阅读说明：本技术 一种催化剂及其制备方法，以及一种气相重排反应制备十二内酰胺的方法 (Catalyst and preparation method thereof, and method for preparing laurolactam by gas phase rearrangement reaction ) 是由 边新建 李俊平 吴训锟 陈海波 黎源 张永振 袁帅 于 2019-09-24 设计创作，主要内容包括：本发明公开一种催化剂及其制备方法,以及一种气相重排反应制备十二内酰胺的方法。所述催化剂包括氟化物改性的稀土掺杂的Al-2O-3-SiO-2-ZrO-2和含氟磺化聚醚醚酮,其中含氟磺化聚醚醚酮在催化剂中的负载量为20-50wt％,优选30-45wt％。使用本催化剂催化环十二酮肟气相重排,环十二酮肟的转化率达到99％以上,十二内酰胺的选择性达到99.5％以上,催化剂寿命达到3000h以上,反应无硫铵副产,催化剂机械强度高,解决了传统液相重排工艺的设备腐蚀和环境污染问题。(The invention discloses a catalyst and a preparation method thereof, and a method for preparing laurolactam by gas phase rearrangement reaction. The catalyst comprises fluoride-modified rare earth doped Al 2 O 3 ‑SiO 2 ‑ZrO 2 And fluorosulfonated polyether ether ketone, wherein the loading amount of the fluorosulfonated polyether ether ketone in the catalyst is 20 to 50 wt%, preferably 30 to 45 wt%. The catalyst is used for catalyzing gas phase rearrangement of cyclododecanone oxime, the conversion rate of the cyclododecanone oxime reaches more than 99 percent, the selectivity of laurolactam reaches more than 99.5 percent, the service life of the catalyst reaches more than 3000 hours, no ammonium sulfate byproduct is generated in the reaction, the mechanical strength of the catalyst is high, and the problem of transferring ammonia is solvedThe equipment corrosion and the environmental pollution of the traditional liquid phase rearrangement process.)

1. A catalyst comprising fluoride-modified rare earth doped Al₂O₃-SiO₂-ZrO₂And fluorosulfonated polyether ether ketone, wherein the loading amount of the fluorosulfonated polyether ether ketone in the catalyst is 20 to 50 wt%, preferably 30 to 45 wt%.

2. The catalyst of claim 1 wherein the rare earth comprises scandium and yttrium.

3. A method of preparing the catalyst of claim 1, comprising the steps of:

(1) maintaining the temperature of the system at 0-5 ℃, and dissolving the template agent in deionized water; simultaneously slowly adding rare earth salt and Al (NO)₃)₃·9H₂O、ZrOCl₂·8H₂O, tetraethyl orthosilicate; under the condition of stirring, slowly dropwise adding ammonia water to adjust the pH value of the solution to 9-10, continuously stirring for 1-2h, and stopping stirring and aging for 1-2 h; performing suction filtration and washing to be neutral; drying the filter cake, roasting at 500-550 ℃ for 1-2h, grinding and sieving to obtain the rare earth doped Al₂O₃-SiO₂-ZrO₂A carrier;

(2) rare earth doped Al using fluoride₂O₃-SiO₂-ZrO₂Modifying a carrier;

(3) slowly pouring the dried fluorine-containing polyether-ether-ketone powder into concentrated sulfuric acid at 35-45 ℃, stirring until the powder is completely dissolved, continuing to sulfonate for 10-12h, pouring the reaction liquid into ice water under stirring to terminate the sulfonation reaction, and continuously stirring for 1-2 h; filtering the precipitate, washing with deionized water, and drying to obtain sulfonated polyether ether ketone containing fluorine;

(4) dissolving fluorine-containing sulfonated polyether ether ketone in N, N-dimethylacetamide, and adding rare earth doped Al₂O₃-SiO₂-ZrO₂A carrier; drying after ultrasonic adsorption for 5-8h, and then roasting in a muffle furnace at 400-450 ℃ for 5-10h to obtain rare earth doped fluorine-containing SPEEK/Al₂O₃-SiO₂-ZrO₂And (3) compounding a catalyst.

4. The method of claim 3, wherein Al (NO) in step (1)₃)₃·9H₂O and ZrOCl₂·8H₂The mass ratio of O is 1:1-1.5:1, preferably 1:1-1.2:1, tetraethyl orthosilicate and ZrOCl₂·8H₂The mass ratio of O is 2:1-3:1, preferably 2:1-2.5: 1.

5. The method according to claim 3, wherein the mass ratio of the fluorine-containing polyether ether ketone powder to the concentrated sulfuric acid in the step (3) is 1:20-1:40, preferably 1:20-1: 30.

6. The method of claim 3, wherein in step (4), the rare earth doped Al₂O₃-SiO₂-ZrO₂The mass ratio of the carrier to the fluorine-containing sulfonated polyether ether ketone is 1:1-2:1, preferably 1:1-1.5: 1.

7. The method according to claim 3, wherein in step (1) the rare earth salt comprises a mixture of scandium and yttrium salts, preferably wherein the molar ratio of scandium to yttrium, calculated on the molar amount of the element, is 2:1 to 10:1, preferably 3:1 to 5: 1.

