CN115845916A - Preparation method and application of Au/TS-1 nano microsphere catalyst for propylene gas phase epoxidation - Google Patents
Preparation method and application of Au/TS-1 nano microsphere catalyst for propylene gas phase epoxidation Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 239000004005 microsphere Substances 0.000 title claims abstract description 22
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 20
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 19
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002808 molecular sieve Substances 0.000 claims abstract description 23
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- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
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- 239000010931 gold Substances 0.000 claims description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 24
- 229910052719 titanium Inorganic materials 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
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- 239000000203 mixture Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 9
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
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- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000012495 reaction gas Substances 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 2
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 claims description 2
- POSYVRHKTFDJTR-UHFFFAOYSA-M tetrapropylazanium;fluoride Chemical compound [F-].CCC[N+](CCC)(CCC)CCC POSYVRHKTFDJTR-UHFFFAOYSA-M 0.000 claims description 2
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- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
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- 230000003197 catalytic effect Effects 0.000 abstract description 9
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 5
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
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- 238000000967 suction filtration Methods 0.000 description 4
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- 241000282326 Felis catus Species 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the technical field of petrochemical catalysis, and discloses a preparation method and application of an Au/TS-1 nano microsphere catalyst for propylene gas phase epoxidation. After the TS-1 molecular sieve is crystallized, the molecular sieve and the crystallization mother liquor do not undergo a centrifugal washing process, and no additional binder, pore-forming agent and the like are added, and the suspension formed by the molecular sieve and the crystallization mother liquor is directly subjected to spray drying, molding and roasting to prepare the molecular sieve nano-microsphere with the size of TS-1. And loading the Au species on the TS-1 nano microsphere carrier by a deposition precipitation method. The prepared Au/TS-1 catalyst is used for propylene gas phase epoxidation, shows good catalytic performance at a lower reaction temperature, and is superior to the traditional catalyst prepared by centrifugally washing and TS-1 carrier which is formed by spray drying and is not additionally added with other substances.
Description
Technical Field
The invention belongs to the technical field of petrochemical catalysis, and particularly relates to a preparation method of an Au/TS-1 nano microsphere catalyst for propylene gas phase epoxidation. In particular to a catalyst for carrying out the gas-phase epoxidation reaction of propylene under the condition of an oxyhydrogen system.
Background
Propylene Oxide (Propylene Oxide) is the third largest Propylene derivative, and in recent years, its global yield is second only to polypropylene and acrylonitrile. PO is an important basic organic chemical intermediate, is widely used for producing polyether polyol and further producing polyurethane, and can also be used for producing propylene glycol, nonionic surfactants and the like with wide application.
The Au/TS-1 catalyst realizes the gas-phase epoxidation of propylene to prepare propylene oxide in a hydrogen-oxygen system, and a byproduct in the reaction process is water, so that the Au/TS-1 catalyst has the advantages of high atom utilization rate, environmental friendliness and the like. At present, the preparation of TS-1 mainly adopts a hydrothermal crystallization method, and a product after crystallization is centrifugally washed, dried and roasted to obtain a target product titanium silicalite molecular sieve (TS-1) carrier. However, during the separation, the centrifugal washing requires a large amount of water to reach a suitable pH. If a filter membrane separation method is adopted, the small-size TS-1 crystals can block the micropores of the filter membrane, so that the separation efficiency is greatly reduced, and the subsequent industrial amplification is not facilitated.
European patent (EP 0200260), U.S. patent (US 4701428A), (US 4859785A), (US 4954653A), (US 7182932B 2), (US 6106803A), and the like, and Publications (Advanced Materials research. Trans Tech Publications Ltd, 2014.p.287-291.), (Chemical Engineering Journal325 (2017): 169-175.), (ACS omega4.2 (2019): 4397-4404.) and the like disclose that TS-1 powder is mixed with a binder (silica sol or silica species hydrolysate, etc.) into a slurry and then spray-molded to form high strength microspheres.
