CN111196763A - Catalyst for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile and preparation method thereof - Google Patents

Catalyst for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile and preparation method thereof Download PDF

Info

Publication number
CN111196763A
CN111196763A CN201811372092.0A CN201811372092A CN111196763A CN 111196763 A CN111196763 A CN 111196763A CN 201811372092 A CN201811372092 A CN 201811372092A CN 111196763 A CN111196763 A CN 111196763A
Authority
CN
China
Prior art keywords
catalyst
auxiliary agent
active metal
hydroxypropionitrile
carrier
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
CN201811372092.0A
Other languages
Chinese (zh)
Other versions
CN111196763B (en
Inventor
丁云杰
马雷
严丽
程显波
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.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
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 Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201811372092.0A priority Critical patent/CN111196763B/en
Publication of CN111196763A publication Critical patent/CN111196763A/en
Application granted granted Critical
Publication of CN111196763B publication Critical patent/CN111196763B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8896—Rhenium
    • B01J35/615—
    • B01J35/633—
    • B01J35/635—
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • 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
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups

Abstract

The application discloses a catalyst for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile, which is characterized by comprising an active component and a carrier; the active component comprises an active metal element; the active component comprises an active metal element; the active metal elements include M and Re; m is at least one selected from Ni, Co and Cu; m accounts for 5.0-50.0% of the weight of the catalyst; re accounts for 0.1-15.0% of the weight of the catalyst; the carrier is selected from at least one of inorganic porous materials. The catalyst has high catalytic activity and selectivity.

