably 100-400g/kg.As mentioned above, in favourable embodiment, described 11st race's metal is silver.
Epoxidation catalyst optionally can comprise rhenium.In some embodiments, epoxidation catalyst can comprise carrier material, and described carrier material can deposit the 11st race's metal, optional rhenium and any optional component containing one or more co-accelerators and/or one or more other elements.Disclosed rhenium, applicable co-accelerator component and the component be applicable to containing one or more other elements.To the carrier material be applicable to be described below.
Epoxidation catalyst comprises carrier material.This carrier material can be natural or artificial inorganic material, and can comprise refractory material, carborundum, clay, zeolite, charcoal and alkaline earth metal carbonate, such as calcium carbonate.In favourable embodiment, carrier material comprises one or more refractory materials.The example of the refractory material be applicable to comprises such as aluminium oxide, magnesia, zirconia and silica.In favourable embodiment, carrier material is Alpha-alumina.In this embodiment, relative to the weight of carrier, carrier material comprises the Alpha-alumina of at least 85wt%, more generally at least 90wt%, particularly at least 95wt% usually, usually the Alpha-alumina of 99.9wt% at most.Other component of Alpha-alumina can comprise such as silica, alkaline components as sodium and/or potassium component, and/or alkaline earth metal component is as calcium and/or magnesium component.
Relative to the weight of carrier, the surface area of carrier material can be compatibly at least 0.1m
2/ g, is preferably at least 0.3m
2/ g, is more preferably at least 0.5m
2/ g, and be particularly at least 0.6m
2/ g; With the weight relative to carrier, surface area compatibly can be 10m to the maximum
2/ g, is preferably 5m to the maximum
2/ g, and be particularly 3m to the maximum
2/ g." surface area " as used herein is appreciated that as referring to the surface area measured by B.E.T. (Brunauer, Emmett and the Teller) method such as described in Journal of the American Chemical Society 60 (1938) pp.309-316.High surface area support material, particularly when they are the Alpha-aluminas optionally comprising silica, alkali metal and/or alkaline earth metal component in addition, provides performance and the operational stability of improvement.
The epoxidation catalyst catalysis epoxidation method of regeneration can be used.Described epoxidizing method can carry out according to many modes.In one embodiment, described epoxidizing method is vapor phase method, i.e. the method that contacts with the epoxidation catalyst usually existed as solid material in packed bed using gas phase of its Raw.Usual epoxidizing method is continuation method.
The alkene used in epoxidizing method can be any alkene.The alkene be applicable to comprises atomatic olefins, such as styrene, or conjugation or unconjugated alkadienes, such as 1,9-decadinene or 1,3-butadiene.Usually, alkene is monoolefine, such as 2-butylene or isobutene.In one embodiment, alkene is list-alpha-olefin, such as 1-butylene or propylene.In favourable embodiment, alkene is ethene.
The epoxidation catalyst of this regeneration technology regeneration has higher selective, and catalyst production and fresh catalyst are substantially identical, greatly improve the use value of dead catalyst.
Detailed description of the invention
Embodiment 1
There is provided appropriate spent epoxidation catalyst, the silver that this spent epoxidation catalyst has comprised basic crack is more than or equal to 0.3kT/m with having
3the accumulation alkylene oxide output of spent epoxidation catalyst; With the weight based on spent epoxidation catalyst, the silver that the amount this spent epoxidation catalyst adopting deposition-precipitation method deposit 2wt% is added; It is characterized in that, spent epoxidation catalyst is washed before spent epoxidation catalyst deposits additional silver, spent epoxidation catalyst is washed by making spent epoxidation catalyst contact the regular hour with aqueous solvent, subsequently the spent epoxidation catalyst after washing is reduced 5 hours under 150 DEG C of hydrogen atmospheres, described solvent methanol, ethanol, the ratio of solvent and water is 1:2.