8. The method according to claim 3, wherein in step (1), the rare earth salt is ZrOCl₂·8H₂0.1 to 1%, preferably 0.5 to 1% by mass of O.

9. The method of claim 3, wherein the fluoride in step (2) comprises one or more of sodium fluoride, cesium fluoride, potassium fluoride, calcium fluoride, hydrofluoric acid, ammonium fluoride, tetrabutylammonium fluoride, preferably sodium fluoride; the fluoride in the step (2) is rare earth doped Al₂O₃-SiO₂-ZrO₂0.1 to 5% by mass, preferably 2 to 3% by mass.

10. A method for preparing laurolactam by gas phase rearrangement comprises the following steps: filling the catalyst of claim 1 or 2 in a fixed bed at a reaction temperature of 300-340 ℃, preferably 330-340 ℃; the absolute reaction pressure is 1-10KPa, preferably 4-5 KPa; taking alkane solution of cyclododecanone oxime with the concentration of 1-20 wt%, preferably 5-10 wt% as a raw material, wherein the mass space velocity of the cyclododecanone oxime is 0.1-1 h^-1Preferably 0.2 to 0.3 hour^-1(ii) a The reaction uses an inert gas as a carrier gas.

Technical Field

The invention belongs to the field of catalysts, and particularly relates to a catalyst for preparing laurolactam by a cyclododecanone oxime gas-phase rearrangement reaction.

Background

Nylon 12 belongs to a special polyamide material, is one of the most representative long carbon chain nylon, has the performance advantages of outstanding toughness, low temperature resistance, low water absorption, high chemical stability, wear resistance, light weight and the like, has wide application fields, and is mainly applied to automobile fuel pipes, pneumatic hoses, high-pressure pipelines, land and ocean oil and gas conveying pipes and the like; in addition, the method has important application in the fields of cable protection, electronic and electric appliances, powder coating, 3D printing, sports equipment, additive manufacturing and the like.

Laurolactam is a monomer that produces nylon 12, which is obtained from cyclododecanone oxime (CDOX) via a beckmann rearrangement reaction.

There are two main processes for preparing laurolactam from cyclododecanone oxime: liquid phase beckmann rearrangement and gas phase beckmann rearrangement. Concentrated sulfuric acid is generally used as a catalyst in liquid phase Beckmann rearrangement, ammonia water is used for neutralization after reaction is finished, a large amount of ammonium sulfate wastewater is generated as a byproduct, and the problems of equipment corrosion, serious reaction carbonization and complex oil-water separation exist at the same time.

The solid acid catalysts such as sulfonic acid resin and the like used for liquid phase Beckmann rearrangement have the problems of high mass transfer requirement, low catalyst utilization rate, slow reaction speed and long separation process.

In order to overcome the problems and disadvantages associated with the liquid phase beckmann rearrangement reaction described above, a gas phase beckmann rearrangement under the action of a solid acid catalyst has been developed.

For the gas phase beckmann rearrangement of cyclododecanone oxime, a solid acid or a neutral catalyst is generally used, and documents (Journal of Catalysis, 2009, 263, 42-55) and (J Mater Sci, 2009, 44, 6741-6746) report that when a composite catalyst of mesoporous molecular sieves MCM-41, ZSM-5 and B, Al is used, the cyclododecanone oxime conversion rate is 90-95%, the selectivity of laurolactam reaches 90%, the main by-products of the reaction are cyclododecanone and dodecanonitrile, and the by-product cyclododecanone is polymerized at a high temperature, resulting in the reduction of catalytic performance after the catalyst is used for 40 hours.

Patent CN1058588A reports that boric acid is used as a catalyst, and a carrier is silicon dioxide, aluminum oxide and the like, so that the problem of low conversion rate of cyclododecanone oxime exists in the reaction; patent WO2004037785A1 reports that the highest conversion rate of the reaction is 98 percent by using Si-Al layered metal as a catalyst. Patent WO2010063276A1(CN102388019A) reports the use of Nb-impregnated SiO₂、SiO₂-Al₂O₃、TiO₂ZrO2, zeolite and mesoporous materials are used as catalysts, and the problems of unstable cyclododecanone oxime at high temperature, low reaction conversion rate, low selectivity and unstable by-products, which further cause short service life of the catalysts, are still not solved.

Disclosure of Invention

The invention relates to a catalyst and a preparation method thereof, the catalyst is used for synthesizing laurolactam by gas phase rearrangement of cyclododecanone oxime, has the advantages of high reaction conversion rate, high selectivity, high mechanical strength of the catalyst, long service life and no byproduct of ammonium sulfate in the reaction, and solves the problems of equipment corrosion and environmental pollution of the traditional liquid phase rearrangement process.

In order to achieve the technical effects, the invention provides the following technical scheme:

a catalyst comprising fluoride-modified rare earth doped Al₂O₃-SiO₂-ZrO₂And fluorosulfonated polyether ether ketone, wherein the loading amount of the fluorosulfonated polyether ether ketone in the catalyst is 20 to 50 wt%, preferably 30 to 45 wt%.