Description

Catalyst for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile and preparation method thereof
Technical Field
The application relates to a catalyst for synthesizing 3-aminopropanol, in particular to a catalyst for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile under the ammonia-contacting condition, belonging to the field of catalysis.
Background
3-aminopropanol is an important chemical raw material and a fine chemical intermediate, and has wide application in the fields of medicines, pesticides, dyes, surfactants, daily cosmetics and the like; as a common drug intermediate, can be used for synthesizing anti-cancer drugs such as cyclophosphamide, cardiotrophin and the like, and can also be used for synthesizing DL-panthenol (provitamin B5); the method can also be used for producing panthenol and pantothenic acid derivatives used as ointment components in daily cosmetics, and in recent years, due to the improvement of living standard of people, the application of the panthenol in daily chemical products is continuously improved, especially the application of the panthenol in hair care products and cosmetics is more and more extensive, so that the market demand of 3-aminopropanol is greatly driven.
The conventional method for producing 3-aminopropanol at present is obtained by catalytic hydrogenation of 3-hydroxypropionitrile, and 3-hydroxypropionitrile, Raney Ni, ethanol and ammonia are added into an autoclave for reaction, so that the selectivity of the obtained 3-aminopropanol is 95 percent, and the yield is 60 percent. In addition, 3-aminopropanol can also be synthesized by other routes: synthesizing ketoxime by using methyl isobutyl ketone or cyclohexanone as a raw material, further condensing with acrylonitrile, and preparing 3-aminopropanol by catalytic hydrocracking; 3-aminopropionic acid ethyl ester and 2-cyanoethanol are used as raw materials to synthesize the 3-aminopropanol. However, compared with the 3-hydroxypropionitrile hydrogenation route, other methods have the defects of high raw material cost, complex process, low product yield and the like.
German patent DE573983 reports the purification of hydrogenation products of 3-hydroxypropionitrile by fractional distillation using hydrogenation catalysts synthesized from transition metals of groups 8, 9 and 10. Swiss patent CH244837 reports a catalytic hydrogenation process of nitriles, the hydrogenation reaction is carried out in liquid ammonia, and the patent reports that the liquid ammonia can inhibit byproducts and improve the selectivity of primary amine. German patent DE2655794 reports a process for the hydrogenation of 3-aminopropanol from 3-hydroxypropionitrile, the reaction being carried out in the presence of a hydrogenation catalyst, hydrogen and ammonia, the addition of which makes it possible to suppress the formation of secondary amines and to increase the selectivity of 3-aminopropanol. Japanese patents JP2002201164 and JP05163213 adopt Raney cobalt catalyst to catalyze and hydrogenate 3-hydroxypropionitrile in the presence of ammonia, inhibit the generation of secondary amine and tertiary amine, and improve the yield of 3-aminopropanol. Japanese patent JP59210258 reports that in the preparation of 3-aminopropanol by catalytic hydrogenation of hydroxypropionitrile as a raw material, the catalyst selectivity is low, the number of byproducts is large, and the yield of the 3-aminopropanol is only 70%. In Chinese patent CN103261148A disclosed by BASF corporation, cobalt-based catalyst and P, Mn or alkaline earth metal as auxiliary are adopted to perform catalytic hydrogenation reaction of 3-hydroxypropionitrile in a fixed bed reactor, and the reaction product is subjected to multi-stage distillation to obtain high-purity 3-aminopropionitrile, so as to meet the quality standard of cosmetics and pharmaceutical industry.
The existing catalyst is used for preparing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile, and has the problems of poor catalyst activity, low 3-aminopropanol yield, high byproduct selectivity and the like.
Disclosure of Invention
According to one aspect of the application, a catalyst for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile is provided, and the catalyst has high catalytic activity and high selectivity to 3-aminopropanol.
The catalyst provided by the application comprises three parts of an active component, an auxiliary agent and a carrier: the active component is M-Re bimetal, wherein M is one or more than two of transition metals Ni, Co or Cu, and is preferably metal Ni.
The auxiliary agent is one or more of nonmetal, metal or metal oxide of one or more of Fe, Cr, W, Ru, B, Mg, Ba, Mn, La and Mo, and preferably one or more of the auxiliary agents Ru, B, Mn or Ba.
The carrier is porous material Al2O3、SiO2Or Al2O3-SiO2One or more than two of them.
The weight of the active component M accounts for 5.0-50.0% of the weight of the catalyst, preferably 10.0-25.0%; the weight of Re accounts for 0.1-15.0% of the weight of the catalyst, preferably 1.0-5.0%; the weight of the auxiliary agent accounts for 0.2-10.0% of the weight of the catalyst, preferably 1.0-5.0%; the specific surface area of the porous carrier is 50-600 m2A concentration of 200 to 500m is preferred2(ii)/g; the porous carrier has a pore volume of 0.2 to 1.5ml/g, preferably 0.4 to 1.0 ml/g.
The catalyst is characterized by comprising an active component and a carrier;
the active component comprises an active metal element; the active metal elements include M and Re; m is at least one selected from Ni, Co and Cu; m accounts for 5.0-50.0% of the weight of the catalyst; re accounts for 0.1-15.0% of the weight of the catalyst;
the carrier is selected from at least one of inorganic porous materials.
Optionally, the weight percentage of the active metal element M in the catalyst is 10.0-25.0%
Re accounts for 1.0-5.0% of the weight of the catalyst.
Optionally, the catalyst further comprises an auxiliary agent;
the auxiliary agent comprises an auxiliary agent element, and the auxiliary agent element comprises at least one of Fe, Cr, W, Ru, B, Mg, Ba, Mn, La and Mo;
the auxiliary agent comprises an oxide of the auxiliary agent element;
the weight percentage of the auxiliary agent in the catalyst is 0.2-10.0%.
Optionally, the weight percentage of the auxiliary agent in the catalyst is 1.0-5.0%;
wherein, the weight percentage of the auxiliary agent is calculated by the weight percentage of the auxiliary agent element.
Optionally, the auxiliary element is at least one selected from Ru, B, Mn, Ba.
Optionally, the upper limit of the weight percent content of M in the catalyst is selected from 6.0%, 7.0%, 8.0%, 9.0%, 10.0%, 15.0%, 20.0%, 25.0%, 30.0%, 35.0%, 40.0%, 45.0%, or 50%; the lower limit is selected from 5.0%, 6.0%, 7.0%, 8.0%, 9.0%, 10.0%, 15.0%, 20.0%, 25.0%, 30.0%, 35.0%, 40.0%, 45.0%, 50%.
