CN115591551A - Catalyst in continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam and preparation method and application thereof - Google Patents

Catalyst in continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam and preparation method and application thereof Download PDF

Info

Publication number
CN115591551A
CN115591551A CN202211212437.2A CN202211212437A CN115591551A CN 115591551 A CN115591551 A CN 115591551A CN 202211212437 A CN202211212437 A CN 202211212437A CN 115591551 A CN115591551 A CN 115591551A
Authority
CN
China
Prior art keywords
catalyst
caprolactam
roasting
cyanoethyl
beta
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202211212437.2A
Other languages
Chinese (zh)
Other versions
CN115591551B (en
Inventor
陈兴坤
王雪鹏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Normal University CJNU
Original Assignee
Zhejiang Normal University CJNU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Normal University CJNU filed Critical Zhejiang Normal University CJNU
Priority to CN202211212437.2A priority Critical patent/CN115591551B/en
Publication of CN115591551A publication Critical patent/CN115591551A/en
Application granted granted Critical
Publication of CN115591551B publication Critical patent/CN115591551B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
    • C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D223/08—Oxygen atoms
    • C07D223/10—Oxygen atoms attached in position 2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a catalyst in a continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam, which comprises an active component, an auxiliary agent component and a carrier, wherein the active component is Ni, the auxiliary agent component is Co, fe or Cu, and the carrier is silicon oxide; the active component accounts for 5 to 50 percent of the mass of the Ni simple substance; the auxiliary agent component accounts for 0.3-10% of the mass of the Co, fe or Cu simple substance; the balance is carrier. The invention also discloses a preparation method and application thereof. The Ni-based catalyst system with an eggshell structure prepared by a hydrothermal template and coordination adsorption two-step method enables the N- (beta-cyanoethyl) -epsilon-caprolactam continuous flow hydrogenation to achieve 100% conversion rate, more than or equal to 98% selectivity and more than or equal to 300 hours stability in a micro packed bed reactor under mild reaction conditions (80 ℃,3.0 MPa).

