CN114558577B - Catalyst for preparing 3-aminopropanol and preparation and application thereof - Google Patents

Catalyst for preparing 3-aminopropanol and preparation and application thereof Download PDF

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Publication number
CN114558577B
CN114558577B CN202210153108.9A CN202210153108A CN114558577B CN 114558577 B CN114558577 B CN 114558577B CN 202210153108 A CN202210153108 A CN 202210153108A CN 114558577 B CN114558577 B CN 114558577B
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amino
nickel silicide
aminopropanol
copper
reaction
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CN114558577A (en
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俞宏伟
王钰
李博
胡俊斌
彭志国
王玉岗
张伟
汪秋
张富军
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Zhejiang NHU Co Ltd
Shandong Xinhecheng Fine Chemical Technology Co Ltd
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Zhejiang NHU Co Ltd
Shandong Xinhecheng Fine Chemical Technology Co Ltd
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen 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
    • 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
    • B01J35/50—
    • B01J35/60—
    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
    • 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
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a catalyst for preparing 3-aminopropanol and preparation and application thereof, wherein the preparation of the catalyst comprises two steps of preparation of amino copper nickel silicide and preparation of amino copper nickel silicide porous particles; when the catalyst is used for synthesizing 3-aminopropanol, 1, 3-epoxypropane and liquid ammonia are introduced into a tubular reactor, the crude 3-aminopropanol is obtained by catalytic reaction of the catalyst with high selectivity under the condition of low temperature and normal pressure, and then the 3-aminopropanol is obtained by rectification after ammonia is removed by reduced pressure distillation. The invention synthesizes the porous particle catalyst of amino copper nickel silicide which catalyzes the reaction of 1, 3-epoxypropane and liquid ammonia with high selectivity, the catalyst prepares high purity 3-aminopropanol with high yield under the condition of 90-110 ℃, the yield of 3-aminopropanol is 95.3-96.5 percent based on 1, 3-epoxypropane, and the purity is 99.2-99.8 percent.

Description

Catalyst for preparing 3-aminopropanol and preparation and application thereof
Technical Field
The invention belongs to the technical field of synthesis of chemical intermediates, and particularly relates to a catalyst for preparing 3-aminopropanol, and preparation and application thereof.
Background
The 3-aminopropanol is an important fine chemical intermediate, has wide application in the aspects of medicines, pesticides, fuels and the like, is used for synthesizing cyclophosphamide, heart can and other medicines, is a raw material for synthesizing provitamin B5 (panthenol), has been increasingly applied to daily chemicals due to the improvement of living standard of people in recent years, and particularly has been applied more and more widely in hair care products and other cosmetics for local use, so that the market demand of the 3-aminopropanol is greatly promoted.
In 2004, sylvie Picard et al synthesized 3-aminopropanol using DMSO and dichloromethane, resulting in a product purity of 98%, but only 12% yield; in 2007, springerta et al synthesized 3-aminopropanol from ethyl 3-aminopropionate and 3-cyanoethanol, which also gave high purity product, but the yield was still low; CN103012165a reports a method for preparing 3-aminopropanol by using 1, 4-butyrolactone as a raw material, opening a ring under the action of hydrazine hydrate, adding an aqueous solution of sodium nitrite to generate acyl azide, and then rearranging. The method has complex flow, and the yield of the target product 3-aminopropanol is low, so that the method is not suitable for large-scale production; feng Xiaoliang reports a process for the preparation of 3-aminopropanol by the synthesis of cyclohexanone oxime starting from cyclohexanone, followed by condensation with acrylonitrile and catalytic hydrocracking. The method also has the problems of complicated steps, poor selectivity of target products and low product yield.
In 1994 Marco Chini et al disclosed that amine/ammonia as a nucleophile could undergo a nucleophilic ring-opening reaction on oxetane using LiBF 4 Acetonitrile as a promoter and oxetane reacted with amine/ammonia at 80 c to give the corresponding gamma-amino alcohol. LiBF during the reaction 4 Slowly releasing BF 3 ，BF 3 Acting on the oxygen atom of the oxetane promotes nucleophilic attack of the amine/ammonia on the oxetane, but in this process LiBF 4 The dosage is large and can not be used continuously.
The method commonly used at present is to use 3-hydroxyThe patent CH 244837 B,DE 2655794 B,EP 1132371 A1,JP 2002201164A reports a method for producing 3-aminopropanol by reacting 3-hydroxypropionitrile with hydrogen. The method can directly synthesize the target product 3-aminopropanol in one step, but the problem of low target product selectivity still exists. JP 1993163213A discloses a Raney cobalt catalyst for the hydrogenation of 3-hydroxypropionitrile to 3-aminopropanol, which has high risk and is not easy to realize industrial application. Patent CN103261148A reports a process for producing and purifying 3-aminopropanol, the selectivity of 3-aminopropanol is as high as 93%, but the reaction pressure is as high as 18MPa, and the mass space time yield is only 0.3kg/kg.h -1 。
In summary, the above reports have problems that the catalyst is difficult to be used for continuous production or has low catalyst activity, short service life and harsh reaction conditions, the industrial application value is low, and the technical method with the industrial application value has the problems of complicated steps, poor safety, low selectivity, low yield and the like. Therefore, a preparation method of 3-aminopropanol with simple process and high yield is urgently needed at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a catalyst for preparing 3-aminopropanol, and preparation and application thereof, and the high-selectivity catalyst is used for preparing 3-aminopropanol, so that 3-aminopropanol can be obtained in high yield and high purity, and the use of high-pressure hydrogen is avoided.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the preparation method of the amino copper nickel silicide porous particles comprises the following steps:
(1) Modifying silica sol and a silane coupling agent in an alcohol solvent, then adding a copper salt aqueous solution, a nickel salt aqueous solution and amino-substituted benzoic acid for hydrothermal reaction, and after the reaction is finished, performing post-treatment to obtain an amino copper nickel silicide, wherein the post-treatment comprises filtering, drying, washing, drying and crushing;
(2) And (3) heating the amino copper nickel silicide, the quaternary ammonium salt and the titanate obtained in the step (1) in an alcohol solvent for reaction, and after the reaction is finished, obtaining the amino copper nickel silicide porous particles through post-treatment, wherein the post-treatment comprises drying, roasting and crushing.
The amino copper nickel silicide porous particles obtained by the preparation method can be used as a high-selectivity catalyst to catalyze the reaction of 1, 3-epoxypropane and liquid ammonia to prepare 3-aminopropanol, the reaction yield and purity are high, and the method has high safety and high industrial utilization value because hydrogen with high pressure is not used.
Preferably, in step (1) and step (2), the alcoholic solvent is independently selected from C 1 ～C 4 An alkyl alcohol; further preferred are methanol, ethanol, n-propanol or n-butanol, most preferred is absolute ethanol.
Preferably, in the step (1), the silica sol has a mass fraction of 25-35%, a particle diameter of 15-18 nm, and a ph=8.0-9.0; the silane coupling agent is silane coupling agent KH560, KH550, KH570 or KH1770.
Preferably, in the step (1), the copper salt is one or more of copper chloride, copper bromide, copper acetate, copper sulfate, copper nitrate or hydrate thereof;
the nickel salt is one or more of nickel nitrate, nickel sulfate, nickel acetate, nickel chloride, nickel bromide or hydrate thereof.
Preferably, in the step (1), the amino-substituted benzoic acid is para-aminobenzoic acid, meta-aminobenzoic acid or ortho-aminobenzoic acid.
Preferably, in the step (1), the mass ratio of the silica sol to the alcohol solvent is 40-44:3-8;
the mass ratio of the silica sol to the silane coupling agent is 40-44:2-3;
preferably, in the step (1), the mass fraction of the copper salt aqueous solution is 20-26%, and the addition amount is 45-55% of the mass of the silica sol; the mass fraction of the nickel salt aqueous solution is 24-30%, and the addition amount is 35-48% of the mass of the silica sol; the adding amount of the p-aminobenzoic acid is 22-32% of the mass of the silica sol.