Alternatively, the upper limit of the weight percent content of Re in the catalyst is selected from 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 8%, 10%, 12%, or 15%; the lower limit is selected from 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 8%, 10% or 12%.
Optionally, the upper limit of the weight percent of promoter in the catalyst is selected from 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 8%, or 10%; the lower limit is selected from 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% or 8%.
Optionally, the specific surface area of the carrier is 50-600 m2The pore volume is 0.2-1.5 ml/g.
Optionally, the specific surface area of the carrier is 200-500 m2The pore volume is 0.4-1.0 ml/g.
Optionally, the support is selected from porous Al2O3Porous SiO2Porous Al2O3-SiO2At least one of (1).
Optionally, the support is selected from Al2O3、SiO2、Al2O3-SiO2。
Optionally, the support is selected from porous inorganic oxides.
Optionally, the specific surface area of the carrier is 50-600 m2The pore volume is 0.2-1.5 ml/g.
Optionally, the metal element M includes at least one of Ni, Co, and Cu.
Optionally, the active component is metal Ni, metal Re; the active component accounts for 10.0-25.0% of the weight of the catalyst; re accounts for 1.0-5.0% of the weight of the catalyst; the auxiliary agent comprises at least one of Ru, B, Mn and Ba elements; the auxiliary agent accounts for 1.0-5.0% of the weight of the catalyst; the specific surface area of the carrier is 200-500 m2The pore volume is 0.4 to 1.0 ml/g.
According to another aspect of the present application, a preparation method of the catalyst is provided, which is simple and feasible and is suitable for industrial production.
The preparation method of the catalyst is characterized in that the catalyst adopts an impregnation method and/or a precipitation method to load the active component and the auxiliary agent on the carrier.
Optionally, the impregnation method comprises the steps of:
and (3) soaking the carrier in an aqueous solution containing an active component precursor and an auxiliary agent precursor, naturally airing, and roasting I to obtain the catalyst.
Optionally, the roasting I temperature is 300-700 ℃, the heating rate is 0.5-20.0 ℃/min, and the roasting I time is 0.5-10.0 h.
Optionally, the precipitation method comprises the steps of:
adding an active component precursor and an auxiliary agent precursor into a suspension containing a carrier, adding a precipitator, and aging, washing, filtering, drying and roasting II to obtain the catalyst.
Optionally, the temperature of the roasting II is 300-700 ℃, the heating rate is 0.5-20.0 ℃/min, and the time of the roasting II is 0.5-10.0 h.
Optionally, the active component precursor comprises soluble salts of Ni, Co, Cu and Re.
Optionally, the promoter precursor comprises a soluble precursor of B.
Specifically, the active component M-Re (M is one or more than two of transition metals Ni, Co or Cu) bimetal.
The soluble salt of Ni may be nickel nitrate, nickel acetate, nickel chloride, nickel sulfate or nickel citrate, preferably nickel nitrate or nickel acetate.
The soluble salt of Co used may be cobalt chloride, cobalt nitrate, cobalt carbonate or cobalt sulphate, with cobalt nitrate being preferred.
The soluble salt of Cu used may be copper nitrate, copper chloride, copper carbonate or copper sulfate, preferably copper nitrate, copper sulfate.
The soluble salt of Re used is ammonium rhenate, perrhenic acid or rhenium chloride, preferably ammonium rhenate; the soluble salt of the metal auxiliary agent is nitrate or chloride.
The nonmetal auxiliary agent B is boric acid.
Alternatively, the preparation method of the catalyst can adopt one or a combination of an impregnation method and a precipitation method to load the active component and the auxiliary agent on the carrier.
In a preferred embodiment, the catalyst precursor is supported on the support material by impregnation.
Alternatively, in the impregnation embodiment, the active ingredient and the adjunct may be supported on the carrier by co-impregnation or stepwise impregnation.
Alternatively, the impregnation method may include the steps of: preparing an aqueous solution containing an active component M-Re (M is one or more than two of transition metals of Ni, Co and Cu) and an auxiliary agent, wherein the weight of the active component M accounts for 5.0-50.0% of the weight of the catalyst, the weight of the active component Re accounts for 0.1-15.0% of the weight of the catalyst, and the weight of the auxiliary agent accounts for 0.2-10.0% of the weight of the catalyst, impregnating the carrier with the aqueous solution containing the active component and the auxiliary agent, and naturally airing and roasting the impregnated carrier.
Alternatively, the impregnation method may be one-time impregnation or multi-stage impregnation.
Optionally, the roasting temperature is usually 300-700 ℃, the heating rate is usually 0.5-20.0 ℃/min, and the roasting time is usually 0.5-10.0 h.
Alternatively, the catalyst precursor may also be supported on a carrier by a precipitation method.
Alternatively, the step of preparing the catalyst by the precipitation method can be as follows: the carrier material is suspended in water, soluble precursors of active components M-Re (M is one or more of transition metals Ni, Co and Cu) and auxiliary agents, such as metal salts, are added, and then a precipitant is added to precipitate the precursors on the suspended carrier. Wherein the weight of the active component M accounts for 5.0-50.0% of the weight of the catalyst, the weight of the active component Re accounts for 0.1-15.0% of the weight of the catalyst, and the weight of the auxiliary agent accounts for 0.2-10.0% of the weight of the catalyst. And (4) aging, washing, filtering, drying and roasting the precipitated sample.
Alternatively, the precipitant used is preferably an inorganic base, preferably sodium hydroxide, sodium carbonate, potassium hydroxide or potassium carbonate.
Optionally, the precipitating agent is an inorganic base.
Optionally, the precipitant is selected from at least one of sodium hydroxide, sodium carbonate, potassium hydroxide, and potassium carbonate.
Alternatively, the precipitant used may also be an ammonium salt, which may be ammonium carbonate, ammonium hydroxide or ammonium halide.
Alternatively, the precipitant used is an ammonium salt.
Optionally, the precipitant is selected from at least one of ammonium carbonate, ammonium hydroxide, ammonium halide. Optionally, the precipitation temperature may be 20 to 90 ℃, preferably 40 to 70 ℃.
Optionally, the roasting temperature is usually 300-700 ℃, the heating rate is usually 0.5-20.0 ℃/min, and the roasting time is usually 0.5-10.0 h.
According to still another aspect of the present application, there is provided a process for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile under ammonia-contacting conditions, characterized in that a feed comprising ammonia and 3-hydroxypropionitrile is reacted in the presence of a catalyst under a hydrogen atmosphere to produce an amine;
