CN1142147C - Method for synthesizing hexanolactam by using titanium silicon molecular sieve to catalyze gas phase rearrangement of cyclohexanone-oxime - Google Patents
Method for synthesizing hexanolactam by using titanium silicon molecular sieve to catalyze gas phase rearrangement of cyclohexanone-oxime Download PDFInfo
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- CN1142147C CN1142147C CNB011101385A CN01110138A CN1142147C CN 1142147 C CN1142147 C CN 1142147C CN B011101385 A CNB011101385 A CN B011101385A CN 01110138 A CN01110138 A CN 01110138A CN 1142147 C CN1142147 C CN 1142147C
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- cyclohexanone
- oxime
- molecular sieve
- caprolactam
- gas
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- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 title claims abstract description 154
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 26
- 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 26
- 230000008707 rearrangement Effects 0.000 title claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000007789 gas Substances 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 239000012159 carrier gas Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 238000006462 rearrangement reaction Methods 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 2
- 235000011089 carbon dioxide Nutrition 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000012071 phase Substances 0.000 abstract 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 239000010936 titanium Substances 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 description 11
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 230000009466 transformation Effects 0.000 description 10
- 238000005303 weighing Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011973 solid acid Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- YPRQFESOPJGYLW-UHFFFAOYSA-N n-cyclohexylidenehydroxylamine;methanol Chemical compound OC.ON=C1CCCCC1 YPRQFESOPJGYLW-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- -1 cyclohexanone-oxime propanol Chemical compound 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for synthesizing hexanolactam from cyclohexanone oxime by gas-phase rearrangement under the catalysis of a titanium silicon molecular sieve, which belongs to the technical field of catalysis in petrochemical industry. The method adopts the titanium silicon molecular sieve prepared by a solid-phase method as a catalyst, and the atomic ratio of silicon to titanium is less than 200. The cyclohexanone oxime raw material is dissolved in low-carbon alcohol solvent, mixed with inert carrier gas and preheated into a gas phase; then, the gas phase and the titanium silicon molecular sieve catalyst are in contact and are treated by rearrangement reaction to synthesize the caprolactam; the reaction temperature is from 280 to 420 DEG C, and the weight space velocity of the cyclohexanone oxime is from 0 to 15h<-1>. The method has the advantages of simple preparation of the used catalyst, low cost, high catalyst activity, caprolactam selectivity and stability and good regeneration performance and has good industrial application prospects.
Description
The invention belongs to the petrochemical complex catalysis technical field, particularly use the method for titanium silicon molecular sieve to catalyze gas phase rearrangement of cyclohexanone-oxime synthesis of caprolactam.
Hexanolactam is a kind of crucial petrochemical materials as the monomer of polyamide 6.But the preparing process of caprolactam of existing industrial application exists equipment corrosion and hazardous emission owing to use oleum as catalyzer, and the utmost point does not meet eco-friendly developing direction, and a large amount of cheap ammonium sulfate of by-product, deficiency in economic performance.Therefore, be conceived to avoid fully or reduce the use vitriol oil, thus reduce or the generation of avoiding ammonium sulfate fully to increase economic efficiency and the research and development of the novel preparing process of caprolactam of environmental benefit have become the numerous and confused key areas that drops into of external each major company.Be the use that the rearrangement reaction technology of the cyclohexanone-oxime of catalyzer can be avoided sulfuric acid and liquefied ammonia with the solid acid, both met eco-friendly developing direction, and the cost of hexanolactam be expected to reduce greatly.New technique with the gas phase rearrangement of cyclohexanone-oxime of solid acid catalysis reaction synthesis of caprolactam has been obtained important progress.The solid acid catalyst of being reported has multiple (Appl.Catal., 1999,188:361; Chem.Comm.2000,1121; J.Catal., 1994,148:138; USP4,717,769; USP 4,709, and 024; USP 4,717, and 770; EP 0236,096; USP 5,304, and 643; Stud.Surf.Sci.Catal., 1997,105:1189; EP 0,251, and 168; Appl.Catal., 1999,189:237; .Catal., 1992,137:252; Catal.Lett., 1993,17:139).Wherein over-all properties (referring to activity, hexanolactam selectivity and stability) is titanium-silicon molecular sieve catalyst preferably, and this catalyzer adopts hydrothermal method synthetic, and template is the tetrapropyl oxyammonia that the title of " gold " is arranged, so the cost of catalyzer is very expensive; And the very difficult appearance of controlling anatase octahedrite in hydro-thermal synthetic process, thereby the circulation ratio of catalyzer is relatively poor.In addition, the screening operation to solvent even is not second to selecting of catalyzer.Therefore, the work climate of optimizing catalyzer also be exploitation gas phase rearrangement of cyclohexanone-oxime reaction synthesis of caprolactam technology important content.
