CN1762584A - Integrated silver-supported catalyst, its preparation method and application in ethylene epoxy process - Google Patents

Integrated silver-supported catalyst, its preparation method and application in ethylene epoxy process Download PDF

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Publication number
CN1762584A
CN1762584A CNA2005100150669A CN200510015066A CN1762584A CN 1762584 A CN1762584 A CN 1762584A CN A2005100150669 A CNA2005100150669 A CN A2005100150669A CN 200510015066 A CN200510015066 A CN 200510015066A CN 1762584 A CN1762584 A CN 1762584A
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silver
catalyst
monoblock type
integral
carrier
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辛峰
赵阳
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Tianjin University
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Tianjin University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to preparation for integral carrier Ag catalyst with application in ethane epoxidation, which comprises: with integral cordierite as carrier and Ag as active constituent, carrying Ag on said cordierite with dipping method. Wherein, in the ethane epoxidation reaction, with said catalyst and tubular reactor, the material gas comprises 4~16v% C2H4, 68~78v% N2, and 16~20v% O2; the reaction pressure is 0,1MPaA, gas volume air-speed varies in 35-350h-1, and the temperature is 230~20Deg. This product has 81% selectivity without co-catalyst and inhibitor on normal pressure, which is near to the selectivity on industrial condition.

Description

Integral supported silver catalyst and preparation method and be used for epoxidation of ethylene
Technical field
The present invention relates to the synthetic technical field that reaches Preparation of Catalyst of organic chemical industry's product.Specifically relate to the preparation of integral supported silver catalyst and the application in epoxidation of ethylene.
Background technology
Industrial epoxidation of ethylene carries out in the fixed bed reactors that use pellet type catalyst usually, and the carrier of described pellet type catalyst is for being the spherical or circulus of main component with the aluminium oxide, and active component is a silver.
The selection of support shapes should make the bearing capacity of active component moderate, even fluid distribution in the bed, and mass-and heat-transfer is effective, and pressure falls little.A kind of Intalos shape of a saddle or the saddle-shaped porous, inorganic refractory material of Bell carrier have been described among the EP149584, the contrast experiment shows, shape of a saddle catalyst is higher 1 percentage point than oxirane (EO) selectivity of annular and spheric catalyst, and the catalyst bed stressor layer falls little.Described a kind of double-deck combined type carrier among US3207700 and the BP950363, this carrier is made up of low hole kernel and porous outer layer.Kernel is by the material that conducts electricity very well, and as formations such as SiC, porosity is less than 10%, outerly is coated on the kernel and formed by small-particulate materials.Described small-particulate materials can be aluminium oxide, magnesia etc., and porosity is 15%～40%, preferred 25%～30%.When above-mentioned carrier impregnation active component, active component concentrates on described skin, is protein type and distributes.
A critical function of carrier provides the surface area of enough load silver, and these surface areas are mainly provided by the duct on the carrier.The service life that the specific area that improves carrier helps the dispersion of silver-colored particle, improves catalytic activity, reduces suitable reaction temperature and prolong catalyst.But specific area is the diffusional resistance of conference augmenting response product EO in aperture too, makes the speed of EO disengaging catalyst surface slack-off, causes the further oxidation of EO, thereby reduce its selectivity.The carrier specific area that the beginning of the nineties, external each company adopted is generally at 0.3～0.4m 2/ g.From the situation of recent patent report, the specific area of carrier has trend of rising, and Shell company has been 0.5～2m at specific surface on probation 2The carrier of/g, SD company is also on probation＞2m 2The carrier of/g specific area.
The carrying method of active component silver has two kinds of mechanical mixing and infusion processes.Almost all adopt the sixties in last century mechanical mixing to prepare silver catalyst.The shortcoming of mechanical mixing is: the bad adhesion between silver granuel and silver granuel and the carrier, and after peeling off, the pressure that has not only increased bed falls; and silver granuel can be brought to the reactor hypomere by reaction gas flow; make product EO that tail take place and burn, even " temperature runaway ", reduced selectivity and the catalyst life of EO.At present, the preparation silver catalyst adopts infusion process substantially.Infusion process can be according to the characteristics of epoxidation of ethylene, that selects that adaptive response requires has