CN1322927C - Method for preparing catalyst of containing MFI structured molecular sieve - Google Patents
Method for preparing catalyst of containing MFI structured molecular sieve Download PDFInfo
- Publication number
- CN1322927C CN1322927C CNB031264387A CN03126438A CN1322927C CN 1322927 C CN1322927 C CN 1322927C CN B031264387 A CNB031264387 A CN B031264387A CN 03126438 A CN03126438 A CN 03126438A CN 1322927 C CN1322927 C CN 1322927C
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- catalyst
- content
- sio
- accordance
- 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.)
- Expired - Lifetime
Links
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
- Catalysts (AREA)
Abstract
The present invention relates to a method for preparing an MFI structure molecular sieve catalyst which is used for preparing caprolactam from cyclohexanone oxime by gas-phase Beckmann rearrangement. An MFI structure molecular sieve with high ratio of silicon/ aluminum is combined with alkaline silica gel with the pH value of 8 to 10 according to the weight ratio of the molecular sieve to SiO2 of 60 to 90: 40 to 10. Then, the combined substance is formed, dried and roasted for 4 to 24 hours at the temperature of 500 to 650 DEG C. The conversion rate of the cyclohexanone oxime as the catalyst prepared by the method of the present invention achieves more than 98 %, and the selectivity of the caprolactam is approximately 97%. The catalyst crushing intensity can meet the requirements for fixed bed technologies, for example, the strip squeezing forming crushing intensity can achieve as high as 80 N/cm. Furthermore, the catalyst has favorable regeneration performance and can meet the requirements for industrial use.
Description
Technical field
The invention relates to a kind of preparation method of molecular sieve catalyst of the MFI of containing structure.More particularly, the invention relates to a kind of cyclohexanone oxime gas phase beckmann rearrangement that is used for and prepare preparation method caprolactam, that contain the molecular sieve catalyst of MFI structure.
Background technology
The product caprolactam of cyclohexanone oxime generation Beckmann rearrangement is a primary raw material of producing polyamide fibre, industrial cord fabric thread and nylon engineering plastic three big series of products, its demand is more prosperous always, estimates that whole world caprolactam demand in 2004 will be above 4,000,000 tons.Domestic caprolactam breach is bigger always, and year import volume is generally more than 300,000 tons, and along with the increase of consumption figure, the breach of caprolactam will be bigger from now on.
Industrial, making cyclohexanone oxime carry out that Beckmann rearrangement all adopts with the concentrated sulfuric acid or oleum is the liquid phase rearrangement technology of catalyst.The caprolactam of this explained hereafter accounts for about 90% of world's caprolactam production total amount, its maximum shortcoming is: this reaction is the reaction that the atom number does not change before and after the reaction, but to consume a large amount of sulfuric acid and ammoniacal liquor in the reaction, generate cheap ammonium sulfate, produce 1 ton of caprolactam by-product 1.3-1.8 ton ammonium sulfate.The use of sulfuric acid can cause problems such as equipment corrosion and environmental pollution in addition.
Making and producing technology more economical, that more meet the greenization requirement is vapor phase method.The method that makes cyclohexanone oxime carry out gas phase beckmann rearrangement system caprolactam is not used sulfuric acid and ammoniacal liquor, has no equipment corrosion, non-environmental-pollution and advantage such as by-product sulphur ammonium not.In the vapor phase method Beckmann rearrangement, have as the solid acid of catalyst multiple, as GB881, the silica-alumina catalyst that adopts in 927; GB881, the solid phosphoric acid catalyst that adopts in 956; GB1, the borated catalyst that adopts in 178,057; The high silicon that adopts among the CN1269360A/aluminum ratio MFI structural molecule sieve catalyst etc.
EP576, propose in 295, under the situation of not adding any binding agent, molecular sieve is made microballoon by spray-drying, in water, heat-treat then improving the mechanical strength of microballoon, so that this microspherical catalyst can be used in the fluidized-bed reactor that cyclohexanone oxime is converted into caprolactam.Obviously, such intensity can not satisfy the commercial Application demand.