Embodiment 2
There is provided appropriate spent epoxidation catalyst, the silver that this spent epoxidation catalyst has comprised basic crack is more than or equal to 0.4kT/m with having
3the accumulation alkylene oxide output of spent epoxidation catalyst; With the weight based on spent epoxidation catalyst, the silver that the amount this spent epoxidation catalyst adopting deposition-precipitation method deposit 1.5wt% is added; It is characterized in that, spent epoxidation catalyst is washed before spent epoxidation catalyst deposits additional silver, spent epoxidation catalyst is washed by making spent epoxidation catalyst contact the regular hour with aqueous solvent, subsequently the spent epoxidation catalyst after washing is reduced 4 hours under 160 DEG C of hydrogen atmospheres, described solvent methanol, ethanol, the ratio of solvent and water is 1:8.
Embodiment 3
There is provided appropriate spent epoxidation catalyst, the silver that this spent epoxidation catalyst has comprised basic crack is more than or equal to 0.25kT/m with having
3the accumulation alkylene oxide output of spent epoxidation catalyst; With the weight based on spent epoxidation catalyst, the silver that the amount this spent epoxidation catalyst adopting deposition-precipitation method deposit 2.5wt% is added; It is characterized in that, spent epoxidation catalyst is washed before spent epoxidation catalyst deposits additional silver, spent epoxidation catalyst is washed by making spent epoxidation catalyst contact the regular hour with aqueous solvent, subsequently the spent epoxidation catalyst after washing is reduced 5 hours under 140 DEG C of hydrogen atmospheres, described solvent methanol, ethanol, the ratio of solvent and water is 1:9.
Claims (1)
1. prepare a method for the epoxidation catalyst of regeneration, it is characterized in that the method comprises:
There is provided appropriate spent epoxidation catalyst, the silver that this spent epoxidation catalyst has comprised basic crack is more than or equal to 0.20kT/m with having
3the accumulation alkylene oxide output of spent epoxidation catalyst; With the weight based on spent epoxidation catalyst, the silver that the amount this spent epoxidation catalyst adopting deposition-precipitation method deposition be more than or equal to 1wt% is added; It is characterized in that, spent epoxidation catalyst is washed before spent epoxidation catalyst deposits additional silver, spent epoxidation catalyst is washed by making spent epoxidation catalyst contact the regular hour with aqueous solvent, subsequently the spent epoxidation catalyst after washing is reduced 4-6 hour under 120-180 DEG C of hydrogen atmosphere, described solvent methanol, ethanol, propyl alcohol, isopropyl alcohol, oxolane, ethylene glycol, glycol dimethyl ether, diethylene glycol dimethyl ether, acetone and MEK, the ratio of solvent and water is 1:15-2:1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105363476A (en) * | 2015-11-23 | 2016-03-02 | 安徽千和新材料科技发展有限公司 | Palladium/carbon catalyst regeneration and mechanical application method |
Citations (3)
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|---|---|---|---|---|
| CN101384359A (en) * | 2005-12-22 | 2009-03-11 | 国际壳牌研究有限公司 | Method for regenerated epoxide catalyst preparation |
| CN102049320A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Regeneration method for preparing diphenylamine catalyst by continuous condensation of phenylamine |
| EP2554268A1 (en) * | 2010-03-29 | 2013-02-06 | Nippon Kayaku Kabushiki Kaisha | Process for production of catalyst from recovered catalyst |
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2014
- 2014-11-05 CN CN201410621451.7A patent/CN104549573A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101384359A (en) * | 2005-12-22 | 2009-03-11 | 国际壳牌研究有限公司 | Method for regenerated epoxide catalyst preparation |
| CN102049320A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Regeneration method for preparing diphenylamine catalyst by continuous condensation of phenylamine |
| EP2554268A1 (en) * | 2010-03-29 | 2013-02-06 | Nippon Kayaku Kabushiki Kaisha | Process for production of catalyst from recovered catalyst |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105363476A (en) * | 2015-11-23 | 2016-03-02 | 安徽千和新材料科技发展有限公司 | Palladium/carbon catalyst regeneration and mechanical application method |
| CN105363476B (en) * | 2015-11-23 | 2017-12-22 | 安徽千和新材料科技发展有限公司 | The regeneration of palladium/carbon catalyst and using method |
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Application publication date: 20150429 |