a good carrier of suitable specific area, pore structure, pore size distribution and heat conductivility, active component is carried on the hole wall of carrier equably, bonding firmly, conduct heat better the caducous shortcoming of active component when having overcome mechanical mixing and preparing silver catalyst.Shell company has compared the silver catalyst of various immersion process for preparing, finds AgNO 3The silver catalyst silver particle that aqueous solution dipping makes is too big, and adds the silver-colored ammonium complex solution impregnated carrier that the organic amine reducing agent makes with silver carboxylate solution, and the catalyst silver particle of gained is smoothly even, and bonding firmly.Each company has also developed different silver-colored maceration extracts afterwards.JP55-106542 has described use sec-butylamine, water, AgNO 3, and the methanol solution dipping Norton aluminium oxide formed of surfactant (as NPE and cesium hydroxide), obtain the very meticulous catalyst of silver-colored crystal grain after the drying, its EO selectivity reaches 82.5%.JP58-70838 has described the silver salt solution impregnated carrier that uses normal propyl alcohol or isopropyl alcohol to make, and under same reaction condition, makees catalyst that solvent obtains to do the catalyst EO selectivity that solvent obtains than water high by 6% with pure.The complex solution impregnated carrier of forming with polypropylene nitrile and silver salt has been described among the BP1483074, then 600 ℃ of following high-temperature process, polypropylene nitrile decomposes, silver salt is decomposed into particle less than 0.15 μ m attached on the carrier.
The first industrial application of integral catalyzer is in 1966, humans such as Anderen its to the NO in the nitric acid workshop tail gas XDo reduction-decolor.The mid-1970s, the U.S. and Japan use it for and handle CO, NO in the vehicle exhaust XWith imperfect combustion hydro carbons, up to the present, basically formed the cleaning catalyst for tail gases of automobiles technology of widely used maturation, promptly make carrier, with γ-Al with integral honeycomb shape cordierite 2O 3And CeO 2Deng making coatings, and be active component, can remove CO, NO simultaneously with noble metal XAnd the three-way catalyst (TWC) of HnCm.Because integral catalyzer has advantages such as bed pressure drop is low, catalytic efficiency is high, enlarge-effect is little, many in recent years researchers attempt using it for the synthetic reaction of chemical products, as: the steam-reforming of methanation, Water gas shift/WGS, hydrocarbon, hydrogenation, dehydrogenation, catalytic oxidation and F-T are synthetic etc., but yet there are no report for the integral catalyzer that is used for the reaction of ethylene epoxidizing epoxy ethane.
Summary of the invention
The objective of the invention is to, preparation is a carrier with the monoblock type cordierite, and silver is the integral catalyzer of active component, is used for epoxidation of ethylene.
Catalyst of the present invention is: adopt the monoblock type cordierite to make catalyst carrier, silver is active component.
Above-mentioned monoblock type cordierite be shaped as column, arranging parallel channels in it vertically, the preferred 1～15m of specific area 2/ g.The cross section of monoblock type cordierite is circular, oval or square; Described channel cross-section is hexagon, circle, square, triangle or sinusoidal.
The preparation method of integral supported silver catalyst of the present invention is to adopt infusion process load active component silver on the monoblock type cordierite; Step is:
(1) compound concentration is 30%～40% silver nitrate (AgNO 3) aqueous solution and concentration is 7.5%～12% ammonium oxalate ((NH 4) C 2O 4) aqueous solution
(2) above-mentioned two kinds of solution are mixed, heating is also stirred, until generating white silver oxalate (Ag 2C 2O 4) precipitation, leave standstill aging about 30～60min, filter out sediment, again with Ag 2C 2O 4It is that 45%～60% ethylenediamine or concentration are in 45%～60% monoethanolamine aqueous solution that precipitation is dissolved in concentration fully, obtains the water or the alcoholic solution of argent-amine complex;
(3) the monoblock type cordierite carrier of choosing is placed boiling water flush away soluble impurity.After the oven dry, place above-mentioned silver-colored amine complex solution to soak 5～10h.Subsequently, take out the monoblock type cordierite from solution, in 240～280 ℃ of roasting 2～4h, preliminary treatment 2～4h in 260～280 ℃ air stream activates 2～4h with hydrogen again under uniform temp then, just can obtain integral catalyzer of the present invention.
Described roasting is to carry out in Muffle furnace.
Accompanying drawing 1 and accompanying drawing 2 are SEM photos of catalyst surface before and after the load silver.
Utilize integral supported silver catalyst of the present invention to carry out epoxidation of ethylene, finish in fixed-bed tube reactor, the volume fraction of feed gas composition is 4%～16%C 2H 4, 68%～78%N 2, 16%～20%O 2, reaction pressure 0.1MPaA, 230 ℃～270 ℃ of temperature, gas volume air speed scope is 35～350h -1
