WO2024082962A1 - Catalyst for caprolactam ammoniation, and preparation method therefor and use thereof - Google Patents

Catalyst for caprolactam ammoniation, and preparation method therefor and use thereof Download PDF

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WO2024082962A1
WO2024082962A1 PCT/CN2023/123152 CN2023123152W WO2024082962A1 WO 2024082962 A1 WO2024082962 A1 WO 2024082962A1 CN 2023123152 W CN2023123152 W CN 2023123152W WO 2024082962 A1 WO2024082962 A1 WO 2024082962A1
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catalyst
caprolactam
amination
metal oxide
active component
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PCT/CN2023/123152
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French (fr)
Chinese (zh)
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杨琦武
庄大为
史文涛
王聪
霍瑜姝
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中国天辰工程有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • 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

Definitions

  • the invention relates to the technical field of organic chemical industry, and in particular to a catalyst for preparing 6-aminocapronitrile by ammoniation of caprolactam, and a preparation method and application thereof.
  • 1,6-Hexanediamine (hereinafter referred to as hexanediamine) is an important chemical intermediate. Its active functional group amino group can undergo condensation reaction to prepare polymer materials such as nylon, fiber, resin, etc. It has extremely high commercial value, and the demand for hexanediamine in the domestic market is increasing year by year.
  • hexanediamine is mainly prepared by hydrogenating adiponitrile or 6-aminocapronitrile. Since adiponitrile is subject to the monopoly of foreign enterprises, and the production technology of caprolactam has been improved, the production process of preparing hexanediamine with caprolactam as raw material has developed rapidly.
  • the method for preparing 6-aminocapronitrile (hereinafter referred to as aminocapronitrile) from caprolactam includes a liquid phase method and a gas phase method, wherein the gas phase method is relatively simpler to operate, has a higher raw material conversion rate, and is more suitable for industrial production.
  • the performance of the catalyst directly affects the raw material conversion rate and product selectivity of the reaction.
  • the cost of the catalyst and the reaction space velocity must also be considered.
  • the reaction space velocity is divided into volume space velocity and weight hourly space velocity, and the unit is h -1 , which refers to the amount of raw materials treated by the catalyst per unit volume or mass per unit time under specified conditions.
  • the reaction space velocity of the catalyst is an important indicator for measuring the process level.
  • Patent CN113413891A discloses a catalyst containing two pores for preparing aminocapronitrile from caprolactam by gas phase method.
  • the technical solution extrudes alkaline earth metal oxide, transition metal oxide, silicon dioxide and/or aluminum oxide powder by kneading. Under the conditions of reaction temperature above 300°C and space velocity of 0.3-0.8h -1 , the raw material conversion rate reaches 89%-90% and product selectivity reaches 98%-99%.
  • Patent CN111672526A modifies the carrier by one or more combinations of calcium phosphate, magnesium phosphate, aluminum phosphate, calcium metaphosphate, etc., and then forms a catalyst for preparing aminocapronitrile from caprolactam by gas phase method.
  • the catalyst should reach the technical effect of reaction conversion rate of about 70% and selectivity of about 92% at reaction temperature of 395°C and space velocity of 3h -1 .
  • Patent CN114832851A loads at least one oxide on the catalyst matrix and modifies titanium oxide on the catalyst surface.
  • the resulting catalyst reacts at 356°C and 2.1h -1 space velocity to obtain an initial conversion rate of 79.5% to 82.3% and an initial selectivity of 90.4% to 98.3%.
  • the conversion rate is 71.2% to 80.2% and the selectivity is 93.5% to 99.5%.
  • the reaction space velocity of the catalyst used, the raw material conversion rate, and the product selectivity do not reach the optimum at the same time, and the catalyst preparation process is also relatively complicated.
  • the present invention discloses a catalyst for the amination of caprolactam, a preparation method and an application thereof.
  • the catalyst has high activity, maintains high raw material conversion rate and product selectivity under the conditions of weight hourly space velocity (calculated as caprolactam) of 1h -1 and 3h -1 , and is suitable for industrial production of aminocapronitrile by gas phase process.
  • the present invention discloses a catalyst for the amination of caprolactam, the catalyst comprising an active component supported on a porous carrier; the active component is a composite metal oxide, and its stoichiometric composition is MaN1 - aOx , wherein M is one or two of Mg, Ca, V, Co, Fe, Zn, Ni, and Cu, and N is one or two of Mo, Zr, Ce, and Sn; 0 ⁇ a ⁇ 0.8, and x is a value that makes the charge of the composite metal oxide balanced.
  • the active components of the catalyst of the present invention include 2 groups of metal oxides, namely, group M metal oxides and group N metal oxides. From the perspective of reducing the cost of catalyst preparation, the types of metal elements included in the group M and group N are all common metals. In addition, the inventors found that the use of composite metal oxides as the active component of the caprolactam amination catalyst can effectively improve the performance of the catalyst. For this reason, the inventors selected the metal element oxides in the third and fourth periods (group M) and the metal element oxides in the fifth and sixth periods (group N) for compounding as the catalyst active component.
  • the subscript a of M represents the ratio of the sum of the molar numbers of each metal element in the M group of metal oxides to the sum of the molar numbers of all metal elements in the catalyst active component.
  • the M group of metal elements in the catalyst active component includes M1 and M2
  • the molar numbers of the two are a1 and a2 respectively
  • the N group of metal elements includes N1 and N2
  • the molar numbers of the two are b1 and b2 respectively
  • a (a1+a2)/(a1+a2+b1+b2).
  • the M group and the N group of metal elements can include one or two of the metal element groups to which they belong, and the a value can be calculated according to the actual situation with reference to the exemplified method.
  • the stoichiometric composition of the catalyst active component is set as MaN1 - aOx in order to show that the catalyst active component of the present invention is a composite metal oxide comprising two metal oxides, wherein the subscript x of the O element is a value that makes the composite metal oxide charge balanced.
  • the higher the reaction space velocity allowed by the catalyst the higher the catalyst activity and the larger the device processing capacity, but the reaction space velocity cannot be infinitely improved.
  • the catalyst dosage 30% is within the economically acceptable range, that is, in other words, the catalyst standby coefficient is 3 times of the amount required to ensure that the process is basically feasible, and the reaction space velocity of the two is 1:3.
  • the inventor has verified in a specific embodiment that the catalyst of embodiment 1-5 is under weight hourly space velocity (in terms of caprolactam) 1h -1 and 3h -1 conditions, the raw material conversion rate and product selectivity of preparing aminocapronitrile by gas phase process.
  • the preferred value range of a in the stoichiometric composition is 0.28 to 0.79, and more preferably 0.38 to 0.4.
  • the mass ratio of the metal element in the composite metal oxide to the porous carrier is (0.01-0.8):1, preferably 0.26-0.7:1.
  • weight hourly space velocity (WHSV) in the present invention is the weight of feed (liquid or gas) per hour/the loading weight of the catalyst.
  • the porous carrier is one of molecular sieve, alumina or activated carbon, preferably molecular sieve.
  • the analytical sieve is preferably a configuration molecular sieve or a modified molecular sieve;
  • the configuration molecular sieve is preferably MFI, CHA, MEL configuration molecular sieve, further preferably ZSM-5, MCM-41, SAPO-34, TS-1, TS-2; more preferably ZSM-5 (H type), TS-1, SAPO-34.