the catalyst is selected from the group consisting of the catalyst, the catalyst prepared according to the method. Optionally, the reaction conditions are: the reaction temperature is 50-200 ℃, the reaction pressure is 5.0-20.0 MPa, and the volume space velocity of hydrogen is 50.0-2000.0 h-1The molar ratio of ammonia to 3-hydroxypropionitrile is 1.0:20.0 to 80.0: 1.0.
Optionally, the catalyst is subjected to an activation treatment under the following conditions: reduction activation in hydrogen-containing atmosphere; the pressure is 0.1-1.0 MPa, the temperature is 300-700 ℃, and the volume space velocity of hydrogen gas is 500-5000 h-1The reduction time is 0.5-10.0 h.
Alternatively, the conditions of the activation treatment are: reduction activation in hydrogen-containing atmosphere; the pressure is normal pressure, the temperature is 350-550 ℃, and the volume space velocity of hydrogen gas is 1000-3000 h-1And the reduction time is 1.5-6.0 h.
Specifically, the catalyst prepared by the impregnation method or the precipitation method is usually activated in a reducing atmosphere before use.
The reducing atmosphere may be hydrogen or a mixture of hydrogen and other inert gases, preferably hydrogen.
Alternatively, the reaction conditions are: the catalyst loading was 05 to 10.0ml, the reaction temperature is 50 to 200 ℃, the reaction pressure is 5.0 to 20.0MPa, and the volume space velocity of the 3-hydroxypropionitrile liquid is 0.1 to 10.0h-1The volume space velocity of the hydrogen gas is 50.0-2000.0 h-1The molar ratio of ammonia to 3-hydroxypropionitrile is 1.0:20.0 to 80.0: 1.0.
Preferably, the filling amount of the catalyst is 2.0-5.0 ml, the reaction temperature is 70-150 ℃, the reaction pressure is 6.0-10.0 MPa, and the liquid volume space velocity of the 3-hydroxypropionitrile is 0.2-1.0 h-1The volume space velocity of the hydrogen gas is 200.0-800.0 h-1The molar ratio of ammonia to 3-hydroxypropionitrile is 1.0:1.0 to 20.0: 1.0.
The catalyst is applied to the reaction of preparing 3-aminopropanol by catalytic hydrogenation of 3-hydroxypropionitrile. The reaction is carried out in a fixed bed reactor, and the reactant 3-hydroxypropionitrile can be hydrogenated and converted into a 3-aminopropanol product with high activity and high selectivity under the ammonia critical condition. With the formation of small amounts of by-products.
Specifically, the product is mainly 3-aminopropanol, and the by-products may be n-propylamine, propylenediamine, dipropylenetriamine (H)2N(CH2)3NH(CH2)3NH2) And hydroxypropyl propylenediamine (HO (CH)2)3NH(CH2)3NH2) And the like.
As an embodiment, the catalyst is used for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile, and is characterized in that a liquid mixture of the 3-hydroxypropionitrile and ammonia is pumped into a preheater, mixed with hydrogen, preheated to 100 ℃, and then fed into a fixed bed reactor. 3-hydroxypropionitrile and ammonia are dissolved and diluted without adding any solvent.
Alternatively, the reaction conditions are: the filling amount of the catalyst can be 0.5-10.0 ml, preferably 2.0-5.0 ml; the reaction temperature can be 50-200 ℃, and preferably 70-150 ℃; the reaction pressure is 5.0-20.0 MPa, preferably 6.0-10.0 MPa; the liquid volume space velocity of the 3-hydroxypropionitrile is 0.1-10.0 h-1Preferably 0.2 to 1.0 hour-1(ii) a The volume space velocity of the hydrogen gas is 50.0-2000.0 h-1Preferably 200.0 to 800.0 hours-1(ii) a The molar ratio of ammonia to 3-hydroxypropionitrile is 1.0:20.0 to 80.0:1.0, preferably 1.0:1.0 to 20.0: 1.0.
Compared with the prior art, the catalyst provided by the invention can obviously improve the conversion rate of 3-hydroxypropionitrile, improve the yield of the target product 3-aminopropanol and prolong the service life of the catalyst to more than 5000 h.
In the present application, an "element" is present in the form of a simple substance or a compound;
for example, "reactive metal elements include M, Re; m comprises at least one of Ni, Co and Cu, and represents that the active metal element can be an active metal simple substance or an active metal compound; the active metal compound can be an active metal oxide or an active metal salt;
for example, "the additive comprises at least one of Fe, Cr, W, Ru, B, Mg, Ba, Mn, La and Mo elements", and means that the additive is a simple substance or a compound of Fe, Cr, W, Ru, B, Mg, Ba, Mn, La and Mo; the compound may be an oxide or a salt.
The beneficial effects that this application can produce include:
1) the catalyst for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile provided by the application can improve the conversion rate of 3-hydroxypropionitrile;
2) the catalyst for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile provided by the application improves the yield of the target product 3-aminopropanol;
3) the catalyst for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile provided by the application reduces the selectivity of by-product amines;
4) the catalyst for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile provided by the application reduces the cost of the catalyst;
5) the catalyst for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile provided by the application has the advantages that the service life of the catalyst is prolonged;
6) the catalyst for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile provided by the application is easy to operate.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Examples of the present application are not specifically describedThe raw materials in the examples were all purchased commercially. Al (Al)2O3Purchased from Shandong aluminum industries; SiO 22Purchased from Qingdao ocean chemical; al (Al)2O3-SiO2Purchased from Shandong aluminum industries, Inc.
The mesh number refers to the number of meshes in a length of 1 inch, for example, 20-40 mesh has a particle size of 0.425-0.850 mm;
the percentage of the catalyst composition is the weight percentage of each component in the catalyst.
Example 1
The catalyst is 10% Ni-2% Re/Al2O3. Weighing 8.8 g of 20-40 mesh Al2O3Oven-drying at 120 deg.C for 4 hr before use, and preparing 20ml solution containing 4.955 g Ni (NO)3)2·6H2O, 0.288 g NH4ReO4With which the above-mentioned Al is impregnated2O3And naturally airing the carrier, drying at 100 ℃ for 2 hours, roasting at 400 ℃ for 3 hours, and raising the temperature at the rate of 5 ℃/min.
Example 2
The catalyst is 15 percent of Ni-1 percent of Re-1.5 percent of B/SiO2. Weighing 8.25 g of 20-40 mesh SiO2Dried at 120 ℃ for 4 hours before use to prepare 20ml of Ni (NO) containing 7.432 g3)2·6H2O, 0.144 g NH4ReO40.859 g H3BO3By impregnating the above SiO with the aqueous solution2And naturally airing the carrier, drying at 100 ℃ for 4 hours, roasting at 400 ℃ for 5 hours, and raising the temperature at the rate of 5 ℃/min.
Example 3