The method that the purpose of this invention is to provide a kind of new synthesis of caprolactam has overcome problems such as equipment corrosion that traditional sulfuric acid process brings, noxious emission on the one hand; On the other hand, than existing solid acid catalyst, Preparation of catalysts of the present invention is simple, with low cost, and active, hexanolactam selectivity, and especially stability is high, and regenerability is good.Be one of gas phase rearrangement of cyclohexanone-oxime reaction solid catalyst that performance is the most superior up to now, have better industrial application prospect.
A kind of method that the present invention proposes with the titanium silicon molecular sieve to catalyze gas phase rearrangement of cyclohexanone-oxime synthesis of caprolactam, it is characterized in that, the HTS that adopts the gas solid method preparation is as catalyzer, and the silicon titanium atom of this molecular sieve ratio is greater than 0 and be not more than 200, and this method may further comprise the steps:
1) the cyclohexanone-oxime raw material is dissolved in the low-carbon alcohol solvent, with pump this raw material is inputed in the reactor then, and be preheated to gas phase after inert carrier gas mixes;
2) more said gas phase cyclohexanone-oxime is contacted generation rearrangement reaction synthesis of caprolactam with said titanium-silicon molecular sieve catalyst; Its reaction conditions comprises: temperature is 280-420 ℃, cyclohexanone-oxime weight space velocity 0-15h
-1
Above-mentioned carrier gas can be a kind of of helium, argon gas, nitrogen and carbonic acid gas.
Can add a spot of water in the above-mentioned low-carbon alcohol solvent, the amount of substance of the addition of water is 0-3 a times of cyclohexanone-oxime raw material.
Above-mentioned preferred temperature is 300-400 ℃, and said cyclohexanone-oxime preferred weight air speed is 1.5-10h
-1, said low-carbon alcohol solvent is preferably methyl alcohol and/or ethanol, and the amount of substance that adds entry in the said solvent is preferably 0.2-2 times of cyclohexanone-oxime raw material.
Above-mentioned used titanium-silicon molecular sieve catalyst adopts the gas solid method preparation, concrete preparation process comprises: HZSM-5 molecular sieve or B-ZSM-5 molecular sieve with high silica alumina ratio (＞50) are presoma (preferred B-ZSM-5 molecular sieve), at acid solution (preferred nitric acid and hydrochloric acid, concentration: 4-12M) behind 80-100 ℃ of reflow treatment 6-20h, dry, moulding is put in the fixed-bed reactor, with rare gas element such as N
2Or He purging 30-60min, feeding contains halogenated titanium (preferred TiCl then
4) inert carrier gas such as the N of steam
2, Ar and He, in 400-800 ℃ (preferred 500-750 ℃) and halogenated titanium generation gas-solid reaction, reaction times 6-20h, the carrier gas air speed is 40-150mL/ (g.cat.min), obtains titanium-silicon molecular sieve catalyst with alcohol washing, drying, roasting again.Below introduce embodiments of the invention, but be not limitation of the present invention.
Embodiment 1:
Taking by weighing titanium-silicon molecular sieve catalyst that the 0.5g gas solid method makes, to place internal diameter be the glass reactor of 10mL, and silicon titanium atom ratio is 26, carries out the Beckmann rearrangement of cyclohexanone-oxime on reaction unit, before the reaction earlier at 400 ℃ of N
2Pretreatment catalyst 1.5h under the atmosphere is cooled to 360 ℃ then, and uses CO
210% cyclohexanone-oxime methanol solution is brought in the reactor, and the air speed of reactant cyclohexanone-oxime is WHSV=7h
-1Reaction result is: the initial conversion of cyclohexanone-oxime reaches 100%, and the hexanolactam selectivity reaches 97%, keeps the cyclohexanone-oxime transformation efficiency and is not less than 100% and is not less than one way reaction times of 95% with the hexanolactam selectivity and surpasses 90h.
