CN114425347A - Selective ammoniation hydrogenation catalyst, preparation method thereof and synthesis method of cycloheximide - Google Patents

Selective ammoniation hydrogenation catalyst, preparation method thereof and synthesis method of cycloheximide Download PDF

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CN114425347A
CN114425347A CN202011180162.XA CN202011180162A CN114425347A CN 114425347 A CN114425347 A CN 114425347A CN 202011180162 A CN202011180162 A CN 202011180162A CN 114425347 A CN114425347 A CN 114425347A
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selective
cycloheximide
hydrogenation catalyst
metal component
catalyst
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CN114425347B (en
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刘凌涛
王海京
宗保宁
毛俊义
朱振兴
罗一斌
张同旺
朱丙田
韩颖
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J23/835—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 germanium, tin or lead
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8966—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
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    • 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
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
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    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
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    • Y02P20/584—Recycling of catalysts

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Abstract

The selective ammoniation hydrogenation catalyst consists of active metal Ni, 0.01-10 wt% of first modified component Sn, optional heat-resistant inorganic oxide carrier and optional second modified metal component, wherein the second modified metal component is one or more selected from Pt, Ag, Pd, Co and Cu. The synthesis method of the cycloheximide provided by the invention uses the hexanedial and the hexanedial acetal as reaction raw materials, is cheaper and easily available, has milder reaction conditions and has better economic benefit.

Description

Selective ammoniation hydrogenation catalyst, preparation method thereof and synthesis method of cycloheximide
Technical Field
The invention relates to the field of chemical synthesis, and particularly relates to a selective ammoniation hydrogenation catalyst and a method for synthesizing cycloheximide.
Background
Cycloheximide is an important organic compound. The compound can be combined with alkyl aluminum to form a metal organic compound. In addition, the special cyclic structure of the cycloheximide and its derivatives also makes it an important pharmaceutical intermediate. Furthermore, cycloheximides are also used to prepare specific ionic liquids. For example, CN102146058A discloses an ionic liquid using imine nitrogen-containing heterocycles as cations and a preparation method of the ionic liquid. The sulfonic acid ionic liquid prepared by using the cycloheximide has good catalytic activity on esterification reaction of acid catalytic reaction and the like. CN102516203A discloses an ionic liquid type solid acid synthesized from cycloheximide and heteropoly acid radical, which can catalyze esterification reaction and has convenient product separation.
In the early stage, hexamethylenediamine is adopted to prepare the cyclohexylimine through deamination and cyclization under the action of a catalyst, but the technical problem of intermolecular deamination cannot be thoroughly solved, so that the conventional route is eliminated. The catalytic hydrogenation of caprolactam to prepare cycloheximide is already in industrial production at home and abroad, and the technical key is to select a proper catalyst. CN1483725A discloses a method for producing cycloheximide from caprolactam, which utilizes 99.9% hydrogen and melted caprolactam to perform reduction reaction in a reactor under the action of a catalyst to produce cycloheximide, wherein the reaction formula is that the accompanying product is water.
US4786727 discloses the reaction of caprolactam with hydrogen at a reaction temperature of 200 ℃ and a hydrogen pressure of less than 10bar to give cyclohexylimine under the action of a Cu, Cr, Al catalyst prepared by precipitation.
Caprolactam is however expensive, resulting in a high cost of the final product, cycloheximide. On the other hand, the noble metal catalyst is expensive, which also leads to an increase in product cost. Therefore, there is a need to develop catalytic systems with low precious metal content, even without precious metals.
Disclosure of Invention
One of the technical problems to be solved by the present invention is to provide a method for synthesizing cyclohexylimine based on the prior art.
The second technical problem to be solved by the invention is to provide a selective ammoniation hydrogenation catalyst and a preparation method thereof on the basis of the prior art.
The selective ammoniation hydrogenation catalyst provided by the invention consists of active metal Ni, 0.01-10 wt% of first modified component Sn, optional heat-resistant inorganic oxide carrier and optional second modified metal component, wherein the second modified metal component is selected from one or more of Pt, Ag, Pd, Co and Cu.
Optionally, the heat-resistant inorganic oxide support is selected from one or a mixture of more of alumina, silica, magnesia, titania, niobia and ZSM-5.