  • the present invention discloses a method for preparing a catalyst for the amination of caprolactam, the preparation method comprising the following steps: S1, selecting a metal oxide precursor to prepare a metal salt solution; S2, impregnating the metal salt solution onto a porous carrier; S3, subjecting the fully impregnated porous carrier to a drying process, a molding process and a heat treatment process to obtain the catalyst; wherein the active component of the catalyst is a composite metal oxide, including one or two of metal Mg, Ca, V, Co, Fe, Zn, Ni, and Cu oxides, and one or two of metal Mo, Zr, Ce, and Sn oxides.
  • the metal oxide precursor includes nitrates, chlorides, sulfates of Mg, Ca, Co, Fe, Zn, Ni, Cu, Ce, as well as ammonium metavanadate, ammonium molybdate, sodium molybdate, zirconium sulfate, and sodium stannate.
  • the step S1 also includes adjusting the pH value of the metal salt solution to between 1 and 6 using a pH adjuster; the pH adjuster is hydrochloric acid or nitric acid.
  • the temperature of the drying process is 60-120°C, and the temperature of the heat treatment process is 350-550°C; the heating rate of the drying process and the heat treatment process is 1-5°C/min, and when the specified temperature is reached, it is maintained for 1-15 hours.
  • the present invention discloses the use of the above catalyst in the gas phase process of preparing aminocapronitrile using caprolactam as a raw material.
  • the catalyst of the present invention achieves a high raw material conversion rate and a high product selectivity under a weight hourly space velocity (calculated as caprolactam) of 1 h -1 , and can still maintain a high raw material conversion rate and a high product selectivity under a weight hourly space velocity (calculated as caprolactam) of 3 h -1 , and is suitable for industrial production;
  • the metal elements selected by the present invention are common metal elements in the third to sixth periods, the raw materials are simple and easy to obtain, the preparation process is simple, the production cost of preparing aminocapronitrile by a gas phase method can be greatly reduced, and it is conducive to the scale-up of industrial production.
  • FIG1 is an electron microscope morphology image of the caprolactam amination catalyst prepared in Example 1;
  • FIG2 is an electron microscope morphology image of the caprolactam amination catalyst prepared in Example 3.
  • FIG3 is an electron microscope morphology image of the caprolactam amination catalyst prepared in Example 5.
  • test reagents used in the following examples are all conventional biochemical reagents; the experimental methods, unless otherwise specified, are all conventional methods.
  • the metal salts, hydrochloric acid and ammonia water used in the embodiments of the present invention are all chemically pure; the molecular sieves ZSM-5 (H type), TS-1 and SAPO-34 used are produced by Tianjin Tianchen Green Energy Engineering Technology Research and Development Co., Ltd.
  • S1 weigh 18gMg(NO 3 ) 2 , 7gZnCl 2 , 100gZr(SO 4 ) 2 ⁇ 4H 2 O, add into 250ml water, adjust pH to 1 with nitric acid solution, stir and dissolve to obtain metal salt solution;
  • S2 slowly pour the solution obtained from S1 into a crucible containing 80gZSM-5 (H type) molecular sieve, slowly stir and mix evenly, and let stand for 1h;
  • S3, without filtering directly put the molecular sieve fully impregnated with S2 into an oven for drying, heating at a rate of 1°C/min from room temperature to 80°C, and dry; after drying, transfer to a muffle furnace, heating at a rate of 10°C/min from room temperature to 550°C, and keep at 550°C for 6 hours to obtain catalyst cat-1, whose electron microscope morphology is shown in Figure 1.
  • S1 weigh 47gCa(NO 3 ) 2 ⁇ 4H 2 O and 180gZr(SO 4 ) 2 ⁇ 4H 2 O, add them into 200ml water, adjust pH to 1 with nitric acid solution, stir and dissolve to obtain metal salt solution;
  • S2 slowly pour the solution obtained from S1 into a crucible containing 90gZSM-5 (H type) molecular sieve, slowly stir and mix evenly, and let stand for 1h;
  • S3, without filtering directly put the molecular sieve fully impregnated with S2 into an oven for drying, heating up at a rate of 1°C/min from room temperature to 80°C, and drying. After drying, transfer to a muffle furnace, heating up at a rate of 10°C/min from room temperature to 550°C, and keep at 550°C for 6 hours to obtain catalyst cat-2.
  • S1 weigh 18.8gCu(NO 3 ) 2 ⁇ 3H 2 O, 13.7gZnCl 2 , 58.9g(NH 4 ) 2 MoO 4 , add them into 150ml water, adjust the pH to 4 with nitric acid solution, stir and dissolve to obtain a metal salt solution;
  • S2 slowly pour the solution obtained in S1 into a crucible containing 102g SAPO-34 molecular sieve, slowly stir and mix evenly, and then let it stand for 1h;
  • S3, without filtering directly put the molecular sieve fully impregnated with S2 into an oven for drying, and heat up the temperature at a rate of 1°C/min from room temperature to 80°C for drying; After drying, the catalyst was transferred to a muffle furnace and heated at a rate of 10°C/min from room temperature to 550°C. The temperature was maintained at 550°C for 6 hours to obtain catalyst cat-3, whose electron microscope morphology is shown in FIG2 .
  • S1 weigh 60gCa(NO 3 ) 2 ⁇ 4H 2 O, 30gMg(NO 3 ) 2 , 30gCe(NO 3 ) 3 ⁇ 6H 2 O, 14gNa 2 SnO 3 ⁇ 3H 2 O, add them into 200ml water, adjust pH to 2 with nitric acid solution, stir and dissolve to obtain metal salt solution;
  • S2 slowly pour the solution obtained in S1 into a crucible containing 120g SAPO-34 molecular sieve, slowly stir and mix evenly, and then stand for 1h;
  • S3, without filtering directly put the molecular sieve fully impregnated with S2 into an oven for drying, heating at a rate of 1°C/min from room temperature to 80°C, and drying. After drying, transfer to a muffle furnace, heating at a rate of 10°C/min from room temperature to 550°C, and keep at 550°C for 6 hours to obtain catalyst cat-4.
  • S1 weigh 27gFeCl 3 ⁇ 6H 2 O, 12gNH 4 VO 3 , 39g(NH 4 ) 2 MoO 4 , 85gZr(SO 4 ) 2 ⁇ 4H 2 O, add them into 200ml water, adjust pH to 1 with nitric acid solution, stir and dissolve to obtain metal salt solution;
  • S2 slowly pour the solution obtained from S1 into a crucible containing 81.5gTS-1 molecular sieve, slowly stir and mix evenly, and then stand for 1h;
  • S3 directly put the molecular sieve fully impregnated with S2 into an oven, heat up at a rate of 1°C/min, from room temperature to 80°C, and dry. After drying, transfer to a muffle furnace, heat up at a rate of 10°C/min, from room temperature to 550°C, and keep at 550°C for 6 hours to obtain catalyst cat-5, the electron microscope morphology of which is shown in Figure 3.
  • the catalyst prepared in Examples 1 to 5 was evaluated using a fixed bed reactor. Specifically, the catalysts of Examples 1 to 5 were used to carry out the gas phase method of preparing aminocapronitrile under the condition of a weight hourly space velocity of 1 h -1 based on the weight of caprolactam, and the results correspond to Test Examples 1 to 5; the catalysts of Examples 1 to 5 were used to carry out the gas phase method of preparing aminocapronitrile under the condition of a weight hourly space velocity of 3 h -1 based on the weight of caprolactam, and the results correspond to Test Examples 6 to 10.
  • the raw material caprolactam is fed through a pump with a heated pump head, the catalyst loading is 60 g, the caprolactam feed amount is 1.0 g/min, and the weight hourly space velocity is 1 h -1 (or the caprolactam feed amount is 3.0 g/min, and the weight hourly space velocity is 3 h -1 ), and the ammonia feed amount is controlled by a mass flow meter so that the feed mass ratio of ammonia to caprolactam is 1.9:1.
