CN100497316C - Process for preparing caprolactam by cyclohexanone-oxime gas phase rearrangement - Google Patents
Process for preparing caprolactam by cyclohexanone-oxime gas phase rearrangement Download PDFInfo
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- CN100497316C CN100497316C CNB2003101155143A CN200310115514A CN100497316C CN 100497316 C CN100497316 C CN 100497316C CN B2003101155143 A CNB2003101155143 A CN B2003101155143A CN 200310115514 A CN200310115514 A CN 200310115514A CN 100497316 C CN100497316 C CN 100497316C
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- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 title claims abstract description 111
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 230000008707 rearrangement Effects 0.000 title description 11
- 238000004519 manufacturing process Methods 0.000 title description 8
- 238000000034 method Methods 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000006237 Beckmann rearrangement reaction Methods 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 239000006227 byproduct Substances 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002808 molecular sieve Substances 0.000 claims abstract description 13
- 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 13
- 239000000047 product Substances 0.000 claims description 31
- 230000001476 alcoholic effect Effects 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 239000012159 carrier gas Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000008016 vaporization Effects 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 description 14
- 239000012808 vapor phase Substances 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000006462 rearrangement reaction Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- -1 nitrogenous compound Chemical class 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 101000809257 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 4 Proteins 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 102100038463 Ubiquitin carboxyl-terminal hydrolase 4 Human genes 0.000 description 2
- 229910021529 ammonia Inorganic materials 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
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Other In-Based Heterocyclic Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The process of preparing caprolactam with cyclohexanone oxime includes the vapor Beckmann rearrangement reaction of cyclohexanone oxime inside one first fixed bed reactor in the presence of MFI structure molecular sieve catalyst; the decomposition and conversion of the reaction side product O-alkyl-epsilon-caprolactim into caprolactam inside one second fixed bed reactor in the presence of MFI structure molecular sieve catalyst and water; and the separation and purification of the reaction effluent. Compared with single vapor Beckmann rearrangement reaction process of cyclohexanone oxime, the present invention has 1-3 % raised caprolactam yield.
Description
Technical field
The invention relates to the method for cyclohexanone-oxime gas phase beckmann rearrangement system hexanolactam.More particularly, be about in fixed-bed reactor, use the MFI structure molecular screen to carry out the method that Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement is produced hexanolactam as catalyzer.
Background technology
The product hexanolactam of cyclohexanone-oxime generation Beckmann rearrangement is a main raw material of producing polyamide fibre, industrial cord thread and nylon engineering plastic three big series product, and its demand is more prosperous always, estimates that whole world hexanolactam demand in 2004 will be above 400 * 10
4Ton.Domestic hexanolactam breach is bigger always, and year import volume is generally 30 * 10
4More than the ton, along with the increase of consumption, the breach of hexanolactam will be bigger from now on.
Industrial adopt with the vitriol oil or oleum is the cyclohexanone-oxime liquid phase Beckmann rearrangement explained hereafter ε-Ji Neixianan (following brief note is a hexanolactam) of catalyzer more.Adopt the hexanolactam of this explained hereafter to account for about 90% of world's caprolactam production total amount.Though this liquid phase process method reaches 98.5% to the selectivity of hexanolactam, its maximum shortcoming is: 1 ton of hexanolactam of every production will producing ammonium sulfate byproduct 1.3-1.8 ton.Use the vitriol oil or oleum can cause equipment corrosion and environmental pollution in addition, this today of advocating atom economy and environmental protection and economy be difficult to gratifying.
In decades, various countries, each major company are all at the various novel procesies of exploitation, raw catalyst, make the production of hexanolactam avoid as far as possible or reduce the generation of by product, make its production more economical, more meet the requirement of greenization, as the divinyl/carbon monoxide technology of the common exploitation of divinyl/methane technology, DuPont company and DSM N. V. of the common exploitation of DuPont company and BASF AG.These technologies have that flow process is short, cost is low, the advantage of producing ammonium sulfate byproduct not, reached industrialized level, but they only are applicable to the construction new device.The liquid phase rearrangement of the non-vitriol oil or oleum, and with BF
3, the glue bundle body under the H type storng-acid cation exchange resin, acidic conditions etc. is the technology of catalyzer, still is in conceptual phase at present.
