CN106311234A - Preparation method for composite silver catalyst, and composite silver catalyst and application thereof - Google Patents
Preparation method for composite silver catalyst, and composite silver catalyst and application thereof Download PDFInfo
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- CN106311234A CN106311234A CN201510383319.1A CN201510383319A CN106311234A CN 106311234 A CN106311234 A CN 106311234A CN 201510383319 A CN201510383319 A CN 201510383319A CN 106311234 A CN106311234 A CN 106311234A
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- Prior art keywords
- silver
- compound
- catalyst
- rhenium
- weight
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 107
- 239000004332 silver Substances 0.000 title claims abstract description 105
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 title abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 53
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 21
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 16
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 14
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005977 Ethylene Substances 0.000 claims abstract description 13
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 239000011651 chromium Substances 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 12
- -1 cesium compound Chemical class 0.000 claims description 11
- 150000001845 chromium compounds Chemical class 0.000 claims description 11
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 150000003282 rhenium compounds Chemical class 0.000 claims description 8
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000002484 inorganic compounds Chemical class 0.000 claims description 6
- 229910010272 inorganic material Inorganic materials 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000011265 semifinished product Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 2
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 claims description 2
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VZSXFJPZOCRDPW-UHFFFAOYSA-N carbanide;trioxorhenium Chemical compound [CH3-].O=[Re](=O)=O VZSXFJPZOCRDPW-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 2
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims 1
- HRLYFPKUYKFYJE-UHFFFAOYSA-N tetraoxorhenate(2-) Chemical compound [O-][Re]([O-])(=O)=O HRLYFPKUYKFYJE-UHFFFAOYSA-N 0.000 claims 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract description 6
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 3
- 238000002791 soaking Methods 0.000 abstract 2
- 238000007598 dipping method Methods 0.000 description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052916 barium silicate Inorganic materials 0.000 description 1
- HMOQPOVBDRFNIU-UHFFFAOYSA-N barium(2+);dioxido(oxo)silane Chemical compound [Ba+2].[O-][Si]([O-])=O HMOQPOVBDRFNIU-UHFFFAOYSA-N 0.000 description 1
- QKYBEKAEVQPNIN-UHFFFAOYSA-N barium(2+);oxido(oxo)alumane Chemical compound [Ba+2].[O-][Al]=O.[O-][Al]=O QKYBEKAEVQPNIN-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a preparation method for a composite silver catalyst used for producing ethylene oxide through ethylene oxidation. The preparation method comprises the following steps: 1) dissolving a compound containing silver and a compound containing chromium in an amine-contained solution or ammonia water so as to prepare a silver-ammonia solution; 2) subjecting an alpha-Al2O3 carrier to soaking in the silver-ammonia solution prepared in the step 1), taking out the soaked alpha-Al2O3, then carrying out draining, and carrying out calcination treatment so as to prepare a semi-finished silver catalyst; 3) dissolving the compound containing silver, the compound containing rhenium and an optional compound containing cesium in the amine-contained solution or the ammonia water so as to prepare the silver-ammonia solution; and 4) subjecting the semi-finished silver catalyst prepared in the step 2) to soaking in the silver-ammonia solution obtained in the step 3), taking out the soaked semi-finished silver catalyst, then carrying out draining, and carrying out calcination treatment so as to prepare the composite silver catalyst. The invention also relates to the composite catalyst and application of the catalyst in production of ethylene oxide.
Description
Technical field
The present invention relates to the preparation method of a kind of catalyst, be specifically related to a kind of for producing urging of oxirane
The preparation method of agent.The invention still further relates to this composite catalyst, and this catalyst is producing oxirane
In application.
Background technology
Under silver catalyst effect, oxidation of ethylene mainly generates oxirane, occurs side reaction to generate titanium dioxide simultaneously
Carbon and water, wherein activity, selectivity and stability are the main performance index of silver catalyst.So-called activity refers to
Process for ethylene oxide production reaches necessarily to react reaction temperature required during load.Reaction temperature is the lowest, catalyst
Activity the highest.So-called selectivity refers to that in reaction, ethylene changes into the molal quantity of oxirane and the total anti-of ethylene
Answer the ratio of molal quantity.So-called stability is then expressed as the fall off rate of activity and selectivity, and fall off rate is the least urges
The stability of agent is the best.Oxidation of ethylene produce use during oxirane high activity, high selectivity and
The silver catalyst having good stability can be greatly improved economic benefit, therefore manufactures high activity, high selectivity and good
The silver catalyst of 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 performance and the preparation method of the carrier also used with catalyst have important
Relation.