  • ammonia is preheated to 350°C through two preheaters and then mixed with caprolactam, and reacted in a fixed bed.
  • the bed temperature is controlled at 350°C by heat transfer oil, and the reaction pressure is 0.01MPa(G).
  • the liquid product is collected through a cooler and a gas-liquid separator.
  • Gas chromatography is used to perform quantitative analysis using the area normalization method to calculate the caprolactam raw material conversion rate and product selectivity; the raw material conversion rate and product selectivity are the average values of the evaluation results.
  • the raw material conversion rate (1-caprolactam content in the reaction solution) ⁇ 100%
  • product selectivity aminocapronitrile in the reaction solution Content/(1-caprolactam content in reaction solution) ⁇ 100%
  • the catalyst gas phase method provided by the present invention is used to prepare aminocapronitrile.
  • the raw material conversion rate of caprolactam is 89.4% to 96.3%
  • the product selectivity is 96.2% to 98.5%
  • the life of the catalyst is greater than 1500h;
  • test examples 6-10 it can be confirmed that under the condition of a weight hourly space velocity of 3h - 1 based on caprolactam, the raw material conversion rate of caprolactam is 83% to 95.5%, the product selectivity is 96.1% to 98.9%, and the catalyst life is greater than 400h.
  • the caprolactam amination catalyst with a composite metal oxide as an active component provided by the present invention obtains good raw material conversion rate and product selectivity at weight hourly space velocities of 1h -1 and 3h -1 , the catalyst life is long and the performance is stable, and it is suitable for the industrial production of aminocapronitrile by gas phase method.
  • the value range of a can be set to 0 ⁇ a ⁇ 0.8, preferably 0.28 to 0.79, and more preferably 0.38 to 0.4.

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Abstract

A catalyst for caprolactam ammoniation, comprising an active component loaded on a porous carrier. The active component is a composite metal oxide, and the stoichiometric composition of the active component is MaN1-aOx, wherein M is one or two of Mg, Ca, V, Co, Fe, Zn, Ni and Cu, N is one or two of Mo, Zr, Ce and Sn, 0<a≤0.8, and x is a value for balancing the charge of the composite metal oxide. The catalyst can keep high raw material conversion rate and product selectivity in the cases of weight hourly space velocities (in caprolactam) of 1h-1 and 3h-1. Raw materials for the catalyst are simple and easy to obtain, and the catalyst has simple preparation process, and is suitable for industrial production of aminocapronitrile by a gas phase method.

Description

一种用于己内酰胺氨化的催化剂及其制备方法和应用A catalyst for amination of caprolactam and its preparation method and application 技术领域Technical Field
本发明涉及有机化工技术领域，具体涉及一种用于己内酰胺氨化制备6-氨基己腈的催化剂及其制备方法和应用。The invention relates to the technical field of organic chemical industry, and in particular to a catalyst for preparing 6-aminocapronitrile by ammoniation of caprolactam, and a preparation method and application thereof.
背景技术Background technique
1，6-己二胺(以下简称己二胺)是重要的化工中间体，其活泼性官能团氨基能进行缩合反应制备尼龙、纤维、树脂等聚合材料，具有极高的商业价值，国内市场对己二胺的需求逐年增长。目前，己二胺主要通过己二腈或6-氨基己腈加氢而制得，由于己二腈受限于国外企业垄断，而己内酰胺的生产技术得到改进，以己内酰胺为原料制备己二胺的生产工艺得到快速发展。1,6-Hexanediamine (hereinafter referred to as hexanediamine) is an important chemical intermediate. Its active functional group amino group can undergo condensation reaction to prepare polymer materials such as nylon, fiber, resin, etc. It has extremely high commercial value, and the demand for hexanediamine in the domestic market is increasing year by year. At present, hexanediamine is mainly prepared by hydrogenating adiponitrile or 6-aminocapronitrile. Since adiponitrile is subject to the monopoly of foreign enterprises, and the production technology of caprolactam has been improved, the production process of preparing hexanediamine with caprolactam as raw material has developed rapidly.
由己内酰胺制备6-氨基己腈(以下简称氨基己腈)的方法包括液相法和气相法，其中气相法的操作相对更简单，原料转化率更高，更适合于工业化生产。气相法中，催化剂的性能直接影响反应的原料转化率和产品选择性，在连续放大的工业化生产中还需考虑催化剂的成本和反应空速。反应空速分为体积空速和重时空速，单位为h-1，是指规定的条件下单位时间单位体积或质量的催化剂处理的原料量，变换催化剂的反应空速是衡量工艺水平的重要指标。The method for preparing 6-aminocapronitrile (hereinafter referred to as aminocapronitrile) from caprolactam includes a liquid phase method and a gas phase method, wherein the gas phase method is relatively simpler to operate, has a higher raw material conversion rate, and is more suitable for industrial production. In the gas phase method, the performance of the catalyst directly affects the raw material conversion rate and product selectivity of the reaction. In the continuous scale-up industrial production, the cost of the catalyst and the reaction space velocity must also be considered. The reaction space velocity is divided into volume space velocity and weight hourly space velocity, and the unit is h -1 , which refers to the amount of raw materials treated by the catalyst per unit volume or mass per unit time under specified conditions. The reaction space velocity of the catalyst is an important indicator for measuring the process level.
专利CN113413891A公开了一种含有两种孔道的催化剂用于己内酰胺气相法制备氨基己腈，该技术方案通过捏合将碱土金属氧化物、过渡金属氧化物、二氧化硅和/或氧化铝粉末挤压成型，在反应温度在300℃以上、空速0.3～0.8h-1的条件下，达到原料转化率89％～90％、产品选择性98％～99％。专利CN111672526A将磷酸钙、磷酸镁、磷酸铝、偏磷酸钙等一种或几种组合，对载体进行改性，而后成型得到己内酰胺气相法制备氨基己腈催化剂，该催化剂应在反应温度395℃、空速3h-1，达到反应转化率约70％、选择性约92％的技术效果。专利CN114832851A在催化剂母体上负载至少一种氧化物并在催化剂表面修饰氧化钛，所得催化剂在356℃、2.1h-1空速下反应得到初始转化率79.5～82.3％、初始选择性90.4％～98.3％，1000h后得到转化率71.2％～80.2％、选择性93.5％～99.5％。以上专利技术方案中，所用催化剂的反应空速与原料转化率、产品选择性并没有同时达到最佳，催化剂的制备工艺流程也较为复杂。Patent CN113413891A discloses a catalyst containing two pores for preparing aminocapronitrile from caprolactam by gas phase method. The technical solution extrudes alkaline earth metal oxide, transition metal oxide, silicon dioxide and/or aluminum oxide powder by kneading. Under the conditions of reaction temperature above 300°C and space velocity of 0.3-0.8h -1 , the raw material conversion rate reaches 89%-90% and product selectivity reaches 98%-99%. Patent CN111672526A modifies the carrier by one or more combinations of calcium phosphate, magnesium phosphate, aluminum phosphate, calcium metaphosphate, etc., and then forms a catalyst for preparing aminocapronitrile from caprolactam by gas phase method. The catalyst should reach the technical effect of reaction conversion rate of about 70% and selectivity of about 92% at reaction temperature of 395°C and space velocity of 3h -1 . Patent CN114832851A loads at least one oxide on the catalyst matrix and modifies titanium oxide on the catalyst surface. The resulting catalyst reacts at 356°C and 2.1h -1 space velocity to obtain an initial conversion rate of 79.5% to 82.3% and an initial selectivity of 90.4% to 98.3%. After 1000h, the conversion rate is 71.2% to 80.2% and the selectivity is 93.5% to 99.5%. In the above patent technical solutions, the reaction space velocity of the catalyst used, the raw material conversion rate, and the product selectivity do not reach the optimum at the same time, and the catalyst preparation process is also relatively complicated.