Description

Catalyst in continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam and preparation method and application thereof
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a catalyst in a continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam, and a preparation method and application thereof.
Background
DBU has the chemical name of 1, 5-diazabicyclo [5,4,0] -5-undecene, is an amidine with a bicyclic structure, is colorless or light yellow oily liquid, is a strong organic base reagent, and is widely applied to the synthetic reaction of chemical products such as medicines, spices and the like. According to different purposes, DBU can be a catalyst, an epoxy resin hardener, an antirust agent, a cross-linking agent, a protective agent, an initiator, a curing accelerator and an absorbent, and can be used for preparing a high corrosion inhibitor; can also participate in elimination, condensation, dehydrohalogenation, desulfonation, isomerization, cyclization, esterification, polymerization and other reactions. In China, the demand of each industry for DBU is as high as more than 1000 tons every year, but the price is very high. With the rapid development of economy in China, the problems of environmental protection, health and safety are increasingly emphasized, and the demand of DBU is further improved.
Figure BDA0003872003330000011
DBU is generally synthesized by the addition of caprolactam to acrylonitrile to form N- (. Beta. -cyanoethyl) -epsilon-caprolactam, followed by catalytic hydrogenation to form N- (3-aminopropyl) caprolactam, and finally dehydration and cyclization. If the hydrogenation conversion rate of the second step can be improved, more final products can be produced, the utilization rate of raw materials is greatly improved, and the production cost is reduced. Therefore, the hydrogenation of N- (. Beta. -cyanoethyl) -epsilon-caprolactam is particularly important in the overall process. In order to increase the hydrogenation yield of N- (. Beta. -cyanoethyl) -epsilon-caprolactam, researchers have conducted a number of experiments to achieve a hydrogenation yield of 70% by improving the performance of the catalyst (Arkivoc, 2008 (12): 95-102). In patent CN200810016369.6, raney nickel is used as a catalyst, and a reaction kettle process is used to catalyze hydrogenation of N- (beta-cyanoethyl) -epsilon-caprolactam, but the catalyst is not recycled. In patent CN200310115849.5, self-made Raney nickel is used as catalyst, and the selectivity of hydrogenation product can reach 95% under the optimum reaction condition. Although currently raney nickel is used as a catalyst, the catalytic hydrogenation of N- (beta-cyanoethyl) -epsilon-caprolactam can be realized by using a reaction kettle as a reactor. However, the raney nickel catalyst is easy to pulverize in the reaction process of the reaction kettle, and the pulverized raney nickel catalyst is not easy to recover in the reaction kettle, so that the product is difficult to purify; secondly, the pyrophoric nature of raney nickel catalysts in air poses a very serious risk to industrial production. From the perspective of production safety and production cost reduction, a new hydrogenation catalyst is needed to realize the catalysis of N- (beta-cyanoethyl) -epsilon-caprolactam hydrogenation, so that the high-efficiency synthesis of DBU is ensured.
The reports on N- (beta-cyanoethyl) -epsilon-caprolactam hydrogenation catalysts in the DBU synthesis process so far mainly relate to the adoption of a Raney nickel catalyst system and a reaction kettle process. In combination with the problems of severe catalyst loss, high production cost, difficult product separation of the catalyst, low reaction production efficiency of a reaction kettle and the like in the current production process, the development of a catalyst with low cost, high activity, high selectivity and good stability for continuous flow hydrogenation of N- (beta-cyanoethyl) -epsilon-caprolactam is still needed in the DBU synthesis field.
Disclosure of Invention
The invention aims to provide a catalyst in a continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam, a preparation method and application thereof, so as to solve the defects of the prior art.
The invention adopts the following technical scheme:
a catalyst in the continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam comprises an active component, an auxiliary agent component and a carrier, wherein the active component is Ni, the auxiliary agent component is Co, fe or Cu, and the carrier is silicon oxide; the active component accounts for 5 to 50 percent of the mass of the Ni simple substance; the auxiliary agent component accounts for 0.3-10% of the mass of the Co, fe or Cu simple substance; the rest is a carrier;
the catalyst is prepared by the following steps:
(I) Dissolving the ethylene oxide-propylene oxide-ethylene oxide triblock copolymer in ethanol, and stirring for 2-6h;
(II) dropwise adding an HCl solution into the solution prepared in the step (I), and stirring for 2-6h at 30-50 ℃;
(III) adding polystyrene spheres into the mixed material prepared in the step (II), and stirring for 3-8h;
(IV) dropwise adding ethyl orthosilicate into the mixture prepared in the step (III), and stirring for 24-48h at 30-50 ℃;
(V) transferring the mixture prepared in the step (IV) to a hydrothermal reaction kettle, heating to 80-100 ℃, reacting for 96-180h, cooling to room temperature, filtering, washing the solid with deionized water for 3-5 times, and drying at 100-120 ℃ for 5-12h; roasting in a muffle furnace at 350 ℃ for 0.5-5h, roasting at 500-650 ℃ for 3-8h to obtain hollow SiO with microstructure 2 A ball;
(VI) dissolving soluble nickel salt and ammonia water in deionized water, and adding the hollow SiO prepared in the step (V) 2 Reacting the spheres in a hydrothermal reaction kettle at 140-180 ℃ for 8-12h, cooling to room temperature, filtering, washing the solid with deionized water for 3-5 times, and drying at 100-120 ℃ for 5-12h; roasting in a muffle furnace at 500-650 ℃ for 3-8h to obtain Ni/SiO 2 A sample;
(VII) dissolving soluble auxiliary agent metal salt and 1, 3-propane diamine in deionized water, and adding the Ni/SiO prepared in the step (VI) 2 Stirring the sample at 30-50 ℃ for reaction for 5-20h, filtering, washing the solid with deionized water for 3-5 times, and drying at 100-120 ℃ for 5-12h; roasting in a muffle furnace at 500-650 ℃ for 3-8h to obtain M-Ni/SiO 2 Catalyst, M is Co, fe or Cu.
Further, the concentration of the ethylene oxide-propylene oxide-ethylene oxide triblock copolymer in the step (I) is 0.1 to 10g/ml; in the step (II), the concentration of the HCl solution is 1-3M; in the step (III), the particle size of the polystyrene spheres is 100nm-5 mu m.
Further, the soluble nickel salt in the step (VI) is one or more of nickel nitrate, nickel acetate, nickel chloride and nickel acetylacetonate; in the step (VII), the soluble assistant metal salt is one or more of cobalt nitrate, cobalt sulfate, cobalt acetate and cobalt chloride, or one or more of copper nitrate, copper acetate and copper chloride, or one or more of ferric nitrate, ferrous nitrate, ferric acetate, ferric chloride and ferrous chloride.
Further, the rotation speed of stirring in the steps (I), (II), (III), (IV) and (VII) is 200-800r/min; the roasting temperature rise rate in the roasting in the steps (V), (VI) and (VII) is 0.5-2 ℃/min.
A method for preparing a catalyst in a continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam comprises the following steps:
(I) Dissolving the ethylene oxide-propylene oxide-ethylene oxide triblock copolymer in ethanol, and stirring for 2-6h;
(II) dropwise adding an HCl solution into the solution prepared in the step (I), and stirring for 2-6h at 30-50 ℃;
(III) adding polystyrene spheres into the mixed material prepared in the step (II), and stirring for 3-8h;
(IV) dropwise adding ethyl orthosilicate into the mixture prepared in the step (III), and stirring for 24-48h at 30-50 ℃;
(V) transferring the mixture prepared in the step (IV) to a hydrothermal reaction kettle, heating to 80-100 ℃, reacting for 96-180h, cooling to room temperature, filtering, washing the solid with deionized water for 3-5 times, and drying at 100-120 ℃ for 5-12h; roasting in a muffle furnace at 350 ℃ for 0.5-5h, roasting at 500-650 ℃ for 3-8h to obtain hollow SiO with microstructure 2 A ball;
(VI) dissolving soluble nickel salt and ammonia water in deionized water, and adding the hollow SiO prepared in the step (V) 2 Reacting the spheres in a hydrothermal reaction kettle at 140-180 ℃ for 8-12h, cooling to room temperature, filtering, washing the solid with deionized water for 3-5 times, and drying at 100-120 ℃ for 5-12h; roasting in a muffle furnace at 500-650 ℃ for 3-8h to obtain Ni/SiO 2 A sample;