In prior art, the preparation method of silver catalyst includes the preparation of porous carrier (such as aluminium oxide) and applies to live
Property component and auxiliary agent are to the two process on described carrier.In the preparation process of silver catalyst, for
α-Al2O3For the carrier of key component, needing suitable specific surface and pore structure, on the one hand it be ethylene ring
Oxidation reaction provides enough spaces, makes reaction heat spread out, and is on the other hand also beneficial to product epoxy
Ethane is desorbed in time, it is to avoid deep oxidation generates by-product carbon dioxide.Chinese patent CN1009437B uses
It is 0.2～2m that the gibbsite of ratio appropriate mix is mixed with out specific surface2/ g, pore volume are more than 0.5ml/g
Alumina support, wherein pore radius accounts for less than 25% more than the hole of 30 μm, can for epoxidation of ethylene
Reach the selectivity of 83～84%.
Also have on a small quantity about adding other component improvement carrier in alumina support, improve the property of silver catalyst
The research of energy.Additionally, by alumina support is carried out chemical treatment, it is possible to improve the performance of silver catalyst.
European patent EP 0150238 use in the manufacture process of surface oxidation alumina supporter high-purity, low a small amount of barium aluminate or
Barium silicate binding agent, allegedly improves crushing strength and the wear resistance of carrier, the ratio table of the carrier that patent manufactures
Face is less than 0.3m2/ g, the catalyst activity and selectivity made all ratios are relatively low.US4740493、US4829043
Containing a certain amount of Ca, Al, K, Na soluble salt in the alumina support used with EP0501317 patent, sound
Claim to reduce the fall off rate of catalyst choice during use.US5384302 claims and passes through pretreatment
α-Al2O3Reduce Na, K, Ca, Al ion concentration in carrier and improve the crushing strength of carrier and wear-resistant
Performance.
Although above-mentioned patent documentation is respectively adopted multiple method to improve alumina support, catalyst is brought difference
The improvement of degree, but along with the heavy industrialization of rhenium-containing height selectivity silver catalyst is applied, to carrier property
Require also improving constantly.Therefore, this area needs a kind of more preferable rhenium-containing catalysts of combination property.
Summary of the invention
In order to solve the problem that above-mentioned prior art exists, the present inventor is carried out in silver catalyst field
Research extensively and profoundly, result is it was unexpectedly found that by using step impregnation technique, i.e. at silver for the first time
Ammonia solution adds appropriate containing chromium compound, puts into carrier, complete dipping, drain with roasting after, then exist
For the second time silver ammino solution adds appropriate containing rhenium compound, put into baked carrier, complete dipping, drain
With roasting, the compound silver catalyst thus made has higher selectivity.
Therefore, it is an advantage of the invention to provide a kind of answering for oxidation of ethylene production oxirane
The preparation method of mould assembly silver catalyst, comprises the steps:
1) it is dissolved in containing in amine aqueous solution or ammonia by Ag-containing compound with containing chromium compound, is made into silver ammino solution；
2) by α-Al2O3Carrier puts into step 1) prepare silver ammino solution in soak, taking-up drains, then carries out
Calcination process, makes silver catalyst semi-finished product；
3) by Ag-containing compound, containing rhenium compound and optional being dissolved in containing amine aqueous solution or ammonia containing cesium compound
In, it is made into silver ammino solution；
4) by step 2) prepare silver catalyst semi-finished product put into step 3) silver ammino solution in soak, take out
Drain, then carry out calcination process, make described compound silver catalyst.
Wherein step 1) to step 4) can carry out with random order, as long as meeting step 1) prior to step
2), step 2) and step 3) prior to step 4).In an embodiment of the invention, step 1)
With step 3) carry out simultaneously.In the further embodiment of the present invention, step 1) and step 3) enter simultaneously
OK.In yet further embodiment of the invention, step 1) in step 3) after carry out.