Disclosed among the CN1256967A a kind of be used for cyclohexanone oxime be converted into caprolactam reaction, contain MFI structure molecular screen Preparation of catalysts method.The basic point of departure of this method is to be binding agent with the acidic silica gel, its concrete grammar is: the siliceous oligomer that the alkoxyl silicone acidic hydrolysis is made mixes with the water or the alcohol-aqueous dispersions of the subparticle of the MFI structure molecular screen of pH≤5, makes emulsifying mixture, curing, washing, roasting make gel micro-ball.This catalyst is applicable to fluidized-bed reactor.
USP4, disclosing a kind of in 859,785 is the method that adhesive preparation contains titanium-silicon molecular sieve catalyst with the alkaline silica gel.This alkaline silica gel is by tetraalkyl silicate, and preferably the tetraalkyl orthosilicate makes in the tetra-alkyl ammonium hydroxide aqueous solution, at room temperature to 200 ℃ hydrolysis 0.2-10 hour, its pH 〉=10.Prepared catalyst is the microspherical catalyst that is applicable to fluidized-bed reactor.
Because fluidized-bed process cost of investment height, and cyclohexanone oxime has only and about 95% transformed (require on the isolation technics 100% transform), and it is essential that the fixed bed new technology of therefore developing Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement becomes commercial Application institute.Simultaneously, the development of Preparation of catalysts method that is applied to the non-microspheroidal of fixed-bed process is also just put on the agenda.But do not see the preparation method's that the non-micro-spherical catalyst that is applied to fixed-bed process is arranged relevant report up to now as yet.
Summary of the invention
Purpose of the present invention is exactly that a kind of preparation method who is applicable to the non-micro-spherical catalyst of Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement fixed-bed process is provided on the basis of above-mentioned prior art.
We find: for the vapor phase beckmann rearrangement reaction catalyst, can not adopt the higher binding agent of Lewis acid content (as aluminium colloidal sol), otherwise will have a strong impact on the catalytic performance of catalyst; Guarantee simultaneously the crushing strength of catalyst again, make it can be applicable to fixed bed.
Preparation method provided by the invention makes the alkaline silica gel of the MFI structure molecular screen of high silicon/aluminum ratio and pH8-10 according to molecular sieve and SiO
2The weight ratio of 60-90: 40-10 combines, moulding then, drying, 500-650 ℃ following roasting 4-24 hour.
The MFI structure molecular screen of said high silicon/aluminum ratio is meant the ZSM-5 molecular sieve of total silicon molecular sieve or silicon/aluminum ratio 〉=500 in the inventive method.These molecular sieves can be directly used in the inventive method, also can handle through the alkaline aqueous solution of nitrogen-containing compound in advance.Suitable nitrogen-containing 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 nitrogen-containing compound aqueous solution can be carried out under 40-100 ℃ 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.Said 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 alkaline silica gel of said pH8-10 has 100-250m in the inventive method
2The specific area of/g and＜sodium ions content of 3000ppm, its SiO
2Content should be 25-45%.This alkaline silica gel can be made according to one of following method:
Method one: according to silica flour and NaOH10-40: 1 weight ratio, the concentration that silica flour is joined 60-85 ℃ is in the sodium hydrate aqueous solution of 0.1-1%, stirring reaction 2-3 hour, treat that pH reduces to 8-10, cooling, filter, be concentrated into its SiO
2Content 25-45%.
Method two: the Ludox that will make according to method one successively by acrylic type weak-acid cation-exchange resin and styrene type weak-base anion-exchange resin, is regulated its pH to 8-10 with ammoniacal liquor with the flow of 10-100ml/h then, is concentrated into its SiO
2Content 25-45%.
Method three: the flow with 10-100ml/h behind the waterglass filtration removal impurity of dilution is passed through acrylic type weak-acid cation-exchange resin and styrene type weak-base anion-exchange resin successively, regulate its pH to 8-10 with ammoniacal liquor then, be concentrated into its SiO
2Content 25-45%.