(VII) dissolving soluble auxiliary agent metal salt and 1, 3-propane diamine in deionized water, and adding the Ni/SiO prepared in the step (VI) 2 Stirring and reacting a sample at 30-50 ℃ for 5-20h, filtering, washing the solid with deionized water for 3-5 times, and drying at 100-120 ℃ for 5-12h; roasting in a muffle furnace at 500-650 ℃ for 3-8h to obtain M-Ni/SiO 2 Catalyst, M is Co, fe or Cu;
the catalyst comprises an active component, an auxiliary agent component and a carrier, wherein the active component is Ni, the auxiliary agent component is Co, fe or Cu, and the carrier is silicon oxide; the active component accounts for 5-50% of the mass of the Ni simple substance; the auxiliary agent component accounts for 0.3-10% of the mass of the Co, fe or Cu simple substance; the balance being carriers.
Further, the concentration of the ethylene oxide-propylene oxide-ethylene oxide triblock copolymer in the step (I) is 0.1 to 10g/ml; in the step (II), the concentration of the HCl solution is 1-3M; in the step (III), the particle size of the polystyrene spheres is 100nm-5 mu m.
Further, the soluble nickel salt in the step (VI) is one or more of nickel nitrate, nickel acetate, nickel chloride and nickel acetylacetonate; in the step (VII), the soluble assistant metal salt is one or more of cobalt nitrate, cobalt sulfate, cobalt acetate and cobalt chloride, or one or more of copper nitrate, copper acetate and copper chloride, or one or more of ferric nitrate, ferrous nitrate, ferric acetate, ferric chloride and ferrous chloride.
Further, the rotation speed of stirring in the steps (I), (II), (III), (IV) and (VII) is 200-800r/min; the roasting temperature rise rate in the roasting in the steps (V), (VI) and (VII) is 0.5-2 ℃/min.
The application of the catalyst in the continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam comprises the following steps: firstly, filling a catalyst into a micro packed bed reactor, and activating the catalyst in hydrogen or hydrogen inert gas mixed gas before use under the following activation conditions: the pressure is 0.05-1.0MPa, and the space velocity of hydrogen gas is 5-500h -1 The activation temperature is 400-750 ℃, the roasting temperature rise rate is 0.5-20 ℃/min, and the activation time is 0.5-96h; after activation, adjusting the system to a specified reaction condition, pumping a mixture of N- (beta-cyanoethyl) -epsilon-caprolactam and a solvent, wherein the reaction condition is as follows: the temperature is 30-150 ℃, the pressure is 0.5-8.0MPa, and the hourly space velocity of the N- (beta-cyanoethyl) -epsilon-caprolactam liquid is 0.01-5.0h -1 The space velocity of hydrogen is 10-5000h -1 。
Furthermore, the solvent in the reaction system is one or more of m-xylene, toluene and p-xylene.
The invention has the beneficial effects that:
1. the catalyst is a supported heterogeneous catalyst which has a microscopic eggshell structure and in which an active component and an auxiliary agent component are highly dispersed in an eggshell layer, and the preparation method of the catalyst uniformly supports the active component on the surface of the prepared eggshell type silicon oxide by a two-step method in sequence, and firstly utilizes an ammonia-assisted hydrothermal reaction method to support the active component on the surface of the prepared eggshell type silicon oxideNi, so that the active component Ni is highly dispersed in the shell layer part of the microscopic eggshell type silicon oxide carrier, is uniformly distributed and has strong acting force with the carrier; followed by a first step of an eggshell structure of Ni/SiO 2 On the basis of the sample, the organic amine assisted adsorption method of the second step is utilized to ensure that the auxiliary agent component is subjected to Ni/SiO reaction in the first step 2 And adsorbing the shell layer on the surface of the sample to ensure that the auxiliary agent component and the active component Ni form closely contacted microstructure shell layer distribution on the surface of the catalyst, and the active component and the auxiliary agent component form a typical eggshell structure on the surface of the catalyst. The hollow eggshell structure in the microstructure not only improves the hydrogen storage capacity of the microscopic cavity of the catalyst, is beneficial to the dissociation and transfer of hydrogen and the improvement of catalytic hydrogenation performance, but also facilitates the release of heat energy generated in the hydrogenation process by the space of the eggshell structure, and improves the catalytic hydrogenation performance to prevent coking. The high-performance site is Ni modified by an auxiliary component M (Co, fe or Cu) which is highly dispersed on an eggshell structure, the active component of the catalyst has high dispersibility, and the auxiliary component and the active component are tightly combined to enhance the electron conduction effect and improve the hydrogenation capacity. The distribution of the active components of the catalyst in an eggshell structure is beneficial to the adsorption and desorption of raw material molecules, reduces the inactivation caused by the close combination of the raw material molecules and the active components, and obviously improves the catalytic hydrogenation stability.
2. The Ni-based catalyst system with an eggshell structure, which is prepared by a hydrothermal template and a coordination adsorption two-step method, is used in the continuous flow hydrogenation reaction process of N- (beta-cyanoethyl) -epsilon-caprolactam for the first time, and has excellent catalytic hydrogenation performance: the continuous flow hydrogenation of N- (beta-cyanoethyl) -epsilon-caprolactam in a micro packed bed reactor can obtain 100 percent of single-pass conversion rate, selectivity of more than or equal to 98 percent and stability of more than or equal to 300 hours under a milder reaction condition (80 ℃,3.0 MPa).
3. The catalyst provided by the invention has the advantages of simple preparation steps, low cost, greenness, no pollution, high utilization rate of active components, good preparation repeatability, simple separation of the catalyst and a product by combining with a continuous flow micro packed bed reactor, simple production process, high product purity and great reduction of production cost.
Drawings
FIG. 1 is a schematic diagram of a catalyst preparation process according to the present invention.
FIG. 2 is a physisorption drawing of the catalyst prepared in example 1.
FIG. 3 is a chromatogram of the reaction product of example 1.
FIG. 4 is a graph of stability test data for the catalyst of example 1.
Detailed Description
The invention is explained in more detail below with reference to exemplary embodiments and the accompanying drawings. The following examples are provided only for illustrating the present invention and are not intended to limit the scope of the present invention.
A catalyst in the continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam comprises an active component, an auxiliary agent component and a carrier, wherein the active component is Ni, the auxiliary agent component is Co, fe or Cu, and the carrier is silicon oxide; the active component accounts for 5-50% of the mass of the Ni simple substance; the auxiliary agent component, by the mass of Co, fe or Cu simple substance, the content is 0.3-10%; the rest is a carrier;
as shown in fig. 1, the catalyst is prepared by the following steps:
(I) Dissolving ethylene oxide-propylene oxide-ethylene oxide triblock copolymer in ethanol, wherein the concentration of the ethylene oxide-propylene oxide-ethylene oxide triblock copolymer is 0.1-10g/ml, and stirring at 200-800r/min for 2-6h;
(II) dropwise adding an HCl solution into the solution prepared in the step (I), and stirring for 2-6h at the temperature of 30-50 ℃ at the speed of 200-800r/min; wherein the concentration of the HCl solution is 1-3M;
(III) adding polystyrene spheres into the mixed material prepared in the step (II), and stirring for 3-8h at 200-800r/min; wherein the particle size of the polystyrene spheres is 100nm-5 mu m;
(IV) dropwise adding tetraethoxysilane into the mixture prepared in the step (III), and stirring for 24-48h at the temperature of 30-50 ℃ at 200-800r/min;
(V) transferring the mixture prepared in the step (IV) to a hydrothermal reaction kettle, heating to 80-100 ℃, reacting for 96-180h, cooling to room temperature, filtering, washing the solid with deionized water for 3-5 times, and drying at 100-120 ℃ for 5-12h; roasting in a muffle furnace at 350 deg.C for 0.5-5h with a roasting temperature rise rate of 0.5-2 deg.C/min and at 500-650 deg.C for 3-8h,the roasting temperature rise rate is 0.5-2 ℃/min, and the SiO with a hollow microstructure is obtained 2 A ball;