The catalyst is 8 percent of Ni-8 percent of Co-2 percent of Re-1 percent of Mn/Al2O3. Weighing 8.9 g of 20-40 mesh Al2O3Dried at 120 ℃ for 4 hours before use to prepare 20ml of Ni (NO) containing 3.964 g3)2·6H2O, 3.951 g Co (NO)3)2·6H2O, 0.288 g NH4ReO40.651 g of Mn (NO)3)2With which the above-mentioned Al is impregnated2O3Naturally drying the carrier at 100 deg.C for 4 hr, and cooling to 400 deg.CRoasting for 1 hour, wherein the heating rate is 10 ℃/min.
Example 4
The catalyst is 20 percent of Ni-2.5 percent of Re-1 percent of Ru-1 percent of B/SiO2. Weighing 7.55 g of 20-40 mesh SiO2Dried at 120 ℃ for 4 hours before use to prepare 20ml of Ni (NO) containing 9.909 g3)2·6H2O, 0.360 g NH4ReO40.205 g RuCl3·3H2O, 0.573 g H3BO3By impregnating the above SiO with the aqueous solution2And naturally airing the carrier, drying at 120 ℃ for 4 hours, roasting at 500 ℃ for 10 hours, and raising the temperature at a rate of 10 ℃/min.
Example 5
The catalyst is 10 percent of Co-10 percent of Cu-1.5 percent of Re-1.5 percent of Cr/SiO2-Al2O3. Weighing 7.7 g of 20-40 mesh SiO2-Al2O3Dried at 120 ℃ for 4 hours before use to prepare 20ml of solution containing 4.939 g of Co (NO)3)2·6H2O, 2.951 g Cu (NO)3)20.216 g NH4ReO40.687 g Cr (NO)3)3By impregnating the above SiO with the aqueous solution2-Al2O3And naturally airing the carrier, drying at 120 ℃ for 4 hours, roasting at 500 ℃ for 8 hours, and raising the temperature at the rate of 15 ℃/min.
Example 6
The catalyst is 10 percent of Ni-10 percent of Cu-3 percent of Re/SiO2-Al2O3. Weighing 7.7 g of 100 mesh SiO2-Al2O3Drying at 120 deg.C for 4 hr before use to remove SiO2-Al2O3Dispersing in water to form a suspension, and stirring at a constant temperature of 50 deg.C with medium speed. The formulation contained 4.955 g of Ni (NO)3)2·6H2O, 2.951 g Cu (NO)3)20.432 g NH4ReO4The precursor liquid of (4). The precipitant is 4mol/L KOH solution. Dripping precursor liquid and precipitant into the suspension at 2mL/min, keeping pH at 9 until precipitation is complete, washing the precipitate with deionized water to neutrality, filtering, air drying, oven drying at 120 deg.C for 4 hr, baking at 500 deg.C for 8 hr, and heating at high speedThe rate was 2 ℃/min.
Example 7
The catalyst is 15 percent of Cu-2 percent of Re/SiO2. Weighing 8.3 g of 100 mesh SiO2Drying at 120 deg.C for 4 hr before use to remove SiO2Dispersing in water to form a suspension, and stirring at a constant temperature of 50 deg.C with medium speed. The formulation contained 4.427 g of Cu (NO)3)20.288 g NH4ReO4The precursor liquid of (4). The precipitant is 4mol/L (NH)4)2·CO3And (3) solution. And (3) slowly dripping the precursor liquid and a precipitator into the suspension liquid at the same time, keeping the pH value at 7-9 until the precipitation is complete, washing the precipitate to be neutral by using deionized water, filtering, airing, drying for 4 hours at 120 ℃, roasting for 5 hours at 600 ℃, and raising the temperature at the rate of 2 ℃/min.
Example 8
The catalyst is 15 percent of Co-15 percent of Cu-5 percent of Re-2.5 percent of La/Al2O3. Weighing 6.25 g of 20-40 mesh Al2O3Dried at 120 ℃ for 4 hours before use to prepare 20ml of a mixture containing 7.408 g of Co (NO)3)2·6H2O, 4.427 g Cu (NO)3)20.720 g NH4ReO40.779 g La (NO)3)3·6H2An aqueous solution of O, and impregnating the Al with the aqueous solution2O3And naturally airing the carrier, drying at 120 ℃ for 4 hours, roasting at 600 ℃ for 10 hours, and raising the temperature at the rate of 20 ℃/min.
Example 9
The catalyst is 25 percent of Ni-2.5 percent of Re-2 percent of W/SiO2. Weighing 7.05 g of 20-40 mesh SiO2Dried at 120 ℃ for 4 hours before use to prepare 20ml of Ni (NO) containing 12.387 g3)2·6H2O, 0.360 g NH4ReO40.359 g Na2WO4·2H2An aqueous solution of O, impregnating the above SiO with the aqueous solution2And naturally airing the carrier, drying at 120 ℃ for 4 hours, roasting at 600 ℃ for 3 hours, and raising the temperature at a rate of 10 ℃/min.
Comparative example 1
The catalyst is 20 percent of Ni-5 percent of Ru/SiO2-Al2O3. Weighing 7.5 g of 20-40 mesh SiO2-Al2O3Dried at 120 ℃ for 4 hours before use to prepare 20ml of Ni (NO) containing 9.909 g3)2·6H2O, 1.026 g RuCl3·3H2An aqueous solution of O, impregnating the above SiO with the aqueous solution2-Al2O3And naturally airing the carrier, drying at 100 ℃ for 4 hours, roasting at 400 ℃ for 8 hours, and raising the temperature at a speed of 10 ℃/min.
Comparative example 2
The catalyst is 15 percent of Ni-15 percent of Cu-3 percent of Ba/Al2O3. 6.7 g of 100 mesh Al are weighed out2O3Drying at 120 deg.C for 4 hr before use, and mixing Al2O3Dispersing in water to form a suspension, and stirring at a constant temperature of 50 deg.C with medium speed. The formulation contained 7.432 g of Ni (NO)3)2·6H2O, 4.427 g Cu (NO)3)20.571 g of Ba (NO)3)2The precursor liquid of (4). The precipitant is 4mol/L KOH solution. And (3) slowly dripping the precursor liquid and a precipitator into the suspension liquid at the same time, keeping the pH value at 7-9 until the precipitation is complete, washing the precipitate to be neutral by using deionized water, filtering, airing, drying for 4 hours at 120 ℃, roasting for 5 hours at 500 ℃, and raising the temperature at the rate of 5 ℃/min.
Comparative example 3
The catalyst is 1 percent of Ni-1 percent of Cu-5 percent of Re-2 percent of Mn/SiO2. Weighing 9.1 g of 20-40 mesh SiO2Dried at 120 ℃ for 4 hours before use, and prepared into 20ml containing 0.495 g of Ni (NO)3)2·6H2O, 0.295 g Cu (NO)3)20.720 g NH4ReO41.303 g Mn (NO)3)2By impregnating the above SiO with the aqueous solution2And naturally airing the carrier, drying at 100 ℃ for 4 hours, roasting at 600 ℃ for 3 hours, and raising the temperature at the rate of 2 ℃/min.
Example 10 evaluation of the Performance of the catalysts prepared in examples 1 to 9 and comparative examples 1 to 3
The catalyst prepared by the method adopts a fixed bed reactor for reaction evaluation. Before reaction, activating in hydrogen atmosphere at 500 deg.C, normal pressure and hydrogen gas volume space velocity of 1500h-1The activation time is 5 h. After activation treatmentThe temperature is lowered to the reaction temperature. The reaction temperature is 100 ℃, the reaction pressure is 8.0MPa, and the liquid volume space velocity of the 3-hydroxypropionitrile is 0.5h-1The volume space velocity of hydrogen gas is 1000h-1The molar ratio of ammonia to 3-hydroxypropionitrile was 5.0: 1.0. Sampling and analyzing by adopting an Agilent7890 gas chromatograph, wherein the chromatographic column is a DB-35 capillary chromatographic column, and the detector is a hydrogen flame detector. Quantitative analysis was performed using N, N-Dimethylformamide (DMFA) as an internal standard. The results are summarized in Table 1.
The terms conversion of 3-hydroxypropionitrile, n-propylamine, propylenediamine, dipropylenetriamine H in Table 12N(CH2)3NH(CH2)3NH2) And hydroxypropyl propylenediamine (HO (CH)2)3NH(CH2)3NH2) The selectivity of (a) is defined as follows:
Figure BDA0001868869280000111
Figure BDA0001868869280000112