The patent (CN 102989503A) discloses a spray forming method of a high-strength TS-1 titanium silicalite molecular sieve catalyst, which is characterized in that TS-1 raw powder is added with silica sol and boric acid to prepare uniform slurry according to a proportion, the uniform slurry is formed by adopting a spray forming method, and then the formed TS-1 catalyst is obtained by drying and roasting.
The patent (CN 102614911A) discloses a method for one-step molding a titanium silicalite molecular sieve, which comprises the steps of crystallizing a hydrothermally synthesized titanium silicalite molecular sieve, omitting separation and washing with water, without roasting, directly adding a matrix substance, a binder and a pore-expanding agent, performing spray molding after pulping, roasting the molded microspheres to remove the template agent, and further obtaining large-particle molded titanium silicalite molecular sieve particles, wherein hydrogen peroxide is used as an oxidant in cyclohexanone ammoximation and olefin epoxidation reactions.
In the gas phase epoxidation of propylene, the active site of Au is the key of the reaction process. In the process of loading Au by a deposition precipitation method, the Au species precursor [ Au (OH) is generated due to isoelectric point x (Cl) 4-x ] - More tending to fall near titanium species, matrix substances (such as boric acid and kaolin), binders (such as silica sol and alumina sol), peptizing agents (such as nitric acid and citric acid), pore-enlarging agents (such as sesbania powder and polyethylene glycol) and the like are additionally added, on one hand, the process flow is complicated, the economic cost is improved, and on the other hand, the introduction of the binders and the like is bound to cover a part of titanium species, so that the capture efficiency and the fall of Au are influenced, and the performance of the catalyst is further influenced.
Disclosure of Invention
The invention relates to a preparation method of an Au/TS-1 nano microsphere catalyst suitable for gas phase propylene epoxidation. Different from the found published documents and patents, the method omits the separation and water washing processes of the titanium silicalite molecular sieve synthesized by hydrothermal crystallization, does not add any other substances (matrix substance, binder, peptizer and pore-expanding agent) and directly carries out spray forming to prepare the TS-1 nano molecular sieve microspheres with the size of (2-5 um). The method aims to ensure good catalytic performance of the catalyst, and simultaneously, the separation process is simplified by utilizing the formation of micron-sized molecular sieve microspheres. The roasted TS-1 molecular sieve nano-microspheres have hollow structures, and a large number of intercrystalline pores are formed among nano TS-1 crystal grains, so that on one hand, the heat transfer efficiency in the epoxidation process is improved, and the agglomeration growth caused by unfavorable heat dissipation of active gold species is avoided; on the other hand, the mass transfer efficiency in the catalytic process can be promoted, secondary side reaction and catalyst inactivation caused by product retention are avoided, and the service life of the catalyst is prolonged.
The technical scheme of the invention is as follows:
a preparation method of Au/TS-1 nano microsphere catalyst for gas-phase epoxidation of propylene, which comprises the following steps:
(1) Stirring and mixing a surfactant, a template agent and deionized water uniformly, and adding a silicon source for sufficient hydrolysis to obtain gel A;
(2) Uniformly mixing a titanium source and an organic solvent, slowly dripping the mixture into the gel A, uniformly stirring the mixture, and removing alcohol to obtain silicon-titanium gel B;
the silicon-titanium gel B comprises SiO in a molar ratio 2 ：TiO 2 : template agent: surfactant (B): organic solvent: h 2 O＝1：(0.01-0.033)：(0.15-0.3)：(0.002-0.01)：(0.3-1.4)：(7-21)；
(3) Crystallizing the silicon-titanium gel B at 130-200 ℃ for 16-72h, directly spraying, drying, molding and roasting with crystallized mother liquor without a centrifugal washing process to prepare TS-1 molecular sieve nano microspheres;
the TS-1 molecular sieve nano microsphere has the silicon-titanium molar ratio of (30-100): 1;
(4) And loading gold on the titanium silicalite TS-1 nano microspheres by a deposition precipitation method to obtain the supported catalyst Au/TS-1.