In step 1) in, Ag-containing compound and can dissolving with random order containing chromium compound.The present invention's
In one embodiment, it is dissolved in containing amine aqueous solution or ammonia by Ag-containing compound with containing chromium compound simultaneously
In.In yet another embodiment of the present invention, first Ag-containing compound is dissolved in containing in amine aqueous solution or ammonia,
Chromium compound will be contained again be dissolved in containing in amine aqueous solution or ammonia.In yet another embodiment of the present invention, first
Chromium compound will be contained and be dissolved in containing in amine aqueous solution or ammonia, then Ag-containing compound is dissolved in containing amine aqueous solution or
In ammonia.
Similarly, in step 3) in, Ag-containing compound, containing rhenium compound and optional also may be used containing cesium compound
To dissolve with random order.
One of the present invention preferred embodiment in, step 1) described in Ag-containing compound and closing containing chromaking
The proportion of thing is preferably 1:5000～5000:1 in terms of silver element and chromium element, and more preferably 1:
3000～3000:1.
One of the present invention preferred embodiment in, step 3) described in Ag-containing compound, rhenium-containing chemical combination
Thing and the optional proportion containing cesium compound are preferably in terms of silver element, rhenium element and cesium element
(1～5000): 1:(0～10), more preferably (5～3000): 1:(0～5).
One of the present invention preferred embodiment in, step 1) with step 3) described in argentiferous chemical combination
Thing is organic compound or the inorganic compound of argentiferous, the preferably acylate of argentiferous, inorganic acid salt and oxygen
One or more in compound, particularly preferably silver nitrate and/or silver oxalate.
One of the present invention preferred embodiment in, step 1) described in described be chromium containing chromium compound
Oxide, halogenide, hydroxide, nitrate, chromate and bichromate in one or more, excellent
Elect one or more in ammonium chromate, chromic nitrate and potassium dichromate as.
One of the present invention preferred embodiment in, step 3) described in be containing caesium containing cesium compound
The oxide of organic compound or inorganic compound, preferably caesium, halogenide, hydroxide, nitrate, sulfur
One or more in hydrochlorate, carbonate, bicarbonate, carboxylate and tungstates.
One of the present invention preferred embodiment in, step 3) described in be having of rhenium-containing containing rhenium compound
The oxide of machine compound or inorganic compound, preferably rhenium, perrhenic acid, perrhenate and methyl rhenium trioxide
In one or more.
One of the present invention preferred embodiment in, step 2) and step 4) described in roasting be at sky
The nitrogen oxygen atmosphere of gas and/or oxygen content no more than 21% is carried out.
One of the present invention preferred embodiment in, the temperature of described roasting is the scope of 180～700 DEG C
In, preferably in the range of 200～500 DEG C, and the time of described roasting is in the range of 1～120 minute,
Preferably in the range of 1.5～30 minutes.
One of the present invention preferred embodiment in, step 2) described in α-Al2O3α-Al in carrier2O3
Content be more than 90 weight %, and preferably have the feature that crushing strength is 20～200N/ grains；Compare table
Face is 0.2～3.0m2/g；Water absorption rate is not less than 30%；Pore volume is 0.30～0.85ml/g.
It is a further object of the invention to provide a kind of compound silver catalysis prepared according to above-mentioned method
Agent, based on compound silver total catalyst weight in described compound silver catalyst, the content of silver is 2～50wt%,
It is preferably 10～39wt%.One of the present invention preferred embodiment in, in described compound silver catalyst
Based on compound silver total catalyst weight, the content of caesium is preferably 0～3000 weight ppm, more preferably 0～2000
Weight ppm；The content of rhenium is preferably 0.1～2000 weight ppm, more preferably 0.5～1500 weight ppm；
The content of chromium is preferably 0.05～3000 weight ppm, more preferably 0.1～2000 weight ppm.
One of the present invention preferred embodiment in, in described compound silver catalyst containing two kinds each
Comprise the silver granuel of different auxiliary agent, the first silver granuel comprise based on the silver that total catalyst weight is 1～30wt% and 1～
The chromium of 2000 weight ppm, the second silver granuel comprise based on the silver that total catalyst weight is 1～30wt% and 5～
The rhenium of 2000 weight ppm, the second silver granuel the most also includes that based on total catalyst weight be 5～2000 weights
The caesium of amount ppm.