(VI) dissolving soluble nickel salt and ammonia water in deionized water, and adding the hollow SiO prepared in the step (V) 2 Reacting the spheres in a hydrothermal reaction kettle at 140-180 ℃ for 8-12h, cooling to room temperature, filtering, washing the solid with deionized water for 3-5 times, and drying at 100-120 ℃ for 5-12h; roasting in a muffle furnace at 500-650 deg.C for 3-8h at a heating rate of 0.5-2 deg.C/min to obtain Ni/SiO 2 A sample; wherein the soluble nickel salt is one or more of nickel nitrate, nickel acetate, nickel chloride and nickel acetylacetonate;
(VII) dissolving soluble auxiliary agent metal salt and 1, 3-propane diamine in deionized water, and adding the Ni/SiO prepared in the step (VI) 2 Stirring and reacting a sample at the temperature of 30-50 ℃ for 5-20h at the speed of 200-800r/min, filtering, washing the solid with deionized water for 3-5 times, and drying at the temperature of 100-120 ℃ for 5-12h; roasting in a muffle furnace at 500-650 deg.C for 3-8h at a heating rate of 0.5-2 deg.C/min to obtain M-Ni/SiO 2 Catalyst, M is Co, fe or Cu; wherein the soluble assistant metal salt is one or more of cobalt nitrate, cobalt sulfate, cobalt acetate and cobalt chloride, or one or more of copper nitrate, copper acetate and copper chloride, or one or more of ferric nitrate, ferrous nitrate, ferric acetate, ferric chloride and ferrous chloride.
The application of the catalyst in the continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam comprises the following steps: firstly, filling a catalyst into a micro packed bed reactor, and activating the catalyst in hydrogen or hydrogen inert gas mixed gas before use under the following activation conditions: the pressure is 0.05-1.0MPa, and the space velocity of hydrogen gas is 5-500h -1 The activation temperature is 400-750 ℃, the roasting temperature rise rate is 0.5-20 ℃/min, and the activation time is 0.5-96h; after activation, adjusting the system to a specified reaction condition, pumping a mixture of N- (beta-cyanoethyl) -epsilon-caprolactam and a solvent, wherein the solvent is one or more of m-xylene, toluene and p-xylene, and the reaction condition is as follows: the temperature is 30-150 ℃, the pressure is 0.5-8.0MPa, and the hourly space velocity of the N- (beta-cyanoethyl) -epsilon-caprolactam liquid is 0.01-5.0h -1 The space velocity of hydrogen is 10-5000h -1 。
Example 1
Dissolving 3.0g of ethylene oxide-propylene oxide-ethylene oxide triblock copolymer in 30ml of ethanol, and stirring for 2 hours at the speed of 500 r/min; dropwise adding 7ml of 2M HCl solution into the prepared solution, and stirring at 35 deg.C for 3h at 500 r/min; adding 4.0g polystyrene spheres (particle size of 500 nm) into the above mixture, and stirring at 500r/min for 3h; 7ml of ethyl orthosilicate is added into the mixture prepared above in a dropwise manner, and the mixture is stirred for 48 hours at the temperature of 35 ℃ at the speed of 500 r/min; transferring the prepared mixture into a hydrothermal reaction kettle, heating to 80 ℃, reacting for 120h, cooling to room temperature, filtering, washing the solid with deionized water for 3 times, and drying at 120 ℃ for 10h; roasting at 350 deg.C for 1h in muffle furnace at 1 deg.C/min for 5h at 550 deg.C to obtain hollow SiO with microstructure of 1 deg.C/min 2 A ball;
2g of nickel nitrate and 5ml of an aqueous ammonia solution (25-28%) were dissolved in 20ml of deionized water, and 3g of the hollow SiO prepared as described above were added 2 The ball is put in a hydrothermal reaction kettle to react for 12 hours at 160 ℃; cooling to room temperature, filtering, washing the solid with deionized water for 3 times, and drying at 120 ℃ for 10h; roasting at 550 ℃ for 5h in a muffle furnace at the roasting temperature rise rate of 1 ℃/min to obtain Ni/SiO 2 A sample; 0.1g of cobalt nitrate and 2.0ml of propane diamine are dissolved in 20ml of deionized water, and 3.0g of Ni/SiO are added 2 Stirring and reacting a sample at 40 ℃ for 5h at 500r/min, filtering, washing the solid with deionized water for 5 times, and drying at 120 ℃ for 5h; roasting at 550 ℃ for 5h in a muffle furnace at the roasting heating rate of 1 ℃/min to obtain 1-Co-Ni/SiO 2 A catalyst. The physical adsorption diagram of the catalyst is shown in figure 2.
Firstly, 1-Co-Ni/SiO 2 The catalyst is filled in a micro packed bed reactor, and is activated in hydrogen before use, and the activation conditions are as follows: the pressure is 0.2MPa, and the space velocity of hydrogen gas is 300h -1 The activation temperature is 600 ℃, the roasting temperature rise rate is 1 ℃/min, and the activation time is 8h; after the activation was completed, the system was adjusted to the specified reaction conditions, and 20wt% of N- (. Beta. -cyanoethyl) - ε -caprolactam xylene solution was pumped in, and the reaction conditions were: the temperature is 80 ℃, the pressure is 3.0MPa, the hourly space velocity of the N- (beta-cyanoethyl) -epsilon-caprolactam liquid is 0.5h -1 The space velocity of hydrogen is 300h -1 . The chromatogram of the reaction product is shown in FIG. 3, the conversion of N- (. Beta. -cyanoethyl) - ε -caprolactam is 100%, the target product: the selectivity to N- (3-aminopropyl) caprolactam was 99.0%.
Example 2
Dissolving 3.0g of ethylene oxide-propylene oxide-ethylene oxide triblock copolymer in 30ml of ethanol, and stirring for 2 hours at a speed of 500 r/min; dropwise adding 7ml of 2M HCl solution into the prepared solution, and stirring at 35 deg.C for 3h at 500 r/min; adding 4.0g polystyrene spheres (with particle size of 500 nm) into the above mixture, and stirring at 500r/min for 3 hr; 7ml of ethyl orthosilicate is added into the mixture prepared above in a dropwise manner, and the mixture is stirred for 48 hours at the temperature of 35 ℃ at the speed of 500 r/min; transferring the prepared mixture to a hydrothermal reaction kettle, heating to 80 ℃, reacting for 120h, cooling to room temperature, filtering, washing the solid with deionized water for 3 times, and drying at 120 ℃ for 10h; roasting at 350 deg.C for 1h in muffle furnace at a heating rate of 1 deg.C/min and 550 deg.C for 5h to obtain SiO with hollow microstructure 2 A ball;
2g of nickel nitrate and 5ml of an aqueous ammonia solution (25-28%) were dissolved in 20ml of deionized water, and 3g of the hollow SiO prepared as described above were added 2 The ball is put in a hydrothermal reaction kettle to react for 12 hours at 160 ℃; cooling to room temperature, filtering, washing the solid with deionized water for 3 times, and drying at 120 ℃ for 10h; roasting at 550 ℃ for 5h in a muffle furnace at the roasting temperature rise rate of 1 ℃/min to obtain Ni/SiO 2 A sample; 0.05g of cobalt nitrate and 2.0ml of propane diamine are dissolved in 20ml of deionized water, and 3.0g of Ni/SiO are added 2 Stirring and reacting a sample at 40 ℃ for 5h at 500r/min, filtering, washing the solid with deionized water for 5 times, and drying at 120 ℃ for 5h; roasting at 550 ℃ for 5h in a muffle furnace at the roasting temperature rise rate of 1 ℃/min to obtain 2-Co-Ni/SiO 2 A catalyst.
Firstly, 2-Co-Ni/SiO 2 The catalyst is filled in a micro packed bed reactor, and is activated in hydrogen before use, and the activation conditions are as follows: the pressure is 0.2MPa, and the space velocity of hydrogen gas is 300h -1 The activation temperature is 600 ℃, the roasting temperature rise rate is 1 ℃/min, and the activation time is 8h; after the activation, the system was adjusted to the specified reaction conditions, and 20wt% was pumped inThe reaction conditions are as follows: the temperature is 80 ℃, the pressure is 3.0MPa, the hourly space velocity of the N- (beta-cyanoethyl) -epsilon-caprolactam liquid is 0.5h -1 The space velocity of hydrogen is 300h -1 . The conversion of N- (. Beta. -cyanoethyl) -epsilon-caprolactam is 100%, the target product: the selectivity to N- (3-aminopropyl) caprolactam was 98.3%.
Example 3
Dissolving 3.0g of ethylene oxide-propylene oxide-ethylene oxide triblock copolymer in 30ml of ethanol, and stirring for 2 hours at a speed of 500 r/min; dropwise adding 7ml of 2M HCl solution into the prepared solution, and stirring at 35 deg.C for 3h at 500 r/min; adding 4.0g polystyrene spheres (particle size of 500 nm) into the above mixture, and stirring at 500r/min for 3h; 7ml of ethyl orthosilicate is added into the mixture prepared above in a dropwise manner, and the mixture is stirred for 48 hours at the temperature of 35 ℃ at the speed of 500 r/min; transferring the prepared mixture to a hydrothermal reaction kettle, heating to 80 ℃, reacting for 120h, cooling to room temperature, filtering, washing the solid with deionized water for 3 times, and drying at 120 ℃ for 10h; roasting at 350 deg.C for 1h in muffle furnace at 1 deg.C/min for 5h at 550 deg.C to obtain hollow SiO with microstructure of 1 deg.C/min 2 A ball;