The rare earth of the present invention comprises scandium and yttrium.

The preparation method of the catalyst comprises the following steps:

(1) maintaining the temperature of the system at 0-5 ℃, and dissolving the template agent in deionized water; simultaneously slowly adding rare earth salt and Al (NO)₃)₃·9H₂O、ZrOCl₂·8H₂O, tetraethyl orthosilicate (TEOS), the adding time is 1-2h, Al (NO)₃)₃·9H₂O and ZrOCl₂·8H₂The mass ratio of O is 1:1-1.5:1, preferably 1:1-1.2:1, TEOS and ZrOCl₂·8H₂The mass ratio of O is 2:1-3:1, preferably 2:1-2.5: 1; under the condition of stirring, slowly dropwise adding ammonia water to adjust the pH value of the solution to 9-10, continuously stirring for 1-2h, and stopping stirring and aging for 1-2 h; performing suction filtration and washing to be neutral; drying the filter cake at the temperature of 100-120 ℃ for 24-28h, roasting at the temperature of 500-550 ℃ for 1-2h, grinding and sieving to obtain the rare earth doped Al₂O₃-SiO₂-ZrO₂And (3) a carrier.

(2) Rare earth doped Al using fluoride₂O₃-SiO₂-ZrO₂And (4) modifying the carrier.

(3) Drying the powder of fluoropolyether ether ketone (FPEEK) at 120 deg.C overnight; slowly pouring the dried FPEEK powder into 98 wt% concentrated sulfuric acid at the temperature of 35-45 ℃, wherein the mass ratio of the FPEEK powder to the concentrated sulfuric acid is 1:20-1:40, preferably 1:20-1:30, stirring until the FPEEK is completely dissolved, continuing to sulfonate for 10-12h, pouring the reaction liquid into ice water under stirring to stop the sulfonation reaction, and continuously stirring for 1-2 h; filtering the fluorine-containing SPEEK precipitate, washing the precipitate with deionized water for multiple times until the pH of the washing water is close to neutral, and drying the precipitate at the temperature of 110 ℃ and 120 ℃ for 10 to 15 hours to obtain the fluorine-containing sulfonated polyether ether ketone (fluorine-containing SPEEK).

(4) Dissolving fluorine-containing SPEEK in N, N-Dimethylacetamide (DMAC) to form a 10-12 wt% solution, and adding rare earth doped Al₂O₃-SiO₂-ZrO₂A carrier, wherein the mass ratio of the carrier to the fluorine-containing SPEEK is 1:1-2:1, preferably 1:1-1.5: 1; drying after ultrasonic adsorption for 5-8h, and then roasting in a muffle furnace at 400-450 ℃ for 5-10h to obtain rare earth doped fluorine-containing SPEEK/Al₂O₃-SiO₂-ZrO₂Compounding catalyst, cooling to room temperature and setting in drier for further use.

The template agent comprises one or more of n-butylamine, hexamethylenediamine, tetrapropylammonium bromide, tetrapropylammonium hydroxide (TPAOH), tetrabutylammonium hydroxide, ethanolamine, tetraethylammonium chloride, tetrabutylammonium chloride, tetraethylphosphine oxide, tetrabutylphosphine oxide, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium hydroxide, dodecyl phosphate, hexadecyl phosphate and octadecyl phosphate, and preferably tetrapropylammonium hydroxide.

The dosage of the template agent is ZrOCl₂·8H₂10 to 50 wt.%, preferably 20 to 30 wt.%, based on the mass of O.

The rare earth salt of the invention comprises a mixture of scandium and yttrium salts, more preferably, the molar ratio of scandium to yttrium, calculated as the molar amount of the element, is from 2:1 to 10:1, preferably from 3:1 to 5: 1.

The scandium salt is selected from nitrate, chloride, sulfate or phosphate of scandium.

The yttrium salt is selected from nitrate, chloride, sulfate or phosphate of yttrium.

The dosage of the rare earth salt is ZrOCl₂·8H₂0.1 to 1%, preferably 0.5 to 1% by mass of O.

The fluorine atom in the fluorine-containing polyether ether ketone (FPEEK) is derived from a fluorine ketone monomer or a fluorine-containing bisphenol monomer, the fluorine atom content is 10-30% of the molar weight of the PEEK bisphenol monomer, and the polyether ether ketone powder of the U.S. RTP 2200LF TFE15 (containing 15% mol/mol of fluorine) is preferred.

The fluoride in step (2) of the present invention comprises one or more of sodium fluoride, cesium fluoride, potassium fluoride, calcium fluoride, hydrofluoric acid, ammonium fluoride, tetrabutylammonium fluoride, preferably sodium fluoride.

The fluoride in the step (2) is rare earth doped Al₂O₃-SiO₂-ZrO₂0.1 to 5% by mass, preferably 2 to 3% by mass.