In the step (2), the structural formula of the quaternary ammonium salt is R 4 N + X - Wherein R is a hydrocarbon group, wherein four hydrocarbon groups may be the same or different, X - Preferably a halogen anion; preferably, the quaternary ammonium salt is cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride or cetyl dimethyl benzyl ammonium bromide;
the titanate is tetrabutyl titanate, tetraisopropyl titanate or tetraethyl titanate.
Preferably, in the step (2), the mass ratio of the amino copper nickel silicide to the quaternary ammonium salt ester is 75-80:4-8;
the mass ratio of the amino copper nickel silicide to the titanate is 75-80:12-21;
the addition amount of the alcohol solvent is 33-46% of the total mass of the amino copper nickel silicide, the quaternary ammonium salt and the titanate.
Preferably, the preparation method of the amino copper nickel silicide porous particles comprises the following steps:
(1) Preparation of amino copper nickel silicide
Adding silica sol, absolute ethyl alcohol and a silane coupling agent KH560 into a reaction kettle according to a certain mass ratio, heating to 90-110 ℃ under the conditions of 2-4 ℃/min and 1500-2000 rpm, reacting at constant temperature for 3-5 hours, cooling to room temperature, transferring into a stainless steel water heating reaction kettle with a polytetrafluoroethylene lining, adding a certain amount of copper chloride aqueous solution, nickel nitrate aqueous solution and p-aminobenzoic acid, heating to 120-140 ℃ at a heating rate of 3-5 ℃/min, reacting at constant temperature for 16-20 hours, cooling to room temperature, filtering to obtain pale blue solid, drying at 70-90 ℃ after drying, washing with absolute ethyl alcohol for three times, naturally airing, and crushing into 600-800 meshes, wherein the obtained pale blue powder is amino copper nickel silicide;
(2) Preparation of porous particles of amino copper nickel silicide
Adding the amino copper nickel silicide, the cetyl trimethyl ammonium bromide and the tetrabutyl titanate into absolute ethyl alcohol according to a certain mass ratio, heating to 30-40 ℃ and keeping the temperature, stirring and reacting for 1-2 hours at 1000-1600 r/min, vacuum drying the obtained product at 60-80 ℃ to remove the ethanol, then placing the product into a muffle furnace, heating to 300-450 ℃ at a speed of 1-2.5 ℃ per minute, baking for 2-3 hours at a constant temperature, cooling to room temperature, and crushing into 60-100 mesh particles, thus obtaining the amino copper nickel silicide porous particles.
As a further preferred aspect, the method for preparing the porous particles of amino copper nickel silicide includes the steps of:
(1) Preparation of amino copper nickel silicide
Adding silica sol, absolute ethyl alcohol and a silane coupling agent KH560 into a reaction kettle according to the conditions of 3 ℃/min and 1800 rpm, heating to 100 ℃, reacting at constant temperature for 4.5 hours, cooling to room temperature, transferring into a hydrothermal reaction kettle, adding a copper chloride aqueous solution, a nickel nitrate aqueous solution and p-aminobenzoic acid, heating to 130 ℃ at the heating rate of 4 ℃/min, reacting at constant temperature for 18 hours, cooling to room temperature, drying the light blue solid obtained by filtering at 80 ℃, washing with absolute ethyl alcohol for three times, naturally airing, and crushing into 750 meshes, wherein the light blue powder is amino copper nickel silicide;
the mass ratio of the silica sol to the absolute ethyl alcohol to the silane coupling agent KH560 is 84:11:5;
the mass fraction of the copper chloride aqueous solution is 24%, and the addition amount is 50% of the mass of the silica sol;
the mass fraction of the nickel nitrate aqueous solution is 27%, and the addition amount is 40% of the mass of the silica sol;
the adding amount of the p-aminobenzoic acid is 28% of the mass of the silica sol;
(2) Preparation of porous particles of amino copper nickel silicide
Adding amino copper nickel silicide, cetyl trimethyl ammonium bromide and tetrabutyl titanate into absolute ethyl alcohol, heating to 35 ℃ and keeping the temperature, stirring for reacting for 1.6 hours at 1400 rpm, vacuum drying the obtained product at 70 ℃ to remove the ethanol, then placing the product into a muffle furnace, heating to 380 ℃ at the speed of 2 ℃/min, baking at the constant temperature for 2.5 hours, cooling to room temperature, and crushing into 80-mesh particles, thus obtaining the high-selectivity catalyst;
the mass ratio of the amino copper nickel silicide to the cetyl trimethyl ammonium bromide to the tetrabutyl titanate is 155:12:33;
the addition amount of the absolute ethyl alcohol is 40% of the total mass of the amino copper nickel silicide, the cetyl trimethyl ammonium bromide and the tetrabutyl titanate.
The invention also provides an amino copper nickel silicide porous particle which is prepared by the preparation method.
The invention further provides a preparation method of the 3-aminopropanol, under the action of a high-selectivity catalyst, the 1, 3-epoxypropane reacts with liquid ammonia to obtain a 3-aminopropanol crude product, and the 3-aminopropanol crude product is obtained by rectification after ammonia is removed by reduced pressure distillation;
the high-selectivity catalyst is the amino copper nickel silicide porous particles.
Preferably, the reaction is carried out in a tubular reactor, the tubular reactor comprises a preheating section and a reaction section which are communicated, the porous amino copper nickel silicide particles are filled in the reaction section of the tubular reactor during the reaction, liquid ammonia is pumped into the preheating section of the tubular reactor for preheating, and then the liquid ammonia is pumped into the reaction section of the tubular reactor together with 1, 3-epoxypropane for reaction.
Preferably, the temperature of the liquid ammonia preheated in the preheating section is 80-100 ℃, the temperature of the reaction section is 90-110 ℃, and the residence time is 13-20 s;
the mass ratio of the 1, 3-epoxypropane to the liquid ammonia is 1:8-10.
Preferably, the preparation method of the 3-aminopropanol comprises the following steps:
the preheating temperature of the preheating section is 90 ℃, then 1, 3-epoxypropane is pumped into the tubular reactor reaction section according to the mass ratio of 1, 3-epoxypropane to liquid ammonia of 1:9, the temperature of the tubular reactor reaction section is set to 95 ℃, the pressure is controlled to be 0.35MPa, the reaction residence time is 16s, the reaction product is continuously collected to obtain crude 3-aminopropanol, and the crude 3-aminopropanol is distilled under reduced pressure to remove ammonia and then is rectified to obtain the product 3-aminopropanol.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention synthesizes the porous particle catalyst of the amino copper nickel silicide which catalyzes the reaction of the 1, 3-epoxypropane and the liquid ammonia with high selectivity, the catalyst is adopted to prepare the 3-aminopropanol, the yield is 95.3 to 96.5 percent based on the 1, 3-epoxypropane, the purity is 99.2 to 99.8 percent, and the yield and the purity are obviously improved;
(2) The catalyst of the invention is used for synthesizing 3-aminopropanol, thereby avoiding the use of high-pressure hydrogen, ensuring safer operation and higher industrial application value.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and explanation only and is not intended to limit the present invention.
The silica sol used in the present invention can be directly purchased from the market.
Example 1
1. High selectivity catalyst preparation
(1) Preparation of amino copper nickel silicide
840kg of silica sol, 110kg of absolute ethyl alcohol and 50kg of silane coupling agent KH560 are added into a reaction kettle, the temperature is raised to 100 ℃ under the conditions of 3 ℃/min and 1800 rpm, after the constant temperature reaction is carried out for 4.5 hours, the mixture is cooled to room temperature and then is transferred into a stainless steel water thermal reaction kettle with a polytetrafluoroethylene lining, 420kg of 24wt% copper chloride aqueous solution, 336kg of 27wt% nickel nitrate aqueous solution and 235.2kg of para-aminobenzoic acid are added, after the temperature is raised to 130 ℃ at the heating rate of 4 ℃/min, the mixture is reacted for 18 hours at constant temperature, the mixture is cooled to room temperature, the light blue solid obtained by filtration is dried at 80 ℃, washed for three times by absolute ethyl alcohol and then naturally dried, and then crushed into 750 meshes, and the light blue powder is the amino copper nickel silicide;
the silica sol has a silica mass fraction of 30%, a particle size of 15-18 nm and a ph=8.5;
(2) Preparation of porous particles of amino copper nickel silicide
620kg of amino copper nickel silicide, 48kg of cetyl trimethyl ammonium bromide and 132kg of tetrabutyl titanate are added into 320kg of absolute ethyl alcohol, the mixture is heated to 36 ℃ and kept at constant temperature, 1400 revolutions per minute is stirred for 1.6 hours, the product obtained after the reaction is dried in vacuum at 70 ℃ to remove the ethanol, then the product is put into a muffle furnace, the temperature is raised to 380 ℃ at the speed of 2 ℃/min and the mixture is baked at constant temperature for 2.5 hours, and the product is crushed into 80-mesh particles after the product is cooled to room temperature, thus obtaining the high-selectivity catalyst.
2. Synthesis of 3-aminopropanol
The high-selectivity catalyst is filled in a reaction section of the tubular reactor, liquid ammonia is pumped into a preheating section of the tubular reactor, the preheating temperature is 90 ℃, then 1, 3-epoxypropane is pumped into the reaction section of the tubular reactor according to the mass ratio of 1, 3-epoxypropane to liquid ammonia of 1:9, the temperature of the reaction section of the tubular reactor is set to 95 ℃, and the mass space velocity is 7h -1 Continuously collecting a reaction product to obtain crude 3-aminopropanol, decompressing and distilling the crude 3-aminopropanol to remove ammonia, and rectifying to obtain the product 3-aminopropanol;
the GC purity of the 3-aminopropanol obtained in example 1 was 99.8% and the yield was 96.5% based on 1, 3-propylene oxide.
Example 2
The method comprises the following steps:
1. high selectivity catalyst preparation
(1) Preparation of amino copper nickel silicide
800kg of silica sol, 60kg of absolute ethyl alcohol and 40kg of silane coupling agent KH560 are added into a reaction kettle, the temperature is raised to 90 ℃ under the conditions of 2 ℃/min and 1500 rpm, the mixture is cooled to room temperature and then is transferred into a stainless steel water thermal reaction kettle with a polytetrafluoroethylene lining after being reacted at constant temperature for 3 hours, 360kg of 20wt% copper chloride aqueous solution, 280kg of 24wt% nickel nitrate aqueous solution and 176kg of p-aminobenzoic acid are added, the mixture is heated to 120 ℃ at a heating rate of 3 ℃/min and then is reacted at constant temperature for 16 hours, the mixture is cooled to room temperature and then is filtered to obtain pale blue solid, the pale blue solid is dried at 70 ℃, washed for three times by absolute ethyl alcohol and then naturally dried, and then crushed into 600 meshes, and the obtained pale blue powder is amino copper nickel silicide;
the silica sol has a silica mass fraction of 30%, a particle size of 15-18 nm and a ph=8.5;
(2) Preparation of porous particles of amino copper nickel silicide
600kg of amino copper nickel silicide, 32kg of cetyl trimethyl ammonium bromide and 168kg of tetrabutyl titanate are added into 264kg of absolute ethyl alcohol, the mixture is heated to 30 ℃ and kept at constant temperature, 1000 revolutions per minute is stirred for reaction for 1 hour, the obtained product after the reaction is dried in vacuum at 60 ℃ to remove the ethanol, then the obtained product is put into a muffle furnace, the temperature is raised to 300 ℃ at the speed of 1 ℃/min, the mixture is baked for 2 hours at constant temperature, and the mixture is crushed into 60-mesh particles after being cooled to room temperature, thus obtaining the high-selectivity catalyst.
2. Synthesis of 3-aminopropanol
Filling a high-selectivity catalyst into a reaction section of a tubular reactor, pumping liquid ammonia into a preheating section of the tubular reactor, wherein the preheating temperature is 80 ℃, and then pumping 1, 3-epoxypropane into the reaction section of the tubular reactor according to the mass ratio of 1, 3-epoxypropane to liquid ammonia of 1:8, wherein the temperature of the reaction section of the tubular reactor is set to 90 ℃ and the mass space velocity is 8h -1 Continuously collecting a reaction product to obtain crude 3-aminopropanol, decompressing and distilling the crude 3-aminopropanol to remove ammonia, and rectifying to obtain the product 3-aminopropanol;
the GC purity of the 3-aminopropanol obtained in example 2 was 99.3% and the yield was 95.3% based on 1, 3-propylene oxide.
Example 3
1. High selectivity catalyst preparation
(1) Preparation of amino copper nickel silicide
880kg of silica sol, 160kg of absolute ethyl alcohol and 40kg of silane coupling agent KH560 are added into a reaction kettle, the temperature is raised to 110 ℃ under the conditions of 4 ℃/min and 2000 rpm, after the reaction is carried out for 5 hours at constant temperature, the reaction kettle is cooled to room temperature and then transferred into a stainless steel water thermal reaction kettle with a polytetrafluoroethylene lining, 484kg of 26wt% copper chloride aqueous solution, 422.4kg of 30wt% nickel nitrate aqueous solution and 281.6kg of p-aminobenzoic acid are added, after the reaction kettle is heated to 140 ℃ at a temperature rise rate of 5 ℃/min, the reaction kettle is reacted for 20 hours at constant temperature, the reaction kettle is cooled to room temperature, the light blue solid obtained by filtration is dried at 90 ℃ after being washed for three times by absolute ethyl alcohol, and then is naturally dried and crushed into 800 meshes, and the light blue powder is the amino copper nickel silicide;
the silica sol has a silica mass fraction of 30%, a particle size of 15-18 nm and a ph=8.5;
(2) Preparation of porous particles of amino copper nickel silicide
480kg of amino copper nickel silicide, 48kg of cetyl trimethyl ammonium bromide and 72kg of tetrabutyl titanate are added into 276kg of absolute ethyl alcohol, the mixture is heated to 40 ℃ and kept at constant temperature, 1600 revolutions per minute is stirred for 2 hours, the obtained product after the reaction is dried in vacuum at 80 ℃ to remove the ethanol, then the obtained product is put into a muffle furnace, the temperature is raised to 450 ℃ at the speed of 2.5 ℃/min, the mixture is baked for 3 hours at constant temperature, and the mixture is crushed into 100-mesh particles after being cooled to room temperature, thus obtaining the high-selectivity catalyst.
2. Synthesis of 3-aminopropanol
Filling a high-selectivity catalyst into a reaction section of a tubular reactor, pumping liquid ammonia into a preheating section of the tubular reactor, wherein the preheating temperature is 100 ℃, and then pumping 1, 3-epoxypropane into the reaction section of the tubular reactor according to the mass ratio of 1, 3-epoxypropane to liquid ammonia of 1:10, wherein the temperature of the reaction section of the tubular reactor is set to be 110 ℃, and the mass space velocity is 4h -1 Continuously collecting a reaction product to obtain crude 3-aminopropanol, decompressing and distilling the crude 3-aminopropanol to remove ammonia, and rectifying to obtain the product 3-aminopropanol;
the GC purity of the 3-aminopropanol obtained in example 3 was 99.2% and the yield was 95.9% based on 1, 3-propylene oxide.
Example 4
In example 3, 48Kg of cetyltrimethylammonium bromide in step 1 (2) was changed to 48Kg of cetyltrimethylammonium chloride, and the other conditions were kept unchanged, and the GC purity of the finally obtained 3-aminopropanol was 99.2%, and the yield was 95.3% based on 1, 3-epoxypropane.
Comparative example 1: the 80 mesh high selectivity catalyst of example 1 was replaced with 80 mesh silicon nitride ceramic particles
1. Synthesis of 3-aminopropanol
The 80-mesh silicon nitride ceramic particles are filled into a reaction section of a tubular reactor, liquid ammonia is pumped into a preheating section of the tubular reactor, the preheating temperature is 90 ℃, then 1, 3-epoxypropane is pumped into the reaction section of the tubular reactor according to the mass ratio of 1, 3-epoxypropane to liquid ammonia of 1:9, the temperature of the reaction section of the tubular reactor is set to 95 ℃, and the mass airspeed is 7h -1 Continuously collecting a reaction product to obtain crude 3-aminopropanol, decompressing and distilling the crude 3-aminopropanol to remove ammonia, and rectifying to obtain the product 3-aminopropanol;
the purity of the 3-aminopropanol obtained in comparative example 1 was 10.1%, and the yield was 8.3% based on 1, 3-epoxypropane.
Comparative example 2: according to the method disclosed in patent CN109456207A, raney Nickel is used as a catalyst, and the method is carried out according to the detailed operation of example 1 in the patent
Sucking nickel catalyst and silver nitrate into a high-pressure reduction kettle through a vacuum pump, then sucking methanol and 3-hydroxy propionitrile, closing a vacuum valve, opening a vent valve, replacing air in the kettle with nitrogen for at least three times, slowly exhausting air at 0.2MPa each time, closing the vent valve and the vent valve after replacement, opening an ammonia valve, opening stirring, opening a jacket cooling water, and introducing liquid ammonia; stopping stirring after ammonia introduction, closing an ammonia introduction valve, opening a hydrogen introduction valve, replacing hydrogen for three times to remove residual nitrogen, slowly exhausting and emptying under 0.2MPa each time, starting stirring after the replacement is finished, opening a steam valve to raise the temperature to 45 ℃, starting to introduce hydrogen, keeping the pressure in the kettle to 3MPa, introducing cooling water into a reduction kettle jacket and an inner coil, and controlling the reaction temperature in the kettle to 75 ℃;
when the hydrogen pressure no longer drops, indicating that the reaction is finished, stopping stirring, standing for half an hour, cooling the reaction kettle to the temperature of 40 ℃ by using jacket water, releasing pressure, then introducing nitrogen for three times, pressing the reaction kettle into a high-position sedimentation cylinder by using nitrogen for static sedimentation for 6 hours, collecting a small amount of catalyst and impurities at the lower layer, and distilling the upper layer liquid; the nickel catalyst at the bottom of the reduction kettle still sinks at the bottom, and the supplementary methanol is reserved for next use; placing the upper liquid of the sedimentation tank into a distillation kettle, opening a vent valve, heating, and collecting methanol when the liquid temperature is 95 ℃; the cooling kettle temperature after the methanol is collected is 60 ℃ for reduced pressure distillation, the vacuum degree is kept to be less than-0.09 MPa, a front cut fraction (little methanol) is collected when the top temperature reaches 90 ℃, a main cut fraction is collected when the top temperature reaches 95 ℃, the liquid temperature is controlled to be 110 ℃ when the main cut fraction is collected until the collection is finished, and the yield is 98% after chromatographic detection, wherein the content is more than 99%; the molar ratio of the 3-hydroxy propionitrile to the ammonia water is 1:1.15; the dosage of the Raney nickel catalyst is 0.006% of the mass of the 3-hydroxy propionitrile;
the purity of the 3-aminopropanol obtained in comparative example 2 was 97.9%, the yield was 99.2% based on 3-hydroxypropionitrile, and the purity of the 3-aminopropanol obtained in this example was slightly lower than that of examples 1, 2 and 3, but the yield was relatively high, but hydrogen gas having relatively high risk was used in comparative example 2, the pressure of 3MPa was maintained during the reaction, the complexity of the production operation was high, and the safety was low.

Claims (12)

1. The preparation method of the amino copper nickel silicide porous particles is characterized by comprising the following steps of:
(1) Modifying silica sol and a silane coupling agent in an alcohol solvent, then adding a copper salt aqueous solution, a nickel salt aqueous solution and amino-substituted benzoic acid for hydrothermal reaction, and after the reaction is finished, performing post-treatment to obtain an amino copper nickel silicide, wherein the post-treatment comprises filtering, drying, washing, drying and crushing;
(2) And (3) heating the amino copper nickel silicide, the quaternary ammonium salt and the titanate obtained in the step (1) in an alcohol solvent for reaction, and after the reaction is finished, obtaining the amino copper nickel silicide porous particles through post-treatment, wherein the post-treatment comprises drying, roasting and crushing.