2g of nickel nitrate and 5ml of ammonia solution (25-28%) are dissolved in 20ml of deionized water, and 3g of the hollow SiO prepared as described above are added 2 The ball is put in a hydrothermal reaction kettle to react for 12 hours at 160 ℃; cooling to room temperature, filtering, washing the solid with deionized water for 3 times, and drying at 120 ℃ for 10h; roasting at 550 ℃ for 5h in a muffle furnace at the roasting temperature rise rate of 1 ℃/min to obtain Ni/SiO 2 A sample; 0.1g of copper nitrate and 2.0ml of propane diamine are dissolved in 20ml of deionized water, and 3.0g of Ni/SiO are added 2 Stirring and reacting a sample at 40 ℃ for 5h at 500r/min, filtering, washing the solid with deionized water for 5 times, and drying at 120 ℃ for 5h; roasting at 550 ℃ for 5h in a muffle furnace at the roasting heating rate of 1 ℃/min to obtain 3-Cu-Ni/SiO 2 A catalyst.
Firstly, 3-Cu-Ni/SiO 2 The catalyst is filled in a micro packed bed reactor, and is activated in hydrogen before use under the following activation conditions: the pressure is 0.2MPa, and the space velocity of hydrogen gas is 300h -1 The activation temperature is 550 ℃, the roasting temperature rise rate is 1 ℃/min, and the activation time is 8h; end of activationThereafter, the system was adjusted to the specified reaction conditions, and 20wt% of N- (. Beta. -cyanoethyl) - ε -caprolactam xylene solution was pumped in, the reaction conditions were: the temperature is 80 ℃, the pressure is 3.0MPa, and the hourly space velocity of the N- (beta-cyanoethyl) -epsilon-caprolactam liquid is 0.5h -1 The space velocity of hydrogen is 300h -1 . The conversion of N- (. Beta. -cyanoethyl) -epsilon-caprolactam is 100%, the target product: the selectivity to N- (3-aminopropyl) caprolactam was 98.1%.
Example 4
Dissolving 3.0g of ethylene oxide-propylene oxide-ethylene oxide triblock copolymer in 30ml of ethanol, and stirring for 2 hours at the speed of 500 r/min; dropwise adding 7ml of 2M HCl solution into the prepared solution, and stirring at 35 deg.C for 3h at 500 r/min; adding 4.0g polystyrene spheres (particle size of 500 nm) into the above mixture, and stirring at 500r/min for 3h; 7ml of ethyl orthosilicate is added into the mixture prepared above in a dropwise manner, and the mixture is stirred for 48 hours at the temperature of 35 ℃ at the speed of 500 r/min; transferring the prepared mixture into a hydrothermal reaction kettle, heating to 80 ℃, reacting for 120h, cooling to room temperature, filtering, washing the solid with deionized water for 3 times, and drying at 120 ℃ for 10h; roasting at 350 deg.C for 1h in muffle furnace at 1 deg.C/min for 5h at 550 deg.C to obtain hollow SiO with microstructure of 1 deg.C/min 2 A ball;
2g of nickel nitrate and 5ml of ammonia solution (25-28%) are dissolved in 20ml of deionized water, and 3g of the hollow SiO prepared as described above are added 2 The ball is put in a hydrothermal reaction kettle to react for 12 hours at 160 ℃; cooling to room temperature, filtering, washing the solid with deionized water for 3 times, and drying at 120 ℃ for 10h; roasting at 550 ℃ for 5h in a muffle furnace at the roasting temperature rise rate of 1 ℃/min to obtain Ni/SiO 2 A sample; 0.15g of copper nitrate and 2.0ml of propane diamine are dissolved in 20ml of deionized water, and 3.0g of Ni/SiO are added 2 Stirring and reacting a sample at 40 ℃ for 5h at 500r/min, filtering, washing the solid with deionized water for 5 times, and drying at 120 ℃ for 5h; roasting at 550 ℃ for 5h in a muffle furnace at the roasting heating rate of 1 ℃/min to obtain 4-Cu-Ni/SiO 2 A catalyst.
Firstly, 4-Cu-Ni/SiO 2 The catalyst is filled in a micro packed bed reactor, and is activated in hydrogen before use under the following activation conditions: pressure of 0.2MPa and space velocity of hydrogen gas of300h -1 The activation temperature is 550 ℃, the roasting temperature rise rate is 1 ℃/min, and the activation time is 8h; after the activation was completed, the system was adjusted to the specified reaction conditions, and 20wt% of N- (. Beta. -cyanoethyl) - ε -caprolactam xylene solution was pumped in, and the reaction conditions were: the temperature is 80 ℃, the pressure is 3.0MPa, and the hourly space velocity of the N- (beta-cyanoethyl) -epsilon-caprolactam liquid is 0.5h -1 The space velocity of hydrogen is 300h -1 . The conversion of N- (. Beta. -cyanoethyl) -epsilon-caprolactam is 100%, the target product: the selectivity to N- (3-aminopropyl) caprolactam was 98.3%.
Example 5
Dissolving 3.0g of ethylene oxide-propylene oxide-ethylene oxide triblock copolymer in 30ml of ethanol, and stirring for 2 hours at the speed of 500 r/min; dropwise adding 7ml of 2M HCl solution into the prepared solution, and stirring at 35 deg.C for 3h at 500 r/min; adding 4.0g polystyrene spheres (with particle size of 500 nm) into the above mixture, and stirring at 500r/min for 3 hr; 7ml of ethyl orthosilicate is added into the mixture prepared above in a dropwise manner, and the mixture is stirred for 48 hours at the temperature of 35 ℃ at the speed of 500 r/min; transferring the prepared mixture to a hydrothermal reaction kettle, heating to 80 ℃, reacting for 120h, cooling to room temperature, filtering, washing the solid with deionized water for 3 times, and drying at 120 ℃ for 10h; roasting at 350 deg.C for 1h in muffle furnace at 1 deg.C/min for 5h at 550 deg.C to obtain hollow SiO with microstructure of 1 deg.C/min 2 A ball;
2g of nickel nitrate and 5ml of ammonia solution (25-28%) are dissolved in 20ml of deionized water, and 3g of the hollow SiO prepared as described above are added 2 The ball is put in a hydrothermal reaction kettle to react for 12 hours at 160 ℃; cooling to room temperature, filtering, washing the solid with deionized water for 3 times, and drying at 120 ℃ for 10h; roasting at 550 ℃ for 5h in a muffle furnace at the roasting temperature rise rate of 1 ℃/min to obtain Ni/SiO 2 A sample; 0.1g of ferric nitrate and 2.0ml of propane diamine are dissolved in 20ml of deionized water, and 3.0g of Ni/SiO are added 2 Stirring and reacting a sample at 40 ℃ for 5h at 500r/min, filtering, washing the solid with deionized water for 5 times, and drying at 120 ℃ for 5h; roasting at 550 ℃ for 5h in a muffle furnace at the roasting heating rate of 1 ℃/min to obtain 5-Fe-Ni/SiO 2 A catalyst.
Firstly, 5-Fe-Ni/SiO 2 The catalyst is filled in a micro packed bed reactor and is used for preparing the catalystThe agent is activated in hydrogen before use, under the following conditions: the pressure is 0.2MPa, and the space velocity of hydrogen gas is 300h -1 The activation temperature is 600 ℃, the roasting temperature rise rate is 1 ℃/min, and the activation time is 8h; after the activation was completed, the system was adjusted to the specified reaction conditions, and a 20wt% solution of N- (. Beta. -cyanoethyl) -. Epsilon. -caprolactam xylene was pumped in under the reaction conditions: the temperature is 80 ℃, the pressure is 3.0MPa, and the hourly space velocity of the N- (beta-cyanoethyl) -epsilon-caprolactam liquid is 0.5h -1 The space velocity of hydrogen is 300h -1 . The conversion of N- (. Beta. -cyanoethyl) -epsilon-caprolactam is 100%, the target product: the selectivity to N- (3-aminopropyl) caprolactam was 98.0%.
Example 6
Dissolving 3.0g of ethylene oxide-propylene oxide-ethylene oxide triblock copolymer in 30ml of ethanol, and stirring for 2 hours at a speed of 500 r/min; dropwise adding 7ml of 2M HCl solution into the prepared solution, and stirring at 35 deg.C for 3h at 500 r/min; adding 4.0g polystyrene spheres (particle size of 500 nm) into the above mixture, and stirring at 500r/min for 3h; 7ml of tetraethoxysilane is added into the prepared mixture dropwise, and the mixture is stirred for 48 hours at the temperature of 35 ℃ at the speed of 500 r/min; transferring the prepared mixture to a hydrothermal reaction kettle, heating to 80 ℃, reacting for 120h, cooling to room temperature, filtering, washing the solid with deionized water for 3 times, and drying at 120 ℃ for 10h; roasting at 350 deg.C for 1h in muffle furnace at 1 deg.C/min for 5h at 550 deg.C to obtain hollow SiO with microstructure of 1 deg.C/min 2 A ball;
2g of nickel nitrate and 5ml of ammonia solution (25-28%) are dissolved in 20ml of deionized water, and 3g of the hollow SiO prepared as described above are added 2 The ball is put in a hydrothermal reaction kettle to react for 12 hours at 160 ℃; cooling to room temperature, filtering, washing the solid with deionized water for 3 times, and drying at 120 ℃ for 10h; roasting at 550 ℃ for 5h in a muffle furnace at the roasting temperature rise rate of 1 ℃/min to obtain Ni/SiO 2 A sample; 0.15g of ferric nitrate and 2.0ml of propane diamine are dissolved in 20ml of deionized water, and 3.0g of Ni/SiO are added 2 Stirring and reacting a sample at 40 ℃ for 5h at 500r/min, filtering, washing the solid with deionized water for 5 times, and drying at 120 ℃ for 5h; roasting at 550 ℃ for 5h in a muffle furnace at the roasting temperature rise rate of 1 ℃/min to obtain 6-Fe-Ni/SiO 2 A catalyst.
