CN114558577A - 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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CN114558577A
CN114558577A CN202210153108.9A CN202210153108A CN114558577A CN 114558577 A CN114558577 A CN 114558577A CN 202210153108 A CN202210153108 A CN 202210153108A CN 114558577 A CN114558577 A CN 114558577A
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nickel
copper
aminopropanol
silicide
amino
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CN114558577B (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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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

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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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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 porous particles of amino copper nickel silicide; when the catalyst is used for synthesizing 3-aminopropanol, 1, 3-epoxypropane and liquid ammonia are introduced into a tubular reactor, the high-selectivity catalyst is used for catalyzing and reacting at low temperature and normal pressure to obtain crude 3-aminopropanol, and the crude 3-aminopropanol is rectified after the ammonia is removed through reduced pressure distillation to obtain the 3-aminopropanol. The invention synthesizes the copper amide nickel silicide porous particle catalyst for catalyzing the reaction of 1, 3-epoxypropane and liquid ammonia with high selectivity, and the catalyst prepares high-purity 3-aminopropanol with high yield under the condition of 90-110 ℃, wherein the yield of the 3-aminopropanol is 95.3-96.5% calculated by 1, 3-epoxypropane, and the purity is 99.2-99.8%.

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, Xinkean and other medicines, is a raw material for synthesizing provitamin B5 (panthenol), has continuously improved application in daily chemicals due to improvement of living standard of people in recent years, and particularly has more and more wide application in hair care products and other cosmetics for local use, and greatly drives market demand of the 3-aminopropanol.
In 2004, Sylvie Picard et al synthesized 3-aminopropanol using DMSO and dichloromethane, and obtained a product with a purity of 98%, but a yield of only 12%; in 2007, Springgata et al used ethyl-3-aminopropionate and 3-cyanoethanol to synthesize 3-aminopropanol, and also obtained high-purity products, but the yield was still very low; CN103012165A reports a method for generating 3-aminopropanol by using 1, 4-butyrolactone as a raw material, opening the ring under the action of hydrazine hydrate, adding sodium nitrite aqueous solution to generate acyl azide, and then carrying out rearrangement. The method has complex flow, and the target product 3-aminopropanol has low yield, thus being not suitable for large-scale production; von Willebrand discloses a method for preparing 3-aminopropanol by synthesizing cyclohexanone oxime by using cyclohexanone as a raw material, then condensing the cyclohexanone oxime with acrylonitrile and then carrying out 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 can undergo nucleophilic ring-opening reactions on oxetanes using LiBF4As promoter acetonitrile as solvent oxetane was reacted with amine/ammonia at 80 ℃ to give the corresponding γ -amino alcohol. LiBF in the reaction process4Slowly release BF3，BF3Acting on the oxetane oxygen atom to promote amine/ammonia nucleophilic attack on oxetanes, but in this process LiBF4The dosage is large and the continuous use cannot be realized.
The currently used method is obtained by catalytic hydrogenation of 3-hydroxypropionitrile, and patents CH 244837B, DE 2655794B, EP 1132371 a1, JP 2002201164 a, etc. report a method for reacting 3-hydroxypropionitrile with hydrogen to produce 3-aminopropanol. The method can directly synthesize the target product 3-aminopropanol by one step, but still has the problem of low selectivity of the target product. JP 1993163213A discloses a Raney cobalt catalyst used in the reaction of synthesizing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile, and the catalyst system has high danger and is not easy to realize industrial application. Patent CN103261148A reports a process for the production and purification of 3-aminopropanol, with a selectivity of 3-aminopropanol of up to 93%, but with a reaction pressure of up to 18MPa and a mass space-time yield of 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 the catalyst has low activity, short life and harsh reaction conditions, and the industrial application value is low, and the technical method having industrial application value has 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 in the prior art, the invention provides the catalyst for preparing the 3-aminopropanol and the preparation and application thereof.
