CN104722332A - Production process of caprolactam catalyst - Google Patents
Production process of caprolactam catalyst Download PDFInfo
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- CN104722332A CN104722332A CN201510126686.3A CN201510126686A CN104722332A CN 104722332 A CN104722332 A CN 104722332A CN 201510126686 A CN201510126686 A CN 201510126686A CN 104722332 A CN104722332 A CN 104722332A
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- China
- Prior art keywords
- molecular sieve
- hexanolactam
- production technology
- distilled water
- catalyst
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Links
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002808 molecular sieve Substances 0.000 claims abstract description 35
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000002425 crystallisation Methods 0.000 claims abstract description 30
- 230000008025 crystallization Effects 0.000 claims abstract description 30
- 239000003513 alkali Substances 0.000 claims abstract description 23
- 239000012153 distilled water Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 16
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 13
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000001994 activation Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000007789 sealing Methods 0.000 claims abstract description 5
- 230000004913 activation Effects 0.000 claims abstract description 4
- 238000005516 engineering process Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 230000002977 hyperthermial effect Effects 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 238000010792 warming Methods 0.000 abstract 2
- ZJQPLBFKBQYYIO-UHFFFAOYSA-N dodecasodium;trisilicate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] ZJQPLBFKBQYYIO-UHFFFAOYSA-N 0.000 abstract 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- HYBIIGFUKKOJJM-UHFFFAOYSA-N cyclohexanone;hydroxylamine Chemical compound ON.O=C1CCCCC1 HYBIIGFUKKOJJM-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 238000007034 nitrosation reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention relates to a production process of a caprolactam catalyst. The production process comprises the following steps: (1) forming gel, namely adding silicon source substance, distilled water, tetrapropyl ammonium substance, butyl titanate and isopropanol in a crystallization reactor, stirring, warming to remove alcohol so as to obtain transparent sol, wherein the silicon source substance is selected from silica sol, sodium trisilicate and tetraethyl orthosilicate; (2) ageing, namely adding a TS-1 molecular sieve seed crystal in the transparent sol, sealing and stirring at room temperature; (3) crystallizing, namely warming after ageing, crystallizing for 12-96 hours, filtering, washing and drying to obtain TS-1 molecular sieve raw powder; (4) carrying out alkali treatment, namely adding the TS-1 molecular sieve raw powder, TPAOH and the distilled water in the crystallization reactor to obtain the alkali-treated TS-1 molecular sieve; (5) carrying out acid activation, namely carrying out acid activation on the alkali-treated TS-1 molecular sieve to obtain the caprolactam catalyst. According to the caprolactam catalyst prepared by using the production process disclosed by the invention, the mechanical strength is high, the granularity is small, the distribution is uniform, the activity is high, the selectivity is good, the service life is long, and the industrial application prospect is good.
Description
Technical field
The present invention relates to catalyst preparing production field, especially a kind of hexanolactam catalyst production technology.
Background technology
Caprolactam is a kind of important petrochemicals and the raw materials of chemical fibres, is the primary raw material manufacturing Fypro and resin.Due to the development of textile industry, Asia becomes the main consumption area of caprolactam.In recent years, the volume of production and marketing of domestic caprolactam presents the trend of fast development, and estimate that the apparent demand amount of domestic caprolactam in 2015 reaches 2,000,000 tons, the production of caprolactam still has very large development space in China.
What use in industrial production caprolactam technology at present mainly contains cyclohexanone-hydroxylamine assay, photo-nitrosation of cyclohexane process and toluene method.In these techniques, the most generally with benzene or phenol for cyclohexanone prepared by raw material, cyclohexanone prepares cyclohexanone oxime through cyclohexanone-azanol route, and the technique that Beckmann rearrangement obtains caprolactam then occurs in nicotinic acid.These technical process are all very complicated, comprise multiple reactions steps, and the economic utilization rate of atom is very low, and the seriously corroded to equipment, environmental pressure is very large.Therefore in the PRODUCTION TRAITS of caprolactam, researcher is by the reduction of the optimization of the exploitation of friendly process, process route, energy consumption and production cost, the minimizing of environmental pollution is as the emphasis studied, and preparation and the exploitation of its catalyst also become the focus of research.
TS-1 molecular sieve catalyst is widely used in the production of caprolactam.The rearrangement reaction catalytic performance to the molecular sieve containing titanium TS-1 of MFI structure such as Thangaraj is studied, and finds that the introducing of Ti metal can reduce the deactivation rate of catalyst, and the introducing of Ti is to the conversion ratio of reaction with selectively have active influence; A kind of crosslinked TS-1 molecular sieve of the preparation such as Palkovits, this corsslinking molecular sieve can provide more mesoporous confession to react, and greatly improves the catalytic activity of catalyst, is also extended the service life of catalyst simultaneously.But the hexanolactam catalyst mechanical strength of existing explained hereafter is little, granularity large, activity is low, needs to improve.