Preferably add gelatinizing agent in the inventive method in the said forming process, be applicable to that the gelatinizing agent of the inventive method preferably has: the 0.1-5% that ammoniacal liquor or tetraethyl ammonium hydroxide, its consumption are is benchmark with material gross weight to be formed.In the forming process of extrusion or compressing tablet, also can add extrusion aid, as sesbania powder etc.
Preparation method provided by the invention is applicable to 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.
The catalyst rings hexanone oxime conversion ratio height that the inventive method is prepared reaches more than 98%; The caprolactam selectivity is good, near 97%; The catalyst crushing strength can satisfy the requirement of fixed-bed process, can be up to 80N/cm as the crushing strength of extruded moulding.In addition, this catalyst regeneration is functional, can satisfy the requirement that industry is used.
The specific embodiment
Following example will be made further instruction to the present invention, but not thereby limiting the invention.
Employed total silicon molecular sieve is to make according to the method described in the CN1338427A in the example.
Employed Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement fixed bed reactors are stainless steel in the example, internal diameter 5mm, in adorn 0.375 the gram 40～60 molecules of interest sieve catalysts, load 40～60 purpose fine quartz sands below the thick quartz sand of filling high 20～40 purposes of about 30mm above the beds, beds.The rearrangement reaction condition is: normal pressure, 350 ℃ of reaction temperatures, cyclohexanone oxime weight space velocity 2h
-1, reaction dissolvent is the ethanol that accounts for reaction raw materials weight 55-70%, carrier gas N
2Flow is 1800ml/min, and product enters receiving flask and carries out gas-liquid separation after the mixture of ice and water cooling, react and carry out the product composition analysis after 8 hours.
Product adopts Trace GC-MS to carry out qualitative analysis.The GC8000 chromatograph 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 caprolactam, cyclohexanone and cyclonene adopt area normalization method to calculate, and solvent does not participate in integration.This computational methods mainly are because consider: in (1) product, solvent ratios is very big, if it participates in integration, some accessory substances just can not be detected, if it does not participate in integration, then can not adopt internal standard method and external standard method to carry out quantitative analysis; (2) in most rearrangement reactions, the cyclohexanone oxime conversion ratio is near 100%, caprolactam accounts for about 97% in the product, cyclohexanone and cyclonene account for 0.1%, 5-cyano group-1-amylene and own nitrile account for 1%, alcohol accounts for about 1.5% with the caprolactam product, and all the other nearly 10 kinds of unknown accessory substances account for about 0.5%.After testing, cyclohexanone, cyclohexanone oxime and aniline are respectively 0.71,0.77 and 0.67 to the mole relative correction factor of caprolactam, and other accessory substance can not get standard specimen, and therefore, each accessory substance all is considered as 1 to the mole relative correction factor of caprolactam.
Each is about reaction evaluating parameter-definition following (cyclohexanone oxime and caprolactam percentage composition are the chromatography value in the product) in the example:
Example 1
First kind of preparation method of used alkaline silica sol binding agent among this example explanation the present invention.
1500 gram distilled water and 8 gram SILVER REAGENT sodium hydrate solids are added in the reactive tank, be warming up to 65 ℃, stir and add 200 gram silica flours (silicone content is more than 98% for Tianjin Chemical Plant product, 180-240 order) down, the control temperature is below 85 ℃, stirring reaction 2-3 hour, when treating that pH reduces to 8-10, be cooled to 50 ℃ under stirring, filter, be concentrated into its SiO
2Content 25-45% promptly gets the alkaline silica sol that uses among the present invention, notes by abridging to be Ludox-1.Its physical and chemical performance and wherein the content of contained various impurity metal ions all list in table 1, wherein metal ion content records (down with) with plasma coupling mass spectrum.
Example 2
Second kind of preparation method of used alkaline silica sol binding agent among this example explanation the present invention.