Further, in the step (1), the silicon source is one or a mixture of more than two of tetraethyl orthosilicate, tetramethyl orthosilicate, tetrapropyl orthosilicate and tetrabutyl orthosilicate, or one of silica sol and white carbon black.
Further, in the step (1), the template agent is one or a mixture of more than two of tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium chloride and tetrapropylammonium fluoride.
Further, in the step (1), the stirring temperature is 40-60 ℃, and the stirring time is 2-12h; in the step (2), the dealcoholization temperature is 60-90 ℃, and the organic solvent is one of methanol, ethanol, isopropanol and butanol.
Further, the feeding rate of the spraying process in the step (3) is 7-20 mL/min -1 The temperature of the vaporization chamber is 180-300 ℃.
Further, in the step (3), the drying temperature is 90-110 ℃, the roasting temperature is 450-650 ℃, and the roasting time is 6-10 hours; the roasting atmosphere is one or more of air, nitrogen, argon, helium and ammonia gas.
The catalyst prepared by the method is prepared in an oxyhydrogen systemThe reaction is carried out in a normal pressure fixed bed reaction device, the reaction temperature is 80-300 ℃, and the volume ratio composition of reaction gas is C 3 H 6 /H 2 /O 2 /N 2 =1/1/1/7, and the space velocity is 4000-20000mL · h -1 ·Kg -1 cat. 。
The invention has the beneficial effects that: and (3) directly carrying out aerosol spray drying separation, drying and roasting on the TS-1 molecular sieve suspension mother liquor obtained by hydrothermal crystallization without a centrifugal washing process or adding any other substances (a binder, a pore-forming agent and the like) to prepare the titanium silicalite TS-1 nano microspheres. Compared with a centrifugal washing process and a forming method of additionally adding a matrix substance, a binder, a pore-expanding agent and the like, the method simplifies the process flow, reduces the economic cost, and effectively avoids the problems that a part of titanium species can be covered by the introduction of the binder and the like and the Au species is influenced in the position.
Drawings
FIG. 1 (a) is a schematic diagram of the formation of a carrier according to examples 1-3 of the present invention;
FIG. 1 (b) is an SEM image (x 2500 times) of example 2;
FIG. 1 (c) is an SEM photograph (x 11000 times) of example 2;
FIG. 1 (d) is an SEM photograph (x 30000 times) of example 2;
FIG. 1 (e) is an SEM image (x 75000 times) of example 2;
FIG. 2 is an XRD pattern of the supports of examples 1-3 of the present invention and the support of comparative example 1;
FIG. 3 is a UV-Vis diagram of the supports of examples 1 to 3 according to the invention and of the support of comparative example 1;
FIG. 4 is a graph showing the PO formation rate with time for the evaluation of the supports of examples 1 to 3 of the present invention and the catalysts of comparative examples 1 and 2.
Detailed Description
The following detailed description of the embodiments of the invention is provided in connection with the accompanying drawings and the appended claims.
Example 1
2g of Tween 20 was mixed with 32g of deionized water at 40 ℃ in a three-neck flask, 18.8g of 40wt.% TPAOH aqueous solution was added and mixed at 40 ℃ for a while, and then 35.6g of TEOS was added and sufficiently stirred at 40 ℃ for hydrolysis.
Dissolving 1.94g of tetrabutyl titanate in 14.3g of isopropanol, uniformly mixing to obtain titanium gel, dropwise adding the titanium gel into silica sol, heating to 80 ℃ after dropwise adding, opening a three-necked bottle stopper, and stirring at 80 ℃ to remove alcohol for 1h; and finally, filling the obtained solution into a crystallization kettle, crystallizing for 24 hours at 170 ℃, carrying out aerosol-assisted spray drying on a crystallized product, roasting for 10 hours in air at 550 ℃ to obtain a TS-1 (30) carrier, and testing the Si/Ti ratio to be 32.1 by ICP-OES.