Summary of the invention
Main purpose of the present invention is to provide a kind of hexanolactam catalyst production technology, adopt the hexanolactam catalyst that this production technology prepares, mechanical strength is large, granularity is little and be evenly distributed, active high, selective good and there is longer service life, be applicable to industrial production.
For achieving the above object, the invention discloses a kind of hexanolactam catalyst production technology, it is characterized in that, comprise following steps:
(1) plastic: silicon source material, distilled water, tetrapropyl ammonium salts substances, butyl titanate and isopropyl alcohol are joined in crystallization device, stirring, intensification obtain vitreosol except after alcohol; Described silicon source material is selected from Ludox, sodium silicate, ethyl orthosilicate, ethyl orthosilicate; Wherein, the mass fraction of described silicon source material, distilled water, tetrapropyl ammonium salts substances, butyl titanate and isopropyl alcohol is than being 1:(1.50 ~ 6.50): (0.50 ~ 6.00): (0.01 ~ 0.10): (0.10 ~ 1.00);
(2) ageing: add TS-1 molecular sieve crystal seed in above-mentioned vitreosol, room temperature lower seal stirs, and wherein, the mass fraction of described vitreosol and described TS-1 molecular sieve crystal seed is than being (10 ~ 500): 1;
(3) crystallization: the crystallization that heats up after ageing 12 ~ 96h, after filtration, washes and obtains TS-1 molecular screen primary powder after drying;
(4) alkali treatment: TS-1 molecular screen primary powder, TPAOH and distilled water are joined in crystallization device, obtains the TS-1 molecular sieve after alkali treatment;
(5) acid activation: by TS-1 molecular sieve, H after described alkali treatment
2sO
4and H
2o
2join in the tank diameter of band heating, obtain hexanolactam catalyst through acid activation process.
Preferably, described step (1) is further: join in crystallization device by silicon source material, distilled water, tetrapropyl ammonium salts substances, butyl titanate and isopropyl alcohol, join stirring at room temperature 1 ~ 3h in crystallization device, after butyl titanate and isopropyl alcohol are mixed, slowly join in above-mentioned crystallization device, stirring at room temperature 1 ~ 2h, heats up after removing alcohol and obtains vitreosol; Described silicon source material is selected from Ludox, sodium silicate, ethyl orthosilicate, ethyl orthosilicate; Wherein, the mass fraction of described silicon source material, distilled water, tetrapropyl ammonium salts substances, butyl titanate and isopropyl alcohol is than being 1:(1.50 ~ 6.50): (0.50 ~ 6.00): (0.01 ~ 0.10): (0.10 ~ 1.00).
Preferably, in step (1), the mass fraction of described silicon source material, distilled water, tetrapropyl ammonium salts substances, butyl titanate and isopropyl alcohol is than being 1:(2.50 ~ 5.50): (2.50 ~ 4.00): (0.03 ~ 0.08): (0.20 ~ 0.70).
Preferably, in described step (2), the mass fraction of described vitreosol and described TS-1 molecular sieve crystal seed is than being (80 ~ 300): 1.
Preferably, described step (4) is further: be 1:(0.1 ~ 5.0 by mass ratio): (5.0 ~ 20.0) TS-1 molecular screen primary powder, TPAOH and distilled water join in crystallization device, stirring at room temperature 1 ~ 12h, the lower intensification crystallization 12 ~ 96h of sealing, after filtration, obtains the TS-1 molecular sieve after alkali treatment after washing and drying.
Preferably, described step (5) is further: by TS-1 molecular sieve, H after described alkali treatment
2sO
4and H
2o
2join in the tank diameter of band heating, obtain hexanolactam catalyst through acid activation process.
Preferably, TS-1 molecular sieve, H after described alkali treatment
2sO
4and H
2o
2join band heating tank diameter in, hyperthermic treatment 1 ~ 6h, after filtration, washing, dry roasting 1 ~ 12h, obtain hexanolactam catalyst.
Preferably, TS-1 molecular sieve, H after described alkali treatment
2sO
4and H
2o
2mass ratio be 1:(0.003 ~ 0.80): (0.05 ~ 5.0).Described mass ratio is material net content ratio, H
2sO
4and H
2o
2can be dissolved in the solution of variable concentrations, then add.
Preferably, TS-1 molecular sieve, H after described alkali treatment
2sO
4and H
2o
2mass ratio be 1:(0.01 ~ 0.50): (0.1 ~ 3.0).