The Ludox that will make according to example 1 with the flow of 30ml/h successively by acrylic type weak-acid cation-exchange resin (Shanghai Resin Factory's product, trade names 724
#) and styrene type weak-base anion-exchange resin (Shanghai Resin Factory's product, trade names 704
#) remove most foreign ions wherein, regulate its pH to 8-10 with ammoniacal liquor then, be concentrated into its SiO
2Content 25-45% promptly gets the alkaline silica sol that uses among the present invention, notes by abridging to be Ludox-2.Its physical and chemical performance and wherein the content of contained various impurity metal ions all list in table 1.
Example 3
The preparation of used alkaline silica sol binding agent among this example explanation the present invention.
(Haiyang Chemical Plant, Qingdao's product, modulus are 3.5, Na with 30 waterglass that restrain
2O content 7%) with behind the 600 gram distilled water dilutings, filter to remove impurity, with the flow of 30ml/h successively by acrylic type weak-acid cation-exchange resin (Shanghai Resin Factory's product, trade names 724
#) and styrene type weak-base anion-exchange resin (Shanghai Resin Factory's product, trade names 704
#) remove most foreign ions wherein, regulate its pH to 8-10 with ammoniacal liquor then, be concentrated into its SiO
2Content 25-45% promptly gets the alkaline silica sol that uses among the present invention, notes by abridging to be Ludox-3.Its physical and chemical performance and wherein the content of contained various impurity metal ions all list in table 1.
Table 1
| Example | 1 | 2 | 3 |
| The outward appearance dioxide-containing silica, % specific area, m 2/ g sodium ions content, the ppm potassium content, the ppm aluminium composition, the ppm iron ion content, the ppm magnesium ion content, the ppm calcium ion content, ppm pH value relative density colloid diameter, nm viscosity, * 10 -2Pa·s | Milky colloidal solution 30～210＜3000＜5.2＜450＜200＜20＜10 9.4 1.17 10～20 1～1.5 | Milky colloidal solution 40～150＜1000＜4.1＜200＜100＜10＜5 9.3 1.19 10～20 1.5 | Milky colloidal solution 40～135＜800＜3.6＜120＜60＜5＜2 9.1 1.20 10～20 2.0 |
Example 4
The explanation of this example the invention provides the enforcement of method and makes the performance of catalyst thus.
Getting 40 gram total silicon molecular sieves makes solid content and is about 80% slurries, restrain Ludox-1 as binding agent with 25, make gelatinizing agent 3.6 restrain 28% ammoniacal liquor, 1.8 gram sesbania powder is made extrusion aid, adds water 22 grams, mixed grinding is even, with volume is that 100ml, diameter are the mould extruded moulding of 1.5mm, drying, 580 ℃ of roasting 8h get the stripe shape catalyst.On granule strength analyzer QCY-602 type (former Inst. of Alkali-Preparing Industry, Ministry of Chemical Industry produces), record catalyst crushing strength σ=46N/cm according to the RIPP25-90 method among " petrochemical industry analytical method " people such as (, Science Press, nineteen ninety) Yang Cuiding.Vapor phase beckmann rearrangement reaction result: cyclohexanone oxime conversion ratio 98.0%, caprolactam selectivity 95.8%.
Example 5
The explanation of this example the invention provides the enforcement of method and makes the performance of catalyst thus.
Get 40 gram total silicon molecular sieves and make solid content and be about 70% slurries, as binding agent, 4.1 grams, 28% ammoniacal liquor is made gelatinizing agent with 42.8 gram Ludox-2,1.8 gram sesbania powder is made extrusion aid, add water 11.7 grams, mixed grinding is even, makes bar shaped catalyst according to the method for example 4.Record its crushing strength σ=60N/cm.Vapor phase beckmann rearrangement reaction result: cyclohexanone oxime conversion ratio 98.4%, caprolactam selectivity 97.2%.
Example 6
The explanation of this example the invention provides the enforcement of method and makes the performance of catalyst thus.
Get 40 gram total silicon molecular sieves and make solid content and be about 60% slurries, as binding agent, 7.1 grams, 28% ammoniacal liquor is made gelatinizing agent with 66.7 gram Ludox-3, and 1.8 gram sesbania powder are made extrusion aid, and mixed grinding is even, makes bar shaped catalyst according to the method for example 4.Record its crushing strength σ=82N/cm.Vapor phase beckmann rearrangement reaction result: cyclohexanone oxime conversion ratio 99.3%, caprolactam selectivity 97.4%.
