CN115337959A - Catalyst for ammonifying caprolactam and preparation method and application thereof - Google Patents

Catalyst for ammonifying caprolactam and preparation method and application thereof Download PDF

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CN115337959A
CN115337959A CN202211269897.9A CN202211269897A CN115337959A CN 115337959 A CN115337959 A CN 115337959A CN 202211269897 A CN202211269897 A CN 202211269897A CN 115337959 A CN115337959 A CN 115337959A
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catalyst
caprolactam
metal oxide
molecular sieve
temperature
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CN115337959B (en
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杨琦武
庄大为
史文涛
王聪
霍瑜姝
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China Tianchen Engineering Corp
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China Tianchen Engineering Corp
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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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a catalyst for ammoniation of caprolactam, which comprises an active component loaded on a porous carrier; the active component is a composite metal oxide with the stoichiometric composition of M a N 1‑a Ox, 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; a is more than 0 and less than or equal to 0.8, and x is a value which enables the charge balance of the composite metal oxide. The catalyst of the invention is used at a weight hourly space velocity (calculated by caprolactam) of 1h ‑1 And 3h ‑1 Can still maintain high raw material under the conditionConversion and product selectivity; the catalyst has the advantages of simple and easily obtained raw materials and simple preparation process, and is suitable for the industrial production of aminocapronitrile by a gas phase method.

Description

Catalyst for ammonifying caprolactam and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic chemical industry, in particular to a catalyst for preparing 6-aminocapronitrile by ammoniation of caprolactam and a preparation method and application thereof.
Background
1,6-hexanediamine (hereinafter abbreviated as hexanediamine) is an important chemical intermediate, and the active functional group amino can be subjected to condensation reaction to prepare polymeric materials such as nylon, fiber, resin and the like, so that the industrial value is extremely high, and the demand of domestic markets for the hexanediamine is increased year by year. Currently, hexamethylenediamine is mainly prepared by hydrogenation of adiponitrile or 6-aminocapronitrile, and since adiponitrile is limited by monopoly of foreign enterprises, the production technology of caprolactam is improved, and the production process for preparing hexamethylenediamine by using caprolactam as a raw material is rapidly developed.
The method for preparing 6-aminocapronitrile (hereinafter referred to as aminocapronitrile) from caprolactam comprises a liquid phase method and a gas phase method, wherein the gas phase method has relatively simpler operation and higher raw material conversion rate, and is more suitable for industrial production. In the gas phase method, the performance of the catalyst directly influences the conversion rate of raw materials and the selectivity of products in the reaction, and the cost of the catalyst and the reaction space velocity are also considered in the continuous amplification industrial production. The reaction space velocity is divided into volume space velocity and weight hourly space velocity, and the unit is h -1 The catalyst is the raw material amount treated by the catalyst in unit volume or mass per unit time under specified conditions, and the reaction space velocity of the shift catalyst is an important index for measuring the process level.
The patent CN113413891A discloses a catalyst containing two pore canals for preparing aminocapronitrile by a caprolactam gas phase method, the technical proposal is that alkaline earth metal oxide, transition metal oxide, silicon dioxide and/or alumina powder are extruded and molded by kneading, the reaction temperature is more than 300 ℃, and the space velocity is 0.3 to 0.8h -1 Under the condition of (2), the conversion rate of raw materials is 89-90%, and the selectivity of products is 98-99%. CN111672526A is a caprolactam gas phase method for preparing aminocapronitrile catalyst by modifying one or more of calcium phosphate, magnesium phosphate, aluminum phosphate and calcium metaphosphate and then molding the modified carrier, wherein the catalyst is prepared at 395 ℃ and 3h space velocity -1 To achieveTo a reaction conversion of about 70% and a selectivity of about 92%. CN114832851A is used for loading at least one oxide on a catalyst matrix and modifying titanium oxide on the surface of the catalyst, and the obtained catalyst is used for 2.1h at 356 DEG C -1 The reaction at the airspeed obtains an initial conversion rate of 79.5-82.3% and an initial selectivity of 90.4-98.3%, and the reaction is carried out for 1000 hours to obtain a conversion rate of 71.2-80.2% and a selectivity of 93.5-99.5%. In the technical scheme of the patent, the reaction space velocity, the raw material conversion rate and the product selectivity of the used catalyst are not optimal at the same time, and the preparation process flow of the catalyst is complex.
