CN1415607A - Method for synthesizing caprolactam - Google Patents

Method for synthesizing caprolactam Download PDF

Info

Publication number
CN1415607A
CN1415607A CN01134270A CN01134270A CN1415607A CN 1415607 A CN1415607 A CN 1415607A CN 01134270 A CN01134270 A CN 01134270A CN 01134270 A CN01134270 A CN 01134270A CN 1415607 A CN1415607 A CN 1415607A
Authority
CN
China
Prior art keywords
oxime
cyclohexanone
accordance
gram
hour
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN01134270A
Other languages
Chinese (zh)
Other versions
CN1164576C (en
Inventor
程时标
汪顺祖
吴巍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CNB011342706A priority Critical patent/CN1164576C/en
Publication of CN1415607A publication Critical patent/CN1415607A/en
Application granted granted Critical
Publication of CN1164576C publication Critical patent/CN1164576C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A process for preparing caprolactam features that said caprolactam is synthesized from cyclohexanone oxime in fixed-bed reaction system, where the silicon molecular sieve with MFI structure and concave-convex surface for high specific surface area is used as its catalyst. Its advantages are high conversion rate of cyclodexanone oxide (99.5%) and high selectivity to caprolactam (96%).

Description

A kind of synthetic method of hexanolactam
Technical field
The invention relates to a kind of synthetic method of hexanolactam, more specifically say so about a kind of be catalyzer with the si molecular sieves, in the fixed bed reaction system by the method for cyclohexanone-oxime synthesis of caprolactam.
Background technology
Hexanolactam is a main raw material of producing polyamide fibre, industrial cord thread and nylon engineering plastic three big series product, industrial general employing sulfuric acid catalysis liquid phase Beckmann rearrangement technology, this technology be make earlier cyclohexanone-oxime under the vitriol oil or oleum katalysis in 80-100 ℃ take place Beckmann rearrangement, again with ammonia neutralization reaction system acidity, generate the process of hexanolactam and byproduct of ammonium sulfate.This technological reaction condition mitigation, cyclohexanone-oxime transformation efficiency height, hexanolactam selectivity are good, but shortcoming is sulfuric acid and the ammonia that consumes high value, the cheap ammonium sulfate of by-product, and vitriolic uses the problems such as equipment corrosion and environmental pollution that also cause simultaneously.Though since this century the eighties, for reducing the output of by product, people adopt means such as water-content in multistage rearrangement reactor tandem process, the strict gate ring hexanone oxime, reduced by product ammonium sulfate growing amount, but vitriolic uses the problem cause never to be resolved, this today of advocating atom economy and environmental protection and economy be difficult to gratifying.
For addressing the above problem, people have proposed various gas phase beckmann rearrangement technologies with the solid acid as catalyst, and solid acid catalyst commonly used mainly contains oxide compound and molecular sieve.
USP3574193, USP3586668, USP5914398, USP5942613, Appl.Catal., A, 1992,93:75, Chem.Lett., 1985,277, Appl.Catal., 1999,188:361, J.Catal., 1994,148 (1): 138, Catal.Lett., 1998,49 (3-4): 229, Can.J.Chem.Eng., 1980,58 (12): 1266, Stud.Surf.Sci.Catal., 1993, all having with the oxide compound among the 78:615 is the report of the Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement of catalyzer, and these adopt the report of fixed-bed reactor to show that all the oxide catalyst life-span short, and regenerability is bad, the cyclohexanone-oxime transformation efficiency is low, the hexanolactam selectivity is not high, and (hereinafter to be referred as WHSV) is low for the cyclohexanone-oxime weight space velocity, does not have an industrial application value.For example, Appl.Catal., 1999, report B among the 188:361 2O 3/ ZrO 2At B 2O 3It was best to reset performance during load 10%, at WHSV=0.32 hour -1Shi Fanying 4 hours, cyclohexanone-oxime transformation efficiency are 100%, and the hexanolactam selectivity is 97%, but after reacting 10 hours, the cyclohexanone-oxime transformation efficiency has been reduced to below 60%, and the hexanolactam selectivity has reduced to 90%; USP5914398 has disclosed with unformed little mesopore SiO 2-Al 2O 3For catalyzer, at WHSV=2.2 hour -1Under the result, reacting 1 hour cyclohexanone-oxime transformation efficiency is 99.7%, the hexanolactam selectivity is 78.3%, reacts 23 hours cyclohexanone-oxime transformation efficiencys and has reduced to 97.9%, the hexanolactam selectivity is 81.4%.