发明内容Summary of the invention
针对现有技术中的不足，本发明公开一种用于己内酰胺氨化的催化剂及制备方法和应用， 该催化剂具有较高的活性，在重时空速(以己内酰胺计)1h-1和3h-1条件下保持高原料转化率和产品选择性，适用于气相法工业化生产氨基己腈。In view of the deficiencies in the prior art, the present invention discloses a catalyst for the amination of caprolactam, a preparation method and an application thereof. The catalyst has high activity, maintains high raw material conversion rate and product selectivity under the conditions of weight hourly space velocity (calculated as caprolactam) of 1h -1 and 3h -1 , and is suitable for industrial production of aminocapronitrile by gas phase process.
具体的，一方面，本发明公开了一种用于己内酰胺氨化的催化剂，该催化剂包括负载于多孔载体上的活性组分；所述活性组分为复合金属氧化物，其化学计量组成为MaN1-aOx，其中M为Mg、Ca、V、Co、Fe、Zn、Ni、Cu中的一种或两种，N为Mo、Zr、Ce、Sn中的一种或两种；0＜a≤0.8，x为使得复合金属氧化物电荷平衡的数值。Specifically, on the one hand, the present invention discloses a catalyst for the amination of caprolactam, the catalyst comprising an active component supported on a porous carrier; the active component is a composite metal oxide, and its stoichiometric composition is MaN1 - aOx , wherein M is one or two of Mg, Ca, V, Co, Fe, Zn, Ni, and Cu, and N is one or two of Mo, Zr, Ce, and Sn; 0＜a≤0.8, and x is a value that makes the charge of the composite metal oxide balanced.
在上述技术方案中，本发明催化剂的活性成分包括2组金属氧化物，即M组金属氧化物和N组金属氧化物。出于降低催化剂制备成本的角度，所述M组和N组包括的金属元素种类均为普通金属。此外，发明人发现，采用复合金属氧化物作为己内酰胺氨化催化剂的活性组分，可有效地提升催化剂的性能，为此，发明人选取第三、四周期(M组)中的金属元素氧化物和第五、六周期(N组)中的金属元素的氧化物进行复合，作为催化剂活性组分。In the above technical scheme, the active components of the catalyst of the present invention include 2 groups of metal oxides, namely, group M metal oxides and group N metal oxides. From the perspective of reducing the cost of catalyst preparation, the types of metal elements included in the group M and group N are all common metals. In addition, the inventors found that the use of composite metal oxides as the active component of the caprolactam amination catalyst can effectively improve the performance of the catalyst. For this reason, the inventors selected the metal element oxides in the third and fourth periods (group M) and the metal element oxides in the fifth and sixth periods (group N) for compounding as the catalyst active component.
在上述技术方案中，M的角标a代表在催化剂活性组分中，M组金属氧化物中各金属元素的摩尔数之和与所有金属元素摩尔数之和的比值，举例来说(如具体实施方式中的实施例5)，假设催化剂的活性组分中M组金属元素包括M1和M2，两者的摩尔数分别为a1和a2，N组金属元素包括N1和N2，两者的摩尔数分别为b1和b2，那么a＝(a1+a2)/(a1+a2+b1+b2)。需注意，在具体实施例中M组和N组金属元素可以包括所属金属元素组中的1种或2种，可根据实际情况参考所例举的方法计算a值。In the above technical solution, the subscript a of M represents the ratio of the sum of the molar numbers of each metal element in the M group of metal oxides to the sum of the molar numbers of all metal elements in the catalyst active component. For example (such as Example 5 in the specific implementation), assuming that the M group of metal elements in the catalyst active component includes M1 and M2, the molar numbers of the two are a1 and a2 respectively, and the N group of metal elements includes N1 and N2, the molar numbers of the two are b1 and b2 respectively, then a＝(a1+a2)/(a1+a2+b1+b2). It should be noted that in the specific embodiment, the M group and the N group of metal elements can include one or two of the metal element groups to which they belong, and the a value can be calculated according to the actual situation with reference to the exemplified method.
在上述技术方案中，将催化剂活性组分的化学计量组成设为MaN1-aOx，是为了展示本发明催化剂活性组分为包含两种金属氧化物的复合金属氧化物。其中，O元素的角标x为使得复合金属氧化物电荷平衡的数值。In the above technical solution, the stoichiometric composition of the catalyst active component is set as MaN1 - aOx in order to show that the catalyst active component of the present invention is a composite metal oxide comprising two metal oxides, wherein the subscript x of the O element is a value that makes the composite metal oxide charge balanced.
本领域内的普通技术人员将理解，催化剂允许的反应空速越高表示催化剂活性越高、装置处理能力越大，但是，反应空速不能无限提高。在工业化生产中，在催化剂活性不降低的前提下，催化剂用量30％处在经济容许的范围内，即换言之，催化剂备用系数是确保工艺基本可行所需量的3倍，两者的反应空速为1:3。基于此，发明人在具体实施方式中验证了实施例1-5的催化剂在重时空速(以己内酰胺计)1h-1和3h-1条件下，气相法制备氨基己腈的原料转化率和产品选择性。Those skilled in the art will understand that the higher the reaction space velocity allowed by the catalyst, the higher the catalyst activity and the larger the device processing capacity, but the reaction space velocity cannot be infinitely improved. In industrial production, under the premise that the catalyst activity does not decrease, the catalyst dosage 30% is within the economically acceptable range, that is, in other words, the catalyst standby coefficient is 3 times of the amount required to ensure that the process is basically feasible, and the reaction space velocity of the two is 1:3. Based on this, the inventor has verified in a specific embodiment that the catalyst of embodiment 1-5 is under weight hourly space velocity (in terms of caprolactam) 1h -1 and 3h -1 conditions, the raw material conversion rate and product selectivity of preparing aminocapronitrile by gas phase process.
进一步，所述化学计量组成中a的优选取值范围为0.28～0.79，更优选为0.38～0.4。Furthermore, the preferred value range of a in the stoichiometric composition is 0.28 to 0.79, and more preferably 0.38 to 0.4.
进一步，所述复合金属氧化物中金属元素与多孔载体的质量比为(0.01～0.8)：1，优选为0.26～0.7:1。 Furthermore, the mass ratio of the metal element in the composite metal oxide to the porous carrier is (0.01-0.8):1, preferably 0.26-0.7:1.
需注意，本发明中重时空速(WHSV)为每小时进料的重量(液体或气体))/催化剂的装填重量。It should be noted that the weight hourly space velocity (WHSV) in the present invention is the weight of feed (liquid or gas) per hour/the loading weight of the catalyst.
进一步，所述多孔载体为分子筛、氧化铝或活性炭中的一种，优选为分子筛。Furthermore, the porous carrier is one of molecular sieve, alumina or activated carbon, preferably molecular sieve.
更进一步，所述分析筛优选为构型分子筛或改性分子筛；所述构型分子筛优选为MFI、CHA、MEL构型分子筛，进一步优选为ZSM-5、MCM-41、SAPO-34、TS-1、TS-2；更优选为ZSM-5(H型)、TS-1、SAPO-34。Furthermore, the analytical sieve is preferably a configuration molecular sieve or a modified molecular sieve; the configuration molecular sieve is preferably MFI, CHA, MEL configuration molecular sieve, further preferably ZSM-5, MCM-41, SAPO-34, TS-1, TS-2; more preferably ZSM-5 (H type), TS-1, SAPO-34.