In order to realize the purpose, the invention adopts the following technical scheme:
a preparation method of copper amide 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 to perform 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 (2) heating the amino copper nickel silicide obtained in the step (1), quaternary ammonium salt and titanate in an alcohol solvent to react, and after the reaction is finished, performing post-treatment to obtain the amino copper nickel silicide porous particles, wherein the post-treatment comprises drying, roasting and crushing.
The porous particles of the nickel-copper amide silicide 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 the purity are higher, and the method does not use hydrogen with higher pressure, so the method has good safety and high industrial utilization value.
Preferably, in the step (1) and the step (2), the alcohol solvent is independently selected from C1～C4An alkyl alcohol; further preferred is methanol, ethanol, n-propanol or n-butanol, and most preferred is absolute ethanol.
Preferably, in the step (1), the silica sol contains 25 to 35 mass% of silica, has a particle size of 15 to 18nm, and has a pH of 8.0 to 9.0; the silane coupling agent is a silane coupling agent KH560, KH550, KH570 or KH 1770.
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 hydrates thereof.
Preferably, in step (1), the amino-substituted benzoic acid is p-aminobenzoic acid, m-aminobenzoic acid or o-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 adding 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 adding amount is 35-48% of the mass of the silica sol; the addition 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 R4N+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 hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride or hexadecyl 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 adding 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 copper amide 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 ℃ at the speed of 2-4 ℃/min and at the speed of 1500-2000 rpm, reacting at a constant temperature for 3-5 hours, cooling to room temperature, transferring to 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 the heating rate of 3-5 ℃/min, reacting at a constant temperature for 16-20 hours, cooling to room temperature, filtering to obtain light blue solid, drying at 70-90 ℃, washing with absolute ethyl alcohol for three times, naturally drying, and crushing to 600-800 meshes to obtain light blue powder which is an amino copper nickel silicide;
(2) preparation of porous particles of nickel amido copper silicide
Adding amino copper nickel silicide, hexadecyl trimethyl ammonium bromide and tetrabutyl titanate into absolute ethyl alcohol according to a certain mass ratio, heating to 30-40 ℃, keeping the temperature constant, stirring at 1000-1600 rpm for reaction for 1-2 hours, carrying out vacuum drying on a product obtained after the reaction at 60-80 ℃ to remove ethanol, then putting the product into a muffle furnace, heating to 300-450 ℃ at the speed of 1-2.5 ℃/min, roasting at the constant temperature for 2-3 hours, cooling to room temperature, and crushing into 60-100-mesh particles, namely the amino copper nickel silicide porous particles.
As a further preferred, the preparation method of the copper amide 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, heating to 100 ℃ at the speed of 3 ℃/min under the condition of 1800 revolutions per minute, reacting at constant temperature for 4.5 hours, cooling to room temperature, transferring to 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, filtering to obtain a light blue solid, drying at 80 ℃, washing with absolute ethyl alcohol for three times, naturally drying, and crushing into 750 meshes to obtain light blue powder, namely an 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 adding amount is 50% of the mass of the silica sol;
the mass fraction of the nickel nitrate aqueous solution is 27 percent, and the adding amount is 40 percent of the mass of the silica sol;
the addition amount of the p-aminobenzoic acid is 28 percent of the mass of the silica sol;
(2) preparation of porous particles of nickel amido copper silicide
Adding amino copper nickel silicide, hexadecyl trimethyl ammonium bromide and tetrabutyl titanate into absolute ethyl alcohol, heating to 35 ℃ and keeping the temperature constant, stirring at 1400 rpm for reaction for 1.6 hours, drying the product obtained after the reaction in vacuum at 70 ℃ to remove the ethyl alcohol, then putting the product into a muffle furnace, heating to 380 ℃ at the speed of 2 ℃/min, roasting at the constant temperature for 2.5 hours, cooling to room temperature, and crushing into 80-mesh particles to obtain the high-selectivity catalyst;
the mass ratio of the amino copper nickel silicide to the hexadecyl trimethyl ammonium bromide to the tetrabutyl titanate is 155:12: 33;
the addition amount of the absolute ethyl alcohol is 40 percent of the total mass of the amino copper nickel silicide, the hexadecyl trimethyl ammonium bromide and the tetrabutyl titanate.
The invention also provides the copper amide nickel silicide porous particle prepared by the preparation method.
The invention also provides a preparation method of the 3-aminopropanol, 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 product is obtained by rectification after ammonia is removed by reduced pressure distillation;
the high-selectivity catalyst is the copper amide 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 particles of the copper-amino-nickel silicide are filled into 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 and the 1, 3-propylene oxide are pumped into the reaction section of the tubular reactor together for reaction.
Preferably, the preheating temperature of the liquid ammonia in the preheating section is 80-100 ℃, the temperature of the reaction section is 90-110 ℃, and the retention 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 reaction section of the tubular reactor according to the mass ratio of 1:9 of 1, 3-epoxypropane to liquid ammonia, the temperature of the reaction section of the tubular reactor is set to be 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 rectified to obtain the product 3-aminopropanol after the ammonia is removed by pressure reduction and evaporation.
Compared with the prior art, the invention has the following beneficial effects:
(1) the porous particle catalyst of the nickel amido copper silicide for catalyzing the reaction of the 1, 3-epoxypropane and the liquid ammonia with high selectivity is synthesized, the catalyst is used for preparing the 3-aminopropanol, the yield is 95.3-96.5% in terms of 1, 3-epoxypropane, the purity is 99.2-99.8%, and the yield and the purity are obviously improved;
(2) the catalyst of the invention is adopted to synthesize the 3-aminopropanol, the use of high-pressure hydrogen is avoided, the operation is safer, and the industrial application value is higher.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
The silica sol used in the present invention can be directly commercially available.
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 ℃ at the speed of 3 ℃/min and 1800 revolutions per minute, the mixture is reacted for 4.5 hours at constant temperature, the mixture is cooled to room temperature and then transferred into a stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, 420kg of 24 wt% copper chloride aqueous solution, 336kg of 27 wt% nickel nitrate aqueous solution and 235.2kg of p-aminobenzoic acid are added, the mixture is heated to 130 ℃ at the temperature raising rate of 4 ℃/min and then reacted for 18 hours at constant temperature, the mixture is cooled to room temperature, light blue solid obtained by filtration is dried at 80 ℃, washed for three times by absolute ethyl alcohol and then naturally aired, and then the mixture is crushed into 750 meshes, and the light blue powder is amino copper nickel silicide;
the silica sol comprises 30 mass percent of silica, the particle size is 15-18 nm, and the pH value is 8.5;
(2) preparation of porous particles of nickel amido copper silicide
Adding 620kg of amino copper nickel silicide, 48kg of hexadecyl trimethyl ammonium bromide and 132kg of tetrabutyl titanate into 320kg of absolute ethyl alcohol, heating to 36 ℃ and keeping the temperature constant, stirring at 1400 rpm for reaction for 1.6 hours, drying the product obtained after the reaction in vacuum at 70 ℃ to remove the ethyl alcohol, then putting the product into a muffle furnace, heating to 380 ℃ at the speed of 2 ℃/min, roasting at the constant temperature for 2.5 hours, cooling to room temperature, and crushing into 80-mesh particles, namely 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 90 ℃, 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 1:9, the temperature of the reaction section of the tubular reactor is set to be 95 ℃, and the mass space velocity is 7h-1Continuously collecting reaction products to obtain crude 3-aminopropanol, decompressing and distilling the crude 3-aminopropanol to remove ammonia, and rectifying to obtain a product 3-aminopropanol;
the 3-aminopropanol obtained in example 1 had a GC purity of 99.8% and a yield of 96.5% based on 1, 3-epoxypropane.
Example 2
The method comprises the following steps:
1. high selectivity catalyst preparation
(1) Preparation of amino copper nickel silicide
Adding 800kg of silica sol, 60kg of absolute ethyl alcohol and 40kg of silane coupling agent KH560 into a reaction kettle, heating to 90 ℃ at the speed of 2 ℃/min and 1500 rpm, reacting for 3 hours at constant temperature, cooling to room temperature, transferring to a stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, adding 360kg of 20 wt% copper chloride aqueous solution, 280kg of 24 wt% nickel nitrate aqueous solution and 176kg of p-aminobenzoic acid, heating to 120 ℃ at the heating rate of 3 ℃/min, reacting for 16 hours at constant temperature, cooling to room temperature, filtering to obtain light blue solid, drying at 70 ℃, washing with absolute ethyl alcohol for three times, naturally drying, and crushing to 600 meshes to obtain light blue powder which is an amino copper nickel silicide;
the silica sol comprises 30 mass percent of silica, the particle size is 15-18 nm, and the pH value is 8.5;
(2) preparation of porous particles of nickel amido copper silicide
Adding 600kg of amino copper nickel silicide, 32kg of hexadecyl trimethyl ammonium bromide and 168kg of tetrabutyl titanate into 264kg of absolute ethyl alcohol, heating to 30 ℃ and keeping the temperature constant, stirring at 1000 rpm for reaction for 1 hour, drying the product obtained after the reaction in vacuum at 60 ℃ to remove the ethanol, then putting the product into a muffle furnace, heating to 300 ℃ at the speed of 1 ℃/min, roasting at the constant temperature for 2 hours, cooling to room temperature, and crushing into 60-mesh particles to obtain the high-selectivity catalyst.
2. Synthesis of 3-aminopropanol
Filling a high-selectivity catalyst into a reaction section of the tubular reactor, pumping liquid ammonia into a preheating section of the tubular reactor, wherein the preheating temperature is 80 ℃, 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, setting the temperature of the reaction section of the tubular reactor to be 90 ℃, and the mass space velocity to be 8h-1Continuously collecting reaction products to obtain crude 3-aminopropanol, decompressing and distilling the crude 3-aminopropanol to remove ammonia, and rectifying to obtain a product 3-aminopropanol;
the 3-aminopropanol obtained in example 2 had a GC purity of 99.3% and a yield of 95.3% based on 1, 3-epoxypropane.
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 ℃ at 4 ℃/min and 2000 rpm, the mixture is reacted for 5 hours at constant temperature, the mixture is cooled to room temperature and then transferred into a stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, 484kg of 26 wt% copper chloride aqueous solution, 422.4kg of 30 wt% nickel nitrate aqueous solution and 281.6kg of p-aminobenzoic acid are added, the mixture is heated to 140 ℃ at the heating rate of 5 ℃/min and then reacts for 20 hours at constant temperature, the mixture is cooled to room temperature and then filtered to obtain light blue solid, the light blue solid is dried at 90 ℃, the light blue solid is washed with absolute ethyl alcohol for three times and then is naturally dried, and then the light blue solid is crushed into 800 meshes, and the obtained light blue powder is an amino copper nickel silicide;
the silica sol comprises 30 mass percent of silica, the particle size is 15-18 nm, and the pH value is 8.5;
(2) preparation of porous particles of nickel amido copper silicide
480kg of amino copper nickel silicide, 48kg of hexadecyl 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 the constant temperature, the mixture is stirred at 1600 rpm for reaction for 2 hours, the product obtained after the reaction is dried in vacuum at 80 ℃ to remove the ethanol, then the product is put into a muffle furnace, the temperature is raised to 450 ℃ at the speed of 2.5 ℃/min and roasted at the constant temperature for 3 hours, and the product is crushed into 100-mesh particles after being cooled to the room temperature, so that the high-selectivity catalyst is obtained.
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 ℃, 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, the temperature of the reaction section of the tubular reactor is set to be 110 ℃, and the mass space velocity is 4h-1Continuously collecting reaction products to obtain crude 3-aminopropanol, decompressing and distilling the crude 3-aminopropanol to remove ammonia, and rectifying to obtain a product 3-aminopropanol;
the 3-aminopropanol obtained in example 3 had a GC purity of 99.2% and a yield of 95.9% based on 1, 3-epoxypropane.
Example 4
In example 3, 48Kg of cetyltrimethylammonium bromide was changed to 48Kg of cetyltrimethylammonium chloride in step 1(2), and the other conditions were maintained, whereby the 3-aminopropanol obtained finally had a GC purity of 99.2% and a yield of 95.3% based on 1, 3-propylene oxide.
Comparative example 1: example 1 replacement of 80 mesh high selectivity catalyst with 80 mesh silicon nitride ceramic particles
1. Synthesis of 3-aminopropanol
Filling 80-mesh silicon nitride ceramic particles into a reaction section of a tubular reactor, pumping liquid ammonia into a preheating section of the tubular reactor, wherein the preheating temperature is 90 ℃, 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 1:9, the temperature of the reaction section of the tubular reactor is set to 95 ℃, and the mass space velocity is 7h-1Continuously collecting reaction products to obtain crude 3-aminopropanol, decompressing and steaming the crude 3-aminopropanol to remove ammonia, and then rectifying to obtain a product 3-aminopropanol;
the 3-aminopropanol obtained in comparative example 1 had a purity of 10.1% and a yield of 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 operation is carried out according to the detailed description of example 1 in the patent
Sucking a nickel catalyst and silver nitrate into a high-pressure reduction kettle through a vacuum pump, sucking methanol and 3-hydroxypropionitrile, closing a vacuum valve, opening an air vent valve, replacing air in the kettle with nitrogen for at least three times, exhausting and emptying slowly at 0.2MPa each time, closing the air vent valve and the air emptying valve after the replacement is finished, opening an ammonia inlet valve, starting stirring, opening jacket cooling water, and introducing liquid ammonia; stopping stirring after ammonia introduction is finished, closing an ammonia introduction valve, opening a hydrogen introduction valve, replacing hydrogen for three times to remove residual nitrogen, discharging air slowly at 0.2MPa each time, closing the valve after replacement is finished, starting stirring, opening a steam valve, heating to 45 ℃, starting introducing hydrogen, keeping the pressure in the kettle at 3MPa, introducing cooling water into a reduction kettle jacket and an inner coil pipe, and controlling the reaction temperature in the kettle at 75 ℃;
when the hydrogen pressure does not drop any more, indicating that the reaction has reached the end point, stopping stirring, standing for half an hour, cooling to the temperature of 40 ℃ in the kettle by using jacket water, releasing pressure, introducing nitrogen for three times for replacement, pressing nitrogen into a high-level settling tank, standing for 6 hours for precipitation, collecting a small amount of catalyst and impurities at the lower layer, and distilling the upper layer; the nickel catalyst at the bottom of the reduction kettle still sinks at the bottom, and the methanol is supplemented for use; putting the upper layer liquid of the settling tank into a distillation kettle, opening an emptying valve, heating, and collecting methanol after the liquid temperature is 95 ℃; after the methanol is collected, the temperature of the cooling kettle is 60 ℃ for reduced pressure distillation, the vacuum degree is kept to be less than-0.09 MPa, a front fraction (a very small amount of methanol) is collected when the top temperature reaches 90 ℃, a main fraction is collected when the top temperature reaches 95 ℃, the temperature of the liquid is controlled to be 110 ℃ when the main fraction is collected until the collection is finished, and the qualified product with the content of more than 99 percent is obtained through chromatographic detection, and the yield is 98 percent; the mol ratio of the 3-hydroxypropionitrile to the ammonia water is 1: 1.15; the dosage of the Raney nickel catalyst is 0.006 percent of the mass of the 3-hydroxypropionitrile;
the purity of 3-aminopropanol obtained in comparative example 2 is 97.9%, the yield is 99.2% calculated by 3-hydroxypropionitrile, and compared with examples 1, 2 and 3, the 3-aminopropanol obtained in the example has slightly lower purity and higher yield, but in comparative example 2, hydrogen with higher risk is needed, the pressure of 3MPa needs to be maintained in the reaction process, the production operation complexity is high, and the safety is low.