Another object of the present invention is, according to said method prepare compound silver catalyst or according to upper
State compound silver catalyst in the application being produced in oxirane by oxidation of ethylene.Epoxy is being produced by oxidation of ethylene
During ethane, especially in the industrial processes being produced oxirane by oxidation of ethylene, employ root
According to said method prepare compound silver catalyst or be catalyzed according to above-mentioned compound silver catalyst.
The beneficial effects of the present invention is, by using step impregnation technique, i.e. add in first time silver ammino solution
Add appropriate containing chromium compound, put into carrier, complete dipping, drain with roasting after, then at second time silver ammonia
Solution adds appropriate containing rhenium compound and optional containing cesium compound, put into baked carrier, complete leaching
Stain, draining and roasting, the compound silver catalyst thus made has higher selectivity, is particularly well-suited to second
Alkene oxidation produces the reaction of oxirane.
Detailed description of the invention
The detailed description of the invention of the present invention is further illustrated below by way of nonrestrictive experimental example.This area skill
Art personnel it should be understood that all examples below is illustrative, and is not intended that required by the present invention
The scope of protection carries out any restriction.
Wherein initial alpha-Al2O3α-Al in carrier2O3Content be more than 90%, and have the feature that pressure
Broken intensity is 20～200N/ grains；Specific surface is 0.2～3.0m2/g；Water absorption rate is not less than 30%；Pore volume be 0.30～
0.85ml/g.The carrier used in embodiment and comparative example is identical carrier.
Embodiment 1
Dipping for the first time:
In the container of band stirring, add 2.68g ethylenediamine, 0.9g ethanolamine and 36.21g deionized water, obtain
Mixed liquor.Continuously stirred lower being slowly added in mixed liquor by 6.21g silver oxalate, temperature is maintained at less than 30 DEG C,
Silver oxalate is made all to dissolve.Then (concentration is 0.0025g/ml, former with chromium to add 4.0ml potassium dichromate aqueous solution
Sub-weight meter), it is stand-by that mix homogeneously makes 50g the first dipping solution.Gross mass based on the first dipping solution,
The concentration of silver is 8wt% (in terms of silver atoms weight), and the concentration of chromium is that 200 weight ppm are (with chromium atom weight
Gauge).
Take the α-Al of 15g2O3Carrier, puts it in the container of energy evacuation, and adds above first dipping
Solution, is totally submerged carrier.Being evacuated to more than 10mmHg, after keeping about 15 minutes, leaching is gone
Except unnecessary solution.Finally impregnated support samples is placed in the air stream of 270 DEG C and heats about 3 minutes,
I.e. make compound silver catalyst semi-finished product.
Second time dipping:
17.39g ethylenediamine, 5.88g ethanolamine and 32.32g deionized water is added in the glass beaker of band stirring,
Obtain mixed liquor.Continuously stirred lower being slowly added in mixed liquor by 40.35g silver oxalate, temperature is maintained at 30 DEG C
Hereinafter, silver oxalate is made all to dissolve.Add the most successively 1.59ml cesium sulfate aqueous solution (concentration is 0.0503g/ml,
In terms of Cs atom weight), 2.47ml ammonium perrhenate aqueous solution is (concentration as 0.0162g/ml, with rhenium atom weight
Meter), it is stand-by that mix homogeneously makes 100g the second dipping solution.
The compound silver catalyst semi-finished product prepared through dipping for the first time, roasting are put into the appearance of energy evacuation
In device, and add the second dipping solution, be totally submerged carrier.It is evacuated to more than 10mmHg, keeps
After about 15 minutes, unnecessary solution is removed in leaching.Finally impregnated sample is placed on the air of 270 DEG C
Stream heats about 3 minutes, i.e. make silver catalyst 1.
Embodiment 2
Method same as in Example 1 prepares compound silver catalyst, the difference is that only leaching for the first time
The amount of the silver oxalate added in stain is adjusted to 3.11g so that gross mass based on the first dipping solution, the first leaching
In stain solution silver concentration be 4wt% (in terms of silver atoms weight), the concentration of chromium be 200 weight ppm (with
Chromium atom weight meter), i.e. make silver catalyst 2.
Embodiment 3
Method same as in Example 1 prepares compound silver catalyst, the difference is that only leaching for the first time
The volume of potassium dichromate added in stain is adjusted to 6.0ml (concentration of potassium dichromate is constant) so that based on the
The gross mass of one dipping solution, in the first dipping solution, the concentration of silver is 8wt% (in terms of silver atoms weight),
The concentration of chromium is that 300 weight ppm (in terms of chromium atom weight) i.e. make silver catalyst 3.