Disclosure of Invention
Aiming at the defects in the prior art, the invention discloses a catalyst for ammonifying caprolactam, a preparation method and application thereof, wherein the catalyst has higher activity and is used at a weight hourly space velocity (calculated by caprolactam) of 1h -1 And 3h -1 The method keeps high raw material conversion rate and product selectivity under the condition, and is suitable for the industrial production of aminocapronitrile by a gas phase method.
In particular, in one aspect, the invention discloses a catalyst for ammonifying caprolactam, which comprises an active component supported on a porous carrier; the active component is a composite metal oxide with the stoichiometric composition of M a N 1-a O x 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; a is more than 0 and less than or equal to 0.8, and x is a value which enables the charge balance of the composite metal oxide.
In the above technical scheme, the active component of the catalyst of the present invention comprises 2 groups of metal oxides, i.e. M group metal oxide and N group metal oxide. From the viewpoint of reducing the preparation cost of the catalyst, the metal element types included in the M group and the N group are common metals. In addition, the inventor finds that the performance of the catalyst can be effectively improved by adopting the composite metal oxide as the active component of the caprolactam ammoniation catalyst, and for this purpose, the inventor selects the metal element oxide in the third period and the fourth period (M group) and the metal element oxide in the fifth period and the sixth period (N group) to be compounded as the active component of the catalyst.
In the above technical scheme, the subscript a of M represents the ratio of the sum of the moles of each metal element in the M group metal oxide to the sum of the moles of all metal elements in the active component of the catalyst, for example (as in example 5 in the specific embodiment), and if the M group metal elements in the active component of the catalyst include M1 and M2, the moles of which are a1 and a2, respectively, and the N group metal elements include N1 and N2, the moles of which are b1 and b2, respectively, then a = (a 1+ a 2)/(a 1+ a2+ b1+ b 2). It is to be noted that in the specific embodiment, the metal elements in the M group and the N group may include 1 or 2 of the metal elements in the group, and the value a may be calculated according to the actual situation by referring to the exemplified method.
In the above technical solution, the stoichiometric composition of the catalyst active component is set as M a N 1-a O x It is intended to show that the active component of the catalyst of the present invention is a composite metal oxide comprising two metal oxides. Wherein the subscript x of the O element is a value such that the composite metal oxide is charge-balanced.
One of ordinary skill in the art will appreciate that higher reaction space velocities allowed by the catalyst indicate higher catalyst activity and greater plant throughput, however, reaction space velocities cannot be increased indefinitely. In commercial production, 30% of the catalyst is used within an economically acceptable range without a decrease in catalyst activity, i.e., in other words, the catalyst stand-by factor is 3 times the amount required to ensure a substantially feasible process, both at a reaction space velocity of 1:3. Based on this, the inventors have verified in a specific embodiment that the catalysts of examples 1-5 are at a weight hourly space velocity (in caprolactam) of 1h -1 And 3h -1 Under the condition, the conversion rate of raw materials and the selectivity of products for preparing the aminocapronitrile by the gas phase method.
Further, the preferable range of a in the stoichiometric composition is 0.28 to 0.7, and more preferably 0.38 to 0.4.
Further, the mass ratio of the metal element to the porous carrier in the composite metal oxide is (0.01 to 0.8): 1, preferably 0.26 to 0.7.
It is noted that the Weight Hourly Space Velocity (WHSV) in the present invention is the weight of feed (liquid or gas)) per hour/weight of catalyst loading.