Claims (12)

1. A preparation method of porous particles of nickel amido copper silicide is characterized by comprising 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 to perform hydrothermal reaction, and after the reaction is finished, performing post-treatment to obtain an amino-copper-nickel silicide;
(2) and (2) heating the amino copper nickel silicide obtained in the step (1), quaternary ammonium salt and titanate in an alcohol solvent for reaction, and after the reaction is finished, carrying out post-treatment to obtain the amino copper nickel silicide porous particles.
2. The method for preparing porous particles of nickel amino silicide as defined in claim 1, wherein the alcohol is used in the step (1) and the step (2)The solvent is independently selected from C1～C4An alkyl alcohol.
3. The method for preparing porous particles of nickel amide silicide according to claim 1, wherein in the step (1), the silica sol contains 25 to 35 mass% of silica, has a particle size of 15 to 18nm, and has a pH of 8.0 to 9.0; the silane coupling agent is a silane coupling agent KH560, KH550, KH570 or KH 1770.
4. The method for preparing porous particles of copper nickel amide 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 hydrates thereof.
5. The method for preparing porous particles of copper nickel amide silicide as claimed in claim 1, wherein the amino-substituted benzoic acid is p-aminobenzoic acid, m-aminobenzoic acid or o-aminobenzoic acid in the step (1).
6. The method for preparing the porous nickel amino silicide particles 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 adding 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 adding amount is 35-48% of the mass of the silica sol; the adding amount of the amino-substituted benzoic acid is 22-32% of the mass of the silica sol.
7. The method for preparing porous particles of nickel amido silicide according to claim 1, characterized in that, in the step (2), the quaternary ammonium salt is cetyltrimethyl ammonium bromide, cetyltrimethyl ammonium chloride or cetyldimethyl benzyl ammonium bromide;
the titanate is tetrabutyl titanate, tetraisopropyl titanate or tetraethyl titanate.
8. The method for preparing the porous particles of the 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 adding 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. A porous particle of nickel amide silicide, which is prepared by the preparation method of any one of claims 1 to 8.
10. A preparation method of 3-aminopropanol is characterized in that 1, 3-epoxypropane reacts with liquid ammonia under the action of a high-selectivity catalyst to obtain a 3-aminopropanol crude product, and the 3-aminopropanol product is obtained by rectification after ammonia is removed by reduced pressure distillation;
the high selectivity catalyst is the copper amide nickel silicide porous particles of claim 9.
11. The process for preparing 3-aminopropanol according to claim 10, wherein said reaction is carried out in a tubular reactor, said tubular reactor comprises a preheating section and a reaction section which are communicated, said porous particles of aminocopper-nickel silicide are filled into said reaction section of said tubular reactor during the reaction, and liquid ammonia is pumped into said preheating section of said tubular reactor to be preheated, and then pumped into said reaction section of said tubular reactor together with 1, 3-propylene oxide to be reacted.
12. The method for preparing 3-aminopropanol according to claim 11, wherein the preheating temperature of 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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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101033193A (en) * 2007-04-11 2007-09-12 浙江大学 Method of synthesizing 2-aminopropanol
CN110981738A (en) * 2019-12-30 2020-04-10 杭州新本立医药有限公司 Synthesis method of 2-aminopropanol
CN113121368A (en) * 2021-03-29 2021-07-16 安徽华恒生物科技股份有限公司 Method for preparing gamma-aminopropanol by one-step catalytic hydrogenation and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101033193A (en) * 2007-04-11 2007-09-12 浙江大学 Method of synthesizing 2-aminopropanol
CN110981738A (en) * 2019-12-30 2020-04-10 杭州新本立医药有限公司 Synthesis method of 2-aminopropanol
CN113121368A (en) * 2021-03-29 2021-07-16 安徽华恒生物科技股份有限公司 Method for preparing gamma-aminopropanol by one-step catalytic hydrogenation and application thereof

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