Taking 5mL of chloroauric acid aqueous solution with the concentration of 0.04867mol/L, adding 27mL of deionized water for dilution, adding 0.8g of the TS-1 molecular sieve carrier obtained above, and respectively using 1M and 0.1M Na 2 CO 3 And (2) adjusting the pH value of the solution adjusting system to be 7.9-8.0, stirring for 6h at 35 ℃, then performing suction filtration and washing, then drying for about 10h at 35 ℃ under vacuum, tabletting and sieving the obtained product for 20-40 meshes, and reducing 0.15g in hydrogen, propylene and nitrogen atmosphere at 300 ℃ for 2h to obtain the Au/TS-1 (30) catalyst. The activity was tested at 160 ℃ and the results of the catalytic epoxidation are shown in table 1;
table 1 shows the catalyst of examples 1-3 of the present invention and the catalyst of comparative examples 1 and 2, which were evaluated for the product distribution and PO formation rate at 20 h.
TABLE 1 catalyst evaluation of product distribution and PO formation Rate at 20h
Reaction conditions C 3 H 6 /O 2 /H 2 /N 2 =1/1/1/7 (volume ratio), reaction temperature: 160 ℃, reaction pressure: 0.1MPa, space velocity: 14000mL h -1 g cat. -1 All data are taken from the 20 th run after the reaction has run smoothly.
Example 2
2g of Tween 20 was mixed with 32g of deionized water at 40 ℃ in a three-neck flask, 18.8g of 40wt.% TPAOH aqueous solution was added and mixed at 40 ℃ for a while, and then 35.6g of TEOS was added and sufficiently stirred at 40 ℃ for hydrolysis.
Dissolving 0.97g of tetrabutyl titanate in 7.2g of isopropanol, uniformly mixing to obtain titanium gel, dropwise adding the titanium gel into silica sol, heating to 80 ℃ after dropwise adding is finished, opening a bottle stopper of a three-necked bottle, and stirring at 80 ℃ to remove alcohol for 1 hour; and finally, filling the obtained solution into a crystallization kettle, crystallizing for 24 hours at 170 ℃, carrying out aerosol-assisted spray drying on a crystallized product, roasting for 10 hours in air at 550 ℃ to obtain a TS-1 (60) carrier, and testing the Si/Ti ratio to be 58.2 by ICP-OES.
Taking 5mL of chloroauric acid aqueous solution with the concentration of 0.04867mol/L, adding 27mL of deionized water for dilution, adding 0.8g of the TS-1 molecular sieve carrier obtained above, and respectively using 1M and 0.1M Na 2 CO 3 And (2) adjusting the pH value of the solution adjusting system to be 7.9-8.0, stirring for 6h at 35 ℃, then performing suction filtration and washing, then drying for about 10h at 35 ℃ in vacuum, tabletting and sieving an obtained product by 20-40 meshes, and reducing 0.15g of the product in hydrogen, propylene and nitrogen atmosphere at 300 ℃ for 2h to obtain the Au/TS-1 (60) catalyst. The activity was tested at 160 ℃ and the results of the catalytic epoxidation are shown in table 1.
Example 3
2g of Tween 20 was mixed with 32g of deionized water at 40 ℃ in a three-neck flask, 18.8g of 40wt.% TPAOH aqueous solution was added and mixed at 40 ℃ for a while, and then 35.6g of TEOS was added and sufficiently stirred at 40 ℃ for hydrolysis.
Dissolving 0.49g of tetrabutyl titanate in 3.6g of isopropanol, uniformly mixing to obtain titanium gel, dropwise adding the titanium gel into silica sol, heating to 80 ℃ after dropwise adding, opening a three-necked bottle stopper, and stirring at 80 ℃ to remove alcohol for 1h; and finally, filling the obtained solution into a crystallization kettle, crystallizing at 170 ℃ for 24 hours, carrying out aerosol-assisted spray drying on a crystallized product, roasting in air at 550 ℃ for 10 hours to obtain a TS-1 (120) carrier, and testing the Si/Ti ratio to be 107.8 by ICP-OES.