A method for preparing laurolactam by gas phase rearrangement comprises the following steps: rare earth doped fluorine-containing SPEEK/Al₂O₃-SiO₂-ZrO₂The composite catalyst is filled in a fixed bed, and the reaction temperature is 300-340 ℃, preferably 330-340 ℃; the reaction pressure is 1-10KPa (A), preferably 4-5KPa (A); taking alkane solution of cyclododecanone oxime with the concentration of 1-20 wt%, preferably 5-10 wt% as a raw material, wherein the mass space velocity of the cyclododecanone oxime is 0.1-1 h^-1Preferably 0.2 to 0.3 hour^-1(ii) a The reaction uses an inert gas as a carrier gas.

The alkane in the alkane solution of cyclododecanone oxime can be one or more selected from cyclohexane, methylcyclohexane, ethylcyclohexane, isopropylcyclohexane, dodecane, toluene, ethylbenzene and cumene.

The invention uses rare earth doped fluorine-containing SPEEK/Al₂O₃-SiO₂-ZrO₂Compared with common sulfonic acid resin, the fluorine-containing SPEEK of the composite catalyst has higher melting point (above 350 ℃) and stability (below 400 ℃, without obvious thermal weight loss), meets the requirement of gas phase rearrangement, and has long service life.

Meanwhile, fluorine atoms and oxygen atoms in the fluorine-containing SPEEK can generate hydrogen bonds with cyclododecanone oxime, so that the stability of the cyclododecanone oxime is improved, the decomposition rate of the cyclododecanone oxime at high temperature is reduced, and the selectivity of a gas phase rearrangement reaction is improved.

Fluorinating fluorine atoms in SPEEK improves the acidity of sulfonic acid groups and solid catalysts, and the conversion rate of gas phase rearrangement reaction is further improved. Because the reaction conversion rate and the selectivity are improved, the generation amount of reaction tar and carbide is reduced, and the service life of the catalyst is further prolonged.

Rare earth doped Al using fluoride₂O₃-SiO₂-ZrO₂The carrier is modified, and fluoride can react with silicon dioxide, so that the specific surface area of the carrier is improved, the polarity of the carrier is enhanced, the adhesive force of fluorine-containing SPEEK and the carrier is improved, and the stability of the catalyst is further improved.

The scandium and the yttrium which are doped into the composite catalyst are taken as auxiliary agents, and have synergistic effect, so that the fluorine-containing SPEEK is improved in SiO₂-ZrO₂The binding force on the carrier and the melting temperature of SPEEK, and simultaneously, lone pair electrons on scandium and yttrium can generate an electronic effect with an oxygen atom which is cyclododecanone, so that the stability of cyclododecanone oxime is further improved, and the reaction selectivity is improved. In addition, scandium and yttrium atoms are smaller in radius, so that the stability of the catalyst framework is higher, and the mechanical strength of the catalyst is increased.

Detailed Description

The present invention is further illustrated by the following examples, which should be construed as limiting the scope of the invention.

(1) Gas chromatography

The conversion rate and selectivity are determined by using gas chromatography area correction normalized analysis, and the chromatographic analysis conditions are as follows:

the instrument model is as follows: shimadzu GC 2010; a chromatographic column: DB-5 (30X 0.32X 0.25); column temperature: temperature programming (50 ℃ for 3min, then heating to 110 ℃ at the heating rate of 5 ℃/min, then heating to 300 ℃ at the heating rate of 30 ℃/min, and keeping for 5 min); sample inlet temperature: 250 ℃; FID temperature: 300 ℃; n is a radical of₂Flow rate: 1 mL/min; h₂Flow rate: 40 mL/min; shock insulator purging (N)₂) Flow rate: 4 mL/min; carrier gas (N)₂) Flow rate: 2 mL/min; split-flow sample introduction, split-flow ratio: 50; sample introduction amount: 0.2. mu.L.

(2) Degree of sulfonation of SPEEK

The sulfonation Degree (DS) of SPEEK is measured by an acid-base titration method using 0.1mol/L NaOH solution and 0.1mol/L HCl solution as titration solutions and phenolphthalein as an indicator.

(3) Characterization of the composite catalyst

The loading of SPEEK in the composite catalyst was analyzed using Thermogravimetry (TGA), the TGA analyzer model number being METTLER TGA/DSC 3+, analytical standard ISO 11358 plastics-thermal weight loss method.

The BET specific surface area of the catalyst was analyzed by using a Kangta (NOVA touch) instrument, and the analysis standard was GB/T19587-containing 2004.

The mechanical strength of the catalyst was tested using a Nanjing Kogyo KHKQ-100 particle Strength tester, analysis Standard HG/T2782-.