Figure BDA0001868869280000113
Figure BDA0001868869280000121
Figure BDA0001868869280000122
Figure BDA0001868869280000123
table 1: evaluation results of the catalyst for preparing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile.
Figure BDA0001868869280000124
The evaluation results show that: the catalyst adopts M-Re (M is one or more than two of transition metals of Ni, Co and Cu) bimetal as an active component, the conversion rate of 3-hydroxypropionitrile is higher, and the selectivity of the product 3-aminopropanol is high; the catalyst adopts Ni-Re bimetal as an active component, and has high activity and high yield of the product 3-aminopropanol when Ru, B, Mn or Ba is added as an auxiliary agent; M-Re (M is one or more than two of transition metals of Ni, Co and Cu) bimetal is used as an active component, when one or more of additives of Ru, B, Mn or B is added, the catalyst prepared by adopting an impregnation method or a precipitation method is used for 3-hydroxypropionitrile hydrogenation reaction under the ammonia-contacting condition, and the catalyst has the characteristics of high activity, high 3-aminopropanol yield and good stability. The kind and content of the M component also have influence on the catalytic performance, as shown in comparative example 3, comparative example 5 and comparative example 7, the catalytic performance of M metal with Ni as the active component is better than that of Cu or Co catalysts, and when the Ni content is reduced, the catalyst activity is slightly reduced.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. A catalyst for hydrogenation production of 3-aminopropanol by 3-hydroxypropionitrile is characterized in that the catalyst comprises an active component and a carrier;
the active component comprises an active metal element; the active metal elements include M and Re; m is at least one selected from Ni, Co and Cu; m accounts for 5.0-50.0% of the weight of the catalyst; re accounts for 0.1-15.0% of the weight of the catalyst;
the carrier is selected from at least one of inorganic porous materials.
2. The catalyst according to claim 1,
the weight percentage content of the active metal element M in the catalyst is 10.0-25.0%;
re accounts for 1.0-5.0% of the weight of the catalyst.
3. The catalyst according to claim 1,
the catalyst also comprises an auxiliary agent;
the auxiliary agent comprises an auxiliary agent element, and the auxiliary agent element comprises at least one of Fe, Cr, W, Ru, B, Mg, Ba, Mn, La and Mo;
the auxiliary agent comprises an oxide of the auxiliary agent element;
the weight percentage content of the auxiliary agent in the catalyst is 0.2-10.0%;
preferably, the weight percentage content of the auxiliary agent in the catalyst is 1.0-5.0%;
wherein, the weight percentage of the auxiliary agent is calculated by the weight percentage of the auxiliary agent element;
preferably, the auxiliary element is at least one selected from Ru, B, Mn and Ba.
4. The catalyst according to claim 1,
the specific surface area of the carrier is 50-600 m2The pore volume is 0.2-1.5 ml/g;
preferably, the specific surface area of the carrier is 200-500 m2The pore volume is 0.4-1.0 ml/g;
preferably, the support is selected from porous Al2O3Porous SiO2Porous Al2O3-SiO2At least one of (1).
5. The method for preparing the catalyst according to any one of claims 1 to 4, comprising at least one of an impregnation method and a precipitation method.
6. The method of claim 5, wherein the method comprises: soaking a carrier in a solution containing an active metal element source, and roasting to obtain the catalyst; or
Adding a solution containing an active metal element source and a precipitator into a suspension containing a carrier, and precipitating to obtain the catalyst;
preferably, the solution contains an auxiliary element source;
preferably, the roasting conditions are as follows: the temperature is 300-700 ℃, and the time is 0.5-10.0 h.
7. The method of claim 6, wherein the source of the active metal element is selected from at least one of soluble salts of the active metal element;
the auxiliary agent element source is selected from at least one of soluble salts of auxiliary agent elements;
preferably, the soluble salt of the active metal element Ni comprises at least one of nickel nitrate, nickel acetate, nickel chloride, nickel sulfate and nickel citrate;
preferably, the soluble salt of the active metal element Co comprises at least one of cobalt chloride, cobalt nitrate, cobalt carbonate and cobalt sulfate;
preferably, the soluble salt of the active metal element Cu comprises at least one of copper nitrate, copper chloride, copper carbonate and copper sulfate;
preferably, the soluble salt of the active metal element Re comprises at least one of ammonium rhenate, perrhenic acid, rhenium chloride;
preferably, the auxiliary element is a metal, and the soluble salt of the auxiliary element comprises at least one of nitrate of the auxiliary element and chloride of the auxiliary element;
the assistant element is B, and the assistant element source is boric acid.
8. A method for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile under the ammonia-contacting condition is characterized in that raw materials containing ammonia and 3-hydroxypropionitrile react to prepare amine under the existence of a catalyst in a hydrogen atmosphere;
the catalyst is selected from the group consisting of the catalyst of any one of claims 1 to 4, the catalyst prepared according to the process of any one of claims 5 to 7.
9. The method according to claim 8, wherein the reaction conditions are: the reaction temperature is 50-200 ℃, the reaction pressure is 5.0-20.0 MPa, and the volume space velocity of hydrogen is 50.0-2000.0 h-1The molar ratio of ammonia to 3-hydroxypropionitrile is 1.0:20.0 to 80.0: 1.0.
10. The method according to claim 9, characterized in that the catalyst is subjected to an activation treatment under the conditions: reduction activation in hydrogen-containing atmosphere; the pressure is 0.1-1.0 MPa, the temperature is 300-700 ℃, and the volume space velocity of hydrogen gas is 500-5000 h-1The reduction time is 0.5-10.0 h;
preferably, the conditions of the activation treatment are: reduction activation in hydrogen-containing atmosphere; the pressure is normal pressure, the temperature is 350-550 ℃, and the volume space velocity of hydrogen gas is 1000-3000 h-1And the reduction time is 1.5-6.0 h.
CN201811372092.0A 2018-11-16 2018-11-16 Catalyst for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile and preparation method thereof Active CN111196763B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811372092.0A CN111196763B (en) 2018-11-16 2018-11-16 Catalyst for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811372092.0A CN111196763B (en) 2018-11-16 2018-11-16 Catalyst for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111196763A true CN111196763A (en) 2020-05-26
CN111196763B CN111196763B (en) 2021-06-01