Embodiment 2:
Taking by weighing titanium-silicon molecular sieve catalyst that the 0.5g gas solid method makes, to place internal diameter be the glass reactor of 10mL, and silicon titanium atom ratio is 60, carries out the Beckmann rearrangement of cyclohexanone-oxime on reaction unit, before the reaction earlier at 400 ℃ of N
2Pretreatment catalyst 1.5h under the atmosphere is cooled to 320 ℃ then, and uses N
210% cyclohexanone-oxime methanol solution is brought in the reactor, and the air speed of also having added water (amount of substance of interpolation is 1 times of cyclohexanone-oxime) reactant cyclohexanone-oxime in this solution is WHSV=2h
-1Reaction result is: the initial conversion of cyclohexanone-oxime reaches 100%, and the hexanolactam selectivity reaches 97%, keeps the cyclohexanone-oxime transformation efficiency and is not less than 97% and is not less than one way reaction times of 95% with the hexanolactam selectivity and surpasses 190h.With the catalyzer behind the inactivation through twice regeneration after, the performance of catalyzer is constant.
Embodiment 3:
Taking by weighing titanium-silicon molecular sieve catalyst that the 0.5g gas solid method makes, to place internal diameter be the glass reactor of 10mL, and silicon titanium atom ratio is 35, carries out the Beckmann rearrangement of cyclohexanone-oxime on reaction unit, before the reaction earlier at 400 ℃ of N
2Pretreatment catalyst 1.5h under the atmosphere is cooled to 380 ℃ then, and uses CO
210% cyclohexanone-oxime methanol solution is brought in the reactor, also added water (amount of substance of interpolation is 0.5 times of cyclohexanone-oxime) in this solution, the air speed of reactant cyclohexanone-oxime is WHSV=1.5h
-1Reaction result is: the initial conversion of cyclohexanone-oxime reaches 100%, and the hexanolactam selectivity reaches 97%, keeps the cyclohexanone-oxime transformation efficiency and is not less than 97% and is not less than one way reaction times of 95% with the hexanolactam selectivity and surpasses 300h.
Embodiment 4:
Taking by weighing titanium-silicon molecular sieve catalyst that the 0.5g gas solid method makes, to place internal diameter be the glass reactor of 10mL, and silicon titanium atom ratio is 120, carries out the Beckmann rearrangement of cyclohexanone-oxime on reaction unit, before the reaction earlier at 400 ℃ of N
2Pretreatment catalyst 1.5h under the atmosphere is cooled to 350 ℃ then, and uses N
210% cyclohexanone-oxime propanol solution is brought in the reactor, also added water (amount of substance of interpolation is 1.5 times of cyclohexanone-oxime) in this solution, the air speed of reactant cyclohexanone-oxime is WHSV=10h
-1Reaction result is: the initial conversion of cyclohexanone-oxime reaches 100%, and the hexanolactam selectivity reaches 97%, keeps the cyclohexanone-oxime transformation efficiency and is not less than 90% and is not less than one way reaction times of 95% with the hexanolactam selectivity and surpasses 70h.
Embodiment 5:
Taking by weighing titanium-silicon molecular sieve catalyst that the 0.5g gas solid method makes, to place internal diameter be the glass reactor of 10mL, and silicon titanium atom ratio is 140, carries out the Beckmann rearrangement of cyclohexanone-oxime on reaction unit, before the reaction earlier at 400 ℃ of N
2Pretreatment catalyst 1.5h under the atmosphere is cooled to 320 ℃ then, and uses N
210% cyclohexanone-oxime ethanolic soln is brought in the reactor, also added water (amount of substance of interpolation is 2.0 times of cyclohexanone-oxime) in this solution, the air speed of reactant cyclohexanone-oxime is WHSV=1.5h
-1Reaction result is: the initial conversion of cyclohexanone-oxime reaches 100%, and the hexanolactam selectivity reaches 97%, keeps the cyclohexanone-oxime transformation efficiency and is not less than 90% and is not less than one way reaction times of 95% with the hexanolactam selectivity and surpasses 250h.