Further, the porous carrier is one of a molecular sieve, alumina or activated carbon, and is preferably a molecular sieve.
Further, the molecular sieve is preferably a configured molecular sieve or a modified molecular sieve; the configuration molecular sieve is preferably MFI, CHA and MEL configuration molecular sieve, and is further preferably ZSM-5, MCM-41, SAPO-34, TS-1 and TS-2; more preferably ZSM-5 (H type), TS-1, SAPO-34.
In particular, in another aspect, the invention discloses a preparation method of a catalyst for ammonifying caprolactam, which comprises the following steps: s1, selecting a metal oxide precursor to prepare a metal salt solution; s2, impregnating and loading the metal salt solution on a porous carrier; s3, drying, molding and heat treating the fully impregnated porous carrier to obtain the catalyst; the active component of the catalyst is a composite metal oxide, and comprises 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.
Further, the metal oxide precursor comprises nitrates, chlorides and sulfates of Mg, ca, co, fe, zn, ni, cu and Ce, and ammonium metavanadate, ammonium molybdate, sodium molybdate, zirconium sulfate and sodium stannate.
Further, the step S1 also comprises the step of adjusting the pH value of the metal salt solution to be 1~6 by using a pH adjusting agent; the pH regulator is hydrochloric acid or nitric acid.
Further, the temperature of the drying process is 60 to 120 ℃, and the temperature of the heat treatment process is 350 to 550 ℃; the heating rate of the drying procedure and the heat treatment procedure is 1-5 ℃/min, and the temperature is kept for 1-15h after the specified temperature is reached.
In particular, the invention discloses the application of the catalyst in the preparation of aminocapronitrile by using caprolactam as a raw material gas phase method.
Compared with the prior art, the invention has the beneficial effects that: 1. the catalyst of the invention is used for 1h at the weight hourly space velocity (calculated by caprolactam) -1 Under the condition of high raw material conversion rate and high product selectivity, and the weight hourly space velocity (calculated by caprolactam) is 3h -1 The conversion rate of raw materials and the product selectivity can be kept high under the condition, and the method is suitable for industrial production; 2. the metal elements selected by the method are common metal elements in the third to sixth periods, the raw materials are simple and easy to obtain, the preparation process flow is simple, the production cost of preparing the aminocapronitrile by the gas phase method can be greatly reduced, and the method is favorable for large-scale industrial production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is an electron microscope topography of caprolactam amination catalyst prepared in example 1;
FIG. 2 is an electron microscope topography of the caprolactam amination catalyst prepared in example 3;
fig. 3 is an electron microscope topography of the caprolactam amination catalyst prepared in the example 5.
Detailed Description
In order that the invention may be more fully understood, preferred embodiments of the invention will now be described. It should be understood that these examples are for illustrative purposes only and are not to be construed as limiting the invention in any way, i.e., not intended to limit the scope of the invention. Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, were all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The metal salt, the hydrochloric acid and the ammonia water adopted in the embodiment of the invention are all chemically pure; the adopted molecular sieves ZSM-5 (H type), TS-1 and SAPO-34 are produced by Tianjin Tianchen green energy and green energy engineering technology research and development Limited company.
Example 1
S1, weighing 18gMg (NO) 3 ) 2 、7gZnCl 2 、100gZr(SO 4 ) 2 ·4H 2 Adding O into 250ml of water, adjusting the pH to 1 by using a nitric acid solution, and stirring for dissolving to obtain a metal salt solution; s2, slowly pouring the solution obtained in the step S1 into a crucible filled with 80g of ZSM-5 (H-type) molecular sieve, slowly stirring and uniformly mixing, and standing for 1 hour; s3, directly putting the fully-impregnated molecular sieve obtained in the step S2 into an oven for drying without filtering, wherein the heating speed is 1 ℃/min, and the temperature is increased from room temperature to 80 ℃ for drying; after drying, transferring the product to a muffle furnace, raising the temperature from room temperature to 550 ℃ at a speed of 10 ℃/min, and keeping the temperature at 550 ℃ for 6 hours to obtain the catalyst cat-1, wherein the appearance image of the electron microscope is shown in figure 1.