Comparative Examples 1
This Comparative Examples illustrates according to prior art USP4, the performance of 859,785 catalyst that make.
Prepare the alkaline silica sol of pH10 according to the prior art embodiment 1 described method: in 91 gram teos solutions, add 97 grams, the 12% TPAOH aqueous solution, stirred 2 hours, 60 ℃ of heating 1 hour, add water 400 grams midway, obtain the limpid alkaline silica sol aqueous solution.
Method according to example 6 is made catalyst: get 40 gram total silicon molecular sieves and pour in the above-mentioned alkaline silica sol aqueous solution, wherein the solid content of molecular sieve is about 60%, add 7.1 grams, 28% ammoniacal liquor again and make gelatinizing agent, 1.8 gram sesbania powder is made extrusion aid, mixed grinding is even, makes bar shaped catalyst according to the method for example 4.Record its crushing strength σ=38N/cm.Vapor phase beckmann rearrangement reaction result: cyclohexanone oxime conversion ratio 98.5%, caprolactam selectivity 96.9%.
Comparative Examples 2
This Comparative Examples illustrates the performance of the catalyst that makes according to prior art CN1256967A.
Prepare the acidic silicasol of pH4 according to the prior art embodiment 1 described method: in 91 gram teos solutions, add 123 gram distilled water, and 1.3 gram concentration are the hydrochloric acid of 1N, stirred 2 hours, obtain the limpid acidic silicasol aqueous solution.
Method according to example 6 is made catalyst: get 40 gram total silicon molecular sieves and pour in the above-mentioned acidic silicasol aqueous solution, wherein the molecular sieve solid content is about 60%, add 7.1 grams, 28% ammoniacal liquor again and make gelatinizing agent, 1.8 gram sesbania powder is made extrusion aid, mixed grinding is even, makes bar shaped catalyst according to the method for example 4.Record its crushing strength σ=32N/cm.Vapor phase beckmann rearrangement reaction result: cyclohexanone oxime conversion ratio 98.1%, caprolactam selectivity 96.6%.
Example 7
The explanation of this example the invention provides the enforcement of method and makes the performance of catalyst thus.
Get 40 gram total silicon molecular sieves and make solid content and be about 80% slurries, as binding agent, 2.5 gram 10%TEAOH make gelatinizing agent with 25 gram Ludox-3,1.8 gram sesbania powder is made extrusion aid, add water 24 grams, mixed grinding is even, makes bar shaped catalyst according to the method for example 4.Record its crushing strength σ=60N/cm.Vapor phase beckmann rearrangement reaction result: cyclohexanone oxime conversion ratio 98.6%, caprolactam selectivity 96.8%.
Example 8
The explanation of this example the invention provides the enforcement of method and makes the performance of catalyst thus.
Get 38.5 gram total silicon molecular sieves and make solid content and be about 73% slurries, as binding agent, 6.8 grams, 28% ammoniacal liquor is made gelatinizing agent with 35.2 gram Ludox-1, and 1.4 gram sesbania powder are made extrusion aid, and mixed grinding is even, makes bar shaped catalyst according to the method for example 4.Record its crushing strength σ=46N/cm.Vapor phase beckmann rearrangement reaction result: cyclohexanone oxime conversion ratio 97.8%, caprolactam selectivity 95.6%.
Claims (7)
1, a kind of cyclohexanone oxime gas phase beckmann rearrangement that is used for prepares preparation method caprolactam, that contain the molecular sieve catalyst of MFI structure, is to make the alkaline silica gel of the ZSM-5 molecular sieve of total silicon molecular sieve or silicon/aluminum ratio 〉=500 and pH8-10 according to molecular sieve and SiO
2Weight ratio with 60-90: 40-10 combines, moulding then, drying, 500-650 ℃ following roasting 4-24 hour.