According to the first embodiment of the selective ammoniation hydrogenation catalyst provided by the invention, the catalyst contains 88 wt% -99.9 wt% of Ni, 0.01-10 wt% of a first modified metal component and 0-2 wt% of a second modified metal component in terms of metal by taking the total weight of the catalyst as a reference.
The preparation method of the first embodiment of the selective ammoniation hydrogenation catalyst provided by the invention comprises the following steps:
a) adding the NiAl alloy into NaOH and/or KOH aqueous solution to dissolve Al in the alloy to obtain Ni solid powder;
b) separating Ni solid powder in the step a) and dispersing the Ni solid powder into low-carbon alcohol, and adding soluble Sn salt and optional second modified metal component precursor salt to obtain a mixture;
c) reducing the mixture obtained in the step c) by using hydrogen or a hydrogen-containing precursor at the temperature of 30-150 ℃, and filtering to obtain a solid which is a selective ammoniation hydrogenation catalyst.
In a second embodiment of the selective amination hydrogenation catalyst provided by the invention, the selective amination hydrogenation catalyst contains 10-50 wt% of active metal Ni, 0.01-10 wt% of Sn, 0-2 wt% of a second modified metal component and the balance of a heat-resistant inorganic oxide carrier, wherein the metal is calculated by taking the total weight of the catalyst as a reference. Wherein, the heat-resistant inorganic oxide carrier is selected from one or a mixture of more of alumina, silica, magnesia, titania, niobium oxide and ZSM-5.
The preparation method of the second embodiment of the selective ammoniation hydrogenation catalyst provided by the invention comprises the following steps:
a) precursor salt of Ni and SnCl2Or SnCl4And optionally a second modified metal component precursor salt impregnated onto the refractory inorganic oxide support;
b) drying the impregnated mixture obtained in a) at 100-130 ℃;
c) reducing the solid obtained in b) with hydrogen at 300-600 ℃.
In the method for synthesizing the cycloheximide, under the existence of the selective ammoniation hydrogenation catalyst provided by the invention, the hexanedial monoacetal or the hexanedial diacetal reacts with hydrogen and ammonia to generate the cycloheximide, wherein the reaction temperature is 50-350 ℃, and the pressure is 0.5-20 MPa.
The main component of the selective ammoniation hydrogenation catalyst provided by the invention is Ni, and the cost is low, so that the catalyst has better economic benefit compared with a noble metal-based catalyst.
The method for synthesizing the cycloheximide provided by the invention has the beneficial effects that: the synthesis method of the cycloheximide provided by the invention uses the hexanedial and the hexanedial acetal as reaction raw materials, is cheaper and easily obtained, and has milder reaction conditions, thereby having better economic benefit.
Detailed Description
The following describes the embodiments of the present invention in detail. The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The selective ammoniation hydrogenation catalyst provided by the invention consists of active metal Ni, 0.01-10 wt% of first modified component Sn, optional heat-resistant inorganic oxide carrier and optional second modified metal component, wherein the second modified metal component is selected from one or more of Pt, Ag, Pd, Co and Cu.
Optionally, the heat-resistant inorganic oxide support is selected from one or a mixture of more of alumina, silica, magnesia, titania, niobia and ZSM-5.
According to the first embodiment of the selective ammoniation hydrogenation catalyst provided by the invention, the catalyst contains 88 wt% -99.9 wt% of Ni, 0.01-10 wt% of a first modified metal component and 0-2 wt% of a second modified metal component in terms of metal by taking the total weight of the catalyst as a reference.
Preferably, the selective ammoniation hydrogenation catalyst contains 0.02-5 wt% of Sn.
Preferably, the second modified metal component is also contained in an amount of 0.02 to 2 wt%.
Preferably, the second modifying metal component is Pd.
A method of making a first embodiment of a selective amination hydrogenation catalyst comprising:
a) adding the NiAl alloy into NaOH and/or KOH aqueous solution to dissolve Al in the alloy to obtain Ni solid powder;
b) separating Ni solid powder in the step a) and dispersing the Ni solid powder into low-carbon alcohol, and adding soluble Sn salt and optional second modified metal component precursor salt to obtain a mixture;
c) reducing the mixture obtained in the step c) by using hydrogen or a hydrogen-containing precursor at the temperature of 30-150 ℃, and filtering to obtain a solid which is a selective ammoniation hydrogenation catalyst.