Preferably, described tetrapropyl ammonium salts substances is specially TPAOH, TPABr, TPACl.
Adopt the hexanolactam catalyst that this production technology prepares, mechanical strength is large, granularity is little and be evenly distributed, active high, selective good and there is longer service life, have good prospects for commercial application.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further.
Specific embodiment 1
(1) 300g distilled water, 100g Ludox and 150gTPAOH are joined stirring at room temperature 2h in crystallization device, after 5g butyl titanate and 20g isopropyl alcohol are mixed, slowly join in above-mentioned crystallization device, stirring at room temperature 1h, heat up after removing alcohol and obtain vitreosol.
(2) in above-mentioned 500g vitreosol, 5gTS-1 molecular sieve crystal seed is added, room temperature lower seal ageing 12h.
(3) heat up after ageing crystallization 48h, after filtration, washes and obtain TS-1 molecular screen primary powder after drying.
(4) 300gTS-1 molecular screen primary powder, 60gTPAOH and 1800g distilled water are joined in crystallization device, stirring at room temperature 10h, the lower intensification crystallization 12h of sealing, after filtration, obtain the TS-1 molecular sieve after alkali treatment after washing and drying.
(5) TS-1 molecular sieve, sulfuric acid, H after weighing alkali treatment is calculated by net content mass ratio 1:0.3:2
2o
2, wherein, it is (also can be the solution of other concentration), H in the solution of 0.25mol/L that sulfuric acid is present in concentration
2o
2being present in concentration is (also can be the solution of other concentration) in the solution of 27.5wt%, joined band heating tank diameter in, hyperthermic treatment 2h, after filtration, washing, dry roasting 5h, obtain hexanolactam catalyst.
Specific embodiment 2
(1) 320kg distilled water, 105kg ethyl orthosilicate and 145kgTPAOH are joined stirring at room temperature 2h in crystallization device, after 5.5kg butyl titanate and 19.0kg isopropyl alcohol are mixed, slowly join in above-mentioned crystallization device, stirring at room temperature 1h, heats up after removing alcohol and obtains vitreosol.
(2) in above-mentioned 550kg vitreosol, 6kgTS-1 molecular sieve crystal seed is added, room temperature lower seal ageing 18h.
(3) heat up after ageing crystallization 48h, after filtration, washes and obtain TS-1 molecular screen primary powder after drying.
(4) 200kgTS-1 molecular screen primary powder, 60kgTPAOH and 1300kg distilled water are joined in crystallization device, stirring at room temperature 10h, the lower intensification crystallization 12h of sealing, after filtration, obtain the TS-1 molecular sieve after alkali treatment after washing and drying.
(5) TS-1 molecular sieve, sulfuric acid, H after weighing alkali treatment is calculated by net content mass ratio 1:0.01:0.1
2o
2, wherein, it is (also can be the solution of other concentration), H in the solution of 0.25mol/L that sulfuric acid is present in concentration
2o
2being present in concentration is (also can be the solution of other concentration) in the solution of 27.5wt%, joined band heating tank diameter in, hyperthermic treatment 2.5h, after filtration, washing, dry roasting 6h, obtain hexanolactam catalyst.
Adopt the hexanolactam catalyst that this production technology prepares, mechanical strength is large, granularity is little and be evenly distributed, active high, selective good and there is longer service life, have good prospects for commercial application.
Above-described embodiment is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, other multi-form change or change can also be made on the basis of the above description.Within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc. are all included among protection scope of the present invention.
Claims (10)
1. a hexanolactam catalyst production technology, is characterized in that, comprises following steps:
(1) plastic: silicon source material, distilled water, tetrapropyl ammonium salts substances, butyl titanate and isopropyl alcohol are joined in crystallization device, stirring, intensification obtain vitreosol except after alcohol; Described silicon source material is selected from Ludox, sodium silicate, ethyl orthosilicate, ethyl orthosilicate; Wherein, the mass fraction of described silicon source material, distilled water, tetrapropyl ammonium salts substances, butyl titanate and isopropyl alcohol is than being 1:(1.50 ~ 6.50): (0.50 ~ 6.00): (0.01 ~ 0.10): (0.10 ~ 1.00);
(2) ageing: add TS-1 molecular sieve crystal seed in above-mentioned vitreosol, room temperature lower seal stirs, and wherein, the mass fraction of described vitreosol and described TS-1 molecular sieve crystal seed is than being (10 ~ 500): 1;
(3) crystallization: the crystallization that heats up after ageing 12 ~ 96h, after filtration, washes and obtains TS-1 molecular screen primary powder after drying;
(4) alkali treatment: TS-1 molecular screen primary powder, TPAOH and distilled water are joined in crystallization device, obtains the TS-1 molecular sieve after alkali treatment;
(5) acid activation: the TS-1 molecular sieve after described alkali treatment is obtained hexanolactam catalyst through acid activation process.