Embodiment 6:
Taking by weighing titanium-silicon molecular sieve catalyst that the 0.5g gas solid method makes, to place internal diameter be the glass reactor of 10mL, and silicon titanium atom ratio is 190, carries out the Beckmann rearrangement of cyclohexanone-oxime on reaction unit, before the reaction earlier at 400 ℃ of N
2Pretreatment catalyst 1.5h under the atmosphere is cooled to 400 ℃ then, and uses N
210% cyclohexanone-oxime ethanolic soln is brought in the reactor, also added water (amount of substance of interpolation is 0.5 times of cyclohexanone-oxime) in this solution, the air speed of reactant cyclohexanone-oxime is WHSV=4.0h
-1Reaction result is: the initial conversion of cyclohexanone-oxime reaches 100%, and the hexanolactam selectivity reaches 97%, keeps the cyclohexanone-oxime transformation efficiency and is not less than 90% and is not less than one way reaction times of 95% with the hexanolactam selectivity and surpasses 100h.With the catalyzer behind the inactivation through twice regeneration after, the performance of catalyzer is constant.
Embodiment 7:
Taking by weighing titanium-silicon molecular sieve catalyst that the 0.5g gas solid method makes, to place internal diameter be the glass reactor of 10mL, and silicon titanium atom ratio is 80, carries out the Beckmann rearrangement of cyclohexanone-oxime on reaction unit, before the reaction earlier at 400 ℃ of N
2Pretreatment catalyst 1.5h under the atmosphere is cooled to 380 ℃ then, and uses CO
210% cyclohexanone-oxime ethanolic soln is brought in the reactor, also added water (amount of substance of interpolation is 0.5 times of cyclohexanone-oxime) in this solution, the air speed of reactant cyclohexanone-oxime is WHSV=6h
-1Reaction result is: the initial conversion of cyclohexanone-oxime reaches 100%, and the hexanolactam selectivity reaches 97%, keeps the cyclohexanone-oxime transformation efficiency and is not less than 90% and is not less than one way reaction times of 95% with the hexanolactam selectivity and surpasses 140h.With the catalyzer behind the inactivation through twice regeneration after, the performance of catalyzer is constant.
Comparative Examples 1:
Get silica alumina ratio and be 56 HZSM-5 compression molding, be broken into 40～80 purpose particles, getting 0.5g, to place internal diameter be the glass reactor of 10mL, carries out the Beckmann rearrangement of cyclohexanone-oxime on self-built reaction unit, before the reaction earlier at 450 ℃ of N
2Pretreatment catalyst 1.5h under the atmosphere is cooled to 370 ℃ then, and uses CO
210% cyclohexanone-oxime ethanolic soln is brought in the reactor, and the air speed of reactant cyclohexanone-oxime is WHSV=0.5h
-1Reaction result is: the initial conversion of cyclohexanone-oxime reaches 100%, and the hexanolactam selectivity reaches 89.4%, is not less than 100% and is not less than one way reaction times of 87.5% with the hexanolactam selectivity and has only 16h but keep the cyclohexanone-oxime transformation efficiency.
Comparative Examples 2:
Get a certain amount of boron oxide charge capacity and be 11% B
2O
3/ ZrO
2The catalyzer compression molding is broken into 40～80 purpose particles, and getting 0.5g, to place internal diameter be the glass reactor of 10mL, carries out the Beckmann rearrangement of cyclohexanone-oxime on self-built reaction unit, before the reaction earlier at 400 ℃ of N
2Pretreatment catalyst 1.5h under the atmosphere is cooled to 340 ℃ then, and uses CO
210% cyclohexanone-oxime ethanolic soln is brought in the reactor, and the air speed of reactant cyclohexanone-oxime is WHSV=0.5h
-1Reaction result is: the initial conversion of cyclohexanone-oxime reaches 100%, and the hexanolactam selectivity reaches 92.0%, is not less than 100% and is not less than one way reaction times of 90% with the hexanolactam selectivity and has only 5h but keep the cyclohexanone-oxime transformation efficiency.