2, in accordance with the method for claim 1, wherein the alkaline silica gel of said pH8-10 has 100-250m
2The specific area of/g and＜sodium ions content of 3000ppm, its SiO
2Content should be 25-45%.
3, in accordance with the method for claim 2, wherein said alkaline silica gel can be made according to following method: according to silica flour and NaOH10-40: 1 weight ratio, the concentration that silica flour is joined 60-85 ℃ is in the sodium hydrate aqueous solution of 0.1-1%, stirring reaction 2-3 hour, treat that pH reduces to 8-10, cooling, filtration are concentrated into its SiO
2Content 25-45%.
4, in accordance with the method for claim 2, wherein said alkaline silica gel can be made according to following method: according to silica flour and NaOH10-40: 1 weight ratio, the concentration that silica flour is joined 60-85 ℃ is in the sodium hydrate aqueous solution of 0.1-1%, stirring reaction 2-3 hour, treat that pH reduces to 8-10, cooling, filtration, then with the Ludox of gained with the flow of 10-100ml/h successively by acrylic type weak-acid cation-exchange resin and styrene type weak-base anion-exchange resin, regulate its pH to 8-10 with ammoniacal liquor then, be concentrated into its SiO
2Content 25-45%.
5, in accordance with the method for claim 2, wherein said alkaline silica gel can be made according to following method: the flow with 10-100ml/h behind the waterglass filtration removal impurity of dilution is passed through acrylic type weak-acid cation-exchange resin and styrene type weak-base anion-exchange resin successively, regulate its pH to 8-10 with ammoniacal liquor then, be concentrated into its SiO
2Content 25-45%.
6, in accordance with the method for claim 1, add ammoniacal liquor or tetraethyl ammonium hydroxide in the wherein said forming process as gelatinizing agent, the 0.1-5% that its consumption is is benchmark with material gross weight to be formed.
It is 7, in accordance with the method for claim 1, wherein said that to add the sesbania powder in the forming process of extrusion or compressing tablet be extrusion aid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031264387A CN1322927C (en) | 2003-09-28 | 2003-09-28 | Method for preparing catalyst of containing MFI structured molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031264387A CN1322927C (en) | 2003-09-28 | 2003-09-28 | Method for preparing catalyst of containing MFI structured molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1600428A CN1600428A (en) | 2005-03-30 |
| CN1322927C true CN1322927C (en) | 2007-06-27 |
Family
ID=34658802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031264387A Expired - Lifetime CN1322927C (en) | 2003-09-28 | 2003-09-28 | Method for preparing catalyst of containing MFI structured molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1322927C (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428235B (en) * | 2007-11-07 | 2010-10-27 | 中国石油化工股份有限公司 | Regeneration method of molecular sieve catalysts |
| 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 |
| 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 |
| CN102989504B (en) * | 2012-12-03 | 2014-06-18 | 大连理工齐旺达化工科技有限公司 | Rolling-ball forming method for high-strength TS-1 titanium silicalite molecular sieve catalyst |
| CN103008003A (en) * | 2012-12-03 | 2013-04-03 | 大连理工齐旺达化工科技有限公司 | Performed forming method of high-strength TS-1 titanium silicalite molecular sieve catalyst |
| CN103008004A (en) * | 2012-12-03 | 2013-04-03 | 大连理工齐旺达化工科技有限公司 | Tabletting molding method of TS-1 titanium silicalite catalyst |
| CN103172535A (en) * | 2013-03-15 | 2013-06-26 | 华东师范大学 | Liquid-phase fixed bed preparation method of cyclohexanone oxime |
| CN105363489A (en) * | 2015-12-02 | 2016-03-02 | 中国天辰工程有限公司 | Extrusion molding method for Ti-Si molecular sieve catalyst with high molecular sieve content |
| CN105854742A (en) * | 2016-04-07 | 2016-08-17 | 中国天辰工程有限公司 | High-performance titanium-silicon molecular sieve catalyst and extrusion molding method thereof |