具体的，另一方面，本发明公开了一种用于己内酰胺氨化的催化剂制备方法，该制备方法包括以下步骤：S1，选择金属氧化物前驱体配置金属盐溶液；S2，将所述金属盐溶液浸渍负载到多孔载体上；S3，充分浸渍后的多孔载体再经干燥工序、成型工序和热处理工序，得到所述催化剂；其中，所述催化剂的活性组分为复合金属氧化物，包括金属Mg、Ca、V、Co、Fe、Zn、Ni、Cu氧化物中的一种或两种，以及金属Mo、Zr、Ce、Sn氧化物中的一种或两种。Specifically, on the other hand, the present invention discloses a method for preparing a catalyst for the amination of caprolactam, the preparation method comprising the following steps: S1, selecting a metal oxide precursor to prepare a metal salt solution; S2, impregnating the metal salt solution onto a porous carrier; S3, subjecting the fully impregnated porous carrier to a drying process, a molding process and a heat treatment process to obtain the catalyst; wherein the active component of the catalyst is a composite metal oxide, including one or two of metal Mg, Ca, V, Co, Fe, Zn, Ni, and Cu oxides, and one or two of metal Mo, Zr, Ce, and Sn oxides.
进一步，所述金属氧化物前驱体包括Mg、Ca、Co、Fe、Zn、Ni、Cu、Ce的硝酸盐、氯化物、硫酸盐，以及偏钒酸铵、钼酸铵、钼酸钠、硫酸锆、锡酸钠。Furthermore, the metal oxide precursor includes nitrates, chlorides, sulfates of Mg, Ca, Co, Fe, Zn, Ni, Cu, Ce, as well as ammonium metavanadate, ammonium molybdate, sodium molybdate, zirconium sulfate, and sodium stannate.
进一步，所述S1步骤中还包括采用pH调节剂将金属盐溶液的pH值调节至1～6之间；所述pH调节剂为盐酸或硝酸。Furthermore, the step S1 also includes adjusting the pH value of the metal salt solution to between 1 and 6 using a pH adjuster; the pH adjuster is hydrochloric acid or nitric acid.
进一步，所述干燥工序的温度为60～120℃，所述热处理工序的温度为350～550℃；所述干燥工序和热处理工序的升温速率为1-5℃/min，当到达指定温度后保持1～15h。Furthermore, the temperature of the drying process is 60-120°C, and the temperature of the heat treatment process is 350-550°C; the heating rate of the drying process and the heat treatment process is 1-5°C/min, and when the specified temperature is reached, it is maintained for 1-15 hours.
具体的，另一方面，本发明公开了上述催化剂在以己内酰胺为原料气相法制备氨基己腈中的应用。Specifically, on the other hand, the present invention discloses the use of the above catalyst in the gas phase process of preparing aminocapronitrile using caprolactam as a raw material.
与现有技术相比，本发明的有益效果为：1.本发明催化剂在重时空速(以己内酰胺计)1h-1下条件下达到高原料转化率和高产品选择性，且在重时空速(以己内酰胺计)3h-1条件下仍能保持高原料转化率和产品选择性，适合工业化生产；2.本发明选用的金属元素为第三至第六周期中的普通金属元素，原料简单易得，制备工艺流程简单，可大大降低气相法制备氨基己腈的生产成本，有利于放大工业化生产。Compared with the prior art, the present invention has the following beneficial effects: 1. The catalyst of the present invention achieves a high raw material conversion rate and a high product selectivity under a weight hourly space velocity (calculated as caprolactam) of 1 h -1 , and can still maintain a high raw material conversion rate and a high product selectivity under a weight hourly space velocity (calculated as caprolactam) of 3 h -1 , and is suitable for industrial production; 2. The metal elements selected by the present invention are common metal elements in the third to sixth periods, the raw materials are simple and easy to obtain, the preparation process is simple, the production cost of preparing aminocapronitrile by a gas phase method can be greatly reduced, and it is conducive to the scale-up of industrial production.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
构成本申请的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中： The drawings constituting a part of the present application are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:
图1为实施例1制备的己内酰胺氨化催化剂的电镜形貌图；FIG1 is an electron microscope morphology image of the caprolactam amination catalyst prepared in Example 1;
图2为实施例3制备的己内酰胺氨化催化剂的电镜形貌图；FIG2 is an electron microscope morphology image of the caprolactam amination catalyst prepared in Example 3;
图3为实施例5制备的己内酰胺氨化催化剂的电镜形貌图。FIG3 is an electron microscope morphology image of the caprolactam amination catalyst prepared in Example 5.
具体实施方式Detailed ways
为了便于理解本发明，下面将对本发明进行更全面的描述，给出了本发明的较佳实施例。但应当理解为这些实施例仅仅是用于更详细说明之用，而不应理解为用以任何形式限制本发明，即并不意于限制本发明的保护范围。除有定义外，以下实施例中所用的技术术语具有与本发明创造所属领域技术人员普遍理解的相同含义。以下实施例中所用的试验试剂，如无特殊说明，均为常规生化试剂；所述实验方法，如无特殊说明，均为常规方法。In order to facilitate the understanding of the present invention, the present invention will be described in more detail below, and preferred embodiments of the present invention are given. However, it should be understood that these embodiments are only used for more detailed description, and should not be understood as limiting the present invention in any form, that is, they are not intended to limit the scope of protection of the present invention. Unless otherwise defined, the technical terms used in the following examples have the same meanings as those generally understood by technicians in the field to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods, unless otherwise specified, are all conventional methods.
本发明实施例中采用的金属盐、盐酸和氨水均为化学纯；采用的分子筛ZSM-5(H型)、TS-1、SAPO-34为天津天辰绿能色绿能工程技术研发有限公司生产。The metal salts, hydrochloric acid and ammonia water used in the embodiments of the present invention are all chemically pure; the molecular sieves ZSM-5 (H type), TS-1 and SAPO-34 used are produced by Tianjin Tianchen Green Energy Engineering Technology Research and Development Co., Ltd.
实施例1Example 1
S1，称取18gMg(NO3)2、7gZnCl2、100gZr(SO4)2·4H2O加入250ml水中，使用硝酸溶液调节pH至1，搅拌溶解，得到金属盐溶液；S2，将S1所得溶液缓慢倒入装有80gZSM-5(H型)分子筛的坩埚中，缓慢搅拌混合均匀，静置1h后；S3，不进行过滤，直接将S2充分浸渍后的分子筛放入烘箱进行干燥，升温速度1℃/min，从室温升到80℃，进行干燥；干燥后，转移至马弗炉，升温速度10℃/min，从室温升到550℃，在550℃保持6小时，得到催化剂cat-1，其电镜形貌图如图1所示。S1, weigh 18gMg(NO 3 ) 2 , 7gZnCl 2 , 100gZr(SO 4 ) 2 ·4H 2 O, add into 250ml water, adjust pH to 1 with nitric acid solution, stir and dissolve to obtain metal salt solution; S2, slowly pour the solution obtained from S1 into a crucible containing 80gZSM-5 (H type) molecular sieve, slowly stir and mix evenly, and let stand for 1h; S3, without filtering, directly put the molecular sieve fully impregnated with S2 into an oven for drying, heating at a rate of 1℃/min from room temperature to 80℃, and dry; after drying, transfer to a muffle furnace, heating at a rate of 10℃/min from room temperature to 550℃, and keep at 550℃ for 6 hours to obtain catalyst cat-1, whose electron microscope morphology is shown in Figure 1.
实施例2Example 2
S1，称取47gCa(NO3)2·4H2O、180gZr(SO4)2·4H2O加入200ml水中，使用硝酸溶液调节pH至1，搅拌溶解得到金属盐溶液；S2，将S1所得溶液缓慢倒入装有90gZSM-5(H型)分子筛的坩埚中，缓慢搅拌混合均匀，静置1h；S3，不进行过滤，直接将S2充分浸渍后的分子筛放入烘箱进行干燥，升温速度1℃/min，从室温升到80℃，进行干燥。干燥后，转移至马弗炉，升温速度10℃/min，从室温升到550℃，在550℃保持6小时，得到催化剂cat-2。S1, weigh 47gCa(NO 3 ) 2 ·4H 2 O and 180gZr(SO 4 ) 2 ·4H 2 O, add them into 200ml water, adjust pH to 1 with nitric acid solution, stir and dissolve to obtain metal salt solution; S2, slowly pour the solution obtained from S1 into a crucible containing 90gZSM-5 (H type) molecular sieve, slowly stir and mix evenly, and let stand for 1h; S3, without filtering, directly put the molecular sieve fully impregnated with S2 into an oven for drying, heating up at a rate of 1℃/min from room temperature to 80℃, and drying. After drying, transfer to a muffle furnace, heating up at a rate of 10℃/min from room temperature to 550℃, and keep at 550℃ for 6 hours to obtain catalyst cat-2.
实施例3Example 3
S1，称取18.8gCu(NO3)2·3H2O，13.7gZnCl2，58.9g(NH4)2MoO4加入150ml水中，使用硝酸溶液调节pH至4，搅拌溶解，得到金属盐溶液；S2，将S1所得溶液缓慢倒入装有102gSAPO-34分子筛的坩埚中，缓慢搅拌混合均匀后静置1h；S3，不进行过滤，直接将S2充分浸渍后的分子筛放入烘箱进行干燥，升温速度1℃/min，从室温升到80℃，进行干燥； 干燥后，转移至马弗炉，升温速度10℃/min，从室温升到550℃，在550℃保持6小时，得到催化剂cat-3，其电镜形貌图如图2所示。S1, weigh 18.8gCu(NO 3 ) 2 ·3H 2 O, 13.7gZnCl 2 , 58.9g(NH 4 ) 2 MoO 4 , add them into 150ml water, adjust the pH to 4 with nitric acid solution, stir and dissolve to obtain a metal salt solution; S2, slowly pour the solution obtained in S1 into a crucible containing 102g SAPO-34 molecular sieve, slowly stir and mix evenly, and then let it stand for 1h; S3, without filtering, directly put the molecular sieve fully impregnated with S2 into an oven for drying, and heat up the temperature at a rate of 1℃/min from room temperature to 80℃ for drying; After drying, the catalyst was transferred to a muffle furnace and heated at a rate of 10°C/min from room temperature to 550°C. The temperature was maintained at 550°C for 6 hours to obtain catalyst cat-3, whose electron microscope morphology is shown in FIG2 .
实施例4Example 4
S1，称取60gCa(NO3)2·4H2O、30gMg(NO3)2、30gCe(NO3)3·6H2O、14gNa2SnO3·3H2O加入200ml水中，使用硝酸溶液调节pH至2，搅拌溶解，得到金属盐溶液；S2，将S1所得溶液缓慢倒入装有120gSAPO-34分子筛的坩埚中，缓慢搅拌混合均匀后静置1h；S3，不进行过滤，直接将S2充分浸渍后的分子筛放入烘箱进行干燥，升温速度1℃/min，从室温升到80℃，进行干燥。干燥后，转移至马弗炉，升温速度10℃/min，从室温升到550℃，在550℃保持6小时，得到催化剂cat-4。S1, weigh 60gCa(NO 3 ) 2 ·4H 2 O, 30gMg(NO 3 ) 2 , 30gCe(NO 3 ) 3 ·6H 2 O, 14gNa 2 SnO 3 ·3H 2 O, add them into 200ml water, adjust pH to 2 with nitric acid solution, stir and dissolve to obtain metal salt solution; S2, slowly pour the solution obtained in S1 into a crucible containing 120g SAPO-34 molecular sieve, slowly stir and mix evenly, and then stand for 1h; S3, without filtering, directly put the molecular sieve fully impregnated with S2 into an oven for drying, heating at a rate of 1℃/min from room temperature to 80℃, and drying. After drying, transfer to a muffle furnace, heating at a rate of 10℃/min from room temperature to 550℃, and keep at 550℃ for 6 hours to obtain catalyst cat-4.
实施例5Example 5
S1，称取27gFeCl3·6H2O、12gNH4VO3、39g(NH4)2MoO4、85gZr(SO4)2·4H2O加入200ml水中，使用硝酸溶液调节pH至1，搅拌溶解，得到金属盐溶液；S2，将S1所得溶液缓慢倒入装有81.5gTS-1分子筛的坩埚中，缓慢搅拌混合均匀后静置1h；S3，直接将S2充分浸渍后的分子筛放入烘箱，升温速度1℃/min，从室温升到80℃，进行干燥。干燥后，转移至马弗炉，升温速度10℃/min，从室温升到550℃，在550℃保持6小时，得到催化剂cat-5，其电镜形貌图如图3所示。S1, weigh 27gFeCl 3 ·6H 2 O, 12gNH 4 VO 3 , 39g(NH 4 ) 2 MoO 4 , 85gZr(SO 4 ) 2 ·4H 2 O, add them into 200ml water, adjust pH to 1 with nitric acid solution, stir and dissolve to obtain metal salt solution; S2, slowly pour the solution obtained from S1 into a crucible containing 81.5gTS-1 molecular sieve, slowly stir and mix evenly, and then stand for 1h; S3, directly put the molecular sieve fully impregnated with S2 into an oven, heat up at a rate of 1℃/min, from room temperature to 80℃, and dry. After drying, transfer to a muffle furnace, heat up at a rate of 10℃/min, from room temperature to 550℃, and keep at 550℃ for 6 hours to obtain catalyst cat-5, the electron microscope morphology of which is shown in Figure 3.
测试例1-10Test Example 1-10
为了进一步验证本发明催化剂在己内酰胺气相法制备氨基己腈反应中的技术效果，采用固定床反应器对实施例1-5所制备的催化剂进行评价。具体的，在以己内酰胺计重时空速1h-1条件下采用实施例1-5的催化剂进行气相法氨基己腈制备反应，结果对应测试例1-5；在以己内酰胺计重时空速3h-1条件下采用实施例1-5的催化剂进行气相法氨基己腈制备反应，结果对应测试例6-10。In order to further verify the technical effect of the catalyst of the present invention in the reaction of preparing aminocapronitrile by the gas phase method of caprolactam, the catalyst prepared in Examples 1 to 5 was evaluated using a fixed bed reactor. Specifically, the catalysts of Examples 1 to 5 were used to carry out the gas phase method of preparing aminocapronitrile under the condition of a weight hourly space velocity of 1 h -1 based on the weight of caprolactam, and the results correspond to Test Examples 1 to 5; the catalysts of Examples 1 to 5 were used to carry out the gas phase method of preparing aminocapronitrile under the condition of a weight hourly space velocity of 3 h -1 based on the weight of caprolactam, and the results correspond to Test Examples 6 to 10.