Taking 5mL of chloroauric acid aqueous solution with the concentration of 0.04867mol/L, adding 27mL of deionized water for dilution, adding 0.8g of the TS-1 molecular sieve carrier obtained above, and respectively using 1M and 0.1M Na 2 CO 3 The pH value of the solution adjusting system is between 7.9 and 8.0, and the solution is stirred for 6 hours at the temperature of 35 ℃ and then is pumpedFiltering, washing, drying at 35 deg.C under vacuum for 10 hr to obtain product, tabletting, sieving with 20-40 mesh sieve, and reducing 0.15g at 300 deg.C in hydrogen, propylene and nitrogen atmosphere for 2 hr to obtain Au/TS-1 (120) catalyst. The activity was tested at 160 ℃ and the results of the catalytic epoxidation are shown in table 1.
Comparative example 1
2g of Tween 20 was mixed with 32g of deionized water at 40 ℃ in a three-neck flask, 18.8g of 40wt.% TPAOH aqueous solution was added and mixed at 40 ℃ for a while, and then 35.6g of TEOS was added and sufficiently stirred at 40 ℃ for hydrolysis.
Dissolving 0.97g of tetrabutyl titanate in 7.2g of isopropanol, uniformly mixing to obtain titanium gel, dropwise adding the titanium gel into silica sol, heating to 80 ℃ after dropwise adding, opening a three-necked bottle stopper, and stirring at 80 ℃ to remove alcohol for 1h; and finally, filling the obtained solution into a crystallization kettle, crystallizing for 24 hours at 170 ℃, centrifugally washing a crystallized product until filtrate is neutral, drying overnight at 110 ℃, roasting for 10 hours in air at 550 ℃ to obtain a TS-1 (60) -N carrier, and testing the Si/Ti ratio to be 62.4 by ICP-OES.
Taking 5mL of chloroauric acid aqueous solution with the concentration of 0.04867mol/L, adding 27mL of deionized water for dilution, adding 0.8g of the TS-1 (60) -N molecular sieve carrier obtained in the previous step, and respectively using 1M Na and 0.1M Na 2 CO 3 And (2) adjusting the pH value of the solution adjusting system to be 7.9-8.0, stirring for 6h at 35 ℃, then performing suction filtration and washing, then drying for about 10h at 35 ℃ under vacuum, tabletting and sieving the obtained product for 20-40 meshes, and reducing 0.15g in hydrogen, propylene and nitrogen atmosphere at 300 ℃ for 2h to obtain the Au/TS-1 (60) -N catalyst. The activity was tested at 160 ℃ and the results of the catalytic epoxidation are shown in table 1.
Comparative example 2
Dissolving 0.97g of tetrabutyl titanate in 7.2g of isopropanol, uniformly mixing to obtain titanium gel, dropwise adding the titanium gel into silica sol, heating to 80 ℃ after dropwise adding, opening a three-necked bottle stopper, and stirring at 80 ℃ to remove alcohol for 1h; and finally, filling the obtained solution into a crystallization kettle, crystallizing at 170 ℃ for 24h, directly adding 2.68g of boric acid and 30 wt% of boric acid into a crystallization product without centrifugal washing, fully mixing uniformly, carrying out aerosol-assisted spray drying, carrying out overnight drying at 110 ℃, roasting in air at 550 ℃ for 10h to obtain a TS-1 (60) -A carrier, and testing by ICP-OES that the Si/Ti ratio is 60.7.
Taking 5mL of chloroauric acid aqueous solution with the concentration of 0.04867mol/L, adding 27mL of deionized water for dilution, adding 0.8g of the TS-1 (60) -A molecular sieve carrier obtained in the previous step, and respectively using 1M Na and 0.1M Na 2 CO 3 And (2) adjusting the pH value of the solution adjusting system to be 7.9-8.0, stirring for 6h at 35 ℃, then performing suction filtration and washing, then drying for about 10h at 35 ℃ under vacuum, tabletting and sieving the obtained product for 20-40 meshes, and reducing 0.15g in hydrogen, propylene and nitrogen atmosphere at 300 ℃ for 2h to obtain the Au/TS-1 (60) -A catalyst. The activity was tested at 160 ℃ and the results of the catalytic epoxidation are shown in table 1.
