CN103910363A - Method for modifying titanium silicalite molecular sieves and application thereof - Google Patents
Method for modifying titanium silicalite molecular sieves and application thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 21
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title abstract description 13
- 229910052719 titanium Inorganic materials 0.000 title abstract description 11
- 239000010936 titanium Substances 0.000 title abstract description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000012670 alkaline solution Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims description 28
- 238000012986 modification Methods 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 16
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 6
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 6
- 229940043276 diisopropanolamine Drugs 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 229940001516 sodium nitrate Drugs 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 3
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 claims description 3
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- 159000000021 acetate salts Chemical class 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 150000003839 salts Chemical class 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 150000003608 titanium Chemical class 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 150000007530 organic bases Chemical class 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- -1 4-propyl bromide Chemical compound 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940001593 sodium carbonate Drugs 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for modifying titanium silicalite molecular sieves and an application thereof. The method comprises the following steps: adding the titanium silicalite molecular sieves to an aqueous solution containing a metal salt and an alkaline solution, crystalizing for 5-72 hours at a temperature ranging from 120 to 200 DEG C, washing with water, drying at a temperature ranging from 80 to 150 DEG C for 1-15 hours, and roasting at a temperature ranging from 400 to 600 DEG C for 2-15 hours, thereby obtaining the titanium silicalite molecular sieves simultaneously modified by the metal salt and the alkaline solution; once the modified titanium silicalite molecular sieves are applied to a cyclohexanone ammoximation reaction, the conversion rate of the reaction can be greatly increased, and the service life of a catalyst also can be prolonged.
Description
Technical field
The invention belongs to a kind of method of modifying of HTS, and be a kind of method of modifying that is adapted at the HTS of application in cyclohexanone oxamidinating reaction.
Background technology
1981, the people such as Macro Taramasso TS-1 disclosed first with become method, through the developments of 40 years and research, the Hydrothermal Synthesis of TS-1 has formed two kinds of systems at present, one is to adopt TPAOH (TPAOH) to do template synthesis of titanium silicon molecular sieve, is called classical formalism, and another kind is to adopt cheap 4-propyl bromide to be the synthetic TS-1 of template, be called cheap system, also have in addition the several different methods such as isomorphous substitution.But because of Ti-O key, compared with Si-O bond distance, it is more difficult that titanium atom enters skeleton, and therefore the synthetic TS-1 of current synthetic method can produce extra-framework titanium, and TS-1 is had a negative impact.First extra-framework titanium itself does not have catalytic oxidation activity but can cause a large amount of decomposition of hydrogen peroxide, causes thus the reduction of TS-1 catalytic performance; Secondly, the content of extra-framework titanium is unmanageable, and this causes the activity stability of HTS poor, has so restricted the industrial application of TS-1.
Patent CN1555923A has proposed a kind of method of utilizing the aqueous solution of metal-salt or other mixtures TS-1 to be carried out to modification, it is characterized in that the aqueous solution of metal-salt and TS-1 to mix by a certain percentage, at 30-100 DEG C, react 6-100h, then dry at 110-200 DEG C, then temperature programming is to 200-800 DEG C, roasting 2-20h.By the HTS of this method modification, have good effect for epoxidation of propylene, but effect is general in cyclohexanone oxamidinating, the performance of the molecular sieve that is not significantly improved.
Open source literature " research of TS-1 catalysis hydrogen peroxide epoxidation vinyl benzene " has been reported the method for a kind of salt that utilizes organic and inorganic alkali solution and meta-alkalescence to TS-1 modification, it is characterized in that TS-1 in the mixing solutions as for organic bases and mineral alkali and salt, at 175 DEG C, react 2h, the dry rear and 540 DEG C of roasting 6h of washing, wherein mineral alkali is ammoniacal liquor, organic bases is TPAOH, 4-propyl bromide, trolamine and urea, and salt comprises sodium carbonate, Trisodium Citrate, SODIUMNITRATE etc.
The Main Function of the modification of mineral alkali to TS-1 is that the skeleton of TS-1 is dissolved, thereby makes inner etching produce hole, general organic bases apart from this effect is outer can also be by the titanium species crystallization again of dissolving, thereby make the titanium of non-skeleton reenter skeleton.But simple mineral alkali modified effect be very desirable, organic bases is not blanket to the modification of TS-1, only for the synthetic TS-1 of some indivedual system.Summary of the invention
The problem to be solved in the present invention is to provide a kind of method of modifying of HTS, is especially applicable to the synthetic TS-1 molecular sieve of classical formalism, can improve the catalytic performance of the cyclohexanone oxamidinating reaction of TS-1, and have economic serviceability.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of method of modifying of HTS, comprises the following steps:
A kind of method of HTS modification, HTS, metal salt solution, alkaline solution and water are mixed, obtain consisting of HTS: metal-salt: alkali: water is 0.01:(0.005～5): (0.001～3): the mixture of (1～100), by mixture crystallization 5～72h at 120～200 DEG C, then wash, be dried, roasting; Drying temperature is 80～150 DEG C, and be 1～15h time of drying; The temperature of roasting is 400 DEG C～600 DEG C, and roasting time is 2-15h; Obtain the HTS after modification, each material is mol ratio.