Example one

1) Rare earth doped fluorine-containing SPEEK/Al₂O₃-SiO₂-ZrO₂Preparation of composite catalyst

a) Maintaining the temperature of the system at 0-5 ℃, dissolving 2g of TPAOH in 300g of deionized water; at the same time, 0.042g of scandium (tri) nitrate hexahydrate,0.008g of yttrium trichloride, 10g of Al (NO)₃)₃·9H₂O、10g ZrOCl₂·8H₂O, 20g TEOS, and the charging time is 1 h; slowly adding 25% ammonia water dropwise under stirring to adjust the pH of the solution to 10, continuing stirring for 2h, and stopping stirring and aging for 1 h; carrying out vacuum filtration and washing with deionized water to be neutral; drying the filter cake at 120 deg.C for 28h, calcining at 500 deg.C for 2h, grinding and sieving to obtain rare earth doped Al₂O₃-SiO₂-ZrO₂And (3) a carrier.

b) Taking 10g of rare earth doped Al₂O₃-SiO₂-ZrO₂Adding the carrier into 30g of sodium fluoride aqueous solution with the mass fraction of 1%, soaking for 30min at 50 ℃, filtering, washing with deionized water, and drying to obtain the fluoride modified rare earth doped Al₂O₃-SiO₂-ZrO₂And (3) a carrier.

c) Drying the powder of RTP 2200LF TFE15 FPEEK at 120 deg.C overnight; slowly pouring 10g of dried fluorine-containing PEEK powder into 200g of concentrated sulfuric acid at the temperature of 40 ℃, stirring until the fluorine-containing PEEK is completely dissolved, continuing sulfonating for 10 hours, pouring the concentrated sulfuric acid solution containing fluorine-containing SPEEK into a large amount of ice water under stirring to stop sulfonation reaction, and continuously stirring for 1 hour; the fluorine-containing SPEEK precipitate is filtered and washed with deionized water for multiple times until the pH of the washing water is close to neutral, and is dried for 10 hours at 110 ℃ to obtain the fluorine-containing SPEEK, and the sulfonation degree of the fluorine-containing SPEEK is 46 percent by titration analysis.

d) 10g of fluorinated SPEEK was dissolved in 90g of DMAC, and 15g of the fluoride modified rare earth doped Al described above was added₂O₃-SiO₂-ZrO₂A carrier; drying after ultrasonic adsorption for 8 hours at 25 kHz; then placing the mixture into a muffle furnace at 400 ℃ for roasting for 10 hours to obtain rare earth doped fluorine-containing SPEEK/Al₂O₃-SiO₂-ZrO₂Compounding catalyst, cooling to room temperature and setting in drier for further use.

Rare earth doped fluorine-containing SPEEK/Al₂O₃-SiO₂-ZrO₂TGA characterization of the composite catalyst shows that fluorine-containing SPEEK is successfully adsorbed on rare earth doped Al₂O₃-SiO₂-ZrO₂On a support, containing fluorine SPEEKIs Al₂O₃-SiO₂-ZrO₂32% of the mass of the support.

2) Gas phase rearrangement reaction using the above catalyst

10g of rare earth doped fluorine-containing SPEEK/Al₂O₃-SiO₂-ZrO₂The composite catalyst is filled in a fixed bed, the reaction temperature is 330 ℃, the reaction pressure is 5KPa (A), a metering pump is used for conveying an isopropyl cyclohexane solution of cyclododecanone oxime to the fixed bed, the concentration of the cyclododecanone oxime is 10 wt%, and the mass space velocity of the cyclododecanone oxime is 0.3h^-1The reaction uses nitrogen as a carrier.

After the reaction product is cooled to 80-100 ℃, the conversion rate of the cyclododecanone oxime is 99.62 percent and the selectivity of the laurolactam is 99.87 percent by gas chromatographic analysis, the compressive strength of the catalyst is reduced to 117N from the initial 122N after the catalyst is continuously used for 3900h, and the specific surface area is reduced from the initial 363m²The/g is reduced to 357m²/g。

Comparative example 1

1) Catalyst preparation

Fluoride modified rare earth doped Al was prepared according to the method of a), b) in the catalyst preparation of example one₂O₃-SiO₂-ZrO₂And (3) a carrier.

Drying 500PF polyetheretherketone powder of Jilin high-performance engineering plastics GmbH at 120 deg.C overnight; slowly pouring 10g of dried ordinary PEEK powder into 200g of concentrated sulfuric acid at the temperature of 40 ℃, stirring until the ordinary PEEK is completely dissolved, continuing sulfonating for 10 hours, pouring the concentrated sulfuric acid solution of the ordinary SPEEK into a large amount of ice water under stirring to stop sulfonation reaction, and continuously stirring for 1 hour; ordinary SPEEK precipitate is filtered and washed with deionized water several times until the pH of the wash water is near neutral, and dried at 110 deg.C for 10h to obtain ordinary SPEEK containing no fluorine, and the SPEEK sulfonation degree is 47% by titration analysis.

10g SPEEK was dissolved in 90g DMAC and 15g of the fluoride modified rare earth doped Al described above was added₂O₃-SiO₂-ZrO₂A carrier; drying after ultrasonic adsorption for 8 hours at 25 kHz; then placing the mixture into a muffle furnace at 400 ℃ for roasting for 10 hours to obtainRare earth doped SPEEK/Al₂O₃-SiO₂-ZrO₂Compounding catalyst, cooling to room temperature and setting in drier for further use.

Rare earth doped SPEEK/Al₂O₃-SiO₂-ZrO₂TGA characterization of the composite catalyst shows that SPEEK is successfully adsorbed on rare earth doped Al₂O₃-SiO₂-ZrO₂On a carrier, SPEEK is about Al₂O₃-SiO₂-ZrO₂26% of the mass of the support.