The catalyst 1-3 analyzing the present invention finds, urges based on compound silver in the compound silver catalyst of the present invention
Agent gross weight, the content of silver is all in the range of 2～50wt%.Further, the compound silver catalyst of the present invention
In all contain the silver granuel of two kinds of each self-contained different auxiliary agents, the first silver granuel comprises and based on total catalyst weight is
The silver of 1～30wt% and the chromium of 1～2000 weight ppm, the second silver granuel comprises and based on total catalyst weight is
The silver of 1～30wt% and the rhenium of 5～2000 weight ppm, the second silver granuel the most also includes based on catalyst
Gross weight is the caesium of 5～2000 weight ppm.
Comparative example 1
Comparative example 1 is only with the second time dipping method of conventional one-dip technique, its step and embodiment 1
Identical, the difference is that only, the compound silver catalyst half that need not will prepare through dipping for the first time, roasting
Finished product is put in the container of energy evacuation, but directly by the α-Al of 15g2O3Carrier puts into the appearance of energy evacuation
In device, the most i.e. make comparative catalyst 1.
Embodiment 4
With in laboratory reactor (following letter " micro-anti-") evaluating apparatus test embodiments of the invention and comparative example
The performance of each silver catalyst prepared.The reactor that micro anti-evaluation device uses is the rustless steel of internal diameter 4mm
Pipe, reactor is placed in heating mantle.The admission space of catalyst is 1ml, and inert filler is arranged at bottom, makes catalysis
Agent bed is positioned at the flat-temperature zone of heating mantle.
Initial activity, optionally measure
The condition determination of the activity and selectivity that the present invention uses is as follows:
Reacting gas composition (mol%)
After stably reaching above-mentioned reaction condition, METHOD FOR CONTINUOUS DETERMINATION reactor enters, exit gas forms.Measurement result
Selectivity is calculated as follows after carrying out volume contraction correction:
Wherein, Δ EO is to work off one's feeling vent one's spleen poor with inlet gas ethylene oxide concentration, takes the flat of more than 10 groups test datas
Mean is as the result of the test on the same day.
Evaluation result is shown in Table 1.
Table 1 silver catalyst comparative example 1 and the 6th day evaluation result of embodiment 1-3
| Catalyst is numbered | Selectivity (%) |
| Comparative catalyst 1 | 82.53 |
| Silver catalyst 1 | 84.35 |
| Silver catalyst 2 | 84.71 |
| Silver catalyst 3 | 84.82 |
It is found that use the compound silver catalyst tool that the step impregnation technique of the present invention is made from table 1
Having higher selectivity, catalytic performance is more preferable.
Claims (11)
1. produce a preparation method for the compound silver catalyst of oxirane for oxidation of ethylene, including such as
Lower step:
1) it is dissolved in containing in amine aqueous solution or ammonia by Ag-containing compound with containing chromium compound, is made into silver ammino solution,
The scope of wherein said Ag-containing compound and the ratio containing chromium compound in terms of silver element and chromium element preferably 1:
5000～5000:1, more preferably 1:3000～3000:1；
2) by α-Al2O3Carrier puts into step 1) prepare silver ammino solution in soak, taking-up drains, then carries out
Calcination process, makes silver catalyst semi-finished product；
3) by Ag-containing compound, containing rhenium compound and optional being dissolved in containing amine aqueous solution or ammonia containing cesium compound
In, it is made into silver ammino solution, wherein said Ag-containing compound, containing rhenium compound and the optional ratio containing cesium compound
The scope of example is preferably (1～5000): 1:(0～10 in terms of silver element, rhenium element and cesium element), more excellent
Elect (5～3000): 1:(0～5 as)；
4) by step 2) prepare silver catalyst semi-finished product put into step 3) silver ammino solution in soak, take out
Drain, then carry out calcination process, make described compound silver catalyst.
Method the most according to claim 1, it is characterised in that step 1) and step 3) described in
Ag-containing compound is the acylate of organic compound or the inorganic compound of argentiferous, preferably argentiferous, inorganic
One or more in hydrochlorate and oxide, particularly preferably silver nitrate and/or silver oxalate.