What be hopeful to replace liquid phase rearrangement technology is to be the cyclohexanone-oxime gas phase beckmann rearrangement technology of catalyzer with the solid acid.It does not consume the be fuming vitriol oil and ammonia in the rearrangement reaction process, have no equipment corrosion, non-environmental-pollution and advantage such as by-product sulphur ammonium not.In the vapor phase process Beckmann rearrangement, have as the solid acid of catalyzer multiple, as GB881, the silica-alumina catalyzer that adopts in 927; GB881, the solid phosphoric acid catalyst that adopts in 956; GB1, the borated catalyzer that adopts in 178,057; The high silicon that adopts among the CN1269360A/aluminum ratio MFI structural molecule sieve catalyst etc.
Having disclosed a kind of among the CN1269360A is the processing method of Catalyst Production hexanolactam with the MFI structure molecular screen in fluidized-bed.In the method, the catalyzer that carries out the 0.1-75% behind the vapor phase beckmann rearrangement reaction is sent to revivifier from reactor continuously or off and on, catalyzer is handled with oxygen-containing gas under high temperature in revivifier, and making the nitrogen content on the regenerated catalyst is 10-2500ppm.When the internal circulating load of catalyzer is 20g/h, reaction after 200 hours, the cyclohexanone-oxime transformation efficiency that this method obtains is 99.6%, and the selectivity of hexanolactam is 95.7%; When the catalyst recirculation amount is 200g/h, reaction after 200 hours, the cyclohexanone-oxime transformation efficiency that this method obtains is 97.8%, and the selectivity of hexanolactam is 94.7%.
What disclose among the CN1273971A is a kind of processing method that adopts fluidized-bed-fixed bed production hexanolactam.The key step of this method is: in the presence of solid catalyst, in fluidized-bed reactor, carry out the vapor phase beckmann rearrangement reaction of cyclohexanone-oxime, make the reaction effluent that contains unreacted cyclohexanone-oxime enter the fixed-bed reactor that solid catalyst is housed again then, replenish and carry out vapor phase beckmann rearrangement reaction to obtain the hexanolactam of high yield.In the method, preferably be provided with a plurality of with the placed in-line fixed-bed reactor of fluidized-bed reactor.
Though fluidized-bed process can be finished the production of hexanolactam continuously, and can solve reaction heat-obtaining problem preferably, but there is following weak point simultaneously: 1, because the cyclohexanone-oxime transformation efficiency only is about 95%, remain in unreacted cyclohexanone-oxime in the reaction product and separate from hexanolactam owing to the thermolability of itself and with close being difficult to of product hexanolactam boiling point, this makes troubles for follow-up purification operation; 2, MFI structural molecule sieve catalyst has active stabilization period preferably, regenerates continually in fluidized-bed and can not utilize the reactivity worth of catalyzer fully; 3, there is the starting stage of a reaction in the catalyzer after the regeneration, and is higher at the transformation efficiency of this stage cyclohexanone-oxime, but the selectivity of hexanolactam is lower, and catalyzer is regenerated continually will certainly influence the selectivity of hexanolactam; 4, by the reason of fluidized-bed self cause such as: in the fluidized-bed gas rise contact efficiency, unreacted material quilt that the swimming phenomenon influence fluidizing agent and granules of catalyst reaction mass dilute and cause degradation under the cyclohexanone-oxime transformation efficiency; 5, material stirs and cyclic motion causes the wearing and tearing of granules of catalyst tempestuously, thereby the wear resisting property of catalyzer is had higher requirement.
On the other hand, carry out with regard to the vapor phase rearrangement as catalyzer with regard to the molecular sieve that uses the MFI structure, though can obtain higher cyclohexanone-oxime transformation efficiency and hexanolactam selectivity, catalyzer has regenerability preferably again, but blemish in an otherwise perfect thing is: 1, this catalyzer need use carbonatoms to be solvent less than 6 Fatty Alcohol(C12-C14 and C12-C18), the easy again and product hexanolactam generation dehydration reaction of Fatty Alcohol(C12-C14 and C12-C18) in the rearrangement reaction process, generate by product o-alkyl-ε-own lactim, its selectivity accounts for 60% of all by products, and this by product has increased free alkalescence, reduced the caprolactam product quality; 2, this vapor phase rearrangement technology generally has only about 96.5% the selectivity of hexanolactam, has influenced its industrialized economic feasibility.
Up to now, not seeing has the independent employing fluidized-bed industrialization construction device of reactor in addition, builds device as the industrialization of fixed-bed reactor, directly carries out the report that Beckmann rearrangement is produced hexanolactam.
Summary of the invention
Purpose of the present invention be exactly provide on the basis of above-mentioned prior art a kind of can fixed-bed reactor in industrial use in, use the MFI structure molecular screen to carry out the method that Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement is produced hexanolactam as catalyzer.
Method provided by the invention is: adopt fixed-bed reactor earlier, carry out Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement in the presence of MFI structural molecule sieve catalyst; And then adopt another fixed-bed reactor, making byproduct of reaction 0-alkyl-ε-own lactim decomposition and inversion in the presence of MFI structural molecule sieve catalyst and water is the product hexanolactam.The embodiment of present method is as follows:
With cyclohexanone-oxime and C
1-C
6The saturated fatty alcoholic solvent mix according to the weight ratio of 10-50:90-50, after vaporizing, enter first fixed-bed reactor that are filled with MFI structural molecule sieve catalyst with the inert carrier gas, in temperature of reaction is 250-500 ℃, when normal pressure, the weight hourly space velocity 1-8 of cyclohexanone-oxime
-1Condition under carry out Beckmann rearrangement, the streams that contains by product o-alkyl-ε-own lactim that reaction back produces with water with the inert carrier gas by being filled with second fixed-bed reactor of MFI structural molecule sieve catalyst, when the weight hourly space velocity of 250-500 ℃, normal pressure and hexanolactam alcoholic solution is 0.5-20
-1Condition under make o-alkyl-ε-own lactim wherein be converted into the product hexanolactam, reacted effluent separates, purifies.
Shape to used fixed-bed reactor in the inventive method has no particular limits, known fixed bed in the available present technique field.
Employed MFI structural molecule sieve catalyst can be the same or different in first and second fixed-bed reactor.Their shape can be all catalyst shape that are suitable for of fixed bed reaction, comprises bar shaped, sphere, sheet and various irregular shape catalyst, as trilobal, quatrefoil, hollow form etc.These catalyzer comprise the ZSM-5 molecular sieve of HTS (also claiming TS-1), total silicon molecular sieve and silicon/aluminum ratio 〉=500.These molecular sieves can be directly used in the inventive method, also can handle through the alkaline aqueous solution of nitrogenous compound in advance.Suitable nitrogenous compound can be selected from ammoniacal liquor, water soluble salt of ammonia and C
1-C
3Among the quaternary amine of alkyl one or more, the processing of the nitrogenous compound aqueous solution can be carried out under 40-95 ℃ 2-4 hour.Elements such as the also available V of being selected from of ZSM-5 molecular sieve wherein, Cr, Zn, Zr, B, Fe, Ca, In carry out modification.These molecular sieves can directly use as catalyzer, and the catalyzer that also can be made into loading type uses.Said HTS can be according to USP4, and 410,501, CN1294030A, Applied Catalysis A:General, the method preparation described in 99 (1993) 71-84; The total silicon molecular sieve can be according to USP4, and 061,724, the method preparation described in CN1338427A, the CN1338428A; The ZSM-5 molecular sieve of high silicon/aluminum ratio can be according to various prior art for preparing.
The inert carrier gas that enters in the fixed-bed reactor with material can be selected from nitrogen or argon gas, and the air speed of reaction mass can be controlled by the flow of carrier gas.
In the inventive method in carrying out first fixed-bed reactor of Beckmann rearrangement the weight ratio of mixture of cyclohexanone-oxime and alcoholic solvent be preferably 20-40:80-60; Said alcoholic solvent is preferably from C
1-C
3Saturated fatty alcohol; Preferred reaction conditions is: temperature of reaction 300-400 ℃, and when normal pressure, the weight hourly space velocity 1-4 of cyclohexanone-oxime
-1
The said streams that contains by product o-alkyl-ε-own lactim that enters second fixed-bed reactor can be to have a kind of in the following component in the inventive method: the streams that 1) contains solvent alcohol, product hexanolactam, o-alkyl-ε-own lactim and other by product; 2) removed the streams that contains o-alkyl-ε-own lactim of pure and mild other by product of partial solvent; 3) removed the streams of the o-alkyl-ε-own lactim of solvent alcohol, product hexanolactam and other by product substantially fully.
The add-on that enters the water of second fixed-bed reactor with streams should be that the 0.1-50% of benchmark is advisable with the streams total mass, is preferably 2-20%.The purpose that adds entry is for by product o-alkyl-ε-own lactim is resolved into the product hexanolactam, to improve the yield of product hexanolactam in the vapor phase beckmann rearrangement reaction.Increase along with the water add-on, the rate of decomposition of by product o-alkyl-ε-own lactim will improve, decomposition reaction will be risen to the selectivity of hexanolactam, but the excessive increase of water add-on will cause the increase of purification caprolactam product subsequent handling energy consumption.
In the inventive method in second fixed-bed reactor preferred reaction conditions be: temperature of reaction 300-400 ℃; Reaction pressure is a normal pressure; When the weight hourly space velocity of hexanolactam alcoholic solution is 1-10
-1
First fixed-bed reactor that are used to carry out Beckmann rearrangement can be provided with a plurality of simultaneously, for example two or three.Like this setting both can be in order to the regeneration of hocket rearrangement reaction and catalyzer so that operation carry out continuously, the alcoholic solution that can make cyclohexanone-oxime again when needed through two reactor successive reactions so that the transformation efficiency of cyclohexanone-oxime reaches is bordering on fully.
Use fixed-bed process to carry out the vapor phase beckmann rearrangement reaction of cyclohexanone-oxime, fluidized-bed process than prior art has following advantage: fixed bed is without fluidized wind, there is the catalyst abrasion loss hardly, reduce the consumption of the higher rearrangement reaction catalyzer of cost, its plant investment, process cost are lower than fluidized-bed process.Suitably reactor design also can solve the heat-obtaining problem.
The rate of decomposition of by product o-alkyl-ε-own lactim that method provided by the invention, cyclohexanone-oxime produce in vapor phase beckmann rearrangement reaction can reach more than 70% until near 100%, decomposes the selectivity that generates hexanolactam and reaches 55-99%.Method provided by the invention is compared with carrying out the cyclohexanone-oxime gas phase beckmann rearrangement merely, can improve the yield 1-3% of hexanolactam.
Embodiment
The following examples will give further instruction to the present invention, but not thereby limiting the invention.
Employed catalyzer is the total silicon molecular sieve catalyst that makes according to the method described in the CN1338427A among the embodiment.
Employed first and second fixed-bed reactor are the normal pressure continuous fixed bed reactor in the example, stainless steel, internal diameter 15mm, the catalyzer of interior dress 20-40 purpose extruded moulding, above the beds and the following 20-40 purpose quartz sand that all is filled with, reactor adopts three sections heating, and beds is positioned at the flat-temperature zone, and temperature of reaction is regulated the control of electric furnace heating power by temperature controller.
Reaction product adopts Trace GC-MS to carry out qualitative analysis.The GC8000 chromatographic instrument is adopted in quantitative analysis, and FID detects, 0V-1 capillary column φ 0.25mm * 30m, and 521 ° of K of temperature of vaporization chamber, sensing chamber's temperature is 513 ° of K, and column temperature is temperature programming, and 383 ° of K constant temperature 8 minutes, 15 ° of K/min are raised to 503 ° of K constant temperature 14 minutes again.
Rearrangement product content such as reaction back hexanolactam, pimelinketone and cyclonene adopt area normalization method to calculate, and solvent does not participate in integration.Each is about reaction evaluating parameter-definition following (cyclohexanone-oxime and hexanolactam percentage composition are the stratographic analysis value in the reaction product) in the example:
Embodiment 1
The present embodiment explanation the invention provides the implementation result of method.
First fixed-bed reactor filling, the 4.5 gram catalyzer that are being used for vapor phase beckmann rearrangement reaction.Reaction raw materials is the ethanolic soln of the cyclohexanone-oxime of concentration 28 weight %, and with the flow charging of constant-flux pump (model is PB-1, and satellite instrument manufactory in Beijing produces) with the ethanolic soln of 64.3 Grams Per Hour cyclohexanone-oximes, the weight space velocity of cyclohexanone-oxime is 4 o'clock
-1, carrier gas N
2Flow is 7.2L/h, and the catalyst bed reaction temperature is 380 ℃.
With constant-flux pump the flow of water with 3 Grams Per Hours is passed in the gaseous product of above-mentioned rearrangement reaction, adorns second fixed-bed reactor of 2.2 gram catalyzer in mixture enters, the weight hourly space velocity of the alcoholic solution of rearrangement product hexanolactam is 8 o'clock
-1, temperature of reaction is 350 ℃, reaction product enters receiving flask and carries out gas-liquid separation after the mixture of ice and water cooling, react and carry out the product compositional analysis after 220 hours.
Analytical results is: the cyclohexanone-oxime transformation efficiency is 99.5%, and the hexanolactam selectivity is 96.8%.
Embodiment 2
The present embodiment explanation the invention provides the implementation result of method.
First fixed-bed reactor filling, the 4.5 gram catalyzer that are being used for vapor phase beckmann rearrangement reaction.Reaction raw materials is the ethanolic soln of the cyclohexanone-oxime of concentration 28 weight %, and with the flow charging of constant-flux pump with the ethanolic soln of 32 Grams Per Hour cyclohexanone-oximes, the weight space velocity of cyclohexanone-oxime is 2 o'clock
-1, carrier gas N
2Flow is 3.6L/h, and the catalyst bed reaction temperature is 380 ℃.
With constant-flux pump the flow of water with 1.5 Grams Per Hours is passed in the gaseous product of above-mentioned rearrangement reaction, adorns second fixed-bed reactor of 2.2 gram catalyzer in mixture enters, the weight hourly space velocity of the alcoholic solution of rearrangement product hexanolactam is 4 o'clock
-1, temperature of reaction is 350 ℃, reaction product enters receiving flask and carries out gas-liquid separation after the mixture of ice and water cooling, react and carry out the product compositional analysis after 1080 hours.
Analytical results is: the cyclohexanone-oxime transformation efficiency is 99.6%, and the hexanolactam selectivity is 97.1%.
Embodiment 3
The present embodiment explanation the invention provides the implementation result of method.
First fixed-bed reactor filling, the 4.5 gram catalyzer that are being used for vapor phase beckmann rearrangement reaction.Reaction raw materials is the ethanolic soln of the cyclohexanone-oxime of concentration 28 weight %, and with the flow charging of constant-flux pump with the ethanolic soln of 32 Grams Per Hour cyclohexanone-oximes, the weight space velocity of cyclohexanone-oxime is 2 o'clock
-1, carrier gas N
2Flow is 3.6L/h, and the catalyst bed reaction temperature is 380 ℃.
With constant-flux pump the flow of water with 6 Grams Per Hours is passed in the gaseous product of above-mentioned rearrangement reaction, adorns second fixed-bed reactor of 2.2 gram catalyzer in mixture enters, the weight hourly space velocity of the alcoholic solution of rearrangement product hexanolactam is 4 o'clock
-1, temperature of reaction is 350 ℃, reaction product enters receiving flask and carries out gas-liquid separation after the mixture of ice and water cooling, react and carry out the product compositional analysis after 1050 hours.
Analytical results is: the cyclohexanone-oxime transformation efficiency is 99.6%, and the hexanolactam selectivity is 97.5%.
Embodiment 4
The present embodiment explanation the invention provides the implementation result of method.
First fixed-bed reactor filling, the 4.5 gram catalyzer that are being used for vapor phase beckmann rearrangement reaction.Reaction raw materials is the ethanolic soln of the cyclohexanone-oxime of concentration 28 weight %, and with the flow charging of constant-flux pump with the ethanolic soln of 32 Grams Per Hour cyclohexanone-oximes, the weight space velocity of cyclohexanone-oxime is 2 o'clock
-1, carrier gas N
2Flow is 3.6L/h, and the catalyst bed reaction temperature is 380 ℃.Reacted gaseous product again by one be filled with 1 the gram catalyzer fixed-bed reactor, reactor temperature is 350 ℃.
With constant-flux pump the flow of water with 6 Grams Per Hours is passed in the gaseous product of above-mentioned rearrangement reaction, adorns second fixed-bed reactor of 2.2 gram catalyzer in mixture enters, the weight hourly space velocity of the alcoholic solution of rearrangement product hexanolactam is 4 o'clock
-1, temperature of reaction is 350 ℃, reaction product enters receiving flask and carries out gas-liquid separation after the mixture of ice and water cooling, react and carry out the product compositional analysis after 1500 hours.
Analytical results is: the cyclohexanone-oxime transformation efficiency is 100%, and the hexanolactam selectivity is 97.3%.
Catalyzer after using through flow as 500 ℃ of regenerated with hot air of 48L/h after 48 hours, be used further to above-mentioned first and second fixed-bed reactor, the result who continues 1200 hours after product compositional analysis of operation is: the cyclohexanone-oxime transformation efficiency is 99.9%, and the hexanolactam selectivity is 97.4%.
Catalyzer after the use carries out the regeneration second time according to above-mentioned same method again, and the result that the catalyzer behind the secondary recycling continues 1020 hours after product compositional analysis of operation is: the cyclohexanone-oxime transformation efficiency is 99.9%, and the hexanolactam selectivity is 97.3%.
Comparative Examples
The explanation of this Comparative Examples only adopts single fixed bed to carry out the effect of Beckmann rearrangement.
Filling 4.5 gram catalyzer in fixed-bed reactor.Reaction raw materials is the ethanolic soln of the cyclohexanone-oxime of concentration 28 weight %, and with the flow charging of constant-flux pump with the ethanolic soln of 64.3 Grams Per Hour cyclohexanone-oximes, the weight space velocity of cyclohexanone-oxime is 4 o'clock
-1, carrier gas N
2Flow is 7.2L/h, and the catalyst bed reaction temperature is 380 ℃.Reaction product enters receiving flask and carries out gas-liquid separation after the mixture of ice and water cooling, react and carry out the product compositional analysis after 220 hours.
Analytical results is: the cyclohexanone-oxime transformation efficiency is 99.5%, and the hexanolactam selectivity is 95.3%.
Claims (9)
1, the method for cyclohexanone-oxime gas phase beckmann rearrangement system hexanolactam is with cyclohexanone-oxime and C
1-C
6The saturated fatty alcoholic solvent mix according to the weight ratio of 10-50:90-50, after vaporizing, enter first fixed-bed reactor that are filled with MFI structural molecule sieve catalyst with the inert carrier gas, in temperature of reaction is 250-500 ℃, when normal pressure, the weight hourly space velocity 1-8 of cyclohexanone-oxime
-1Condition under carry out Beckmann rearrangement, the streams that contains by product o-alkyl-ε-own lactim that reaction back produces with water with the inert carrier gas by being filled with second fixed-bed reactor of MFI structural molecule sieve catalyst, when the weight hourly space velocity of 250-500 ℃, normal pressure and hexanolactam alcoholic solution is 0.5-20
-1Condition under make o-alkyl-ε-own lactim wherein be converted into the product hexanolactam, reacted effluent separates, purifies.
2, according to the process of claim 1 wherein that employed MFI structural molecule sieve catalyst in the said fixed-bed reactor is selected from one of ZSM-5 molecular sieve of load or unsupported HTS, total silicon molecular sieve and silicon/aluminum ratio 〉=500.
3, according to the process of claim 1 wherein that the said inert carrier gas that enters in the fixed-bed reactor with material is selected from nitrogen or argon gas.
4, according to the process of claim 1 wherein that the weight ratio of mixture of cyclohexanone-oxime and alcoholic solvent is 20-40:80-60 in said first fixed-bed reactor; Said alcoholic solvent is selected from C
1-C
3Saturated fatty alcohol; Reaction conditions is: temperature of reaction 300-400 ℃, and when normal pressure, the weight hourly space velocity 1-4 of cyclohexanone-oxime
-1
5, according to the process of claim 1 wherein that the said streams that contains by product o-alkyl-ε-own lactim that enters second fixed-bed reactor is to have a kind of in the following component: the streams that 1) contains solvent alcohol, product hexanolactam, o-alkyl-ε-own lactim and other by product; 2) removed the streams that contains o-alkyl-ε-own lactim of pure and mild other by product of partial solvent.
6, according to the process of claim 1 wherein that the said add-on that enters the water of second fixed-bed reactor with streams should be the 0.1-50% of benchmark with the streams total mass.
7, according to the method for claim 6, wherein the add-on of said water should be the 2-20% of benchmark with the streams total mass.
8, according to the process of claim 1 wherein that the temperature of reaction that should control in said second fixed-bed reactor is 300-400 ℃; Reaction pressure is a normal pressure; When the weight hourly space velocity of hexanolactam alcoholic solution is 1-10
-1
9, according to the process of claim 1 wherein that said first fixed-bed reactor that are used to carry out Beckmann rearrangement are provided with a plurality of simultaneously.
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| TWI426050B (en) * | 2011-04-19 | 2014-02-11 | China Petrochemical Dev Corp Taipei Taiwan | A method for preparing titanium-silicon molecular sieve and method for producing cyclohexanone oxime using the molecular sieve |
| CN102755860B (en) * | 2011-04-29 | 2015-04-29 | 中国石油化工股份有限公司 | Cyclohexanone-oxime vaporizing method |
| CN102863382B (en) * | 2011-07-07 | 2014-03-12 | 中国石油化工股份有限公司 | Solvent recovery method of caprolactam rearrangement reaction products and application thereof |
| CN102875469B (en) * | 2011-07-14 | 2015-01-14 | 中国石油化工股份有限公司 | Method for preparing caprolactam through adopting radial moving bed reactor |
| CN102875468A (en) * | 2011-07-14 | 2013-01-16 | 中国石油化工股份有限公司 | Method for producing caprolactam through gas phase rearrangement of cyclohexanone-oxime |
| CN103285905B (en) * | 2012-02-29 | 2015-03-04 | 北京安耐吉能源工程技术有限公司 | Overall structure catalyst, preparation method of overall structure catalyst, and method for preparing caprolactam |
| CN108543548B (en) * | 2018-04-18 | 2021-07-30 | 中国天辰工程有限公司 | Preparation method of resin catalyst for preparing caprolactam through liquid phase Beckmann rearrangement |
| CN111848482A (en) * | 2020-08-11 | 2020-10-30 | 湖南百利工程科技股份有限公司 | Separation method of cyclohexanone oxime gas phase reaction rearrangement product |
| CN113087641B (en) * | 2021-04-14 | 2023-10-24 | 江苏扬农化工集团有限公司 | Method for preparing 6-aminocapronitrile from cyclohexanone oxime |
| CN114507169B (en) * | 2022-02-24 | 2023-08-25 | 江苏扬农化工集团有限公司 | Method for converting O-alkylcaprolactam into caprolactam and application thereof |
| CN114507171A (en) * | 2022-02-24 | 2022-05-17 | 江苏扬农化工集团有限公司 | Preparation method of caprolactam |
| CN114507170B (en) * | 2022-02-24 | 2024-06-04 | 江苏扬农化工集团有限公司 | Process for preparing caprolactam |
| CN114456096B (en) * | 2022-02-24 | 2023-09-26 | 江苏扬农化工集团有限公司 | Purification method of caprolactam |
| CN114478386B (en) * | 2022-02-24 | 2024-02-09 | 江苏扬农化工集团有限公司 | Process for preparing caprolactam by gas phase method |
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