Example 2
S1, weighing 47gCa (NO) 3 ) 2 ·4H 2 O、180gZr(SO 4 ) 2 ·4H 2 Adding O into 200ml of water, adjusting the pH to 1 by using a nitric acid solution, and stirring and dissolving to obtain a metal salt solution; s2, slowly pouring the solution obtained in the step S1 into a crucible filled with 90g of ZSM-5 (H-type) molecular sieve, slowly stirring and uniformly mixing, and standing for 1H; and S3, directly putting the fully-impregnated molecular sieve obtained in the step S2 into an oven for drying without filtering, wherein the heating speed is 1 ℃/min, and the temperature is increased from room temperature to 80 ℃ for drying. After drying, the mixture is transferred to a muffle furnace, the temperature rising speed is 10 ℃/min, the temperature rises from room temperature to 550 ℃, and the temperature is kept at 550 ℃ for 6 hours, so that the catalyst cat-2 is obtained.
Example 3
S1, weighing 18.8gCu (NO) 3 ) 2 ·3H 2 O，13.7gZnCl 2 ，58.9g(NH 4 ) 2 MoO 4 Adding the mixture into 150ml of water, adjusting the pH to 4 by using a nitric acid solution, and stirring and dissolving to obtain a metal salt solution; s2, slowly pouring the solution obtained in the step S1 into a crucible filled with 102g of SAPO-34 molecular sieve, slowly stirring and uniformly mixing, and standing for 1h; s3, directly putting the fully-impregnated molecular sieve obtained in the step S2 into an oven for drying without filtering, wherein the heating speed is 1 ℃/min, and the temperature is increased from room temperature to 80 ℃ for drying; after drying, the mixture is transferred to a muffle furnace, the temperature is raised to 550 ℃ from room temperature at the heating rate of 10 ℃/min, and the temperature is kept at 550 ℃ for 6 hours, so that the catalyst cat-3 is obtained, and the appearance of the electron microscope is shown as figure 2.
Example 4
S1, weighing 60gCa (NO) 3 ) 2 ·4H 2 O、30gMg(NO 3 ) 2 、30gCe(NO 3 ) 3 ·6H 2 O、14gNa 2 SnO 3 ·3H 2 Adding O into 200ml of water, adjusting the pH to 2 by using a nitric acid solution, and stirring for dissolving to obtain a metal salt solution; s2, slowly pouring the solution obtained in the step S1 into a crucible filled with 120g of SAPO-34 molecular sieve, slowly stirring and uniformly mixing, and standing for 1h; and S3, directly putting the fully-impregnated molecular sieve obtained in the step S2 into an oven for drying without filtering, wherein the heating speed is 1 ℃/min, and the temperature is increased from room temperature to 80 ℃ for drying. After drying, the mixture is transferred to a muffle furnace, the temperature is raised from room temperature to 550 ℃ at the speed of 10 ℃/min, and the temperature is kept at 550 ℃ for 6 hours to obtain the catalyst cat-4.
Example 5
S1, weighing 27g FeCl 3 ·6H 2 O、12gNH 4 VO 3 、39g(NH 4 ) 2 MoO 4 、85gZr(SO 4 ) 2 ·4H 2 Adding O into 200ml of water, adjusting the pH to 1 by using a nitric acid solution, and stirring for dissolving to obtain a metal salt solution; s2, slowly pouring the solution obtained in the step S1 into a crucible containing 81.5g of TS-1 molecular sieve, slowly stirring and uniformly mixing, and standing for 1h; and S3, directly putting the fully impregnated molecular sieve in the S2 into an oven, heating at the speed of 1 ℃/min, heating to 80 ℃ from room temperature, and drying. After drying, transferring the product to a muffle furnace, raising the temperature from room temperature to 550 ℃ at a speed of 10 ℃/min, and keeping the temperature at 550 ℃ for 6 hours to obtain the catalyst cat-5, wherein the appearance image of the electron microscope is shown in figure 3.