Firstly, 6-Fe-Ni/SiO 2 The catalyst is filled in a micro packed bed reactor, and is activated in hydrogen before use under the following activation conditions: the pressure is 0.2MPa, and the space velocity of hydrogen gas is 300h -1 The activation temperature is 600 ℃, the roasting temperature rise rate is 1 ℃/min, and the activation time is 8h; after the activation was completed, the system was adjusted to the specified reaction conditions, and a 20wt% solution of N- (. Beta. -cyanoethyl) -. Epsilon. -caprolactam xylene was pumped in under the reaction conditions: the temperature is 80 ℃, the pressure is 3.0MPa, and the hourly space velocity of the N- (beta-cyanoethyl) -epsilon-caprolactam liquid is 0.5h -1 The space velocity of hydrogen is 300h -1 . The conversion of N- (. Beta. -cyanoethyl) -epsilon-caprolactam is 100%, the target product: the selectivity to N- (3-aminopropyl) caprolactam was 98.3%.
Example 7
Dissolving 3.0g of ethylene oxide-propylene oxide-ethylene oxide triblock copolymer in 30ml of ethanol, and stirring for 2 hours at the speed of 500 r/min; dropwise adding 7ml 2M HCl solution into the above solution, and stirring at 35 deg.C for 3 hr at 500 r/min; adding 4.0g polystyrene spheres (with particle size of 500 nm) into the above mixture, and stirring at 500r/min for 3 hr; 7ml of tetraethoxysilane is added into the prepared mixture dropwise, and the mixture is stirred for 48 hours at the temperature of 35 ℃ at the speed of 500 r/min; transferring the prepared mixture into a hydrothermal reaction kettle, heating to 80 ℃, reacting for 120h, cooling to room temperature, filtering, washing the solid with deionized water for 3 times, and drying at 120 ℃ for 10h; roasting at 350 deg.C for 1h in muffle furnace at a heating rate of 1 deg.C/min and 550 deg.C for 5h to obtain SiO with hollow microstructure 2 A ball;
2g of nickel nitrate and 5ml of an aqueous ammonia solution (25-28%) were dissolved in 20ml of deionized water, and 3g of the hollow SiO prepared as described above were added 2 The ball is put in a hydrothermal reaction kettle to react for 12 hours at 160 ℃; cooling to room temperature, filtering, washing the solid with deionized water for 3 times, and drying at 120 ℃ for 10h; roasting at 550 ℃ for 5h in a muffle furnace at the roasting temperature rise rate of 1 ℃/min to obtain Ni/SiO 2 A sample; 0.1 of cobalt acetate and 2.0ml of propylene diamine are dissolved in 20ml of deionized water, and 3.0g of Ni/SiO is added 2 Stirring and reacting a sample at the temperature of 40 ℃ for 5 hours at a speed of 500r/min, filtering, washing the solid with deionized water for 5 times, and drying at the temperature of 120 ℃ for 5 hours; at muffleRoasting at 550 ℃ for 5h in a furnace, wherein the roasting temperature rise rate is 1 ℃/min, and obtaining 7-Co-Ni/SiO 2 A catalyst.
Firstly, 7-Co-Ni/SiO 2 The catalyst is filled in a micro packed bed reactor, and is activated in hydrogen before use under the following activation conditions: the pressure is 0.2MPa, and the space velocity of hydrogen gas is 300h -1 The activation temperature is 600 ℃, the roasting temperature rise rate is 1 ℃/min, and the activation time is 8h; after the activation was completed, the system was adjusted to the specified reaction conditions, and a 20wt% solution of N- (. Beta. -cyanoethyl) -. Epsilon. -caprolactam xylene was pumped in under the reaction conditions: the temperature is 80 ℃, the pressure is 3.0MPa, the hourly space velocity of the N- (beta-cyanoethyl) -epsilon-caprolactam liquid is 0.5h -1 The space velocity of hydrogen is 300h -1 . The conversion of N- (β -cyanoethyl) -epsilon-caprolactam xylene was 100%, the target product: the selectivity to N- (3-aminopropyl) caprolactam was 98.6%.
Example 8
The best catalyst 1-Co-Ni/SiO in example 1 was taken 2 Loading the catalyst in a micro packed bed reactor, and carrying out a catalyst stability test, wherein the catalyst is activated in hydrogen before use, and the activation conditions are as follows: the pressure is 0.2MPa, and the space velocity of hydrogen gas is 300h -1 The activation temperature is 600 ℃, the roasting temperature rise rate is 1 ℃/min, and the activation time is 8h; after the activation was completed, the system was adjusted to the specified reaction conditions, and a 20wt% solution of N- (. Beta. -cyanoethyl) -. Epsilon. -caprolactam xylene was pumped in under the reaction conditions: the temperature is 80 ℃, the pressure is 3.0MPa, and the hourly space velocity of the N- (beta-cyanoethyl) -epsilon-caprolactam liquid is 0.5h -1 The space velocity of hydrogen is 300h -1 . As shown in fig. 4, the catalyst evaluation performance was maintained at 100% conversion, target product: the selectivity of N- (3-aminopropyl) caprolactam is 98-99%. The catalyst has stable performance after continuous reaction for 300 hours.
Comparative example 1
SiO 2 Soaking a sample (Qingdao ocean chemical industry type C) in a soaking solution for 10 hours, wherein the soaking solution is an aqueous solution of nickel nitrate and cobalt nitrate, the content of the nickel nitrate and the cobalt nitrate is the same as that of example 1 according to the mass fraction of Ni and Co in a catalyst, drying the sample at 120 ℃ for 5 hours, and placing the dried sample in a muffle furnaceRoasting at 550 ℃ for 5h with the roasting temperature rise rate of 1 ℃/min to obtain R1-Co-Ni/SiO 2 A catalyst.
Firstly, R1-Co-Ni/SiO 2 The catalyst is filled in a micro packed bed reactor, and is activated in hydrogen before use under the following activation conditions: the pressure is 0.2MPa, and the space velocity of hydrogen gas is 300h -1 The activation temperature is 600 ℃, the roasting temperature rise rate is 1 ℃/min, and the activation time is 8h; after the activation was completed, the system was adjusted to the specified reaction conditions, and 20wt% of N- (. Beta. -cyanoethyl) - ε -caprolactam xylene solution was pumped in, and the reaction conditions were: the temperature is 80 ℃, the pressure is 3.0MPa, and the hourly space velocity of the N- (beta-cyanoethyl) -epsilon-caprolactam liquid is 0.5h -1 The space velocity of hydrogen is 300h -1 . The conversion of N- (β -cyanoethyl) -e-caprolactam was 53%, target product: the selectivity to N- (3-aminopropyl) caprolactam was 78.6%.
Comparative example 2
SiO 2 Immersing a sample (Qingdao ocean chemical industry type C) in an immersion liquid for 10 hours, wherein the immersion liquid is an aqueous solution of nickel nitrate and copper nitrate, the contents of the nickel nitrate and the copper nitrate are the same as those in example 3 according to the mass fractions of Ni and Cu in a catalyst, drying the sample at 120 ℃ for 5 hours, roasting the sample at 550 ℃ in a muffle furnace for 5 hours, and the roasting temperature rise rate is 1 ℃/min to obtain R2-Cu-Ni/SiO 2 A catalyst.
Firstly, R2-Cu-Ni/SiO 2 The catalyst is filled in a micro packed bed reactor, and is activated in hydrogen before use under the following activation conditions: the pressure is 0.2MPa, and the space velocity of hydrogen gas is 300h -1 The activation temperature is 550 ℃, the roasting temperature rise rate is 1 ℃/min, and the activation time is 8h; after the activation was completed, the system was adjusted to the specified reaction conditions, and a 20wt% solution of N- (. Beta. -cyanoethyl) -. Epsilon. -caprolactam xylene was pumped in under the reaction conditions: the temperature is 80 ℃, the pressure is 3.0MPa, the hourly space velocity of the N- (beta-cyanoethyl) -epsilon-caprolactam liquid is 0.5h -1 The space velocity of hydrogen is 300h -1 . The conversion of N- (β -cyanoethyl) -e-caprolactam was 48%, target product: the selectivity to N- (3-aminopropyl) caprolactam was 82.3%.
Comparative example 3
SiO 2 Soaking a sample (Qingdao ocean chemical industry type C) in a soaking solution for 10 hours, wherein the soaking solution is an aqueous solution of nickel nitrate and ferric nitrate, the content of the nickel nitrate and the ferric nitrate is the same as that of example 5 according to the mass fraction of Ni and Fe in a catalyst, then drying for 5 hours at 120 ℃, roasting for 5 hours at 550 ℃ in a muffle furnace, and the roasting temperature rise rate is 1 ℃/min to obtain R3-Fe-Ni/SiO 2 A catalyst.
Firstly, R3-Fe-Ni/SiO 2 The catalyst is filled in a micro packed bed reactor, and is activated in hydrogen before use under the following activation conditions: the pressure is 0.2MPa, and the space velocity of hydrogen gas is 300h -1 The activation temperature is 600 ℃, the roasting temperature rise rate is 1 ℃/min, and the activation time is 8h; after the activation was completed, the system was adjusted to the specified reaction conditions, and a 20wt% solution of N- (. Beta. -cyanoethyl) -. Epsilon. -caprolactam xylene was pumped in under the reaction conditions: the temperature is 80 ℃, the pressure is 3.0MPa, the hourly space velocity of the N- (beta-cyanoethyl) -epsilon-caprolactam liquid is 0.5h -1 The space velocity of hydrogen is 300h -1 . The conversion of N- (. Beta. -cyanoethyl) -epsilon-caprolactam was 50.2%, the target product: the selectivity to N- (3-aminopropyl) caprolactam was 80.8%.