2) Gas phase rearrangement reaction using the above catalyst

10g of rare earth doped SPEEK/Al₂O₃-SiO₂-ZrO₂The composite catalyst is filled in a fixed bed, the reaction temperature is 330 ℃, the reaction pressure is 5KPa (A), a metering pump is used for conveying an isopropyl cyclohexane solution of cyclododecanone oxime to the fixed bed, the concentration of the cyclododecanone oxime is 10 wt%, and the mass space velocity of the cyclododecanone oxime is 0.3h^-1The reaction uses nitrogen as a carrier.

After the reaction product is cooled to 80-100 ℃, the conversion rate of cyclododecanone oxime is 98.84 percent and the selectivity of laurolactam is 98.03 percent by gas chromatographic analysis, the compressive strength of the catalyst is reduced from the initial 119N to 54N by analysis after the catalyst is continuously used for 3100 hours, and the specific surface area is reduced from the initial 357m²The/g is reduced to 116m²/g。

Example two

1) Rare earth doped fluorine-containing SPEEK/Al₂O₃-SiO₂-ZrO₂Preparation of composite catalyst

a) Maintaining the temperature of the system at 0-5 ℃, and dissolving 3g of TPAOH in 300g of deionized water; at the same time, 0.09g of scandium (tri) nitrate hexahydrate, 0.01g of yttrium trichloride and 12g of Al (NO) are slowly added into the deionized water solution of the template agent₃)₃·9H₂O、10g ZrOCl₂·8H₂O, 25g TEOS, and the charging time is 1 h; slowly dropwise adding 25% ammonia water solution under stirring to adjust the pH of the solution to 9, continuing stirring for 2h, and stopping stirring and aging for 1 h; carrying out vacuum filtration and washing with deionized water to be neutral; drying the filter cake at 120 deg.C for 24 hr, and further at 550 deg.CRoasting for 2h, grinding and sieving to obtain rare earth doped Al₂O₃-SiO₂-ZrO₂And (3) a carrier.

b) Taking 10g of rare earth doped Al₂O₃-SiO₂-ZrO₂Adding the carrier into 20g of sodium fluoride aqueous solution with the mass fraction of 1%, soaking at 50 ℃ for 30min, filtering, washing with deionized water, and drying to obtain the fluoride modified rare earth doped Al₂O₃-SiO₂-ZrO₂And (3) a carrier.

c) Drying the powder of RTP 2200LF TFE15 FPEEK at 120 deg.C overnight; slowly pouring 10g of dried fluorine-containing PEEK powder into 300g of concentrated sulfuric acid at the temperature of 40 ℃, stirring until the fluorine-containing PEEK is completely dissolved, continuing sulfonating for 12 hours, pouring the concentrated sulfuric acid solution containing fluorine-containing SPEEK into a large amount of ice water under stirring to stop sulfonation reaction, and continuously stirring for 1 hour; the fluorine-containing SPEEK precipitate is filtered and washed by deionized water for a plurality of times until the pH of the washing water is close to neutral, and is dried for 15 hours at 110 ℃ to prepare the fluorine-containing SPEEK, and the sulfonation degree of the fluorine-containing SPEEK is 62 percent by titration analysis.

d) 10g of fluorinated SPEEK was dissolved in 73.3g of DMAC, 10g of the fluoride modified rare earth doped Al described above was added₂O₃-SiO₂-ZrO₂A carrier; drying after ultrasonic adsorption for 5 hours at 18 kHz; then placing the mixture into a muffle furnace at 400 ℃ for roasting for 10 hours to obtain rare earth doped fluorine-containing SPEEK/Al₂O₃-SiO₂-ZrO₂Compounding catalyst, cooling to room temperature and setting in drier for further use.

Rare earth doped fluorine-containing SPEEK/Al₂O₃-SiO₂-ZrO₂TGA characterization of the composite catalyst shows that fluorine-containing SPEEK is successfully adsorbed on rare earth doped Al₂O₃-SiO₂-ZrO₂On a support, fluorine-containing SPEEK is about Al₂O₃-SiO₂-ZrO₂39% of the mass of the support.

2) Gas phase rearrangement reaction using the above catalyst

10g of rare earth doped fluorine-containing SPEEK/Al₂O₃-SiO₂-ZrO₂The composite catalyst is filled in a fixed bed and the reaction temperature is highThe temperature is 340 ℃, the reaction pressure is 4KPa (A), a metering pump is used for conveying an isopropyl cyclohexane solution of cyclododecanone oxime to a fixed bed, the concentration of the cyclododecanone oxime is 5wt percent, and the mass space velocity of the cyclododecanone oxime is 0.2h^-1The reaction uses argon as a carrier.