Landis has at first reported HY molecular sieve, the X type molecular sieve of different cationic exchange and the Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement performance that mordenite is catalyzer, under 2 hours situation of reaction, the transformation efficiency of cyclohexanone-oxime is 85%, and the selectivity of hexanolactam is 76%.
USP5403801 reported the si molecular sieves of handling through inorganic alkali solution, at WHSV=8 hour -1The transformation efficiency of cyclohexanone-oxime is 99.5% when reacting 6.25 hours, the selectivity of hexanolactam is 96.5%, feeding the saturated air that contains methyl alcohol then regenerated 23 hours, proceed reaction, so be repeated to the 30th time, reacted 6.25 hours, the transformation efficiency of cyclohexanone-oxime is 95.3%, and the selectivity of hexanolactam is 95.3%.
Through vapor phase beckmann rearrangement reaction production reaction system that hexanolactam adopted, there are fixed bed and fluidized-bed available for cyclohexanone-oxime.The technology of using fluidized-bed is at US3154539, DE2641408, CN1269360A and Stud.Surf.Sci.Catal., and 1997, report is all arranged among the 105:1173.
Adopt the fluidized-bed reaction form to finish Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement continuously and produce hexanolactam, but have the cost of investment height, the catalyzer frequent regeneration influences optionally problem.
J.Catal., 1992,137:252 has reported the application of pure si molecular sieves, has been the reaction result of reaction system with the fixed bed that its catalyst life was less than 30 hours, and transformation efficiency is 90%, and selectivity is 81%.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of high conversion, highly selective, long lifetime, easy and simple to handle and caprolactam production method that production cost is low.
Method provided by the invention be with solvent and cyclohexanone-oxime mol ratio be the mixed solution of 3-12 in the presence of carrier gas by MFI structure si molecular sieves bed, WHSV is 0.1-1 5 hours -1, preferred 2-6 hour -1, temperature 300-500 ℃, preferred 350-400 ℃, more preferably 360-390 ℃, pressure be normal pressure to absolute pressure 0.5MPa, the mol ratio of carrier gas and cyclohexanone-oxime is 1-15, preferably 3-5.5.
In method provided by the invention, said solvent is selected from the Fatty Alcohol(C12-C14 and C12-C18) of 1-6 carbon atom, particular methanol and/or ethanol, preferably ethanol.Add entry in cyclohexanone-oxime, can prolong life of catalyst, the mol ratio of amount of water and cyclohexanone-oxime is 0.01-2.5.
In method provided by the invention, said carrier gas is selected from the rare gas element that comprises nitrogen, argon gas, hydrogen, carbon monoxide and carbonic acid gas etc.; In carrier gas, feed a certain amount of NH 3, (CH 3) 3Nitrogenous alkaline gas such as N is useful to the rearrangement performance of improving catalyzer.
The regeneration pressure of catalyzer is identical with reaction pressure, and regeneration temperature is 350-700 ℃, and preferred 400-500 ℃, regenerating gases used is oxygen-containing gas, and as air, its volume space velocity is 200-40000 hour -1, preferred 4000-20000 hour -1In oxygen-containing gas, feed a certain amount of alcohols steam (as methyl alcohol, ethanol) and nitrogenous alkaline gas (as NH 3, (CH 4) 3N) etc. be useful to the rearrangement performance of improving catalyzer.
In method provided by the invention, described MFI structure molecular screen, application number be 00123576.1 and the application documents of 00123577.x in open, specifically this molecular sieve has the MFI crystalline structure, this zeolite crystal surface is empty male and fomale(M﹠F), and the BET specific surface area is greater than 430 meters 2/ gram and outer specific surface are greater than 50 meters 2/ gram, the absorption of its cryogenic nitrogen absorption is propped up with desorption and is propped up at P/P 0There is hysteresis loop between the=0.45-0.98.
Said MFI structure molecular screen, its X-ray diffraction (XRD) spectrogram and " MicroporousMaterials ", Vol 22, p637, the MFI construction standard XRD spectra feature of record is just the same on 1998; From transmission electron microscope photo as can be seen, its grain surface is different from the form that existing si molecular sieves crystal grain shows fully, is empty male and fomale(M﹠F).