Further, alkali used is one or more the mixture in diethylamine, triethylamine, Di-n-Butyl Amine, tri-n-butylamine, monoisopropanolamine, diisopropanolamine (DIPA), tri-isopropanolamine, diamylamine or amylamine.
Further, metal-salt used is one or more the mixture in metal nitrate, metal acetate salt or metal ammonium salt.
Further, described metal nitrate is the one in Silver Nitrate, SODIUMNITRATE, nickelous nitrate or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES.
Molecular sieve after the modification obtaining according to the method described above reacts for cyclohexanone oxamidinating.
Because the present invention has adopted the aqueous solution of metal-salt and alkaline solution, HTS is carried out to modification, operation steps is simple, two steps or multistep modification are reduced to single stepping, and the relative low price of alkaline solution used, in industrial application, have more economic serviceability.
This modification mixing solutions used can better be modified the surface hydroxyl of molecular sieve, while making it be applied in the reaction of pimelinketone oximate, cyclohexanone-oxime can be faster from the inner desorption of molecular sieve pore passage out, molecular sieve pore passage is not easy blocked, has therefore greatly improved activity and the life-span of catalyzer.
Advantage of the present invention is to have general applicability, be particularly useful for the synthetic HTS of classical way, the HTS after the modification obtaining by the present invention is reacted for cyclohexanone oxamidinating, and reactivity worth increases substantially, and reduced price is cheap, has economic serviceability.
Embodiment
Below by example, technology of the present invention is given to illustrate further.
Comparative example:
The preparation of HTS is carried out according to classical hydrothermal synthesis method, do by TPAOH that template, tetraethoxy are done silicon source, butyl (tetra) titanate does titanium source, reactant mole consists of: tetraethoxy: butyl (tetra) titanate: TPAOH: Virahol=1:0.01～0.3:0.1～0.5:30～60 preparation molecular sieve mother liquor, then crystallization 15～96h at 120～190 DEG C in autoclave, filters, obtains HTS after washing, dry, roasting.
Embodiment 1:
HTS, Silver Nitrate, diethylamine, water that comparative example 1 is obtained mix, and after mixing, the mol ratio of each material is 0.01:0.005:0.001:1,120 DEG C of crystallization 72h, then washing, 80 DEG C of dry 15h, 400 DEG C of roasting 15h, obtain molecular sieve after modification.
Embodiment 2:
HTS, Silver Nitrate, triethylamine, Di-n-Butyl Amine, tri-n-butylamine, water that comparative example 1 is obtained mix, and the mol ratio of the each material of mixing solutions is 0.01:0.01:0.5:0.5:2:1,200 DEG C of crystallization 5h, washing, 150 DEG C of dry 1h, 600 DEG C of roasting 2h, obtain molecular sieve after modification.
Embodiment 3:
HTS, cupric nitrate, monoisopropanolamine, water that comparative example 1 is obtained mix, and the mol ratio of the each material of mixing solutions is 0.01:5:3:100,150 DEG C of crystallization 24h, and washing, 120 DEG C of dry 5h, 550 DEG C of roasting 6h, obtain molecular sieve after modification.
Embodiment 4:
HTS, SODIUMNITRATE, ammoniacal liquor, diisopropanolamine (DIPA), water that comparative example 1 is obtained mix, and the mol ratio of the each material of mixing solutions is 0.01:2:0.5:1:0.5:50,170 DEG C of crystallization 48h, washing, 140 DEG C of dry 10h, 500 DEG C of roasting 8h, obtain molecular sieve after modification.
Embodiment 5:
HTS, sodium-acetate, tri-isopropanolamine, water that comparative example 1 is obtained mix, and the mol ratio of the each material of mixing solutions is 0.01:0.5:0.5:1:50,160 DEG C of crystallization 36h, washing, 100 DEG C of dry 12h, 450 DEG C of roasting 10h, obtain molecular sieve after modification.
Embodiment 6:
HTS, nickelous nitrate, diamylamine, water that comparative example 1 is obtained mix, and the mol ratio of the each material of mixing solutions is 0.01:0.5:0.3:5,130 DEG C of crystallization 64h, and washing, 110 DEG C of dry 14h, 550 DEG C of roasting 4h, obtain molecular sieve after modification.
Embodiment 7:
HTS, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, ammoniacal liquor, amylamine, water that comparative example 1 is obtained mix, and the mol ratio of the each material of mixing solutions is 0.01:0.5:0.5:1:50,160 DEG C of crystallization 36h, washing, 100 DEG C of dry 12h, 450 DEG C of roasting 10h, obtain molecular sieve after modification.
The HTS that above-mentioned comparative example and embodiment are obtained is reacted for cyclohexanone oxamidinating, relatively catalyst performance, and concrete grammar is as follows:
80 DEG C of water-baths, in airtight there-necked flask, add the 50ml trimethyl carbinol, 8g pimelinketone, 15g25% ammoniacal liquor, 2gTS-1,10g hydrogen peroxide slowly adds with micro-sampling pump, reacts after one hour the product obtaining Agilent 7890 transformation efficiencys of chromatographic determination pimelinketone and the selectivity of cyclohexanone-oxime.