Preferably, the soluble Sn salt is SnCl2Or SnCl4。
In the preparation method of the selective ammoniation hydrogenation catalyst provided by the invention, the precursor salt of the second modified metal component is selected from one or more soluble salts of Pt, Ag, Pd, Co and Cu. Preferably, the precursor salt of the second modified metal component is selected from one or more soluble salts of Pt, Cu and Pd. Wherein the soluble salt of Pt is selected from Pt (NH)3)4(NO3)2、H2PtCl6And Pt (acac)2The soluble salt of Cu is selected from one of nitrate, chloride, sulfate and acetylacetone salt, and the soluble salt of Pd is palladium chloride or palladium acetylacetonate.
Preferably, in step b), the separated solid powder in step a) is washed with a lower alcohol or water and then dispersed into a lower alcohol. The lower alcohol is alcohol with 1-3 carbon atoms, preferably ethanol.
Preferably, the solid obtained by filtering in step c) is washed by ethanol, and the washed solid is the selective ammoniation hydrogenation catalyst.
In the preparation method of the selective ammoniation hydrogenation catalyst provided by the invention, the amounts of the NiAl alloy, the soluble Sn salt and the precursor salt of the second modified metal component are added, so that the selective ammoniation hydrogenation catalyst contains 0.01-10 wt% of Sn and 0-2 wt% of the second modified metal component, the second modified metal component is selected from one or more of Pt, Ag, Pd, Co and Cu, and the balance is Ni.
Preferably, the amounts of the NiAl alloy, the soluble Sn salt and the precursor salt of the second modified metal component are added so that the mass fraction of 0.02 to 5 wt% of Sn and Pt is 0 to 1 wt%, preferably 0 to 0.2 wt%; the mass fraction of Cu is 0 to 2 wt%, preferably 0 to 1 wt%; the mass fraction of Pd is 0-2 wt%, preferably 0-0.5 wt%, and the balance is Ni.
Preferably, the second embodiment of the selective amination hydrogenation catalyst provided by the invention comprises an active metal Ni, a heat-resistant inorganic oxide carrier and a first modification component Sn, and comprises 10-50 wt% of Ni, 0.01-10 wt% of Sn and the balance of the heat-resistant inorganic oxide carrier by taking the total weight of the catalyst as the reference, wherein the heat-resistant inorganic oxide carrier is selected from one or a mixture of aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, niobium oxide and ZSM-5.
Preferably, the selective ammoniation hydrogenation catalyst contains 15-30 wt% of Ni, 0.02-5 wt% of Sn and the balance of heat-resistant inorganic oxide carrier.
Preferably, the catalyst also contains 0.02-2 wt% of a second modified metal component, wherein the second modified metal component is selected from Pt or Pd.
The preparation method of the second embodiment of the selective ammoniation hydrogenation catalyst provided by the invention comprises the following steps:
a) precursor salt of Ni and SnCl2Or SnCl4And optionally a second modified metal component precursor salt impregnated onto the support;
b) drying the impregnated mixture obtained in a) at 100-130 ℃;
c) reducing the solid obtained in the step b) by using hydrogen at the temperature of between 300 and 600 ℃ to obtain the selective ammoniation hydrogenation catalyst.
The carrier is at least one of alumina, silica, magnesia, titania, niobium oxide and ZSM-5; preferably alumina, silica, magnesia. The Ni content is 10-50 wt%, preferably 15-30 wt%; the mass fraction of Sn is 0.01-20%, preferably 0.1-10%; the mass fraction of Pt is 0-1%, preferably 0-0.3%; the mass fraction of Cu is 0-4%, preferably 0-2%; the mass fraction of Pd is 0-1%, preferably 0-0.2%.
In the presence of the selective ammoniation hydrogenation catalyst, the hexamethylene dialdehyde or the hexamethylene dialdehyde monoacetal or the hexamethylene dialdehyde diacetal reacts with hydrogen and ammonia to generate the hexamethylene imine, wherein the reaction temperature is 50-350 ℃, and the pressure is 0.5-20 MPa.
In the method for synthesizing the cycloheximide, the structural general formula of the hexanedial monoacetal is as follows:
Figure BDA0002749939310000061
wherein A is1、A2Is a fatty chain with 1-5 carbon atoms, A5Carbon chain with carbon number of 2-3.
In the method for synthesizing the cycloheximide, the structural general formula of the adipaldehyde diacetal is as follows:
Figure BDA0002749939310000071
wherein A1, A2, A3 and A4 are respectively and independently fatty chains with carbon number of 1-5; a5 and A6 are carbon chains with carbon number of 2-3, and optional hydroxyl, halogen and alkyl are arranged on the carbon chains.
In the method for synthesizing the cycloheximide provided by the invention,
the mass ratio of the adipic dialdehyde or the adipic dialdehyde monoacetal or the adipic dialdehyde diacetal to the hydrogen and the ammonia is as follows: 1: 4-100: 1.05-20.
Figure BDA0002749939310000081
In the method provided by the invention, when the reaction is carried out in a reaction kettle, the reaction time is 1-10h, preferably 2-4 h; or in a fixed bed, the space velocity is 0.01 to 10 hours based on the hexanedial-1Preferably 0.1 to 5h-1。
Preferably, the reaction temperature is 200-300 ℃; the pressure is 3-8 MPa.
Through the technical scheme, the invention provides a novel synthesis method of cycloheximide.
The present invention will be described in detail below by way of examples.
In the examples and comparative examples, all reactions were carried out in a 500ml autoclave. The pressures involved are gauge pressures. The reaction results are shown in Table 1.
NiAl alloy, NaOH，KOH，SnCl2，SnCl4，NaBH4Palladium acetylacetonate ethanolate, H2PtCl4，AgNO3，SiO2Activated carbon, Al2O3All are commercially available chemical pure reagents.
The metal content on the catalyst was determined by means of RIPP 128-90 plasma emission Spectroscopy (ICP/AES).
The cyclohexylimine content in the liquid phase is determined by gas chromatography.
Examples 1-7 illustrate a first and second embodiment of a selective amination hydrogenation catalyst and a method of making the same according to the present invention.
Example 1
The preparation method of the catalyst A comprises the following steps:
a) adding 10g of NiAl alloy into a 20 wt% NaOH aqueous solution to dissolve Al in the alloy, so as to obtain 5gNi solid powder;
b) washing the solid powder prepared in step a) with ethanol or water;
c) dispersing the solid powder in b) in 20ml of ethanol, adding 0.2g of SnCl containing tin2；
d) 0.4g of NaBH was added4Reducing the mixture of c);
e) washing the solid obtained in the step d) by using ethanol to obtain the catalyst A.
The composition of catalyst a was: the Ni content was 96 wt%, and the Sn content was 4 wt%.
Example 2
The preparation method of the catalyst B comprises the following steps:
a) adding 10g of NiAl alloy into a 20 wt% NaOH aqueous solution to dissolve Al in the alloy, so as to obtain 5gNi solid powder;
b) washing the solid powder prepared in step a) with ethanol or water;
c) dispersing the solid powder in b) into 20ml ethanol, adding SnCl containing 0.5g of tin4And palladium acetylacetonate containing 0.01g of Pd;
d) reducing the solid obtained in c) under a hydrogen pressure of 70 ℃ and 1 MPa;
e) washing the solid obtained in the step d) by using ethanol to obtain the catalyst B.
The composition of catalyst B was: the Ni content was 90.8 wt%, the Sn content was 9 wt%, and the Pd content was 0.2 wt%.
Example 3
The preparation method of the catalyst C comprises the following steps:
nickel nitrate containing Ni 2g, SnCl4 containing Sn 0.1g and H containing Pt 0.01g2PtCl4Dissolved in water and immersed in an equal volume of 8g of SiO2The above step (1);
b) drying the impregnated mixture obtained in a) at 120 ℃;
c) reducing the solid obtained in the step b) for 6 hours in a hydrogen atmosphere of 500 ℃, and obtaining the catalyst C.
The composition of catalyst C was: ni content of 20 wt%, Sn content of 1 wt%, Pt content of 0.1 wt%, and the balance SiO2。
Example 4
The preparation method of the catalyst D comprises the following steps:
nickel nitrate containing Ni 1.5g and SnCl containing Sn 0.2g4And H containing 0.04g of Pt2PtCl4Dissolved in water and immersed in an equal volume of 8.5g of SiO2The above step (1);
b) drying the impregnated mixture obtained in a) at 110 ℃;
c) reducing the solid obtained in the step b) in a hydrogen atmosphere at 450 ℃ for 6h to obtain the catalyst D.
The composition of catalyst D was: 15 wt% of Ni, 2 wt% of Sn, 0.4 wt% of Pt and the balance of SiO2。
Example 5
The preparation method of the catalyst E comprises the following steps:
nickel nitrate containing 3g of Ni and SnCl containing 0.2g of Sn4And H containing Pt0.04g2PtCl4Dissolved in water and immersed in an equal volume of 7g of SiO2The above step (1);
b) drying the impregnated mixture obtained in a) at 110 ℃;
c) reducing the solid obtained in the step b) for 6 hours in a hydrogen atmosphere with the temperature of 450 ℃, and obtaining the catalyst E.
Of catalyst EComprises the following components: ni content of 30 wt%, Sn content of 2 wt%, Pt content of 0.4 wt%, and the balance SiO2。
Example 6
The preparation method of the catalyst F comprises the following steps: the following were used:
nickel nitrate containing Ni 5g and SnCl containing Sn 0.2g4And H containing Pt0.04g2PtCl4Dissolved in water and immersed in an equal volume of 5g of SiO2The above step (1);
b) drying the impregnated mixture obtained in a) at 110 ℃;
c) reducing the solid obtained in the step b) for 6h in a hydrogen atmosphere at 450 ℃, and obtaining the catalyst F.
The composition of catalyst F was: ni content of 30 wt%, Sn content of 2 wt%, Pt content of 0.4 wt%, and the balance SiO2。
Example 7
The catalyst G was prepared as follows:
a) adding 10g of NiAl alloy into a 20 wt% KaOH aqueous solution to dissolve Al in the alloy to obtain 5gNi solid powder;
b) washing the solid powder prepared in step a) with ethanol or water;
c) dispersing the solid powder in b) into 20ml of ethanol, adding 1g of SnCl containing tin4And palladium acetylacetonate containing 0.01g of Pd;
d) reducing the solid obtained in c) under a hydrogen pressure of 70 ℃ and 1 MPa;
e) washing the solid obtained in the step d) by using ethanol to obtain the catalyst G.
The composition of catalyst G was: the Ni content was 80.8 wt%, the Sn content was 19 wt%, and the Pd content was 0.2 wt%.
Comparative example 1
Comparative catalyst 1 preparation method:
a) pd 0.5g in PdCl2Dissolving in 20ml of dilute hydrochloric acid, and soaking in an equal volume of 10g of carrier Al2O3The above step (1);
b) drying the mixture impregnated in the step a) at 110 ℃;
c) the solid obtained in step b) was reduced at 420 ℃ with hydrogen, thus obtaining comparative catalyst 1.
The catalyst comprises the following components: pd content of 5 wt%, and the balance Al2O3。
2g of adipaldehyde, 0.5g of Pd/Al2O3The catalyst (Pd mass fraction 5%), 200ml methanol, added to the reaction kettle, using 1.0MPa nitrogen replacement 3 times. 10g of ammonia gas is filled in, and the pressure of the hydrogen gas is refilled to 1 MPa. When the temperature is raised to 180 ℃, the pressure is supplemented to 4MPa, and the reaction pressure is maintained in the meantime. After reacting for 6h, cooling to room temperature. Analyzing the content of the cycloheximide in the liquid phase, calculating the cycloheximide selectivity and the cycloheximide yield, and calculating the cycloheximide selectivity and the cycloheximide yield according to the following formula.
Cycloheximide selectivity ═ cycloheximide molar amount in product/(molar amount of adipaldehyde initially charged in the reaction-molar amount of adipaldehyde remaining in product).
The yield of cycloheximide is the molar amount of cycloheximide in the product/molar amount of adipaldehyde initially charged in the reaction.
Comparative example 2
Comparative catalyst 2 preparation method:
ni 2.0g of nickel nitrate was dissolved in water and 8.0g of SiO2Dipping;
b) drying the impregnated mixture obtained in a) at 110 ℃;
c) reducing the solid obtained in the step b) for 6h in a hydrogen atmosphere of 450 ℃, and obtaining the comparative catalyst 2.
The catalyst comprises the following components: ni content of 20 wt%, and SiO balance2。
2g of adipaldehyde, 0.5g of Ni/SiO2 catalyst (Ni mass fraction: 20 wt%), and 200ml of methanol were charged into a reaction vessel, and then replaced with 1.0MPa of nitrogen gas 3 times. 10g of ammonia gas is filled in, and the pressure of the hydrogen gas is refilled to 1 MPa. When the temperature is raised to 220 ℃, the pressure is supplemented to 4MPa, and the reaction pressure is maintained in the period. After reacting for 6h, cooling to room temperature. Analyzing the content of the cycloheximide in the liquid phase, and calculating the selectivity and yield of the cycloheximide.