Family

ID=70741180

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811372092.0A Active CN111196763B (en) 2018-11-16 2018-11-16 Catalyst for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111196763B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114042455A (en) * 2021-11-01 2022-02-15 浙江新和成股份有限公司 Carbonyl selective hydrogenation catalyst, preparation method and application thereof
CN114471582A (en) * 2020-10-27 2022-05-13 中国石油化工股份有限公司 Catalyst for preparing diamine by hydrogenation of dinitrile, method and application

Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3696152A (en) * 1970-06-17 1972-10-03 Dow Chemical Co Hydration of nitriles to amides using heterogeneous cupreous catalysts
US4973769A (en) * 1988-02-06 1990-11-27 Basf Aktiengesellschaft Preparation of 1,2,4-butanetriol
EP0526851A2 (en) * 1991-07-31 1993-02-10 Tosoh Corporation Process and catalyst for producing an ethylenamine
JPH05163213A (en) * 1991-12-13 1993-06-29 Koei Chem Co Ltd Production of 3-aminopropanol
JP2001342166A (en) * 2000-06-01 2001-12-11 Koei Chem Co Ltd Method of purifying 3-aminopropanol
JP2002053535A (en) * 2000-08-11 2002-02-19 Koei Chem Co Ltd Method for purifying 3-aminopropanol
CN1086314C (en) * 1995-06-02 2002-06-19 陶氏化学公司 Catalyst and process for producing amides
JP2002201164A (en) * 2000-12-28 2002-07-16 Koei Chem Co Ltd Method for producing 3-amino-1-propanol
US6534441B1 (en) * 1999-03-06 2003-03-18 Union Carbide Chemicals & Plastics Technology Corporation Nickel-rhenium catalyst for use in reductive amination processes
CN1829568A (en) * 2003-08-04 2006-09-06 催化蒸馏技术公司 Ni hydrogenation catalysts, its manufacture method and use
CN101121665A (en) * 2006-08-09 2008-02-13 三菱瓦斯化学株式会社 Production method of primary amines and catalysts for producing primary amines
CN102688763A (en) * 2011-03-22 2012-09-26 中国科学院大连化学物理研究所 Catalyst for preparing m-xylylenediamine by isophthalonitrile hydrogenation under ammonia reaction conditions
CN103159630A (en) * 2011-12-14 2013-06-19 中国科学院大连化学物理研究所 A method for preparing ethylenediamine by using ethanolamine and ammonia as raw materials
CN103261148A (en) * 2010-12-14 2013-08-21 巴斯夫欧洲公司 Method for producing and purifying 3-minopropanol
CN104662182A (en) * 2012-03-27 2015-05-27 陶氏环球技术有限责任公司 Rhenium recovery from used reductive amination catalysts
CN106807377A (en) * 2015-11-27 2017-06-09 中国科学院大连化学物理研究所 A kind of catalyst for synthesizing hexamethylene diamine
CN106807395A (en) * 2015-11-27 2017-06-09 中国科学院大连化学物理研究所 A kind of catalyst for synthesizing hexamethylene diamine
CN106810683A (en) * 2015-12-02 2017-06-09 中国科学院大连化学物理研究所 A kind of method and device for preparing polyetheramine
CN107913694A (en) * 2017-10-31 2018-04-17 山东玉皇化工有限公司 A kind of modulating method of amination catalysis carrier and its application
CN108067289A (en) * 2016-11-15 2018-05-25 中国科学院大连化学物理研究所 Catalyst and preparation and the application that ethylenediamine and piperazine are produced under hydro condition
CN108424369A (en) * 2017-02-15 2018-08-21 赢创德固赛有限公司 It is used to prepare isophorone amino alcohol（IPAA）Method
CN108435208A (en) * 2018-05-09 2018-08-24 安庆市鑫富化工有限责任公司 A kind of regeneration technology of catalyst Raney's nickel and its application