Comparative Examples 3:
It is even to take by weighing the 5g silica alumina ratio and be 80 HZSM-5 molecular sieve and 0.4g ammonium tungstate mechanically mixing, under flowing nitrogen atmosphere in 650 ℃ of roasting 15h, with the catalyzer compression molding after the roasting, be broken into 40～80 purpose particles, getting 0.5g, to place internal diameter be the glass reactor of 10mL, carry out the Beckmann rearrangement of cyclohexanone-oxime on self-built reaction unit, elder generation is at 450 ℃ of N before the reaction
2Pretreatment catalyst 1.5h under the atmosphere is cooled to 380 ℃ then, and uses N
210% cyclohexanone-oxime ethanolic soln is brought in the reactor, also added water (amount of substance of interpolation is 1 times of cyclohexanone-oxime) in this solution, the air speed of reactant cyclohexanone-oxime is WHSV=4.5h
-1Reaction result is: the initial conversion 98.4% of cyclohexanone-oxime, the hexanolactam selectivity reaches 91.0%, and keeps the cyclohexanone-oxime transformation efficiency and be not less than 100% and be not less than one way reaction times of 85% with the hexanolactam selectivity and have only 43h.
Claims (4)
1, a kind of method with the titanium silicon molecular sieve to catalyze gas phase rearrangement of cyclohexanone-oxime synthesis of caprolactam, it is characterized in that, the HTS that adopts the gas solid method preparation is as catalyzer, and the silicon titanium atom of this molecular sieve ratio is greater than 0 and be not more than 200, and this method may further comprise the steps:
1) the cyclohexanone-oxime raw material is dissolved in the low-carbon alcohol solvent, with pump this raw material is inputed in the reactor then, and be preheated to gas phase after inert carrier gas mixes;
2) more said gas phase cyclohexanone-oxime is contacted the synthetic caprolactam of generation rearrangement reaction with said titanium-silicon molecular sieve catalyst; Its reaction conditions comprises: temperature is 280-420 ℃, cyclohexanone-oxime weight space velocity 0-15h
-1
2, the method for rearrangement synthesis of caprolactam as claimed in claim 1 is characterized in that, said carrier gas is a kind of of helium, argon gas, nitrogen and carbonic acid gas.
3, the method for rearrangement synthesis of caprolactam as claimed in claim 1 is characterized in that, has added a spot of water in the said low-carbon alcohol solvent, and the amount of substance of the addition of water is 0-3 a times of cyclohexanone-oxime raw material.
4, as the method for claim 1, one of 2 or 3 described rearrangement synthesis of caprolactam, it is characterized in that said temperature is 300-400 ℃, said cyclohexanone-oxime weight space velocity is 1.5-10h
-1, said low-carbon alcohol solvent is methyl alcohol and/or ethanol, the amount of substance that adds entry in the said solvent is 0.2-2 a times of cyclohexanone-oxime raw material.
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|---|---|---|---|
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| CNB011101385A CN1142147C (en) | 2001-03-30 | 2001-03-30 | Method for synthesizing hexanolactam by using titanium silicon molecular sieve to catalyze gas phase rearrangement of cyclohexanone-oxime |
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| CN1142147C true CN1142147C (en) | 2004-03-17 |
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| JP4461926B2 (en) * | 2004-06-30 | 2010-05-12 | 住友化学株式会社 | Method for producing zeolite and method for producing ε-caprolactam |
| CN103012263B (en) * | 2011-09-28 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of preparation method of hexanolactam |
| CN102626645B (en) * | 2012-03-27 | 2013-11-27 | 长沙理工大学 | Application of fluorgypsum in ketoxime Beckmann rearrangement |
| CN103964461B (en) * | 2013-01-30 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of tin si molecular sieves and preparation method thereof |
| CN112221537B (en) * | 2020-11-05 | 2021-07-06 | 大连理工大学 | Using white carbon black and TiCl4Method for preparing high-activity propylene and hydrogen peroxide gas phase epoxidation catalyst by gas-solid phase reaction |
| CN113105363B (en) * | 2021-04-14 | 2023-09-29 | 江苏扬农化工集团有限公司 | Method for synthesizing 6-aminocapronitrile from cyclohexanone oxime in one step |
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2001
- 2001-03-30 CN CNB011101385A patent/CN1142147C/en not_active Expired - Fee Related
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