Example 8
2g of adipaldehyde, 0.3g of catalyst A and 200ml of methanol were charged into a reaction vessel, and then replaced with 1.0MPa of argon gas for 3 times. 15g of ammonia gas is filled in, and the pressure of the hydrogen gas is refilled to 1 MPa. When the temperature is raised to 200 ℃, the pressure is supplemented to 5MPa, and the reaction pressure is maintained in the meantime. After 12h of reaction, the temperature is reduced to room temperature. Analyzing the content of the cycloheximide in the liquid phase, and calculating the selectivity and yield of the cycloheximide.
Example 9
4g diethylene glycol adipaldehyde, 0.5g catalyst B, 200ml methanol, after the reaction vessel, using 1.0MPa nitrogen replacement 3 times. 15g of ammonia gas is filled in, and the pressure of the hydrogen gas is refilled to 1 MPa. When the temperature rises to 190 ℃, the pressure is supplemented to 4MPa, and the reaction pressure is maintained in the meantime. After 12h of reaction, the temperature is reduced to room temperature. Analyzing the content of the cycloheximide in the liquid phase, and calculating the selectivity and yield of the cycloheximide.
Example 10
3g of 1, 3-propanediol adipaldehyde, 0.3g of catalyst C and 200ml of methanol were put into a reaction vessel, and then replaced with 1.0MPa of nitrogen gas for 3 times. 15g of ammonia gas is filled in, and the pressure of the hydrogen gas is refilled to 1 MPa. When the temperature rises to 190 ℃, the pressure is supplemented to 4MPa, and the reaction pressure is maintained in the meantime. After 12h of reaction, the temperature is reduced to room temperature. Analyzing the content of the cycloheximide in the liquid phase, and calculating the selectivity and yield of the cycloheximide.
Example 11
3g of di-1, 2-propanediol adipaldehyde, 0.5g of catalyst D and 200ml of methanol were charged into a reaction vessel, and then replaced with 1.0MPa of nitrogen gas for 3 times. 10g of ammonia gas is filled in, and the pressure of the hydrogen gas is refilled to 1 MPa. When the temperature rises to 230 ℃, the pressure is supplemented to 10MPa, and the reaction pressure is maintained in the meantime. After reacting for 6h, cooling to room temperature. Analyzing the content of the cycloheximide in the liquid phase, and calculating the selectivity and yield of the cycloheximide.
Example 12
3g of di-1, 2-propanediol adipaldehyde, 0.5g of catalyst E and 200ml of methanol were put into a reaction vessel, and then replaced with 1.0MPa of nitrogen gas for 3 times. 10g of ammonia gas is filled in, and the pressure of the hydrogen gas is refilled to 1 MPa. When the temperature rises to 230 ℃, the pressure is supplemented to 10MPa, and the reaction pressure is maintained in the meantime. After reacting for 6h, cooling to room temperature. Analyzing the content of the cycloheximide in the liquid phase, and calculating the selectivity and yield of the cycloheximide.
Example 13
3g of di-1, 2-propanediol adipaldehyde, 0.5g of catalyst F and 200ml of methanol were put into a reaction vessel, and then replaced with 1.0MPa of nitrogen gas for 3 times. 10g of ammonia gas is filled in, and the pressure of the hydrogen gas is refilled to 1 MPa. When the temperature rises to 230 ℃, the pressure is supplemented to 10MPa, and the reaction pressure is maintained in the meantime. After reacting for 6h, cooling to room temperature. Analyzing the content of the cycloheximide in the liquid phase, and calculating the selectivity and yield of the cycloheximide.
Example 14
3G of di-1, 2-propanediol adipaldehyde, 0.5G of catalyst G and 200ml of methanol were put into a reaction vessel, and then replaced with 1.0MPa of nitrogen gas for 3 times. 10g of ammonia gas is filled in, and the pressure of the hydrogen gas is refilled to 1 MPa. When the temperature rises to 230 ℃, the pressure is supplemented to 10MPa, and the reaction pressure is maintained in the meantime. After reacting for 6h, cooling to room temperature. Analyzing the content of the cycloheximide in the liquid phase, and calculating the selectivity and yield of the cycloheximide.