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3696152A (en) * 1970-06-17 1972-10-03 Dow Chemical Co Hydration of nitriles to amides using heterogeneous cupreous catalysts
US4973769A (en) * 1988-02-06 1990-11-27 Basf Aktiengesellschaft Preparation of 1,2,4-butanetriol
EP0526851A2 (en) * 1991-07-31 1993-02-10 Tosoh Corporation Process and catalyst for producing an ethylenamine
JPH05163213A (en) * 1991-12-13 1993-06-29 Koei Chem Co Ltd Production of 3-aminopropanol
CN1086314C (en) * 1995-06-02 2002-06-19 陶氏化学公司 Catalyst and process for producing amides
US6534441B1 (en) * 1999-03-06 2003-03-18 Union Carbide Chemicals & Plastics Technology Corporation Nickel-rhenium catalyst for use in reductive amination processes
JP2001342166A (en) * 2000-06-01 2001-12-11 Koei Chem Co Ltd Method of purifying 3-aminopropanol
JP2002053535A (en) * 2000-08-11 2002-02-19 Koei Chem Co Ltd Method for purifying 3-aminopropanol
JP2002201164A (en) * 2000-12-28 2002-07-16 Koei Chem Co Ltd Method for producing 3-amino-1-propanol
CN1829568A (en) * 2003-08-04 2006-09-06 催化蒸馏技术公司 Ni hydrogenation catalysts, its manufacture method and use
CN101121665A (en) * 2006-08-09 2008-02-13 三菱瓦斯化学株式会社 Production method of primary amines and catalysts for producing primary amines
CN103261148A (en) * 2010-12-14 2013-08-21 巴斯夫欧洲公司 Method for producing and purifying 3-minopropanol
CN102688763A (en) * 2011-03-22 2012-09-26 中国科学院大连化学物理研究所 Catalyst for preparing m-xylylenediamine by isophthalonitrile hydrogenation under ammonia reaction conditions
CN103159630A (en) * 2011-12-14 2013-06-19 中国科学院大连化学物理研究所 A method for preparing ethylenediamine by using ethanolamine and ammonia as raw materials
CN104662182A (en) * 2012-03-27 2015-05-27 陶氏环球技术有限责任公司 Rhenium recovery from used reductive amination catalysts
CN106807377A (en) * 2015-11-27 2017-06-09 中国科学院大连化学物理研究所 A kind of catalyst for synthesizing hexamethylene diamine
CN106807395A (en) * 2015-11-27 2017-06-09 中国科学院大连化学物理研究所 A kind of catalyst for synthesizing hexamethylene diamine
CN106810683A (en) * 2015-12-02 2017-06-09 中国科学院大连化学物理研究所 A kind of method and device for preparing polyetheramine
CN108067289A (en) * 2016-11-15 2018-05-25 中国科学院大连化学物理研究所 Catalyst and preparation and the application that ethylenediamine and piperazine are produced under hydro condition
CN108424369A (en) * 2017-02-15 2018-08-21 赢创德固赛有限公司 It is used to prepare isophorone amino alcohol（IPAA）Method
CN107913694A (en) * 2017-10-31 2018-04-17 山东玉皇化工有限公司 A kind of modulating method of amination catalysis carrier and its application
CN108435208A (en) * 2018-05-09 2018-08-24 安庆市鑫富化工有限责任公司 A kind of regeneration technology of catalyst Raney's nickel and its application

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114471582A (en) * 2020-10-27 2022-05-13 中国石油化工股份有限公司 Catalyst for preparing diamine by hydrogenation of dinitrile, method and application
CN114471582B (en) * 2020-10-27 2023-08-29 中国石油化工股份有限公司 Catalyst for preparing diamine by hydrogenation of dinitrile, method and application
CN114042455A (en) * 2021-11-01 2022-02-15 浙江新和成股份有限公司 Carbonyl selective hydrogenation catalyst, preparation method and application thereof
CN114042455B (en) * 2021-11-01 2024-03-26 浙江新和成股份有限公司 Carbonyl selective hydrogenation catalyst and preparation method and application thereof

Also Published As

Publication number Publication date
CN111196763B (en) 2021-06-01

Similar Documents

Publication Publication Date Title
CN112898558B (en) Method for preparing polyether amine by hydroamination of polyether polyol
CN109126823A (en) Nitrobenzene selective hydrogenation prepares the catalyst and preparation method, application of aniline
EP1358935B1 (en) Zinc modified Pd/Ni catalysts
CN105727962B (en) Catalyst and its preparation method and application for dimethyl adipate hexylene glycol
US20120302801A1 (en) Hydrogenation process
WO2003010125A1 (en) A process for the manufacture of diethylenetriamine and higher polyethylenepolyamines
CN111196763B (en) Catalyst for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile and preparation method thereof
US20230174714A1 (en) Supported catalyst used for synthesizing polyether amine, preparation method, and application
CN111153768A (en) Synthetic method of isohexide
CN112898164B (en) Method for preparing 1, 6-hexamethylene diamine from 5-hydroxymethylfurfural
EP2301663B1 (en) Catalyst for fischer-tropsch synthesis and method for producing hydrocarbons
CN109503388A (en) The method of coproduction cyclohexylamine and dicyclohexyl amine and catalyst system for this method
CN108067213B (en) catalyst for resource utilization of aniline rectification residues and preparation method thereof
JP4588848B2 (en) Process for producing pentanediol from alkoxydihydropyran
CN109647394A (en) A kind of catalyst and its preparation method and application for alpha, beta-unsaturated aldehyde selective hydrogenation unsaturated alcohol
CN110256198B (en) Production method of 1, 4-pentanediol
CN112898163B (en) Method for preparing 1, 6-hexamethylene diamine by ammoniation of hexamethylene imine
US5567847A (en) Disproportionation of amines to produce secondary amines
CN111195523B (en) Catalyst for producing amine by hydrogenation of cyanogen compounds, preparation method and application thereof
CN108654609A (en) A kind of platiniferous and or supported palladium catalyst preparation method and catalyst and hydrogenolysis of glycerin method
CN113101928B (en) Catalyst for preparing 1, 4-butenediol from 1, 4-butynediol and preparation method and application thereof
CN109107583A (en) A kind of butynediols half plus hydrogen bimetallic catalyst and the preparation method and application thereof
CN109939686B (en) Catalyst for preparing cis-pinane by hydrogenation
JP3987278B2 (en) Method for converting 1,4-butynediol to 1,4-butenediol
CN101884918B (en) Method for preparing antimony-containing catalyst used for ammoxidation of alkane

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