Test examples 1 to 10
To further verify the technical effect of the catalyst of the invention in the reaction for preparing aminocapronitrile by the gas phase process of caprolactam, the catalysts prepared in examples 1 to 5 were evaluated using a fixed bed reactor. Specifically, the weight hourly space velocity is 1h measured by caprolactam -1 The vapor phase aminocapronitrile preparation reaction was carried out under the conditions using the catalysts of examples 1 to 5, the results corresponding to test examples 1 to 5; at a weight hourly space velocity of 3h counted by caprolactam -1 The vapor phase aminocapronitrile preparation was carried out using the catalysts of examples 1 to 5 under the conditions,the results correspond to test examples 6 to 10.
Specifically, raw material caprolactam is fed by a pump with a heating pump head, the loading amount of the catalyst is 60g, the feeding amount of the caprolactam is 1.0g/min, and the weight hourly space velocity is 1h -1 (or caprolactam feed 3.0g/min, weight hourly space velocity 3h -1 ) And controlling the feeding amount of ammonia gas through a mass flow meter so that the feeding mass ratio of the ammonia gas to caprolactam is 1.9.
The ammonia gas is preheated to 350 ℃ by two preheaters and then mixed with caprolactam, and the mixture is reacted by a fixed bed, wherein the temperature of a bed layer is controlled to be 350 ℃ by heat conducting oil, and the reaction pressure is 0.01MPa (G).
And collecting liquid products through a cooler and a gas-liquid separator after reaction. Performing quantitative analysis by adopting gas chromatography and an area normalization method, and calculating the conversion rate of caprolactam raw materials and the product selectivity; the feedstock conversion and product selectivity were averaged for the evaluation results.
Wherein, the conversion rate of raw materials is = (1-caprolactam content in reaction liquid) multiplied by 100 percent, the product selectivity is = reaction liquid amino capronitrile content/(1-caprolactam content in reaction liquid) multiplied by 100 percent,
the relevant parameter settings and results of test examples 1-10 are shown in table 1.
Watch (A)
Figure DEST_PATH_IMAGE002
Serial number Catalyst and process for preparing same a value WHSV/h -1 Conversion of feedstock Product selectivity Catalyst life/h
Test example 1 cat-1 0.38 1 95.8% 97.3% >1500
Test example 2 cat-2 0.28 1 93.2% 98.5% >1500
Test example 3 cat-3 0.4 1 96.3% 96.2% >1500
Test example 4 cat-4 0.79 1 94.5% 98.3% >1500
Test example 5 cat-5 0.29 1 89.4% 96.5% >1500
Test example 6 cat-1 0.38 3 94.4% 98.8% ＞400h
Test example 7 cat-2 0.28 3 91.6% 98.7% ＞400h
Test example 8 cat-3 0.4 3 95.5% 97.0% ＞400h
Test example 9 cat-4 0.79 3 94.3% 98.9% ＞400h
Test example 10 cat-5 0.29 3 83.0%. 96.1% ＞400h
The combination of test examples 1-5 proves that the catalyst provided by the invention is used for preparing aminocapronitrile by a gas phase method, and the weight hourly space velocity is 1h by using caprolactam -1 Under the condition, the raw material conversion rate of caprolactam is 89.4-96.3%, the product selectivity is 96.2-98.5%, and the service life of the catalyst is longer than 1500h; in combination with test examples 6 to 10, it was possible to establish a weight hourly space velocity in caprolactam of 3h -1 Under the condition, the conversion rate of the raw materials of caprolactam is 83-95.5%, the selectivity of the product is 96.1-98.9%, and the service life of the catalyst is longer than 400h. The caprolactam ammoniation catalyst which takes the composite metal oxide as the active component and is provided by the invention can be verified by combining with the test examples 1-10 at the weight hourly space velocity of 1h -1 And 3h -1 Better raw material conversion rate and product selectivity are obtained, the catalyst has longer service life and stable performance, and the method is suitable for the industrial production of aminocapronitrile by a gas phase method.
In addition, the combination of test examples 1-10 demonstrates that the catalyst performs better when the value of a is 0.38 to 0.4, specifically, the space velocity is 1h when the weight is calculated by caprolactam -1 Under the condition, the conversion rate of raw materials is 95.8-96.3%, the selectivity of products is 96.2-97.3%, and when the weight hourly space velocity of the catalyst is increased to 3h -1 Under the condition, the conversion rate of the raw materials can still be kept to be 95.5-94.4%, and the selectivity of the product can still be kept to be 97-98.8%. Thus, the invention provides a catalyst of stoichiometric composition M a N 1-a O x In the above, a is 0 < a.ltoreq.0.8, preferably 0.29 to 0.79, and more preferably 0.38 to 0.4.
It should be noted that the above-mentioned contents are further detailed descriptions of the present invention in conjunction with the specific embodiments, and it should not be construed that the specific embodiments of the present invention are limited to these descriptions; the size data of this embodiment does not limit the technical solution, but only shows one specific working condition. It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit of the invention.

Claims (10)

1. A catalyst for ammoniation of caprolactam is characterized by comprising an active component supported on a porous carrier; the active component is a composite metal oxide with the stoichiometric composition of M a N 1-a O x 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; a is more than 0 and less than or equal to 0.8, and x is a value which enables the charge balance of the composite metal oxide.
2. Catalyst for the ammonification of caprolactam according to claim 1, wherein a in the stoichiometric composition has a value in the range of 0.28 to 0.79.
3. The catalyst for ammonifying caprolactam according to claim 1, wherein 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. catalyst for the ammonification of caprolactam according to claim 1, wherein the porous support is one of molecular sieve, alumina or activated carbon.
5. Catalyst for amination of caprolactam according to claim 4, characterized in that said molecular sieve is a configured molecular sieve or a modified molecular sieve.
6. A preparation method of a catalyst for ammonifying caprolactam is characterized by comprising the following steps: s1, selecting a metal oxide precursor to prepare a metal salt solution; s2, impregnating and loading the metal salt solution on a porous carrier; s3, drying, forming and heat treating the fully impregnated porous carrier to obtain the catalyst; the active component of the catalyst is a composite metal oxide, which comprises 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. The method for preparing a catalyst for ammonification of caprolactam of claim 6, wherein the metal oxide precursor comprises nitrate, chloride, sulfate of Mg, ca, co, fe, zn, ni, cu, ce, ammonium metavanadate, ammonium molybdate, sodium molybdate, zirconium sulfate, sodium stannate.
8. The method for preparing a catalyst used in the amination of caprolactam according to claim 6, wherein the step S1 further comprises adjusting the pH value of the metal salt solution to 1~6 by using a pH adjusting agent; the pH regulator is hydrochloric acid or nitric acid.
9. The method for preparing a catalyst for ammonification of caprolactam according to claim 6, wherein the temperature of the drying process is 60 to 120 ℃, and the temperature of the heat treatment process is 350 to 550 ℃; the heating rate of the drying procedure and the heat treatment procedure is 1-5 ℃/min, and the temperature is kept for 1-15h after the specified temperature is reached.
10. Use of a catalyst according to any one of claims 1 to 5 for the preparation of aminocapronitrile by ammoniation of caprolactam.
CN202211269897.9A 2022-10-18 2022-10-18 Catalyst for ammonifying caprolactam and preparation method and application thereof Active CN115337959B (en)

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PCT/CN2023/123152 WO2024082962A1 (en) 2022-10-18 2023-10-07 Catalyst for caprolactam ammoniation, and preparation method therefor and use thereof

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