The present invention adopts the air oxidation process synthesize epoxyethane, at normal pressure, do not have not add in load cocatalyst, the unstripped gas under the situation of inhibitor, the selectivity of integral catalyzer has reached 81%, the selectivity of oxirane when very adopting dioxygen oxidation down near industrial condition.
Description of drawings
The SEM photo on Fig. 1 load active component procatalyst surface;
The SEM photo on Fig. 2 load active component rear catalyst surface.
The specific embodiment
Embodiment 1
Choosing specific area is 10.5m 2The monoblock type cordierite carrier of/g, it is shaped as the cylinder of φ 18 * 50mm, along the straight passage of equilateral triangle that axially to be uniform-distribution with 90 length of sides be 1mm of carrier.When integral catalyzer prepares, at first place water to boil 30min the monoblock type cordierite,, then, take by weighing 5g AgNO respectively to remove surface impurity 3And 2.5g (NH 4) C 2O 4With above-mentioned AgNO 3Be dissolved in the 8ml distilled water, be stirred to whole dissolvings.With above-mentioned (NH 4) C 2O 4Be dissolved in about 30ml distilled water, 40 ℃ of water-bath heating also are stirred to whole dissolvings.With AgNO 3The aqueous solution is poured (NH into 4) C 2O 4In the aqueous solution, 40 ℃ of water-bath heating are also stirred, until generating white precipitate A g 2C 2O 4, leave standstill aging 60min.Subsequently, filter out sediment, and it is dissolved in the ethylenediamine solution of 60% (wt.%) fully.The monoblock type cordierite behind the cleaning, drying being put into described argentamine liquid soaked 10 hours again, take out the back 260 ℃ of following roasts 2 hours, in 260 ℃ of air streams, activate 4 hours then, in the hydrogen stream under the uniform temp, activate 4 hours again, obtain the integral catalyzer that the Ag carrying capacity is 14% (wt.%).
The above-mentioned catalyst of packing in the normal pressure tubular reactor of diameter 20mm is with the concentration of oxygen, nitrogen, ethene, carbon dioxide and oxirane in the gas chromatographic detection product.Consist of 4% ethene, 20% oxygen and 76% nitrogen (v%), 230 ℃ of reaction temperatures, pressure 0.1MPaA, gas volume air speed 125h at unstripped gas -1Operating condition under, the selectivity of oxirane is 81%.
Embodiment 2
Monoblock type cordierite carrier shape, size are with embodiment 1.
Take by weighing 5g AgNO respectively 3And 2.5g (NH 4) C 2O 4With above-mentioned AgNO 3Be dissolved in the 10ml distilled water, be stirred to whole dissolvings.With above-mentioned (NH 4) C 2O 4Be dissolved in about 20ml distilled water, 40 ℃ of water-bath heating also are stirred to whole dissolvings.With AgNO 3The aqueous solution is poured (NH into 4) C 2O 4In the aqueous solution, 40 ℃ of water-bath heating are also stirred, until generating white precipitate A g 2C 2O 4, leave standstill aging 30min.Subsequently, filter out sediment, and it is dissolved in the ethylenediamine solution of 45% (wt.%) fully.The monoblock type cordierite behind the cleaning, drying being put into described argentamine liquid soaked 5 hours again, take out the back 260 ℃ of following roasts 4 hours, in 260 ℃ of air streams, activate 2 hours then, under same temperature, activate 3 hours in the hydrogen stream again, obtain the integral catalyzer that the Ag carrying capacity is 11% (wt.%).
The above-mentioned catalyst of packing in the normal pressure tubular reactor of diameter 20mm is with the concentration of oxygen, nitrogen, ethene, carbon dioxide and oxirane in the gas chromatographic detection product.Consist of 16% ethene, 18% oxygen and 66% nitrogen (v%), 270 ℃ of reaction temperatures, pressure 0.1MPaA, gas volume air speed 350h at unstripped gas -1Operating condition under, the selectivity of oxirane is 51%.
Embodiment 3
Adopt the integral supported silver catalyst identical, in the reactor identical, carry out epoxidation of ethylene with embodiment 1 with embodiment 1.Consist of 4.5% ethene, 20% oxygen and 75.5% nitrogen (v%), 240 ℃ of reaction temperatures, pressure 0.1MPaA, gas volume air speed 125h at unstripped gas -1Operating condition under, the selectivity of oxirane is 73%.
Embodiment 4
Adopt the integral supported silver catalyst identical, in the reactor identical, carry out epoxidation of ethylene with embodiment 2 with embodiment 2.Consist of 8.5% ethene, 19% oxygen and 72.5% nitrogen (v%), 230 ℃ of reaction temperatures, pressure 0.1MPaA, gas volume air speed 75h at unstripped gas -1Operating condition under, the selectivity of oxirane is 42%.
The present invention product and method open and that disclose can be by using for reference this paper disclosure.Although product of the present invention and method are described by preferred embodiment, but those skilled in the art obviously can change the techniques described herein in not breaking away from content of the present invention, spirit and scope, more particularly, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.