2. hexanolactam catalyst production technology according to claim 1, it is characterized in that, described step (1) is further: join in crystallization device by silicon source material, distilled water, tetrapropyl ammonium salts substances, butyl titanate and isopropyl alcohol, join stirring at room temperature 1 ~ 3h in crystallization device, after butyl titanate and isopropyl alcohol are mixed, slowly join in above-mentioned crystallization device, stirring at room temperature 1 ~ 2h, heat up after removing alcohol and obtain vitreosol; Described silicon source material is selected from Ludox, sodium silicate, ethyl orthosilicate, ethyl orthosilicate; Wherein, the mass fraction of described silicon source material, distilled water, tetrapropyl ammonium salts substances, butyl titanate and isopropyl alcohol is than being 1:(1.50 ~ 6.50): (0.50 ~ 6.00): (0.01 ~ 0.10): (0.10 ~ 1.00).
3. according to the hexanolactam catalyst production technology one of claim 1-2 Suo Shu, it is characterized in that, in step (1), the mass fraction of described silicon source material, distilled water, tetrapropyl ammonium salts substances, butyl titanate and isopropyl alcohol is than being 1:(2.50 ~ 5.50): (2.50 ~ 4.00): (0.03 ~ 0.08): (0.20 ~ 0.70).
4. according to the hexanolactam catalyst production technology one of claim 1-2 Suo Shu, it is characterized in that, in described step (2), the mass fraction of described vitreosol and described TS-1 molecular sieve crystal seed is than being (80 ~ 300): 1.
5. according to the hexanolactam catalyst production technology one of claim 1-2 Suo Shu, it is characterized in that, described step (4) is further: be 1:(0.1 ~ 5.0 by mass ratio): (5.0 ~ 20.0) TS-1 molecular screen primary powder, TPAOH and distilled water join in crystallization device, stirring at room temperature 1 ~ 12h, the lower intensification crystallization 12 ~ 96h of sealing, after filtration, obtains the TS-1 molecular sieve after alkali treatment after washing and drying.
6. according to the hexanolactam catalyst production technology one of claim 1-2 Suo Shu, it is characterized in that, described step (5) is further: by TS-1 molecular sieve, H after described alkali treatment
2sO
4and H
2o
2join in the tank diameter of band heating, obtain hexanolactam catalyst through acid activation process.
7. hexanolactam catalyst production technology according to claim 6, is characterized in that, described step (5) is further: the TS-1 molecular sieve after described alkali treatment, H
2sO
4and H
2o
2join band heating tank diameter in, hyperthermic treatment 1 ~ 6h, after filtration, washing, dry roasting 1 ~ 12h, obtain hexanolactam catalyst.
8. hexanolactam catalyst production technology according to claim 7, is characterized in that, the TS-1 molecular sieve after described alkali treatment, H
2sO
4and H
2o
2mass ratio be 1:(0.003 ~ 0.80): (0.05 ~ 5.0).
9. hexanolactam catalyst production technology according to claim 8, is characterized in that, the TS-1 molecular sieve after described alkali treatment, H
2sO
4and H
2o
2mass ratio be 1:(0.01 ~ 0.50): (0.1 ~ 3.0).
10. according to the hexanolactam catalyst production technology one of claim 1-9 Suo Shu, it is characterized in that, described tetrapropyl ammonium salts substances is specially TPAOH, TPABr, TPACl.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1245090A (en) * | 1998-08-18 | 2000-02-23 | 中国石油化工集团公司 | Process for modifying Ti-Si molecular sieve |
| CN101767036A (en) * | 2009-12-25 | 2010-07-07 | 湘潭大学 | Titanium silicalite TS-1 catalyst preparation method |
-
2015
- 2015-03-23 CN CN201510126686.3A patent/CN104722332B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1245090A (en) * | 1998-08-18 | 2000-02-23 | 中国石油化工集团公司 | Process for modifying Ti-Si molecular sieve |
| CN101767036A (en) * | 2009-12-25 | 2010-07-07 | 湘潭大学 | Titanium silicalite TS-1 catalyst preparation method |
Non-Patent Citations (2)
| Title |
|---|
| FANGRUI QIU ET AL.: "Preparation and properties of TS-1 zeolite and film using Sil-1 nanoparticles as seeds", 《CHEMICAL ENGINEERING JOURNAL》 * |
| XIAOXUE WU ET AL.: "Effect of TS-1treatment by tetrapropyl ammonium hydroxide on cyclohexanone ammoximation", 《CATALYSIS COMMUNICATIONS》 * |
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