Amount × 100% of the pimelinketone of wherein, pimelinketone transformation efficiency=(amount of the amount-remaining pimelinketone of the pimelinketone adding)/add
Amount × 100% of the pimelinketone of pimelinketone amount/conversion that cyclohexanone-oxime selectivity=change into cyclohexanone-oxime consumes
Concrete analysis the results are shown in following table.
| ? | Transformation efficiency/% | Selectivity/% |
| Comparative example | 88.5 | 98.2 |
| Embodiment 1 | 94.5 | 99.9 |
| Embodiment 2 | 94.3 | 99.9 |
| Embodiment 3 | 95.6 | 99.9 |
| Embodiment 4 | 98.7 | 99.9 |
| Embodiment 5 | 97.5 | 99.9 |
| Embodiment 6 | 97.2 | 99.9 |
| Embodiment 7 | 96.2 | 99.9 |
Can find out by table result, through the HTS of this method modification, be improved significantly in transformation efficiency and the selectivity of cyclohexanone oxamidinating reacting middle catalyst.
Method of modifying of the present invention and purposes are described by specific embodiment.Those skilled in the art can use for reference the links such as content appropriate change raw material of the present invention, processing condition and realize corresponding other object, its relevant change does not all depart from content of the present invention, within all similar replacements and change will become apparent to those skilled in the art that and be all deemed to be included in scope of the present invention.
Claims (5)
1. the method for a HTS modification, it is characterized in that, HTS, metal salt solution, alkaline solution and water are mixed, obtain consisting of HTS: metal-salt: alkali: water is 0.01:(0.005～5): (0.001～3): the mixture of (1～100), by mixture crystallization 5～72h at 120～200 DEG C, then wash, be dried, roasting; Drying temperature is 80～150 DEG C, and be 1～15h time of drying; The temperature of roasting is 400 DEG C～600 DEG C, and roasting time is 2-15h; Obtain the HTS after modification, each material is than being mol ratio.
2. the method for a kind of HTS modification according to claim 1, it is characterized in that, alkali used is one or more the mixture in diethylamine, triethylamine, Di-n-Butyl Amine, tri-n-butylamine, monoisopropanolamine, diisopropanolamine (DIPA), tri-isopropanolamine, diamylamine or amylamine.
3. the method for a kind of HTS modification according to claim 1, is characterized in that, metal-salt used is one or more the mixture in metal nitrate, metal acetate salt or metal ammonium salt.
4. the method for a kind of HTS modification according to claim 3, is characterized in that, described metal nitrate is the one in Silver Nitrate, SODIUMNITRATE, nickelous nitrate or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES.
5. the method for a kind of HTS modification described in the arbitrary claim of claim 1-4, the molecular sieve after the modification obtaining reacts for cyclohexanone oxamidinating.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372535A (en) * | 2019-08-15 | 2019-10-25 | 中触媒新材料股份有限公司 | A kind of method of modifying of the molecular sieve of catalysis of pimelinketone oximation reaction |
| CN110372536A (en) * | 2019-08-15 | 2019-10-25 | 中触媒新材料股份有限公司 | A kind of method of preparing cyclohexanone oxime by ammoximation of cyclohexanone |
| CN112321453A (en) * | 2020-11-03 | 2021-02-05 | 中触媒新材料股份有限公司 | Method for synthesizing diethylhydroxylamine by using slurry bed |
| CN115872896A (en) * | 2022-12-05 | 2023-03-31 | 衢州巨化锦纶有限责任公司 | Preparation method for producing butanone oxime by using nickel-doped titanium silicalite molecular sieve |
| CN115974720A (en) * | 2023-01-09 | 2023-04-18 | 衢州巨化锦纶有限责任公司 | Method for preparing ketoxime by two-stage ammoximation reaction |
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| CN110372535A (en) * | 2019-08-15 | 2019-10-25 | 中触媒新材料股份有限公司 | A kind of method of modifying of the molecular sieve of catalysis of pimelinketone oximation reaction |
| CN110372536A (en) * | 2019-08-15 | 2019-10-25 | 中触媒新材料股份有限公司 | A kind of method of preparing cyclohexanone oxime by ammoximation of cyclohexanone |
| CN112321453A (en) * | 2020-11-03 | 2021-02-05 | 中触媒新材料股份有限公司 | Method for synthesizing diethylhydroxylamine by using slurry bed |
| CN115872896A (en) * | 2022-12-05 | 2023-03-31 | 衢州巨化锦纶有限责任公司 | Preparation method for producing butanone oxime by using nickel-doped titanium silicalite molecular sieve |
| CN115974720A (en) * | 2023-01-09 | 2023-04-18 | 衢州巨化锦纶有限责任公司 | Method for preparing ketoxime by two-stage ammoximation reaction |
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