Claims (6)

1. integral supported silver catalyst is characterized in that: adopt the monoblock type cordierite to do catalyst carrier, silver is active component.
2. a kind of integral supported silver catalyst as claimed in claim 1 is characterized in that the column that is shaped as of described monoblock type cordierite, is arranging parallel channels in it vertically, the preferred 1～15m of specific area 2/ g.
3. a kind of integral supported silver catalyst as claimed in claim 2, the cross section that it is characterized in that described monoblock type cordierite is for circular, oval or square; Described channel cross-section is hexagon, circle, square, triangle or sinusoidal.
4. the preparation method of an integral supported silver catalyst as claimed in claim 1 adopts infusion process load active component silver on the monoblock type cordierite; It is characterized in that:
(1) compound concentration is that 30%～40% silver nitrate aqueous solution and concentration are 7.5%～12% the ammonium oxalate aqueous solution;
(2) above-mentioned two kinds of solution are mixed, heating is also stirred, until generating white silver oxalate precipitation, leave standstill aging 30～60min, filter out sediment, silver oxalate precipitation being dissolved in fully concentration again and being 45%～60% ethylenediamine or concentration is in 45%～60% monoethanolamine aqueous solution, obtains the water or the alcoholic solution of argent-amine complex;
(3) the monoblock type cordierite carrier of choosing is placed boiling water flush away soluble impurity, after the oven dry, place above-mentioned silver-colored amine complex solution to soak 5～10h, from solution, take out the monoblock type cordierite subsequently, in 240～280 ℃ of roasting 2～4h, preliminary treatment 2～4h in 260～280 ℃ air stream activates 2～4h with hydrogen again under uniform temp again, just can obtain integral catalyzer of the present invention.
5. the preparation method of integral supported silver catalyst as claimed in claim 4 is characterized in that described roasting is to carry out in Muffle furnace.
6. the application of an integral supported silver catalyst as claimed in claim 1 in epoxidation of ethylene is characterized in that on tubular reactor unstripped gas component percent by volume is 4%～16%C 2H 4, 68%～78%N 2, 16%～20%O 2, normal pressure 101.0kPa is adopted in reaction, 230 ℃～270 ℃ of temperature, and gas volume air speed scope is 35～350h -1
CNA2005100150669A 2005-09-09 2005-09-09 Integrated silver-supported catalyst, its preparation method and application in ethylene epoxy process Pending CN1762584A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105618047A (en) * 2014-11-03 2016-06-01 中国石油化工股份有限公司 Method for preparation of silver catalyst for epoxidation and application thereof
CN111135824A (en) * 2019-11-27 2020-05-12 北京化工大学 Preparation method of Ag-based nano catalyst
CN113813993A (en) * 2021-10-12 2021-12-21 合肥工业大学 High selectivity Ag2C2O4/Ag2Preparation of O composite catalyst and application thereof in ethylbenzene oxidation
CN115069245A (en) * 2021-03-15 2022-09-20 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

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105618047A (en) * 2014-11-03 2016-06-01 中国石油化工股份有限公司 Method for preparation of silver catalyst for epoxidation and application thereof
CN111135824A (en) * 2019-11-27 2020-05-12 北京化工大学 Preparation method of Ag-based nano catalyst
CN115069245A (en) * 2021-03-15 2022-09-20 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
CN115069245B (en) * 2021-03-15 2024-03-26 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
CN113813993A (en) * 2021-10-12 2021-12-21 合肥工业大学 High selectivity Ag2C2O4/Ag2Preparation of O composite catalyst and application thereof in ethylbenzene oxidation
CN113813993B (en) * 2021-10-12 2023-10-13 合肥工业大学 High selectivity Ag 2 C 2 O 4 /Ag 2 Preparation of O composite catalyst and application thereof in ethylbenzene oxidation

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