2. The method for producing porous particles of amino copper nickel silicide according to claim 1, wherein in step (1) and step (2), the alcohol solvent is independently selected from the group consisting of C 1 ~C 4 Alkyl alcohol.
3. The method for preparing porous particles of amino copper nickel silicide according to claim 1, wherein in the step (1), the silica sol has a mass fraction of 25-35% of silica, a particle diameter of 15-18 nm and a ph=8.0-9.0; the silane coupling agent is silane coupling agent KH560, KH550, KH570 or KH1770.
4. The method for producing the porous particles of amino copper nickel silicide according to claim 1, wherein in the step (1), the copper salt is one or more of copper chloride, copper bromide, copper acetate, copper sulfate, copper nitrate, or a hydrate thereof;
the nickel salt is one or more of nickel nitrate, nickel sulfate, nickel acetate, nickel chloride, nickel bromide or hydrate thereof.
5. The method for producing porous particles of copper nickel silicide with amino group according to claim 1, wherein in the step (1), the amino group-substituted benzoic acid is p-aminobenzoic acid, m-aminobenzoic acid or o-aminobenzoic acid.
6. The method for preparing porous particles of amino copper nickel silicide according to claim 1, wherein in the step (1), the mass ratio of the silica sol to the alcohol solvent is 40-44:3-8;
the mass ratio of the silica sol to the silane coupling agent is 40-44:2-3;
the mass fraction of the copper salt aqueous solution is 20-26%, and the addition amount is 45-55% of the mass of the silica sol; the mass fraction of the nickel salt aqueous solution is 24-30%, and the addition amount is 35-48% of the mass of the silica sol; the addition amount of the amino-substituted benzoic acid is 22-32% of the mass of the silica sol.
7. The method for producing porous particles of amino copper nickel silicide according to claim 1, wherein in the step (2), the quaternary ammonium salt is cetyltrimethylammonium bromide, cetyltrimethylammonium chloride or cetyldimethylbenzyl ammonium bromide;
the titanate is tetrabutyl titanate, tetraisopropyl titanate or tetraethyl titanate.
8. The method for preparing porous particles of amino copper nickel silicide according to claim 1, wherein in the step (2), the mass ratio of the amino copper nickel silicide to the quaternary ammonium salt is 75-80:4-8;
the mass ratio of the amino copper nickel silicide to the titanate is 75-80:12-21;
the addition amount of the alcohol solvent is 33-46% of the total mass of the amino copper nickel silicide, the quaternary ammonium salt and the titanate.
9. Porous particles of copper nickel amino silicide prepared by the preparation method of any one of claims 1-8.
10. A preparation method of 3-aminopropanol is characterized in that under the action of a high-selectivity catalyst, 1, 3-epoxypropane reacts with liquid ammonia to obtain a 3-aminopropanol crude product, and the 3-aminopropanol crude product is rectified after ammonia removal by reduced pressure distillation;
the high selectivity catalyst is the amino copper nickel silicide porous particle as claimed in claim 9.
11. The method for producing 3-aminopropanol according to claim 10, wherein the reaction is carried out in a tubular reactor comprising a preheating section and a reaction section which are connected to each other, wherein the porous particles of the amino copper nickel silicide are filled into the reaction section of the tubular reactor during the reaction, and wherein liquid ammonia is pumped into the preheating section of the tubular reactor to be preheated and then pumped into the reaction section of the tubular reactor together with 1, 3-propylene oxide to carry out the reaction.
12. The method for preparing 3-aminopropanol according to claim 11, wherein the temperature of preheating the liquid ammonia in the preheating section is 80-100 ℃, the temperature of the reaction section is 90-110 ℃, and the residence time is 13-20 s;
the mass ratio of the 1, 3-epoxypropane to the liquid ammonia is 1:8-10.
CN202210153108.9A 2022-02-18 2022-02-18 Catalyst for preparing 3-aminopropanol and preparation and application thereof Active CN114558577B (en)

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