Claims (10)

1. A catalyst in the continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam is characterized by comprising an active component, an auxiliary agent component and a carrier, wherein the active component is Ni, the auxiliary agent component is Co, fe or Cu, and the carrier is silicon oxide; the active component accounts for 5-50% of the mass of the Ni simple substance; the auxiliary agent component accounts for 0.3-10% of the mass of the Co, fe or Cu simple substance; the rest is a carrier;
the catalyst is prepared by the following steps:
(I) Dissolving the ethylene oxide-propylene oxide-ethylene oxide triblock copolymer in ethanol, and stirring for 2-6h;
(II) dropwise adding an HCl solution into the solution prepared in the step (I), and stirring for 2-6h at 30-50 ℃;
(III) adding polystyrene spheres into the mixed material prepared in the step (II), and stirring for 3-8h;
(IV) dropwise adding ethyl orthosilicate into the mixture prepared in the step (III), and stirring for 24-48h at 30-50 ℃;
(V) transferring the mixture prepared in the step (IV) to a hydrothermal reaction kettle, heating to 80-100 ℃, reacting for 96-180h, cooling to room temperature, filtering, washing the solid with deionized water for 3-5 times, and drying at 100-120 ℃ for 5-12h; roasting in a muffle furnace at 350 ℃ for 0.5-5h, roasting at 500-650 ℃ for 3-8h to obtain hollow SiO with microstructure 2 A ball;
(VI) dissolving soluble nickel salt and ammonia water in deionized water, and adding the hollow SiO prepared in the step (V) 2 Reacting the spheres in a hydrothermal reaction kettle at 140-180 ℃ for 8-12h, cooling to room temperature, filtering, washing the solid with deionized water for 3-5 times, and drying at 100-120 ℃ for 5-12h; roasting in a muffle furnace at 500-650 ℃ for 3-8h to obtain Ni/SiO 2 A sample;
(VII) dissolving soluble auxiliary agent metal salt and 1, 3-propane diamine in deionized water, and adding the Ni/SiO prepared in the step (VI) 2 Stirring the sample at 30-50 ℃ for reaction for 5-20h, filtering, washing the solid with deionized water for 3-5 times, and drying at 100-120 ℃ for 5-12h; roasting in a muffle furnace at 500-650 ℃ for 3-8h to obtain M-Ni/SiO 2 Catalyst, M is Co, fe or Cu.
2. The catalyst in the continuous flow hydrogenation of N- (beta-cyanoethyl) -epsilon-caprolactam of claim 1, wherein the concentration of ethylene oxide-propylene oxide-ethylene oxide triblock copolymer of step (I) is 0.1-10g/ml; in the step (II), the concentration of the HCl solution is 1-3M; in the step (III), the particle size of the polystyrene spheres is 100nm-5 mu m.
3. The catalyst in the continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam of claim 1, wherein the soluble nickel salt in the step (VI) is one or more of nickel nitrate, nickel acetate, nickel chloride and nickel acetylacetonate; in the step (VII), the soluble assistant metal salt is one or more of cobalt nitrate, cobalt sulfate, cobalt acetate and cobalt chloride, or one or more of copper nitrate, copper acetate and copper chloride, or one or more of ferric nitrate, ferrous nitrate, ferric acetate, ferric chloride and ferrous chloride.
4. The catalyst for continuous flow hydrogenation of N- (. Beta. -cyanoethyl) -. Epsilon. -caprolactam of claim 1, wherein the stirring speed in steps (I), (II), (III), (IV) and (VII) is 200-800r/min; the roasting temperature rise rate in the roasting in the steps (V), (VI) and (VII) is 0.5-2 ℃/min.
5. A method for preparing a catalyst in a continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam is characterized by comprising the following steps:
(I) Dissolving the ethylene oxide-propylene oxide-ethylene oxide triblock copolymer in ethanol, and stirring for 2-6h;
(II) dropwise adding an HCl solution into the solution prepared in the step (I), and stirring for 2-6h at 30-50 ℃;
(III) adding polystyrene spheres into the mixed material prepared in the step (II), and stirring for 3-8h;
(IV) dropwise adding ethyl orthosilicate into the mixture prepared in the step (III), and stirring for 24-48h at 30-50 ℃;
(V) transferring the mixture prepared in the step (IV) to a hydrothermal reaction kettle, heating to 80-100 ℃, reacting for 96-180h, cooling to room temperature, filtering, washing the solid with deionized water for 3-5 times, and drying at 100-120 ℃ for 5-12h; roasting in a muffle furnace at 350 ℃ for 0.5-5h, roasting at 500-650 ℃ for 3-8h to obtain hollow SiO with microstructure 2 A ball;
(VI) dissolving soluble nickel salt and ammonia water in deionized water, and adding the hollow SiO prepared in the step (V) 2 Reacting the spheres in a hydrothermal reaction kettle at 140-180 ℃ for 8-12h, cooling to room temperature, filtering, washing the solid with deionized water for 3-5 times, and drying at 100-120 ℃ for 5-12h; roasting in a muffle furnace for 3-8h at 500-650 ℃ to obtain Ni/SiO 2 A sample;
(VII) dissolving soluble auxiliary agent metal salt and 1, 3-propane diamine in deionized water, and adding the Ni/SiO prepared in the step (VI) 2 Stirring and reacting a sample at 30-50 ℃ for 5-20h, filtering, washing the solid with deionized water for 3-5 times, and drying at 100-120 ℃ for 5-12h; roasting in a muffle furnace at 500-650 ℃ for 3-8h to obtain M-Ni/SiO 2 Catalyst, M is Co, fe orCu；
The catalyst comprises an active component, an auxiliary agent component and a carrier, wherein the active component is Ni, the auxiliary agent component is Co, fe or Cu, and the carrier is silicon oxide; the active component accounts for 5 to 50 percent of the mass of the Ni simple substance; the auxiliary agent component accounts for 0.3-10% of the mass of the Co, fe or Cu simple substance; the balance is carrier.
6. The process of claim 5, wherein the concentration of the ethylene oxide-propylene oxide-ethylene oxide triblock copolymer of step (I) is 0.1 to 10g/ml; in the step (II), the concentration of the HCl solution is 1-3M; in the step (III), the particle size of the polystyrene spheres is 100nm-5 mu m.
7. The method for preparing the catalyst in the continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam of claim 5, wherein the soluble nickel salt in the step (VI) is one or more of nickel nitrate, nickel acetate, nickel chloride and nickel acetylacetonate; in the step (VII), the soluble assistant metal salt is one or more of cobalt nitrate, cobalt sulfate, cobalt acetate and cobalt chloride, or one or more of copper nitrate, copper acetate and copper chloride, or one or more of ferric nitrate, ferrous nitrate, ferric acetate, ferric chloride and ferrous chloride.
8. The method of claim 5, wherein the stirring speed in the steps (I), (II), (III), (IV) and (VII) is 200-800r/min; the roasting temperature rise rate in the roasting in the steps (V), (VI) and (VII) is 0.5-2 ℃/min.
9. Use of a catalyst according to any one of claims 1-4 in a continuous flow hydrogenation process of N- (β -cyanoethyl) -e-caprolactam comprising the steps of: firstly, filling a catalyst into a micro packed bed reactor, wherein the catalyst is placed in hydrogen before useActivating in gas or hydrogen inert gas mixed gas, wherein the activation conditions are as follows: the pressure is 0.05-1.0MPa, and the space velocity of hydrogen gas is 5-500h -1 The activation temperature is 400-750 ℃, the roasting temperature rise rate is 0.5-20 ℃/min, and the activation time is 0.5-96h; after activation, adjusting the system to a specified reaction condition, pumping a mixture of N- (beta-cyanoethyl) -epsilon-caprolactam and a solvent, wherein the reaction condition is as follows: the temperature is 30-150 ℃, the pressure is 0.5-8.0MPa, and the hourly space velocity of the N- (beta-cyanoethyl) -epsilon-caprolactam liquid is 0.01-5.0h -1 The space velocity of hydrogen is 10-5000h -1 。
10. The method as claimed in claim 9, wherein the solvent in the reaction system is one or more of m-xylene, toluene and p-xylene.
CN202211212437.2A 2022-09-29 2022-09-29 Catalyst in continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam and preparation method and application thereof Active CN115591551B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211212437.2A CN115591551B (en) 2022-09-29 2022-09-29 Catalyst in continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211212437.2A CN115591551B (en) 2022-09-29 2022-09-29 Catalyst in continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115591551A true CN115591551A (en) 2023-01-13
CN115591551B CN115591551B (en) 2023-10-03