The results show that the nanometer microspheres with the silicon-aluminum ratio of 60 are preferably used as the catalyst Au/TS-1 (60), the catalyst Au/TS-1 (60) -N prepared by centrifugal washing shows better catalytic performance compared with the catalyst Au/TS-1 (60) -A prepared by adding (matrix, adhesive, sol agent and pore-expanding agent), and the generation rates of the propylene oxide in the propylene gas-phase epoxidation reaction of the Au/TS-1 (60), au/TS-1 (60) -N and Au/TS-1 (60) -A catalysts are respectively 186.8 g, 138.1 g and 44.8g PO ·Kg cat· -1 ·h -1 。
Claims (9)
1. A preparation method of Au/TS-1 nano microsphere catalyst for propylene gas phase epoxidation is characterized by comprising the following steps:
(1) Stirring and mixing the surfactant, the template agent and the deionized water uniformly, and adding a silicon source for sufficient hydrolysis to obtain gel A;
(2) Uniformly mixing a titanium source and an organic solvent, slowly dripping the mixture into the gel A, uniformly stirring the mixture, and removing alcohol to obtain silicon-titanium gel B;
in silicon-titanium gel BThe composition of the molar ratio of substances is SiO 2 ：TiO 2 : template agent: surfactant (b): organic solvent: h 2 O＝1：(0.01-0.033)：(0.15-0.3)：(0.002-0.01)：(0.3-1.4)：(7-21)；
(3) Crystallizing the silicon-titanium gel B at 130-200 ℃ for 16-72h, directly spraying, drying, molding and roasting with crystallized mother liquor without a centrifugal washing process to prepare TS-1 molecular sieve nano microspheres;
the TS-1 molecular sieve nano microsphere has the silicon-titanium molar ratio of (30-100): 1;
(4) And loading gold on the titanium silicalite TS-1 nano microspheres by a deposition precipitation method to obtain the supported catalyst Au/TS-1.
2. The method according to claim 1, wherein the feeding rate of the spraying process in the step (3) is 7 to 20 mL-min -1 The temperature of the vaporization chamber is 180-300 ℃.
3. The preparation method according to claim 1, wherein the drying temperature in the step (3) is 90-110 ℃, the roasting temperature is 450-650 ℃, and the roasting time is 6-10h; the roasting atmosphere is one or more of air, nitrogen, argon, helium and ammonia gas.
4. The production method according to claim 1,
in the step (1), the stirring temperature is 40-60 ℃, and the stirring time is 2-12h; in the step (2), the dealcoholization temperature is 60-90 ℃, and the organic solvent is one of methanol, ethanol, isopropanol and butanol.
5. The production method according to claim 1,
the template agent is one or a mixture of more than two of tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium chloride and tetrapropylammonium fluoride.
6. The process according to claim 1, wherein in the step (1),
the silicon source is one or a mixture of more than two of tetraethyl orthosilicate, tetramethyl orthosilicate, tetrapropyl orthosilicate and tetrabutyl orthosilicate, or one of silica sol and white carbon black.
7. A catalyst prepared by the process of any one of claims 1 to 6.
8. Use of the catalyst of claim 7 in the vapor phase epoxidation of propylene to propylene oxide in a hydrogen and oxygen system.
9. The use according to claim 8, wherein the reaction is carried out in an atmospheric fixed bed reactor at a temperature of 80 to 300 ℃ and a volume ratio composition C of the reaction gas 3 H 6 /H 2 /O 2 /N 2 =1/1/1/7, and the space velocity is 4000-20000mL · h -1 ·Kg -1 cat. 。
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