Preferred 430～500 meters of the BET specific surface area of si molecular sieves provided by the present invention 2/ gram, preferred 50～100 meters of outer specific surface 2/ gram.
The cryogenic nitrogen adsorption curve of si molecular sieves provided by the present invention is at p/p 0Form hysteresis loop=0.45～0.98 interval the separation, and prop up and there is not hysteresis loop in desorption between propping up substantially with the absorption that the cryogenic nitrogen of the si molecular sieves of prior art for preparing adsorbs.
The preparation method of si molecular sieves provided by the invention is with by weight, after the si molecular sieves that ordinary method synthesizes, organic bases and water mix with 1: 0.05～0.5: 0～8 mixing match, in closed reactor, 100～150 ℃ were reacted 0.1～10 day under the autogenous pressure, reclaimed product then.
The mixing match of the si molecular sieves that said ordinary method synthesizes, organic bases and water is preferred 1: 0.1～0.3: 0.1～2, preferred 0.5～5 day of reaction times.
Also said process can be repeated once or several times among the said preparation method of the present invention.
The ordinary method of said synthetic si molecular sieves among this preparation method, can be method, the method for JP59-164617 record or the method for other bibliographical information that USP4061724 records and narrates, wherein preferably adopting tetraethoxy be that silicon source and TPAOH are the si molecular sieves of alkali source, template preparation.
Described organic bases is selected from fat amine compound, alcamine compound, quaternary amine alkali compounds or two or more mixture among them, wherein preferred quaternary amine alkali compounds.
The general formula of described fat amine compound is R 1(NH 2) n, R 1For having the alkyl of 1～6 carbon atom, n=1 or 2, one of the preferred ethamine of fat amine compound, n-Butyl Amine 99, Tri N-Propyl Amine, quadrol or hexanediamine.
The general formula of described alcamine compound is (HOR 2) mN, R 2For having the alkyl of 1～4 carbon atom, m=1,2 or 3, one of the preferred monoethanolamine of alcamine compound, diethanolamine or trolamine.Said quaternary amine alkali compounds is the alkyl quaternary amine bases compound that contains 1～4 carbon atom, wherein preferred tetraethyl ammonium hydroxide or TPAOH.
In the method provided by the invention, the mean diameter of said silicalite molecular sieve catalyst is the 0.2-5 millimeter, can make by extrusion or compressing tablet.
Method provided by the invention, be in the fixed bed reaction system, MFI structure si molecular sieves with specific physical and chemical performance is that catalyzer carries out the method that Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement prepares hexanolactam, has following advantage: 1) long reaction time, recovery time is short, for example, at WHSV=2 hour -1The time, guarantee that the cyclohexanone-oxime transformation efficiency is 99%, the hexanolactam selectivity is that reaction reaches 1500 hours runtime under 95.5% the prerequisite, and had only about 24 hours the recovery time; 2) single reaction time, unit catalyzer produce hexanolactam amount height, for example WHSV=2 hour -1The time, be 99% at the cyclohexanone-oxime transformation efficiency, the hexanolactam selectivity is that on average each reaction time, every gram catalyzer produces hexanolactam and reaches 2800 grams under 95% the situation.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of embodiment 1 sample.
Fig. 2 is the cryogenic nitrogen adsorption-desorption thermoisopleth of embodiment 1 sample of doing.
Fig. 3 is the transmission electron microscope photo of embodiment 1 sample of doing.
Fig. 4 is the synoptic diagram that the invention provides method.
The BET specific surface of si molecular sieves sample, outer specific surface data and adsorption-desorption thermoisopleth adsorb instrument automatically by U.S.'s Micromeritics ASAP-2400 type and make in the example, the X-ray diffraction spectroscopic data is made by the D5005D type diffractometer of German SIEMENS company, and the grain surface form of sample is by the Hitachi H-800 of NEC company type transmissioning electric mirror determining.
Embodiment
Following example will be described application of the present invention in detail, but scope of the present invention should not be subjected to the restriction of these examples.
In following example, concept definition is as follows:
Figure A0113427000071
Figure A0113427000073
Example 1-8 illustrates the preparation process of si molecular sieves of the present invention.
Example 1
At room temperature 208 gram tetraethoxys (brief note is TEOS) are poured in 1000 ml beakers, stirred 30 minutes, TPAOH with 22.5% (brief note is TPAOH) solution 180 grams add in the tetraethoxy, stir hydrolysis 2～3 hours under the room temperature, be warmed up to 70～75 ℃, stirred 3～5 hours, add water 220 grams, form colloidal sol, stir, volumetric molar concentration is TPAOH/SiO 2=0.2, H 2O/SiO 2=20, said mixture is moved in the stainless steel cauldron of 500 milliliters of inner liner polytetrafluoroethylenes, in 170 ℃ of crystallization 2 days, filter, washing 120 ℃ of dryings 24 hours, 550 ℃ of roastings 5 hours.
The TPAOH aqueous solution 55 gram of getting product of roasting and 22.5% mixes, and 150 ℃ of following crystallization are 1 day in sealed reactor, after filtration, washing, 110 ℃ of dryings 12 hours, 550 ℃ of roastings 4 hours, the si molecular sieves product, numbering A.Its BET specific surface area is 464 meters 2/ gram, outer specific surface are 60 meters 2/ gram, the X-ray diffraction spectrogram of product is seen Fig. 1; The adsorption-desorption spectrogram of cryogenic nitrogen absorption is seen Fig. 2; Transmission electron microscope photo is seen Fig. 3.
Example 2
At room temperature 208 gram tetraethoxys are poured in 500 ml beakers, stirred 30 minutes, the 22.5% TPAOH aqueous solution, 180 grams add among the TEOS, stir hydrolysis 2 hours under the room temperature, add water 220 grams, add ethanol (brief note is EtOH) 184 grams, stirring is colloidal sol, and the chemical constitution that mix clear liquid this moment is H 2O/SiO 2=20, EtOH/SiO 2=8, TPAOH/SiO 2=0.20,110 ℃ of crystallization 2 days, filter, washing 120 ℃ of dryings 24 hours, 550 ℃ of roastings 5 hours.
The TPAOH aqueous solution 55 gram of getting product of roasting and 22.5% mixes, and 150 ℃ of crystallization are 1 day in sealed reactor, after filtration, washing, 110 ℃ of dryings 12 hours, 550 ℃ of roastings 4 hours, the si molecular sieves product, numbering B.Its BET specific surface area is 481 meters 2/ gram, outer specific surface are 70 meters 2/ gram, the X-ray diffraction spectrogram of product has the feature of Fig. 1; The adsorption-desorption spectrogram of cryogenic nitrogen absorption has the feature of Fig. 2; Transmission electron microscope photo has the feature of Fig. 3.
Example 3
At room temperature 208 gram tetraethoxys are poured in 500 ml beakers, stirred 30 minutes, add the 22.5% TPAOH aqueous solution, stir hydrolysis 2 hours under the room temperature, add water and ethanol, stir, making the chemical constitution of mixing clear liquid is H 2O/SiO 2=20, EtOH/SiO 2=16, TPAOH/SiO 2=0.20,110 ℃ of crystallization 2 days are filtered, washing, 120 ℃ of dryings 24 hours, 550 ℃ of roastings 5 hours.
The TPAOH aqueous solution 67.8 gram of getting product of roasting and 22.5% mixes, and 110 ℃ of crystallization are 4 days in sealed reactor, after filtration, washing, 110 ℃ of dryings 12 hours, 550 ℃ of roastings 4 hours, the si molecular sieves product, numbering C.Its BET specific surface area is 488 meters 2/ gram, outer specific surface are 75 meters 2/ gram has the feature of Fig. 1 from the X-ray diffraction spectrogram of product; The adsorption-desorption spectrogram of cryogenic nitrogen absorption has the feature of Fig. 2; Transmission electron microscope photo has the feature of Fig. 3.
Example 4
At room temperature 208 gram tetraethoxys are poured in 500 ml beakers, stirred 30 minutes, TPAOH solution 180 grams with 22.5% add in the tetraethoxy, stir hydrolysis 2～3 hours under the room temperature, be warmed up to 70～75 ℃, catch up with alcohol to stir 3～5 hours, add water 220 grams, form colloidal sol, stir, volumetric molar concentration is TPAOH/SiO 2=0.20, H 2O/SiO 2=20, said mixture is moved in the stainless steel cauldron of 500 milliliters of inner liner polytetrafluoroethylenes, in 170 ℃ of crystallization 2 days, filter, washing 120 ℃ of dryings 24 hours, 550 ℃ of roastings 5 hours.
Get product of roasting and 30 gram quadrols mix, 150 ℃ of following crystallization are 5 days in sealed reactor, after filtration, washing, 110 ℃ of dryings 12 hours, 550 ℃ of roastings 4 hours, the si molecular sieves product, numbering D.Its BET specific surface area is 465 meters 2/ gram, outer specific surface are 61 meters 2/ gram has the feature of Fig. 1 from the X-ray diffraction spectrogram of product; The adsorption-desorption spectrogram of cryogenic nitrogen absorption has the feature of Fig. 2; Transmission electron microscope photo has the feature of Fig. 3.
Example 5
At room temperature 208 gram tetraethoxys are poured in 2000 ml beakers, stirred 30 minutes, TPAOH solution 360 grams with 22.5% add in the tetraethoxy, stir hydrolysis 2～3 hours under the room temperature, be warmed up to 70～75 ℃, catch up with alcohol to stir 3～5 hours, add water 440 grams, form colloidal sol, stir, volumetric molar concentration is TPAOH/SiO 2=0.40, H 2O/SiO 2=40, said mixture is moved in the stainless steel cauldron of 500 milliliters of inner liner polytetrafluoroethylenes, in 170 ℃ of crystallization 2 days, filter, washing 120 ℃ of dryings 24 hours, 550 ℃ of roastings 5 hours.
Get product of roasting and 103 diamines of restraining oneself and mix, 150 ℃ of following crystallization are 4 days in sealed reactor, after filtration, washing, 110 ℃ of dryings 12 hours, 550 ℃ of roastings 4 hours, the si molecular sieves product, numbering E.Its BET specific surface area is 460 meters 2/ gram, outer specific surface are 55 meters 2/ gram, the X-ray diffraction spectrogram of product has the feature of Fig. 1, and the adsorption-desorption spectrogram of cryogenic nitrogen absorption has the feature of Fig. 2, and transmission electron microscope photo has the feature of Fig. 3.
Example 6
At room temperature 208 gram tetraethoxys are poured in 500 ml beakers, stirred 30 minutes, TPAOH solution 90 grams with 22.5% add in the tetraethoxy, stir hydrolysis 2～3 hours under the room temperature, be warmed up to 70～75 ℃, catch up with alcohol to stir 3～5 hours, add water 110 grams, form colloidal sol, stir, volumetric molar concentration is TPAOH/SiO 2=0.1, H 2O/SiO 2=10, said mixture is moved in the stainless steel cauldron of 500 milliliters of inner liner polytetrafluoroethylenes, in 170 ℃ of crystallization 2 days, filter, washing 120 ℃ of dryings 24 hours, 550 ℃ of roastings 5 hours.
Get product of roasting and 76.7 gram monoethanolamines mix, 130 ℃ of following crystallization are 3 days in sealed reactor, after filtration, washing, 110 ℃ of dryings 12 hours, 550 ℃ of roastings 4 hours, the si molecular sieves product, numbering F.Its BET specific surface area is 470 meters 2/ gram, outer specific surface are 59 meters 2/ gram, the X-ray diffraction spectrogram of product has the feature of Fig. 1; The adsorption-desorption spectrogram of cryogenic nitrogen absorption has the feature of Fig. 2; Transmission electron microscope photo has the feature of Fig. 3.
Example 7
At room temperature 208 gram tetraethoxys are poured in 2000 ml beakers, stirred 30 minutes, the 22.5% TPAOH aqueous solution, 180 grams add among the TEOS, stir hydrolysis 2 hours under the room temperature, add water 220 grams, add ethanol 184 grams, stirring is colloidal sol, and the chemical constitution that mix clear liquid this moment is H 2O/SiO 2=20, EtOH/SiO 2=8, TPAOH/SiO 2=0.20,110 ℃ of crystallization temperatures 2 days filter, washing, 120 ℃ of dryings 24 hours, 550 ℃ of roastings 5 hours.
Get product of roasting 30 gram and mix with trolamine 67.5 grams, 120 ℃ of crystallization are 3 days in sealed reactor, after filtration, washing, 110 ℃ of dryings 12 hours, 550 ℃ of roastings 4 hours, the si molecular sieves product, numbering G.Its BET specific surface area is 465 meters 2/ gram, outer specific surface are 62 meters 2/ gram has the feature of Fig. 1 from the X-ray diffraction spectrogram of product; The adsorption-desorption spectrogram of cryogenic nitrogen absorption has the feature of Fig. 2; Transmission electron microscope photo has the feature of Fig. 3.
Example 8
Present embodiment be on the basis of example 1 with preparation process in the process of step (3) repeat once.
Molecular sieve 30 grams that example 1 is prepared mix with 22.5% the TPAOH aqueous solution 25 grams, and 150 ℃ of following crystallization are 1 day in sealed reactor, after filtration, washing, 110 ℃ of dryings 12 hours, 550 ℃ of roastings 4 hours, the si molecular sieves product, numbering H.Its BET specific surface area is 497 meters 2/ gram, outer specific surface are 86 meters 2/ gram.The X-ray diffraction spectrogram of product has the feature of Fig. 1; The adsorption-desorption spectrogram of cryogenic nitrogen absorption has the feature of Fig. 2; Transmission electron microscope photo has the feature of Fig. 3.
Example 9-30 illustrates the reaction and the regenerative process of method provided by the invention.
Example 9-30
Fig. 4 is the synoptic diagram that the invention provides method.
According to shown in Figure 4, during reaction, valve 1 is opened, valve 2 is closed, reaction raw materials (cyclohexanone-oxime, solvent and carrier gas) is heated to 205-350 ℃ through vaporizer earlier, with gaseous form process beds, the temperature of beds is controlled by well heater again, and reaction product enters the product gathering system behind water cooler.
In the scale operation,, can in bed, increase the heat-obtaining facility, also beds can be divided into several sections, spray into cooling gas in each section centre for removing the heat in the beds.In addition, cyclohexanone-oxime, solvent and carrier gas also can two enter beds together or separately behind vaporizer.
The regenerated process is a valve-off 1 behind the catalyst deactivation, opens valve 2, feeds oxygen-containing gas, also can add pure steam (as methyl alcohol, ethanol) in the oxygen-containing gas, regenerates under 350-700 ℃.
After regeneration is finished, feed raw material again and react, so hocket.
Used fixed-bed reactor internal diameter is 5 millimeters in the example, interior dress 40-60 purpose si molecular sieves 0.375 gram, filling 80 millimeters high, 40-60 order quartz sand below 40 millimeters of the catalyst bed floor heights, 30 millimeters high 20-40 order quartz sands of filling above the beds, beds.These quartz sands are all through acid treatment, washing and high-temperature roasting.
Shown in reaction result sees Table.
Table
Example number The si molecular sieves numbering Reactant ratio (mol ratio) The reaction conditions temperature (℃)/absolute pressure (MPa)/WHSV (hour -1) Working time (hour)/cyclohexanone-oxime transformation efficiency (%)/hexanolactam selectivity (%) The regeneration condition temperature (℃)/air air speed (hour-1)/recovery time (hour) Single reaction time, every gram catalyzer produced hexanolactam gram number
????9 ????A Oxime/ethanol/N 2????1/6.36/3.7 350/ normal pressure/8 ????8/98.2/95.4 ????--- ????60
???10 ????B Oxime/ethanol/N 2????1/6.36/3.7 350/ normal pressure/8 ????10/98.3/95.2 ????--- ????76
???11 ????C Oxime/ethanol/N 2????1/6.36/3.7 350/ normal pressure/8 ????12/98.6/95.7 ????---- ????91
???12 ????D Oxime/ethanol/N 2????1/6.36/3.7 350/ normal pressure/8 ????5/98.5/95.4 ????------ ????38
???13 ????E Oxime/ethanol/N 2????1/6.36/3.7 350/ normal pressure/8 ????6/98.4/95.8 ????----- ????46
???14 ????F Oxime/ethanol/N 2????1/6.36/3.7 350/ normal pressure/8 ????7/98.1/95.4 ????--- ????53
???15 ????G Oxime/ethanol/N 2????1/6.36/3.7 350/ normal pressure/8 ????8/98.6/95.5 ????--- ????61
???16 ????H Oxime/ethanol/N 2????1/6.36/3.7 350/ normal pressure/8 ????8/98.0/9?5.7 ????---- ????61
???17 ????C Oxime/methyl alcohol/N 2????1/6.36/3.7 350/ normal pressure/8 ????6/98.9/94.9 ????500/3821/12 ????43
???18 ????C Oxime/ethanol/N 2????1/6.36/3.7 390/ normal pressure/8 ????12/99.9/94.0 ???430/3821/24 ????90
???19 ????C Oxime/ethanol/N 2????1/6.36/3.7 ???390/0.2/8 ????8/99.6/94.2 ???430/3821/24 ????60
???20 ????C Oxime/ethanol/N 2????1/6.36/15 370/ normal pressure/2 ????1032/99.5/95.5 ???430/3821/24 ????1950
???21 ????C Oxime/ethanol/N 2????1/6.36/7.48 370/ normal pressure/4 ????224/98.3/95.7 ???450/4000/36 ????800
???22 ????C Oxime/ethanol/N 2????1/6.36/3 370/ normal pressure/10 ????4/98.3/94.7 ???500/5000/24 ????47
???23 ????C Oxime/ethanol/N 2????1/6.36/4.5 370/ normal pressure/8 ????22/98.9/96.0 ???430/3821/24 ????167
Continuous table 1
Example number The si molecular sieves numbering Reactant ratio (mol ratio) The reaction conditions temperature (℃)/absolute pressure (MPa)/WHSV (hour -1) Working time (hour)/cyclohexanone-oxime transformation efficiency (%)/hexanolactam selectivity (%) The regeneration condition temperature (℃)/the air air speed (hour -1)/the recovery time (hour) Single reaction time, every gram catalyzer produced hexanolactam gram number
24 ??C Oxime/ethanol/water/N 2????1/6.4/0.1/4.5 370/ normal pressure/8 ????30/99.2/95.9 ????430/3821/24 ????229
25 ??C Oxime/ethanol/N 2????1/4.25/4.5 370/ normal pressure/8 ????96/97.6/96.5 ????450/4000/24 ????720
26 ??C Oxime/ethanol/N 2????1/3.19/4.5 370/ normal pressure/8 ????96/99.2/96.3 ????450/4000/24 ????734
27 ??C Oxime/ethanol/N 2????1/3.19/4.5 370/ normal pressure/15 ????14/98.3/96.0 ????480/8000/24 ????200
28 ??B Oxime/ethanol/water/N 2????1/3.2/0.1/4.5 370/ normal pressure/6 ????410/99.1/95.9 ????430/4000/24 ????2337
29 ??C Oxime/ethanol/water/N 2????1/3.2/0.1/4.5 370/ normal pressure/4 ????626/99.4/96.1 ????430/4000/24 ????2379
30 ??C Oxime/ethanol/water/N 2????1/3.2/0.1/4.5 370/ normal pressure/2 ????1500/99.2/96.2 ????430/4000/24 ????2865

Claims (10)

1, a kind of method of cyclohexanone-oxime synthesis of caprolactam, this method may further comprise the steps: (1) is catalyzer with MFI structure si molecular sieves in the fixed bed reaction system, cyclohexanone-oxime weight space velocity 0.1-15 hour -1, temperature 300-500 ℃, pressure be that normal pressure is to absolute pressure 0.5MPa, with the mol ratio of the Fatty Alcohol(C12-C14 and C12-C18) of 1-6 carbon atom and cyclohexanone-oxime is that the mixed solution of 3-12 carries out Beckmann rearrangement by beds in the presence of rare gas element, (2) behind the catalyst deactivation, at 0.1-0.5MPa, 350-700 ℃, the oxygen-containing gas volume space velocity is 200-40000 hour -1Under regenerated 10-50 hour, carry out step (1) again, the grain surface that it is characterized in that this MFI structure silicalite molecular sieve catalyst is empty male and fomale(M﹠F), the BET specific surface area is greater than 430 meters 2/ gram and outer specific surface are greater than 50 meters 2/ gram, the absorption of its cryogenic nitrogen absorption is propped up with desorption and is propped up at P/P 0There is hysteresis loop between the=0.45-0.98.
2, in accordance with the method for claim 1, the BET specific surface area that it is characterized in that said MFI structure silicalite molecular sieve catalyst is a 430-500 rice 2/ gram, outer specific surface is a 50-100 rice 2/ gram.
3, in accordance with the method for claim 1, it is characterized in that reaction is at 2-6 hour -1, 350-400 ℃.
4, in accordance with the method for claim 1, it is characterized in that said Fatty Alcohol(C12-C14 and C12-C18) is methyl alcohol and/or ethanol.
5, in accordance with the method for claim 4, it is characterized in that said Fatty Alcohol(C12-C14 and C12-C18) is an ethanol.
6, in accordance with the method for claim 1, it is characterized in that said carrier gas is selected from the gas that comprises nitrogen, argon gas, hydrogen, carbon monoxide and carbonic acid gas etc., the mol ratio of carrier gas and cyclohexanone-oxime is 1-15.
7, in accordance with the method for claim 6, the mol ratio that it is characterized in that said carrier gas and cyclohexanone-oxime is 3-5.5.
8, in accordance with the method for claim 1, it is characterized in that can adding entry in the said cyclohexanone-oxime, the mol ratio of amount of water and cyclohexanone-oxime is 0.01-2.5.
9, in accordance with the method for claim 1, it is characterized in that said oxygen-containing gas is an air.
10, in accordance with the method for claim 1, the regeneration condition that it is characterized in that said silicalite molecular sieve catalyst is 400-500 ℃, and the oxygen-containing gas volume space velocity is 4000-20000 hour -1
CNB011342706A 2001-10-30 2001-10-30 Method for synthesizing caprolactam Expired - Lifetime CN1164576C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB011342706A CN1164576C (en) 2001-10-30 2001-10-30 Method for synthesizing caprolactam

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB011342706A CN1164576C (en) 2001-10-30 2001-10-30 Method for synthesizing caprolactam

Publications (2)

Publication Number Publication Date
CN1415607A true CN1415607A (en) 2003-05-07
CN1164576C CN1164576C (en) 2004-09-01

Family

ID=4672377

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB011342706A Expired - Lifetime CN1164576C (en) 2001-10-30 2001-10-30 Method for synthesizing caprolactam

Country Status (1)

Country Link
CN (1) CN1164576C (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100383125C (en) * 2003-09-28 2008-04-23 中国石油化工股份有限公司 Method for transforming to epsi-caprolactam O-alkyl-epsi-caprolactim
CN102120589A (en) * 2010-12-30 2011-07-13 中国天辰工程有限公司 S-1 full-silicon molecular sieve and preparation method thereof as well as application of S-1 full-silicon molecular sieve in caprolactam preparation
CN103204809A (en) * 2012-01-13 2013-07-17 中国石油化工股份有限公司 Production method of caprolactam
CN104513202A (en) * 2013-09-29 2015-04-15 中国石油化工股份有限公司 Cyclohexanone oxime conversion method
CN115475655A (en) * 2021-05-31 2022-12-16 中国石油化工股份有限公司 Boron-containing Silicate-1 molecular sieve catalyst, preparation method thereof and method for preparing caprolactam

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100383125C (en) * 2003-09-28 2008-04-23 中国石油化工股份有限公司 Method for transforming to epsi-caprolactam O-alkyl-epsi-caprolactim
CN102120589A (en) * 2010-12-30 2011-07-13 中国天辰工程有限公司 S-1 full-silicon molecular sieve and preparation method thereof as well as application of S-1 full-silicon molecular sieve in caprolactam preparation
CN102120589B (en) * 2010-12-30 2012-09-05 中国天辰工程有限公司 S-1 full-silicon molecular sieve and preparation method thereof as well as application of S-1 full-silicon molecular sieve in caprolactam preparation
CN103204809A (en) * 2012-01-13 2013-07-17 中国石油化工股份有限公司 Production method of caprolactam
CN103204809B (en) * 2012-01-13 2015-07-29 中国石油化工股份有限公司 A kind of method of producing hexanolactam
CN104513202A (en) * 2013-09-29 2015-04-15 中国石油化工股份有限公司 Cyclohexanone oxime conversion method
CN115475655A (en) * 2021-05-31 2022-12-16 中国石油化工股份有限公司 Boron-containing Silicate-1 molecular sieve catalyst, preparation method thereof and method for preparing caprolactam
CN115475655B (en) * 2021-05-31 2024-04-05 中国石油化工股份有限公司 Boron-containing Silicate-1 molecular sieve catalyst, preparation method thereof and method for preparing caprolactam

Also Published As

Publication number Publication date
CN1164576C (en) 2004-09-01

Similar Documents

Publication Publication Date Title
CN101885493B (en) Synthesis method of ZSM-5/beta nuclear shell-shaped molecular sieve
CN103896302B (en) A kind of si molecular sieves and preparation method thereof
CN101327934B (en) Preparation of titanium silicon molecular sieve having MFI structure
US11001503B2 (en) MFI zeolite with microporous and mesoporous hierarchical structure, preparation method therefor, and catalytic use thereof
CN109775714B (en) MFI topological structure silicon molecular sieve containing trace rare earth ions and preparation method thereof
US20070032379A1 (en) Catalyst, process for preparing the catalyst and process for producing lower hydrocarbon with the catalyst
CN101228122B (en) Method for synthesising lauryl lactam (l12) by catalytically rearranging cyclododecanone oxime in a gaseous phase
CN1124978C (en) Silicon molecular sieve and its synthesizing process
CN110615445B (en) Method for synthesizing ZSM-5 zeolite monobloc without template and adhesive
CN1164576C (en) Method for synthesizing caprolactam
CN103360344A (en) Method for catalyzing propylene epoxidation
CN102766032A (en) Oxidation method of cyclohexane
CN1349929A (en) Mesoporous molecular sieve material with strong acidity and high hydrothermal stability and its prepn
CN112537778A (en) Preparation method and application of mordenite with high silica-alumina ratio
CN1962574A (en) Process for producing cyclohexene
CN1600428A (en) Method for preparing catalyst of containing MFI structured molecular sieve
CN104512906B (en) Titanium-silicon molecular sieve and preparation method thereof
CN114405538B (en) Hierarchical pore Fe/ZSM-5 molecular sieve and preparation method and application thereof
CN114425438B (en) Preparation method of titanium-containing catalyst, titanium-containing catalyst and method for preparing epoxy compound
CN1142147C (en) Method for synthesizing hexanolactam by using titanium silicon molecular sieve to catalyze gas phase rearrangement of cyclohexanone-oxime
CN112744831B (en) Method for preparing titanium-containing molecular sieve, titanium-containing molecular sieve produced by method and cyclohexanone oximation reaction method
CN1275529A (en) Process for preparation of titanium-silicon molecular sieve
CN1467034A (en) Method for preparing piperazine and trivinyl-diamine molecular sieve catalyst
CN1119282C (en) Silicon molecular sieve and its preparing process
CN1621348A (en) Synthesis method of NaY molecular sieve

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CX01 Expiry of patent term

Granted publication date: 20040901

CX01 Expiry of patent term