TABLE 1
Figure BDA0002749939310000141
Figure BDA0002749939310000151
It can be seen from the results in table 1 that the examples used with the present invention have significantly better results.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A selective ammoniation hydrogenation catalyst consists of active metal Ni, 0.01-10 wt% of a first modified component Sn, an optional heat-resistant inorganic oxide carrier and an optional second modified metal component, wherein the second modified metal component is selected from one or more of Pt, Ag, Pd, Co and Cu; the heat-resistant inorganic oxide carrier is one or a mixture of more of alumina, silica, magnesia, titania, niobium oxide and ZSM-5.
2. The selective amination hydrogenation catalyst according to claim 1, wherein the catalyst comprises, in terms of metal, 88 wt% to 99.9 wt% of Ni, 0.01 wt% to 10 wt% of the first modifying metal component, and 0 wt% to 2 wt% of the second modifying metal component, based on the total weight of the catalyst;
preferably, the selective ammoniation hydrogenation catalyst contains 0.02-5 wt% of Sn;
preferably, the modified metal also contains 0.02-2 wt% of a second modified metal component;
preferably, the second modifying metal component is Pd.
3. The method of preparing a selective amination hydrogenation catalyst as claimed in claim 2, comprising:
a) adding the NiAl alloy into NaOH and/or KOH aqueous solution to dissolve Al in the alloy to obtain Ni solid powder;
b) separating Ni solid powder in the step a) and dispersing the Ni solid powder into low-carbon alcohol, and adding soluble Sn salt and optional second modified metal component precursor salt to obtain a mixture;
c) reducing the mixture obtained in the step c) by using hydrogen or a hydrogen-containing precursor at the temperature of 30-150 ℃, and filtering to obtain a solid which is a selective ammoniation hydrogenation catalyst.
4. The selective amination hydrogenation catalyst according to claim 1, wherein the selective amination hydrogenation catalyst comprises, in terms of metal, 10 to 50 wt% of active metal Ni, 0.01 to 10 wt% of Sn, 0 to 2 wt% of the second modification metal component, and the balance of a refractory inorganic oxide support, based on the total weight of the catalyst;
preferably 0.02 to 2 wt% of a second modifying metal component;
preferably, the second modifying metal component is Pt or Pd.
5. The method of preparing a selective amination hydrogenation catalyst as claimed in claim 4, comprising:
a) precursor salt of Ni and SnCl2Or SnCl4And optionally a second modified metal component precursor salt impregnated onto the refractory inorganic oxide support;
b) drying the impregnated mixture obtained in a) at 100-130 ℃;
c) reducing the solid obtained in the step b) by using hydrogen at the temperature of between 300 and 600 ℃ to obtain the selective ammoniation hydrogenation catalyst.
6. A method for synthesizing cycloheximide, under the existence of the selective ammoniation hydrogenation catalyst as claimed in any one of claims 1,2 or 4, the reaction of adipaldehyde, adipaldehyde monoacetal or adipaldehyde diacetal with hydrogen and ammonia generates cycloheximide, the reaction temperature is 50-350 ℃, and the pressure is 0.5-20 MPa.
7. The method for synthesizing cycloheximide according to claim 6 wherein said adipaldehyde monoacetal has the general structural formula:
Figure FDA0002749939300000021
or
Figure FDA0002749939300000022
Wherein A is1、A2Is a fatty chain with 1-5 carbon atoms, A5Carbon chain with carbon number of 2-3.
8. The method for synthesizing cycloheximide according to claim 6 wherein said adipaldehyde diacetal has the general structural formula:
Figure FDA0002749939300000031
or
Figure FDA0002749939300000032
Wherein A1, A2, A3 and A4 are respectively and independently fatty chains with carbon number of 1-5; a5 and A6 are carbon chains with carbon number of 2-3, and optional hydroxyl, halogen and alkyl are arranged on the carbon chains.
9. The method for synthesizing cycloheximide according to claim 6, wherein the mass ratio of the adipaldehyde, adipaldehyde monoacetal or adipaldehyde diacetal to the hydrogen gas and ammonia is: 1: 4-100: 1.05 to 20, and reacting in a reaction kettle for 1 to 10 hours; or in a fixed bed at a space velocity of 0.01-10h-1。
10. The method for synthesizing cycloheximide according to claim 9 wherein the reaction temperature is 150-250 ℃ and the pressure is 1-6 MPa; reacting in a reaction kettle for 2-4h or in a fixed bed reactor at a space velocity of 0.1-5h-1。
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