具体的，原料己内酰胺通过带有加热泵头的泵进料，催化剂的装填量为60g，己内酰胺的进料量为1.0g/min、重时空速1h-1(或己内酰胺进料量3.0g/min、重时空速3h-1)，通过质量流量计控制氨气进料量，使氨气和己内酰胺的进料质量比为1.9:1。Specifically, the raw material caprolactam is fed through a pump with a heated pump head, the catalyst loading is 60 g, the caprolactam feed amount is 1.0 g/min, and the weight hourly space velocity is 1 h -1 (or the caprolactam feed amount is 3.0 g/min, and the weight hourly space velocity is 3 h -1 ), and the ammonia feed amount is controlled by a mass flow meter so that the feed mass ratio of ammonia to caprolactam is 1.9:1.
其中，氨气通过两个预热器预热到350℃后与己内酰胺混合，经固定床发生反应，床层温度通过导热油控制在350℃，反应压力0.01MPa(G)。Among them, ammonia is preheated to 350°C through two preheaters and then mixed with caprolactam, and reacted in a fixed bed. The bed temperature is controlled at 350°C by heat transfer oil, and the reaction pressure is 0.01MPa(G).
反应后通过冷却器、气液分离器收集液体产品。采用气相色谱，使用面积归一法进行定量分析，计算己内酰胺原料转化率和产品选择性；原料转化率和产品选择性取评价结果的平均值。After the reaction, the liquid product is collected through a cooler and a gas-liquid separator. Gas chromatography is used to perform quantitative analysis using the area normalization method to calculate the caprolactam raw material conversion rate and product selectivity; the raw material conversion rate and product selectivity are the average values of the evaluation results.
其中，原料转化率＝(1-反应液中己内酰胺含量)×100％，产品选择性＝反应液氨基己腈 含量/(1-反应液中己内酰胺含量)×100％，Among them, the raw material conversion rate = (1-caprolactam content in the reaction solution) × 100%, product selectivity = aminocapronitrile in the reaction solution Content/(1-caprolactam content in reaction solution)×100%,
测试例1-10的相关参数设置和结果如表1所示。The relevant parameter settings and results of test examples 1-10 are shown in Table 1.
表格1
Table 1
结合测试例1-5可验证，采用本发明提供的催化剂气相法制备氨基己腈，在以己内酰胺计重时空速1h-1条件下，己内酰胺的原料转化率为89.4％～96.3％，产品选择性为96.2％～98.5％，催化剂的寿命大于1500h；结合测试例6-10可证实，在以己内酰胺计重时空速3h-1条件下，己内酰胺的原料转化率为83％～95.5％，产品选择性为96.1％～98.9％，催化剂寿命大于400h。结合测试例1-10可验证，本发明提供的以复合金属氧化物为活性组分的己内酰胺氨化催化剂在重时空速1h-1和3h-1下均获得较好的原料转化率和产品选择性，催化剂寿命较长且性能稳定，适合于气相法工业化生产氨基己腈。Combined with test examples 1-5, it can be verified that the catalyst gas phase method provided by the present invention is used to prepare aminocapronitrile. Under the condition of a weight hourly space velocity of 1h -1 based on caprolactam, the raw material conversion rate of caprolactam is 89.4% to 96.3%, the product selectivity is 96.2% to 98.5%, and the life of the catalyst is greater than 1500h; combined with test examples 6-10, it can be confirmed that under the condition of a weight hourly space velocity of 3h - 1 based on caprolactam, the raw material conversion rate of caprolactam is 83% to 95.5%, the product selectivity is 96.1% to 98.9%, and the catalyst life is greater than 400h. Combined with test examples 1-10, it can be verified that the caprolactam amination catalyst with a composite metal oxide as an active component provided by the present invention obtains good raw material conversion rate and product selectivity at weight hourly space velocities of 1h -1 and 3h -1 , the catalyst life is long and the performance is stable, and it is suitable for the industrial production of aminocapronitrile by gas phase method.
此外，结合测试例1-10可证实，当a值为0.38～0.4时催化剂的性能表现更佳，具体的，在以己内酰胺计重时空速1h-1条件下的可达原料转化率95.8％～96.3％、产品选择性96.2％～97.3％，当催化剂的重时空速增加至3h-1条件下后，仍能保持原料转化率95.5％～94.4％、产品选择性97％～98.8％。因此，本发明提供的催化剂化学计量组成MaN1-aOx中，a的取值范围可设为0＜a≤0.8，优选为0.28～0.79，进一步优选为0.38～0.4。In addition, in combination with test examples 1-10, it can be confirmed that when the a value is 0.38 to 0.4, the performance of the catalyst is better. Specifically, under the condition of a weight hourly space velocity of 1h -1 based on caprolactam, the raw material conversion rate can reach 95.8% to 96.3%, and the product selectivity can reach 96.2% to 97.3%. When the weight hourly space velocity of the catalyst is increased to 3h -1 , the raw material conversion rate can still be maintained at 95.5% to 94.4%, and the product selectivity can still be maintained at 97% to 98.8%. Therefore, in the catalyst stoichiometric composition MaN1 - aOx provided by the present invention, the value range of a can be set to 0＜a≤0.8, preferably 0.28 to 0.79, and more preferably 0.38 to 0.4.
需注意的是，以上内容是结合具体的实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施只局限于这些说明；本实施例尺寸数据并不定限定本技术方案，只是展示其中一种具体的工况。对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干简单改进和润饰，都应当视为属于本发明保护的范围。 It should be noted that the above contents are further detailed descriptions of the present invention in combination with specific implementation methods, and it cannot be determined that the specific implementation of the present invention is limited to these descriptions; the dimensional data of this embodiment does not necessarily limit the technical solution, but only shows one of the specific working conditions. For ordinary technicians in the technical field to which the present invention belongs, several simple improvements and modifications can be made without departing from the concept of the present invention, which should be regarded as falling within the scope of protection of the present invention.

Claims (10)

  1. 一种用于己内酰胺氨化的催化剂，其特征在于，包括负载于多孔载体上的活性组分；所述活性组分为复合金属氧化物，其化学计量组成为MaN1-aOx，其中M为Mg、Ca、V、Co、Fe、Zn、Ni、Cu中的一种或两种，N为Mo、Zr、Ce、Sn中的一种或两种；0＜a≤0.8，x为使得复合金属氧化物电荷平衡的数值。A catalyst for the amination of caprolactam, characterized in that it comprises an active component supported on a porous carrier; the active component is a composite metal oxide, and its stoichiometric composition is MaN1 - aOx , wherein M is one or two of Mg, Ca, V, Co, Fe, Zn, Ni, and Cu, and N is one or two of Mo, Zr, Ce, and Sn; 0＜a≤0.8, and x is a value that makes the charge of the composite metal oxide balanced.
  2. 根据权利要求1所述的用于己内酰胺氨化的催化剂，其特征在于，所述化学计量组成中a的取值范围为0.28～0.79。The catalyst for the amination of caprolactam according to claim 1, characterized in that the value of a in the stoichiometric composition ranges from 0.28 to 0.79.
  3. 根据权利要求1所述的用于己内酰胺氨化的催化剂，其特征在于，所述复合金属氧化物中金属元素与多孔载体的质量比为0.01：1～0.8：1。The catalyst for caprolactam amination according to claim 1, characterized in that the mass ratio of the metal element to the porous carrier in the composite metal oxide is 0.01:1 to 0.8:1.
  4. 根据权利要求1所述的用于己内酰胺氨化的催化剂，其特征在于，所述多孔载体为分子筛、氧化铝或活性炭中的一种。The catalyst for caprolactam amination according to claim 1, characterized in that the porous carrier is one of molecular sieve, alumina or activated carbon.