After the reaction product is cooled to 80-100 ℃, the conversion rate of the cyclododecanone oxime is 99.74 percent and the selectivity of the laurolactam is 99.83 percent by gas chromatographic analysis, the catalyst is continuously used for 3800h and then analyzed, the compressive strength of the catalyst is reduced to 118N from the initial 124N, and the specific surface area is reduced to 359m from the initial 359N²The/g is reduced to 354m²/g。

Comparative example No. two

1) Rare earth doped fluorine-containing SPEEK/Al₂O₃-SiO₂-ZrO₂Preparation of composite catalyst

Maintaining the temperature of the system at 0-5 ℃, and dissolving 3g of TPAOH in 300g of deionized water; at the same time, 0.1g scandium (tri) nitrate hexahydrate and 12g Al (NO) are slowly added into the deionized water solution of the template agent₃)₃·9H₂O、10g ZrOCl₂·8H₂O, 25g TEOS, and the charging time is 1 h; slowly dropwise adding 25% ammonia water solution under stirring to adjust the pH of the solution to 9, continuing stirring for 2h, and stopping stirring and aging for 1 h; carrying out vacuum filtration and washing with deionized water to be neutral; drying the filter cake at 120 ℃ for 24h, roasting at 550 ℃ for 2h, grinding and sieving to obtain rare earth doped Al₂O₃-SiO₂-ZrO₂And (3) a carrier.

Al doped with the above rare earth₂O₃-SiO₂-ZrO₂The carrier, according to the methods of b), c), d) of the catalyst preparation of example two, further prepare rare earth doped fluorine-containing SPEEK/Al₂O₃-SiO₂-ZrO₂And (3) compounding a catalyst.

Rare earth scandium doped fluorine-containing SPEEK/Al₂O₃-SiO₂-ZrO₂TGA characterization of the composite catalyst shows that fluorine-containing SPEEK is successfully adsorbed on rare earth scandium-doped Al₂O₃-SiO₂-ZrO₂On a support, fluorine-containing SPEEK is about Al₂O₃-SiO₂-ZrO₂28% of the mass of the support.

2) Gas phase rearrangement reaction using the above catalyst

10g of rare earth doped fluorine-containing SPEEK/Al₂O₃-SiO₂-ZrO₂The composite catalyst is filled in a fixed bed, the reaction temperature is 340 ℃, the reaction pressure is 4KPa (A), a metering pump is used for conveying an isopropyl cyclohexane solution of cyclododecanone oxime to the fixed bed, the concentration of the cyclododecanone oxime is 5 wt%, and the mass space velocity of the cyclododecanone oxime is 0.2h^-1The reaction uses argon as a carrier.

After the reaction product is cooled to 80-100 ℃, the conversion rate of the cyclododecanone oxime is 99.02 percent and the selectivity of the laurolactam is 99.51 percent by gas chromatographic analysis, the compressive strength of the catalyst is reduced to 36N from the initial 109N after the catalyst is continuously used for 3300h, and the specific surface area is reduced from the initial 351m²The/g is reduced to 167m²/g。

Comparative example No. three

1) Rare earth lanthanum doped fluorine-containing SPEEK/Al₂O₃-SiO₂-ZrO₂Preparation of composite catalyst

Maintaining the temperature of the system at 0-5 ℃, and dissolving 3g of TPAOH in 300g of deionized water; at the same time, 0.1g lanthanum (tri) nitrate hexahydrate and 12g Al (NO) are slowly added into the deionized water solution of the template₃)₃·9H₂O、10g ZrOCl₂·8H₂O, 25g TEOS, and the charging time is 1 h; slowly dropwise adding 25% ammonia water solution under stirring to adjust the pH of the solution to 9, continuing stirring for 2h, and stopping stirring and aging for 1 h; carrying out vacuum filtration and washing with deionized water to be neutral; drying the filter cake at 120 ℃ for 24h, roasting at 550 ℃ for 2h, grinding and sieving to obtain rare earth lanthanum-doped Al₂O₃-SiO₂-ZrO₂And (3) a carrier.

Al doped with the rare earth lanthanum₂O₃-SiO₂-ZrO₂The carrier, the method of b), c) and d) of the preparation of the catalyst of the example two, is further used for preparing rare earth lanthanum doped fluorine-containing SPEEK/Al₂O₃-SiO₂-ZrO₂And (3) compounding a catalyst.

For rare earthLanthanum doped fluorine-containing SPEEK/Al₂O₃-SiO₂-ZrO₂TGA characterization of the composite catalyst shows that fluorine-containing SPEEK is successfully adsorbed on rare earth doped Al₂O₃-SiO₂-ZrO₂On a support, fluorine-containing SPEEK is about Al₂O₃-SiO₂-ZrO₂24% of the mass of the support.

2) Gas phase rearrangement reaction using the above catalyst

10g of rare earth lanthanum doped fluorine-containing SPEEK/Al₂O₃-SiO₂-ZrO₂The composite catalyst is filled in a fixed bed, the reaction temperature is 340 ℃, the reaction pressure is 4KPa (A), a metering pump is used for conveying an isopropyl cyclohexane solution of cyclododecanone oxime to the fixed bed, the concentration of the cyclododecanone oxime is 5 wt%, and the mass space velocity of the cyclododecanone oxime is 0.2h^-1The reaction uses argon as a carrier.