Method the most according to claim 1 and 2, it is characterised in that step 1) described in described
It is in the oxide of chromium, halogenide, hydroxide, nitrate, chromate and bichromate containing chromium compound
One or more, preferably one or more in ammonium chromate, chromic nitrate and potassium dichromate.
4. according to the method described in any one in claim 1-3, it is characterised in that step 3) described in
Containing cesium compound be the oxide of the organic compound containing caesium or inorganic compound, preferably caesium, halogenide,
One or many in hydroxide, nitrate, sulfate, carbonate, bicarbonate, carboxylate and tungstates
Kind.
5. according to the method described in any one in claim 1-4, it is characterised in that step 3) described in
Containing the organic compound that rhenium compound is rhenium-containing or the oxide of inorganic compound, preferably rhenium, perrhenic acid, height
One or more in rhenate and methyl rhenium trioxide.
6. according to the method described in any one in claim 1-5, it is characterised in that step 2) and step
4) roasting described in is to carry out in the nitrogen oxygen atmosphere of air and/or oxygen content no more than 21%.
7. according to the method described in any one in claim 1-6, it is characterised in that the temperature of described roasting
In the range of 180～700 DEG C, preferably in the range of 200～500 DEG C, and the time of described roasting exists
In the range of 1～120 minute, preferably in the range of 1.5～30 minutes.
8. according to the method described in any one in claim 1-7, it is characterised in that step 2) described in
α-Al2O3α-Al in carrier2O3Content be more than 90 weight %, and preferably have the feature that crushing strength
It is 20～200N/ grains；Specific surface is 0.2～3.0m2/g；Water absorption rate is not less than 30%；Pore volume be 0.30～
0.85ml/g。
9. the compound silver catalyst prepared according to the method described in any one in claim 1-8, it is special
Levying and be, based on compound silver total catalyst weight in described compound silver catalyst, the content of silver is
2～50wt%, preferably 10～39wt%；The content of caesium is preferably 0～3000 weight ppm, more preferably 0～2000
Weight ppm；The content of rhenium is preferably 0.1～2000 weight ppm, more preferably 0.5～1500 weight ppm；
The content of chromium is preferably 0.05～3000 weight ppm, more preferably 0.1～2000 weight ppm.
Compound silver catalyst the most according to claim 9, it is characterised in that described compound silver is urged
Silver granuel containing two kinds of each self-contained different auxiliary agents in agent, the first silver granuel comprises and based on total catalyst weight is
The silver of 1～30wt% and the chromium of 1～2000 weight ppm, the second silver granuel comprises and based on total catalyst weight is
The silver of 1～30wt% and the rhenium of 5～2000 weight ppm, the second silver granuel the most also includes based on catalyst
Gross weight is the caesium of 5～2000 weight ppm.
11. according to method described in any one in claim 1-8 prepare compound silver catalyst or according to
Compound silver catalyst described in claim 9 or 10 is being produced the application in oxirane by oxidation of ethylene.
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| CN110605115A (en) * | 2018-06-15 | 2019-12-24 | 中国石油化工股份有限公司 | Silver catalyst for producing ethylene oxide by ethylene epoxidation and preparation method and application thereof |
| CN111437826A (en) * | 2019-01-16 | 2020-07-24 | 中国石油化工股份有限公司 | Supported silver catalyst and preparation method and application thereof |
| CN111437816A (en) * | 2019-01-16 | 2020-07-24 | 中国石油化工股份有限公司 | Supported silver catalyst and preparation method and application thereof |
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| CN110605115A (en) * | 2018-06-15 | 2019-12-24 | 中国石油化工股份有限公司 | Silver catalyst for producing ethylene oxide by ethylene epoxidation and preparation method and application thereof |
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| CN111437826A (en) * | 2019-01-16 | 2020-07-24 | 中国石油化工股份有限公司 | Supported silver catalyst and preparation method and application thereof |
| CN111437816A (en) * | 2019-01-16 | 2020-07-24 | 中国石油化工股份有限公司 | Supported silver catalyst and preparation method and application thereof |
| CN111437826B (en) * | 2019-01-16 | 2022-07-12 | 中国石油化工股份有限公司 | Supported silver catalyst and preparation method and application thereof |
| CN111437816B (en) * | 2019-01-16 | 2023-05-02 | 中国石油化工股份有限公司 | Supported silver catalyst and preparation method and application thereof |
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