  5. 根据权利要求4所述的用于己内酰胺氨化的催化剂，其特征在于，所述分析筛为构型分子筛或改性分子筛。The catalyst for caprolactam amination according to claim 4, characterized in that the analytical sieve is a configuration molecular sieve or a modified molecular sieve.
  6. 一种用于己内酰胺氨化的催化剂制备方法，其特征在于，所述制备方法包括以下步骤：S1，选择金属氧化物前驱体配置金属盐溶液；S2，将所述金属盐溶液浸渍负载到多孔载体上；S3，充分浸渍后的多孔载体再经干燥工序、成型工序和热处理工序，得到所述催化剂；其中，所述催化剂的活性组分为复合金属氧化物，包括金属Mg、Ca、V、Co、Fe、Zn、Ni、Cu氧化物中的一种或两种，以及金属Mo、Zr、Ce、Sn氧化物中的一种或两种。A method for preparing a catalyst for the amination of caprolactam, characterized in that the preparation method comprises the following steps: S1, selecting a metal oxide precursor to prepare a metal salt solution; S2, impregnating the metal salt solution onto a porous carrier; S3, subjecting the fully impregnated porous carrier to a drying process, a molding process and a heat treatment process to obtain the catalyst; wherein the active component of the catalyst is a composite metal oxide, including one or two of metal Mg, Ca, V, Co, Fe, Zn, Ni, and Cu oxides, and one or two of metal Mo, Zr, Ce, and Sn oxides.
  7. 根据权利要求6所述的用于己内酰胺氨化的催化剂制备方法，其特征在于，所述金属氧化物前驱体包括Mg、Ca、Co、Fe、Zn、Ni、Cu、Ce的硝酸盐、氯化物、硫酸盐，以及偏钒酸铵、钼酸铵、钼酸钠、硫酸锆、锡酸钠。The method for preparing a catalyst for the amination of caprolactam according to claim 6, characterized in that the metal oxide precursor includes nitrates, chlorides, sulfates of Mg, Ca, Co, Fe, Zn, Ni, Cu, Ce, and ammonium metavanadate, ammonium molybdate, sodium molybdate, zirconium sulfate, and sodium stannate.
  8. 根据权利要求6所述的用于己内酰胺氨化的催化剂制备方法，其特征在于，S1步骤中还包括采用pH调节剂将金属盐溶液的pH值调节至1～6之间；所述pH调节剂为盐酸或硝酸。The method for preparing a catalyst for caprolactam amination according to claim 6, characterized in that step S1 also includes adjusting the pH value of the metal salt solution to between 1 and 6 using a pH adjuster; the pH adjuster is hydrochloric acid or nitric acid.
  9. 根据权利要求6所述的用于己内酰胺氨化的催化剂制备方法，其特征在于，所述干燥工序的温度为60～120℃，所述热处理工序的温度为350～550℃；所述干燥工序和热处理工序的升温速率为1-5℃/min，当到达指定温度后保持1～15h。The method for preparing a catalyst for caprolactam amination according to claim 6 is characterized in that the temperature of the drying process is 60-120°C, and the temperature of the heat treatment process is 350-550°C; the heating rate of the drying process and the heat treatment process is 1-5°C/min, and when the specified temperature is reached, it is maintained for 1-15 hours.
  10. 权利要求1-5任一项所述的催化剂在由己内酰胺氨化制备氨基己腈中的应用。 Use of the catalyst according to any one of claims 1 to 5 in the preparation of aminocapronitrile by amination of caprolactam.
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CN115337959B (en) * 2022-10-18 2023-03-14 中国天辰工程有限公司 Catalyst for ammonifying caprolactam and preparation method and application thereof
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2011105653A (en) * 2008-07-23 2012-08-27 Джапан Петролеум Эксплорейшн Ко., Лтд. (Jp) COMPOSITE OXIDE OF HYDROCARBON REFORMING CATALYST, METHOD FOR ITS PREPARATION AND METHOD FOR PRODUCING SYNTHESIS GAS WITH ITS USE
CN110115995A (en) * 2018-02-05 2019-08-13 天津大学 A kind of iron sodium/molybdenum composite metal oxide catalyst and its preparation method and application
CN111004148A (en) * 2019-12-30 2020-04-14 河南省化工研究所有限责任公司 Method for preparing 6-aminocapronitrile by gas phase method
CN112898163A (en) * 2019-12-03 2021-06-04 中国科学院大连化学物理研究所 Method for preparing 1, 6-hexamethylene diamine by ammoniation of hexamethylene imine
DE112020000187T5 (en) * 2019-07-31 2021-11-18 Shandong Nhu Amino Acid Co., Ltd. Catalyst for the production of acrylic acid or acrolein and its manufacturing process
CN114289060A (en) * 2021-12-30 2022-04-08 美思德(吉林)新材料有限公司 Supported bimetallic catalyst and preparation method and application thereof
CN114917952A (en) * 2022-06-30 2022-08-19 中国天辰工程有限公司 Preparation method of intermediate catalyst for preparing hexamethylene diamine from caprolactam
CN115337959A (en) * 2022-10-18 2022-11-15 中国天辰工程有限公司 Catalyst for ammonifying caprolactam and preparation method and application thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56115759A (en) * 1980-02-18 1981-09-11 Asahi Chem Ind Co Ltd Preparation of nitrile
DE19631522A1 (en) * 1996-08-03 1998-02-05 Basf Ag Process for the preparation of 6-aminocapronitrile
CN112876381B (en) * 2021-04-14 2024-01-26 江苏扬农化工集团有限公司 Simulated moving bed device and method for preparing 6-aminocapronitrile by gas phase method
CN113582876B (en) * 2021-08-02 2023-07-21 江苏扬农化工集团有限公司 Method for preparing amino nitrile organic matter by gas phase method
CN113649062B (en) * 2021-09-16 2023-11-21 北京旭阳科技有限公司 Catalyst for synthesizing 6-aminocapronitrile, preparation method thereof, and method for synthesizing 6-aminocapronitrile using same
CN114832851B (en) * 2022-05-25 2023-11-10 北京旭阳科技有限公司 Fixed bed catalyst for preparing 6-aminocapronitrile by ammonification of caprolactam, preparation method and application thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2011105653A (en) * 2008-07-23 2012-08-27 Джапан Петролеум Эксплорейшн Ко., Лтд. (Jp) COMPOSITE OXIDE OF HYDROCARBON REFORMING CATALYST, METHOD FOR ITS PREPARATION AND METHOD FOR PRODUCING SYNTHESIS GAS WITH ITS USE
CN110115995A (en) * 2018-02-05 2019-08-13 天津大学 A kind of iron sodium/molybdenum composite metal oxide catalyst and its preparation method and application
DE112020000187T5 (en) * 2019-07-31 2021-11-18 Shandong Nhu Amino Acid Co., Ltd. Catalyst for the production of acrylic acid or acrolein and its manufacturing process
CN112898163A (en) * 2019-12-03 2021-06-04 中国科学院大连化学物理研究所 Method for preparing 1, 6-hexamethylene diamine by ammoniation of hexamethylene imine
CN111004148A (en) * 2019-12-30 2020-04-14 河南省化工研究所有限责任公司 Method for preparing 6-aminocapronitrile by gas phase method
CN114289060A (en) * 2021-12-30 2022-04-08 美思德(吉林)新材料有限公司 Supported bimetallic catalyst and preparation method and application thereof
CN114917952A (en) * 2022-06-30 2022-08-19 中国天辰工程有限公司 Preparation method of intermediate catalyst for preparing hexamethylene diamine from caprolactam
CN115337959A (en) * 2022-10-18 2022-11-15 中国天辰工程有限公司 Catalyst for ammonifying caprolactam and preparation method and application thereof

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