| CN109289902B (en) * | 2018-10-22 | 2022-03-15 | 郑州大学 | Method for improving performance of formed MFI molecular sieve in catalyzing Beckmann rearrangement reaction |
| CN114455601B (en) * | 2022-02-24 | 2023-06-06 | 江苏扬农化工集团有限公司 | Preparation method and application of molecular sieve |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4859785A (en) * | 1985-04-23 | 1989-08-22 | Enichem Sintesi S.P.A. | Catalyst on the basis of silicon and titanium having high mechanical strength |
| CN1256967A (en) * | 1998-11-06 | 2000-06-21 | 恩尼彻姆公司 | Process for preparing catalyst containing MFI zeolite |
-
2003
- 2003-09-28 CN CNB031264387A patent/CN1322927C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4859785A (en) * | 1985-04-23 | 1989-08-22 | Enichem Sintesi S.P.A. | Catalyst on the basis of silicon and titanium having high mechanical strength |
| CN1256967A (en) * | 1998-11-06 | 2000-06-21 | 恩尼彻姆公司 | Process for preparing catalyst containing MFI zeolite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1600428A (en) | 2005-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1322927C (en) | Method for preparing catalyst of containing MFI structured molecular sieve | |
| CN100389067C (en) | ZSM-5 type molecular sieve and method for preparing the same | |
| CN102950014B (en) | Catalyst for production of 1,4-butynediol and preparation method of catalyst | |
| CN101468319B (en) | Method for preparing catalyst containing molecular sieve of MFI structure | |
| CN102233277A (en) | Preparation method for catalyst containing MFI structure zeolite | |
| CN102513147B (en) | Preparation method of molecular sieve catalyst used for preparing dimethylamine | |
| CN103896839B (en) | A kind of cyclohexanone-oxime gas phase beckmann rearrangement prepares the method for hexanolactam | |
| CN107335464A (en) | The preparation method and catalyst of Silicate-1 molecular sieve catalysts and the method for preparing caprolactam | |
| CN103638937A (en) | Ethynylation catalyst for synthesizing 1, 4-butynediol | |
| CN103394370B (en) | A kind of silica gel load sulfonic acid double-core ionic-liquid catalyst, preparation method and application | |
| CN107162932B (en) | A method of by benzaldehyde and ionic liquid type hydroxylamine salt one-step synthesis benzonitrile | |
| Li et al. | Preparation of Keggin-type mono-lacunary phosphotungstic-ammonium salt and its catalytic performance in ammoximation of cyclohexanone | |
| Fernández et al. | Insight into the active sites for the Beckmann rearrangement on porous solids by in situ infrared spectroscopy | |
| Xia et al. | Dealumination of HMCM-22 by various methods and its application in one-step synthesis of dimethyl ether from syngas | |
| CN109718825A (en) | Microballoon Silicate-1 molecular sieve catalyst and preparation method thereof and the method for preparing caprolactam | |
| CN102728403B (en) | Organic solid base catalyst for synthesizing alpha-cyanoethyl cinnamate, and preparation method and application thereof | |
| CN103539623B (en) | Side chain alkylation method of toluene with methanol | |
| CN109293515A (en) | A kind of new process using micro passage reaction synthesis ketone musk | |
| CN109847787A (en) | The rotational forming preparation method and applications of the microballoon total silicon molecule sieve catalyst of MFI topology containing trace rare-earth ion | |
| CN107335465A (en) | The preparation method and catalyst of Silicate-1 molecular sieve catalysts and the method for preparing caprolactam | |
| CN102101035B (en) | Reaction device suitable for aldol reaction | |
| CN100457622C (en) | Prepn. of small-grain Ti-Si molecular sieve in cheap hydrothermal system and its application | |
| CN103253683A (en) | Method of in-situ crystallized synthesis of ZSM-5/mordenite compound | |
| CN101786010A (en) | Catalyst for preparing caprolactam by gas phase Beckmann rearrangement method and preparation method thereof | |
| JP4574522B2 (en) | Porous silica derivative |
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: 20070627 |
|
| CX01 | Expiry of patent term |