After the reaction product is cooled to 80-100 ℃, the conversion rate of cyclododecanone oxime is 98.59 percent and the selectivity of laurolactam is 98.97 percent by gas chromatographic analysis, the catalyst is continuously used for 3100h and then analyzed, the compressive strength of the catalyst is reduced from the initial 98N to 26N, and the specific surface area is reduced from the initial 331m²The/g is reduced to 129m²/g。

Comparative example No. four

1) Rare earth doped fluorine-containing SPEEK/Al₂O₃-ZrO₂Preparation of composite catalyst

Maintaining the temperature of the system at 0-5 ℃, and dissolving 3g of TPAOH in 300g of deionized water; at the same time, 0.09g of scandium (tri) nitrate hexahydrate, 0.01g of yttrium trichloride and 12g of Al (NO) are slowly added into the deionized water solution of the template agent₃)₃·9H₂O、10g ZrOCl₂·8H₂O, the charging time is 1 h; slowly dropwise adding 25% ammonia water solution under stirring to adjust the pH of the solution to 9, continuing stirring for 2h, and stopping stirring and aging for 1 h; carrying out vacuum filtration and washing with deionized water to be neutral; drying the filter cake at 120 ℃ for 24h, roasting at 550 ℃ for 2h, grinding and sieving to obtain rare earth doped Al₂O₃-ZrO₂And (3) a carrier.

Al doped with the above rare earth₂O₃-ZrO₂The carrier, according to the methods of b), c), d) of the catalyst preparation of example two, further prepare rare earth doped fluorine-containing SPEEK/Al₂O₃-ZrO₂And (3) compounding a catalyst.

Rare earth doped fluorine-containing SPEEK/Al₂O₃-ZrO₂TGA characterization of the composite catalyst shows that fluorine-containing SPEEK approximately accounts for Al₂O₃-ZrO₂23% of the mass of the support.

2) Gas phase rearrangement reaction using the above catalyst

10g of rare earth doped fluorine-containing SPEEK/Al₂O₃-ZrO₂The composite catalyst is filled in a fixed bed, the reaction temperature is 340 ℃, the reaction pressure is 4KPa (A), a metering pump is used for conveying an isopropyl cyclohexane solution of cyclododecanone oxime to the fixed bed, the concentration of the cyclododecanone oxime is 5 wt%, and the mass space velocity of the cyclododecanone oxime is 0.2h^-1The reaction uses argon as a carrier.

After the reaction product is cooled to 80-100 ℃, the conversion rate of the cyclododecanone oxime is 97.32 percent and the selectivity of the laurolactam is 97.01 percent by gas chromatographic analysis, the catalyst is continuously used for 2200 hours and then analyzed, the compressive strength of the catalyst is reduced from initial 97N to 19N, and the specific surface area is reduced from initial 296m²The/g is reduced to 112m²/g。

Comparative example five

According to the methods of a), c), d) of the catalyst preparation of example two, a fluoride-unmodified rare earth doped fluorine-containing SPEEK/Al is obtained₂O₃-SiO₂-ZrO₂And (3) compounding a catalyst.

Fluoride-free rare earth doped fluorine-containing SPEEK/Al₂O₃-SiO₂-ZrO₂TGA characterization of the composite catalyst shows that fluorine-containing SPEEK approximately accounts for Al₂O₃-SiO₂-ZrO₂18% of the mass of the support.

2) Gas phase rearrangement reaction using the above catalyst

10g of rare earth doped fluoride-free SPEEK/Al₂O₃-SiO₂-ZrO₂Composite catalystFilling the mixture into a fixed bed, wherein the reaction temperature is 340 ℃, the reaction pressure is 4KPa (A), a metering pump is used for conveying an isopropyl cyclohexane solution of cyclododecanone oxime to the fixed bed, the concentration of the cyclododecanone oxime is 5 wt%, and the mass space velocity of the cyclododecanone oxime is 0.2h^-1The reaction uses argon as a carrier.

After the reaction product is cooled to 80-100 ℃, the conversion rate of cyclododecanone oxime is 98.95 percent and the selectivity of laurolactam is 99.41 percent by gas chromatographic analysis, the catalyst is continuously used for 2700h and then analyzed, the compressive strength of the catalyst is reduced to 59N from the initial 123N, and the specific surface area is reduced to 248m from the initial²The/g is reduced to 109m²/g。

Comparative example six

10g of heat-resistant sulfonic acid resin Amberlyst-35 is filled in a fixed bed, the reaction temperature is 340 ℃, the reaction pressure is 4KPa (A), a metering pump is used for conveying an isopropyl cyclohexane solution of cyclododecanone oxime to the fixed bed, the concentration of the cyclododecanone oxime is 5 wt%, and the mass space velocity of the cyclododecanone oxime is 0.2h^-1The reaction uses argon as a carrier.

After the reaction product is cooled to 80-100 ℃, the conversion rate of cyclododecanone oxime is 15.13 percent, the selectivity of laurolactam is 11.74 percent and the service life of the catalyst is less than 1 hour by gas chromatographic analysis.