Family

ID=84844902

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211212437.2A Active CN115591551B (en) 2022-09-29 2022-09-29 Catalyst in continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115591551B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101499348A (en) * 2008-10-30 2009-08-05 同济大学 Hollow silicon dioxide/magnetic composite microsphere and its production method
WO2012079496A1 (en) * 2010-12-13 2012-06-21 西南化工研究设计院 Method for preparing ethanol by hydrogenation of acetic ester, catalyst and preparation method thereof
CN105776225A (en) * 2014-12-17 2016-07-20 中国科学院大连化学物理研究所 Metal-doped hollow mesoporous silicon oxide nanosphere and preparation method thereof
WO2020082196A1 (en) * 2018-10-22 2020-04-30 Pujing Chemical Industry Co., Ltd Hydrogenation catalyst and preparation and uses thereof
CN111153768A (en) * 2020-01-21 2020-05-15 浙江师范大学 Synthetic method of isohexide

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101499348A (en) * 2008-10-30 2009-08-05 同济大学 Hollow silicon dioxide/magnetic composite microsphere and its production method
WO2012079496A1 (en) * 2010-12-13 2012-06-21 西南化工研究设计院 Method for preparing ethanol by hydrogenation of acetic ester, catalyst and preparation method thereof
CN105776225A (en) * 2014-12-17 2016-07-20 中国科学院大连化学物理研究所 Metal-doped hollow mesoporous silicon oxide nanosphere and preparation method thereof
WO2020082196A1 (en) * 2018-10-22 2020-04-30 Pujing Chemical Industry Co., Ltd Hydrogenation catalyst and preparation and uses thereof
CN111153768A (en) * 2020-01-21 2020-05-15 浙江师范大学 Synthetic method of isohexide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
孙新枝，等: ""双金属催化剂Ni-Co/SiO2 空心球的可控制备及催化性能"", 《无机材料学报》 *

Also Published As

Publication number Publication date
CN115591551B (en) 2023-10-03

Similar Documents

Publication Publication Date Title
CN109225337B (en) MOFs (metal-organic frameworks) -encapsulated ionic liquid catalyst and preparation and application thereof
CN102658131A (en) Ruthenium-based catalyst for preparing gamma-valerolactone from acetylpropionic acid, and preparation method for ruthenium-based catalyst
CN110117266B (en) Method for preparing biomass fuel oil molecules by hydrogenating biomass platform compound
CN107935816B (en) Method for preparing cyclohexanol by catalytic hydrogenation and deoxidation of guaiacol
CN113231069B (en) Maleic anhydride bulk hydrogenation succinic anhydride preparation composite efficient catalyst and preparation method thereof
CN102744102B (en) Metal modified SAPO-34 zeolite catalyst, preparation method thereof and use method thereof
CN112080484B (en) Immobilized enzyme based on magnetic COFs, synthetic method and application of immobilized enzyme in preparation of biodiesel
CN111087370B (en) Method for preparing furfuryl alcohol by furfural transfer hydrogenation under catalysis of nitrogen-doped carbon supported by non-noble metal
CN112125810A (en) Method for preparing pentamethylene diamine by catalyzing lysine decarboxylation with solid super acid
CN106883090A (en) Solid acid catalysis 4- methyl -3- hexamethylenes cyclohexene carboxaldehyde synthesizes the method for paraxylene
CN108273507B (en) Method for reducing nitrile compound by catalytic hydrogenation
CN115591551A (en) Catalyst in continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam and preparation method and application thereof
CN111215103A (en) Preparation method of graphene modified mesoporous silica supported heteropolyacid catalyst
CN102389832B (en) Catalyst for preparing C5 and C6 alkanes by hydrogenating high-activity sorbierite water phase, and preparation method of catalyst
CN109847777A (en) A kind of solid-carrying type Cu base catalyst and its preparation method and application
CN113649049A (en) Maleic anhydride selective hydrogenation catalyst, and preparation method and application method thereof
CN107649184B (en) Perfusion silica gel/nanogold composite microspheres and preparation method and application thereof
CN116550360B (en) Method for catalyzing conversion of furfural into 2-methylfuran in hydrogen-free system
CN111686811A (en) Titanium supported catalyst and method for preparing hexamethylene diamine by catalytic hydrogenation of adiponitrile
CN101817753B (en) Preparation method of N-(3-aminopropyl)-1,3-propane diamine
CN101176850A (en) Catalyzer for preparing ethylene by ethanol dehydration as well as preparation method and usage
CN116459857B (en) High-selectivity catalyst Co/NS800, preparation method thereof and method for selectively hydrogenating p-chloronitrobenzene in heterogeneous system
CN111943851B (en) Method for preparing methyl nitrite from nitric acid
CN114656442B (en) Method for preparing caprolactone from 5-hydroxymethyl furoic acid
CN110229068B (en) In2.24(NCN)3Method for preparing aniline by catalytic nitrobenzene hydrogenation reduction

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant