CN114425347B - Process for synthesizing cyclohexylimine - Google Patents

Process for synthesizing cyclohexylimine Download PDF

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CN114425347B
CN114425347B CN202011180162.XA CN202011180162A CN114425347B CN 114425347 B CN114425347 B CN 114425347B CN 202011180162 A CN202011180162 A CN 202011180162A CN 114425347 B CN114425347 B CN 114425347B
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cyclohexylimine
selective
hydrogenation catalyst
glyoxal
modified metal
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CN114425347A (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
    • 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
    • B01J23/89—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
    • 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
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • 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
    • C07D295/023—Preparation; Separation; Stabilisation; Use of additives
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    • C07—ORGANIC CHEMISTRY
    • 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
    • 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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Abstract

A selective ammonification hydrogenation catalyst used in the synthesis method of the cyclohexylimine consists of active metal Ni,0.01-10wt% 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 synthesis method of the cyclohexylimine provided by the invention uses the hexanedialdehyde and hexanedialdehyde acetal as reaction raw materials, is cheaper and more easily obtained, has milder reaction conditions and better economic benefit.

Description

Process for synthesizing cyclohexylimine
Technical Field
The invention relates to the field of chemical synthesis, in particular to a selective ammonification hydrogenation catalyst and a method for synthesizing cyclohexylimine.
Background
Cyclohexylimine is an important organic compound. The compounds can be combined with aluminum alkyls to form metal organic compounds. In addition, the special cyclic structure of cyclohexylimine and its derivatives also makes it an important pharmaceutical intermediate. In addition, cyclohexylimine is also used for preparing special ionic liquids. For example, CN102146058A discloses an ionic liquid taking imine nitrogen-containing heterocycle as cation and a preparation method of the ionic liquid. The sulfonic acid ionic liquid prepared by using the cyclohexylimine has good catalytic activity for esterification reactions and the like of acid catalytic reactions. CN102516203a discloses an ionic liquid type solid acid synthesized by cyclohexylimine and heteropolyacid radical, which can catalyze esterification reaction and has convenient product separation.
In the early stage, hexamethylenediamine is adopted to prepare 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 hexyl is eliminated at present. The preparation of the cyclohexylimine by catalytic hydrogenation of caprolactam is industrially produced both at home and abroad, and the technical key is to select a proper catalyst. CN1483725a discloses a method for producing cyclohexylimine by using caprolactam, which uses 99.9% hydrogen and melted caprolactam to make reduction reaction in a reactor under the action of catalyst to produce cyclohexylimine, wherein the reaction formula is that the companion is water.
US4786727 discloses the reaction of caprolactam with hydrogen at a reaction temperature of 200 ℃ and a hydrogen pressure of below 10bar under the action of Cu, cr and Al catalysts prepared by a precipitation method to produce cyclohexylimine.
However, caprolactam is expensive, resulting in higher costs of the final product, cyclohexylimine. On the other hand, noble metal catalysts are costly and also result in increased product costs. Thus, there is a need to develop catalytic systems with low noble metal content or even no noble metal.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide a method for synthesizing cyclohexylimine on the basis of the prior art.
The second technical problem to be solved by the invention is to provide a selective ammonification hydrogenation catalyst and a preparation method thereof based on the prior art.
The selective ammoniation hydrogenation catalyst provided by the invention consists of active metal Ni,0.01-10wt% 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.
Optionally, the heat-resistant inorganic oxide carrier is selected from one or a mixture of more of aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, niobium oxide and ZSM-5.
The first embodiment of the selective ammonification hydrogenation catalyst provided by the invention comprises 88-99.9 wt% of Ni,0.01-10wt% of a first modified metal component and 0-2wt% of a second modified metal component based on the total weight of the catalyst.
The preparation method of the first embodiment of the selective ammonification hydrogenation catalyst provided by the invention comprises the following steps:
a) Adding NiAl alloy into NaOH and/or KOH aqueous solution to dissolve Al in the alloy to obtain Ni solid powder;
b) Separating the 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) at 30-150 ℃ by using hydrogen or a hydrogen-containing precursor, and filtering to obtain a solid which is a selective ammonification hydrogenation catalyst.
The second embodiment of the selective ammonification hydrogenation catalyst provided by the invention comprises 10-50wt% of active metal Ni,0.01-10wt% of Sn, 0-2wt% of second modified metal component and the balance of heat-resistant inorganic oxide carrier 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 aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, niobium oxide and ZSM-5.
The preparation method of the second embodiment of the selective ammonification hydrogenation catalyst provided by the invention comprises the following steps:
a) Precursor salt of Ni and SnCl 2 Or SnCl 4 And optionally a second modified metal component precursor salt onto a refractory inorganic oxide support;
b) Drying the impregnation mixture obtained in a) at 100-130 ℃;
c) Reducing the solid obtained in b) with hydrogen at 300-600 degrees.
In the method for synthesizing the cyclohexylimine, in the presence of the selective ammonification hydrogenation catalyst provided by the invention, the hexanedialdehyde, hexanedialdehyde monoacetal or hexanedialdehyde diacetal reacts with hydrogen and ammonia to generate the cyclohexylimine, wherein the reaction temperature is 50-350 ℃, and the pressure is 0.5-20MPa.
The selective ammoniation hydrogenation catalyst provided by the invention has the main component of Ni and low cost, so that the catalyst has better economic benefit than noble metal-based catalysts.
The method for synthesizing the cyclohexylimine has the beneficial effects that: the synthesis method of the cyclohexylimine provided by the invention uses the hexanedialdehyde and hexanedialdehyde acetal as reaction raw materials, is cheaper and more easily obtained, and has milder reaction conditions, thereby having better economic benefit.
Detailed Description
The following describes specific embodiments of the present invention in detail. The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The selective ammoniation hydrogenation catalyst provided by the invention consists of active metal Ni,0.01-10wt% 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.
Optionally, the heat-resistant inorganic oxide carrier is selected from one or a mixture of more of aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, niobium oxide and ZSM-5.
The first embodiment of the selective ammonification hydrogenation catalyst provided by the invention comprises 88-99.9 wt% of Ni,0.01-10wt% of a first modified metal component and 0-2wt% of a second modified metal component based on the total weight of the catalyst.
Preferably, the selective ammoniation hydrogenation catalyst contains 0.02-5wt% of Sn.
Preferably, 0.02 to 2wt% of a second modifying metal component is also included.
Preferably, the second modified metal component is Pd.
A method of preparing a first embodiment of a selective ammonification hydrogenation catalyst comprising:
a) Adding NiAl alloy into NaOH and/or KOH aqueous solution to dissolve Al in the alloy to obtain Ni solid powder;
b) Separating the 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) at 30-150 ℃ by using hydrogen or a hydrogen-containing precursor, and filtering to obtain a solid which is a selective ammonification hydrogenation catalyst.
Preferably, the soluble Sn salt is SnCl 2 Or SnCl 4 。
In the preparation method of the selective ammonification hydrogenation catalyst provided by the invention, the precursor salt of the second modified metal component is selected from one or more of Pt, ag, pd, co and Cu soluble salts. Preferably, the second modified metal component precursor salt is selected from one or more of soluble salts of Pt, cu, pd. Wherein, the Pt isIs selected from the group consisting of Pt (NH) 3 ) 4 (NO 3 ) 2 、H 2 PtCl 6 And Pt (acac) 2 The soluble salt of Cu is selected from one of nitrate, chloride, sulfate and acetylacetonate, and the soluble salt of Pd is palladium chloride or palladium acetylacetonate.
Preferably, in step b), the solid powder isolated in step a) is washed with a lower alcohol or water and then dispersed into the lower alcohol. The lower alcohol is alcohol with 1-3 carbon atoms, preferably ethanol.
Preferably, the solid obtained by filtration in step c) is washed with ethanol, and the washed solid is the selective ammonification hydrogenation catalyst.
In the preparation method of the selective ammoniation hydrogenation catalyst, the amount of the NiAl alloy, the soluble Sn salt and the precursor salt of the second modified metal component is added, so that the selective ammoniation hydrogenation catalyst contains 0.01-10wt% of Sn and 0-2% of the second modified metal component, wherein the second modified metal component is one or more selected from Pt, ag, pd, co and Cu, and the balance is Ni.
Preferably, the amount of the NiAl alloy, the soluble Sn salt and the second modified metal component precursor salt added is such that 0.02-5wt% Sn, pt is 0-1wt%, preferably 0-0.2wt%; the mass fraction of Cu is 0-2wt%, preferably 0-1wt%; the mass fraction of Pd is 0-2wt%, preferably 0-0.5wt%, with the balance being Ni.
Preferably, the second embodiment of the selective ammonification hydrogenation catalyst provided by the invention comprises active metal Ni, a heat-resistant inorganic oxide carrier and a first modified component Sn, wherein the catalyst comprises 10-50wt% of Ni,0.01-10wt% of Sn and the balance of heat-resistant inorganic oxide carrier based on the total weight of the catalyst, and the heat-resistant inorganic oxide carrier is selected from one or a mixture of more of aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, niobium oxide and ZSM-5.
Preferably, the selective ammonification hydrogenation catalyst contains 15-30wt% of Ni,0.02-5wt% of Sn and the balance of heat-resistant inorganic oxide carrier.
Preferably, 0.02 to 2wt% of a second modified metal component is also included, said second modified metal component being selected from Pt or Pd.
The preparation method of the second embodiment of the selective ammonification hydrogenation catalyst provided by the invention comprises the following steps:
a) Precursor salt of Ni and SnCl 2 Or SnCl 4 And optionally a second modified metal component precursor salt onto the support;
b) Drying the impregnation mixture obtained in a) at 100-130 ℃;
c) Reducing the solid obtained in b) with hydrogen at 300-600 deg.c to obtain the selective ammonification hydrogenation catalyst.
The carrier is at least one of alumina, silica, magnesia, titania, niobium oxide and ZSM-5; preferably aluminum oxide, silicon oxide, magnesium oxide. The Ni content is 10-50wt%, preferably 15-30wt%; 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 ammonification hydrogenation catalyst provided by the invention, the hexanedialdehyde or hexanedialdehyde monoacetal or hexanedialdehyde diacetal reacts with hydrogen and ammonia to generate the cyclohexylimine, wherein the reaction temperature is 50-350 ℃ and the pressure is 0.5-20MPa.
In the method for synthesizing the cyclohexylimine, the structural general formula of the glyoxal monoacetal is as follows:
or alternatively
Wherein A is 1 、A 2 Is a fatty chain with 1-5 carbon atoms, A 5 Carbon chain with carbon number of 2-3.
In the method for synthesizing the cyclohexylimine, the structural general formula of the glyoxal diacetal is as follows:
or alternatively
Wherein A1, A2, A3 and A4 are respectively and independently aliphatic chains with carbon number of 1-5; a5 and A6 are respectively independent carbon chains with 2-3 carbon numbers, and the carbon chains are provided with optional hydroxyl, halogen and alkyl.
In the method for synthesizing the cyclohexylimine provided by the invention,
the mass ratio of the hexadialdehyde or the hexadialdehyde monoacetal or the hexadialdehyde diacetal to the hydrogen and the ammonia is as follows: 1:4-100:1.05-20.
In the method provided by the invention, when the reaction is carried out in a reaction kettle, the reaction time is 1-10h, preferably 2-4h; or in a fixed bed, with a space velocity of 0.01 to 10h, calculated as glyoxal -1 Preferably 0.1-5h -1 。
Preferably, the reaction temperature is 200-300 ℃; the pressure is 3-8MPa.
Through the technical scheme, the invention provides a novel method for synthesizing the cyclohexylimine.
The present invention will be described in detail by 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, snCl 2 ，SnCl 4 ，NaBH 4 Palladium acetylacetonate, H 2 PtCl 4 ，AgNO 3 ，SiO 2 Activated carbon, al 2 O 3 All are commercially available chemical pure reagents.
The metal content on the catalyst was determined by the method of RIPP 128-90 plasma emission spectrometry (ICP/AES).
The cyclohexylimine content in the liquid phase was determined by gas chromatography.
Examples 1-7 illustrate the first and second embodiments of the selective ammonification hydrogenation catalysts and methods of making the same provided herein.
Example 1
The preparation method of the catalyst A comprises the following steps:
a) Adding 10g of NiAl alloy into a 20wt% NaOH aqueous solution to dissolve Al in the alloy, thereby obtaining 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 0.2g tin 2 ；
d) 0.4g NaBH was added 4 Reducing the mixture of c);
e) The solid obtained in d) was washed with ethanol, i.e. catalyst a.
The composition of the catalyst A is as follows: the Ni content was 96wt% and the Sn content was 4wt%.
Example 2
The preparation method of the catalyst B comprises the following steps:
a) Adding 10g of NiAl alloy into a 20wt% NaOH aqueous solution to dissolve Al in the alloy, thereby obtaining 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 tin 4 And palladium acetylacetonate containing Pd 0.01 g;
d) Reducing the solid obtained in c) under a hydrogen pressure of 1MPa at 70 ℃;
e) The solid obtained in d) was washed with ethanol to give catalyst B.
The composition of the catalyst B is as follows: the content of Ni was 90.8wt%, the content of Sn was 9wt%, and the content of Pd was 0.2wt%.
Example 3
The preparation method of the catalyst C comprises the following steps:
nickel nitrate containing Ni 2g, snCl4 containing tin 0.1g and H containing Pt 0.01g 2 PtCl 4 Dissolving in water, soaking in 8g of SiO in equal volume 2 Applying;
b) Drying the impregnation mixture obtained in a) at 120 degrees;
c) And (3) reducing the solid obtained in the step b) for 6 hours in a hydrogen atmosphere at 500 ℃ to obtain the catalyst C.
The composition of catalyst C is: the Ni content was 20wt%, the Sn content was 1wt%, the Pt content was 0.1wt%, and the balance was SiO 2 。
Example 4
The preparation method of the catalyst D comprises the following steps:
nickel nitrate containing 1.5g of Ni and SnCl containing 0.2g of tin 4 And 0.04g of H containing Pt 2 PtCl 4 Dissolved in water and immersed in 8.5g of SiO in equal volume 2 Applying;
b) Drying the impregnation mixture obtained in a) at 110 ℃;
c) And (3) reducing the solid obtained in the step b) for 6 hours in a hydrogen atmosphere at the temperature of 450 ℃ to obtain the catalyst D.
The composition of catalyst D was: the Ni content was 15wt%, the Sn content was 2wt%, the Pt content was 0.4wt%, and the balance was SiO 2 。
Example 5
The preparation method of the catalyst E comprises the following steps:
nickel nitrate containing Ni 3g and SnCl containing tin 0.2g 4 And Pt0.04g of H 2 PtCl 4 Dissolving in water, soaking in equal volume to 7g of SiO 2 Applying;
b) Drying the impregnation mixture obtained in a) at 110 ℃;
c) And (3) reducing the solid obtained in the step b) for 6h in a hydrogen atmosphere at the temperature of 450 ℃ to obtain the catalyst E.
The composition of catalyst E was: the Ni content was 30wt%, the Sn content was 2wt%, the Pt content was 0.4wt%, and the balance was SiO 2 。
Example 6
The preparation method of the catalyst F comprises the following steps: the following are provided:
nickel nitrate containing Ni 5g and SnCl containing tin 0.2g 4 And Pt0.04g of H 2 PtCl 4 Dissolving in water, soaking in 5g of SiO in equal volume 2 Applying;
b) Drying the impregnation mixture obtained in a) at 110 ℃;
c) And (3) reducing the solid obtained in the step b) for 6h in a hydrogen atmosphere at the temperature of 450 ℃ to obtain the catalyst F.
The composition of catalyst F is: the Ni content was 30wt%, the Sn content was 2wt%, the Pt content was 0.4wt% and the balance was SiO 2 。
Example 7
The preparation method of the catalyst G comprises the following steps:
a) Adding 10g of NiAl alloy into 20wt% of 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 ethanol, adding SnCl containing 1g of tin 4 And palladium acetylacetonate containing Pd 0.01 g;
d) Reducing the solid obtained in c) under a hydrogen pressure of 1MPa at 70 ℃;
e) Washing the solid obtained in d) with ethanol to obtain the catalyst G.
The composition of catalyst G was: the content of Ni was 80.8wt%, the content of Sn was 19wt%, and the content of Pd was 0.2wt%.
Comparative example 1
Comparative catalyst 1 preparation method:
a) PdCl containing Pd 0.5g 2 Dissolving in 20ml of diluted hydrochloric acid, soaking in 10g of carrier Al in equal volume 2 O 3 Applying;
b) Drying the mixture impregnated in step a) at 110 degrees;
c) The solid obtained in step b) was reduced at 420 degrees with hydrogen to give comparative catalyst 1.
The composition of the catalyst is as follows: pd content is 5wt%, and the rest is Al 2 O 3 。
2g of glyoxal, 0.5g Pd/Al 2 O 3 The catalyst (Pd mass fraction: 5%), 200ml of methanol, was added to the reaction vessel, and then, 3 times of substitution was performed with 1.0MPa of nitrogen. 10g of ammonia gas is filled, and the pressure of hydrogen gas is again filled to 1MPa. When the temperature was raised to 180 degrees, the pressure was supplemented to 4MPa, during which the reaction pressure was maintained. And after reacting for 6 hours, cooling to room temperature. The content of cyclohexylimine in the liquid phase was analyzed, and the selectivity to cyclohexylimine and the yield of cyclohexylimine were calculated as follows.
Cyclohexylimine selectivity = moles of cyclohexylimine in the product/(moles of glyoxal initially charged in the reaction-moles of glyoxal remaining in the product).
Yield of cyclohexylimine = molar amount of cyclohexylimine in the product/molar amount of glyoxal initially charged for the reaction.
Comparative example 2
Comparative catalyst 2 preparation method:
nickel nitrate containing Ni 2.0g was dissolved in water and 8.0g of SiO was further added 2 Dipping;
b) Drying the impregnation mixture obtained in a) at 110 ℃;
c) And (3) reducing the solid obtained in the step b) for 6 hours in a 450-DEG hydrogen atmosphere to obtain the comparative catalyst 2.
The composition of the catalyst is as follows: ni content of 20wt% and SiO balance 2 。
2g of glyoxal, 0.5g of Ni/SiO2 catalyst (Ni mass fraction: 20 wt%), 200ml of methanol were added to the reaction vessel, and then the reaction vessel was replaced 3 times with 1.0MPa of nitrogen. 10g of ammonia gas is filled, and the pressure of hydrogen gas is again filled to 1MPa. When the temperature was raised to 220 degrees, the pressure was supplemented to 4MPa, during which the reaction pressure was maintained. And after reacting for 6 hours, cooling to room temperature. And analyzing the content of the cyclohexylimine in the liquid phase, and calculating the selectivity of the cyclohexylimine and the yield of the cyclohexylimine.
Example 8
2g of glyoxal, 0.3g of catalyst A,200ml of methanol, and 3 times replaced with 1.0MPa of argon after addition to the reaction vessel. 15g of ammonia gas is filled, and the pressure of hydrogen gas is again filled to 1MPa. When the temperature was raised to 200 degrees, the pressure was supplemented to 5MPa, during which the reaction pressure was maintained. And after reacting for 12 hours, cooling to room temperature. And analyzing the content of the cyclohexylimine in the liquid phase, and calculating the selectivity of the cyclohexylimine and the yield of the cyclohexylimine.
Example 9
4g of diethylene glycol glyoxal, 0.5g of catalyst B,200ml of methanol, and 3 times with 1.0MPa of nitrogen after addition to the reaction vessel. 15g of ammonia gas is filled, and the pressure of hydrogen gas is again filled to 1MPa. When the temperature was raised to 190 degrees, the pressure was supplemented to 4MPa, during which the reaction pressure was maintained. And after reacting for 12 hours, cooling to room temperature. And analyzing the content of the cyclohexylimine in the liquid phase, and calculating the selectivity of the cyclohexylimine and the yield of the cyclohexylimine.
Example 10
3g of 1, 3-propanediol hexadialdehyde, 0.3g of catalyst C and 200ml of methanol were added to the reaction vessel, and the mixture was replaced 3 times with 1.0MPa of nitrogen. 15g of ammonia gas is filled, and the pressure of hydrogen gas is again filled to 1MPa. When the temperature was raised to 190 degrees, the pressure was supplemented to 4MPa, during which the reaction pressure was maintained. And after reacting for 12 hours, cooling to room temperature. And analyzing the content of the cyclohexylimine in the liquid phase, and calculating the selectivity of the cyclohexylimine and the yield of the cyclohexylimine.
Example 11
3g of di-1, 2-propanediol hexadialdehyde, 0.5g of catalyst D and 200ml of methanol were added to the reaction vessel, and the mixture was replaced 3 times with 1.0MPa of nitrogen. 10g of ammonia gas is filled, and the pressure of hydrogen gas is again filled to 1MPa. When the temperature was raised to 230 degrees, the pressure was supplemented to 10MPa, during which the reaction pressure was maintained. And after reacting for 6 hours, cooling to room temperature. And analyzing the content of the cyclohexylimine in the liquid phase, and calculating the selectivity of the cyclohexylimine and the yield of the cyclohexylimine.
Example 12
3g of di-1, 2-propanediol hexadialdehyde, 0.5g of catalyst E and 200ml of methanol were added to the reaction vessel, and the mixture was replaced 3 times with 1.0MPa of nitrogen. 10g of ammonia gas is filled, and the pressure of hydrogen gas is again filled to 1MPa. When the temperature was raised to 230 degrees, the pressure was supplemented to 10MPa, during which the reaction pressure was maintained. And after reacting for 6 hours, cooling to room temperature. And analyzing the content of the cyclohexylimine in the liquid phase, and calculating the selectivity of the cyclohexylimine and the yield of the cyclohexylimine.
Example 13
3g of di-1, 2-propanediol hexadialdehyde, 0.5g of catalyst F and 200ml of methanol were added to the reaction vessel, and the mixture was replaced 3 times with 1.0MPa of nitrogen. 10g of ammonia gas is filled, and the pressure of hydrogen gas is again filled to 1MPa. When the temperature was raised to 230 degrees, the pressure was supplemented to 10MPa, during which the reaction pressure was maintained. And after reacting for 6 hours, cooling to room temperature. And analyzing the content of the cyclohexylimine in the liquid phase, and calculating the selectivity of the cyclohexylimine and the yield of the cyclohexylimine.
Example 14
3G of di-1, 2-propanediol hexadialdehyde, 0.5G of catalyst G and 200ml of methanol were added to the reaction vessel, and the mixture was replaced 3 times with 1.0MPa of nitrogen. 10g of ammonia gas is filled, and the pressure of hydrogen gas is again filled to 1MPa. When the temperature was raised to 230 degrees, the pressure was supplemented to 10MPa, during which the reaction pressure was maintained. And after reacting for 6 hours, cooling to room temperature. And analyzing the content of the cyclohexylimine in the liquid phase, and calculating the selectivity of the cyclohexylimine and the yield of the cyclohexylimine.
TABLE 1
It can be seen from the results of Table 1 that the examples used with the present invention have significantly better results.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (15)

1. A method for synthesizing cyclohexylimine is characterized in that in the presence of a selective ammonification hydrogenation catalyst, hexanedialdehyde monoacetal or hexanedialdehyde diacetal reacts with hydrogen and ammonia to generate cyclohexylimine, wherein the reaction temperature is 50-350 ℃ and the pressure is 0.5-20Mpa;
the selective ammoniation hydrogenation catalyst consists of active metal Ni,0.01-10wt% of first modified component Sn and optional second modified metal components, wherein the second modified metal components are selected from one or more of Pt, ag, pd, co and Cu;
the preparation method of the selective ammonification hydrogenation catalyst comprises the following steps:
a) Adding NiAl alloy into NaOH and/or KOH aqueous solution to dissolve Al in the alloy to obtain Ni solid powder;
b) Separating the 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) at 30-150 ℃ by using hydrogen or a hydrogen-containing precursor, and filtering to obtain a solid which is a selective ammonification hydrogenation catalyst.
2. The method for synthesizing the cyclohexylimine according to claim 1, characterized in that the structural general formula of the glyoxal monoacetal is:
or alternatively
Wherein A is 1 、A 2 Is a fatty chain with 1-5 carbon atoms, A 5 Carbon chain with carbon number of 2-3
Or alternatively
The structural general formula of the glyoxal diacetal is as follows:
or alternatively
Wherein A1, A2, A3 and A4 are respectively and independently aliphatic chains with carbon number of 1-5; a5 and A6 are respectively independent carbon chains with 2-3 carbon numbers, and the carbon chains are provided with optional hydroxyl, halogen and alkyl.
3. The process for the synthesis of cyclohexylimine according to claim 2, characterized in that the catalyst contains, based on the total weight of the catalyst, from 88% to 99.9% by weight of Ni, from 0.01% to 10% by weight of Sn and from 0% to 2% by weight of a second modified metal component, calculated as metal.
4. A process for the synthesis of cyclohexylimine according to claim 3, characterized in that the selective ammoniation hydrogenation catalyst comprises 0.02 to 5% by weight of Sn.
5. A process for the synthesis of cyclohexylimine according to claim 4, characterized in that the selective ammoniation hydrogenation catalyst comprises from 0.02 to 2% by weight of the second modified metal component.
6. Process for the synthesis of cyclohexylimine according to any of claims 1 to 5, characterized in that the second modifying metal component is Pd.
7. The method for synthesizing cyclohexylimine according to any one of claims 1 to 5, wherein the mass ratio of the glyoxal, the monoacetal of the glyoxal or the diacetal of the glyoxal to the hydrogen gas, the ammonia is: 1:4-100:1.05-20, and reacting for 1-10h in a reaction kettle; or in a fixed bed, with a space velocity of 0.01 to 10h -1 。
8. The process for the synthesis of cyclohexylimine according to claim 7, characterized in that the reaction temperature is 150 to 250 ℃ and the pressure is 1 to 6MPa; the reaction is carried out in a reaction kettle for 2 to 4 hours or in a fixed bed reactor with the airspeed of 0.1 to 5 hours -1 。
9. A method for synthesizing cyclohexylimine is characterized in that in the presence of a selective ammonification hydrogenation catalyst, hexanedialdehyde monoacetal or hexanedialdehyde diacetal reacts with hydrogen and ammonia to generate cyclohexylimine, wherein the reaction temperature is 50-350 ℃ and the pressure is 0.5-20Mpa;
the selective ammoniation hydrogenation catalyst consists of active metal Ni,0.01-10wt% of first modified component Sn, a heat-resistant inorganic oxide carrier and optional second modified metal components, wherein the second modified metal components are selected from one or more of Pt, ag, pd, co and Cu; the heat-resistant inorganic oxide carrier is selected from one or a mixture of more of aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, niobium oxide and ZSM-5;
the preparation method of the selective ammonification hydrogenation catalyst comprises the following steps:
a) Precursor salt of Ni and SnCl 2 Or SnCl 4 And optionally a second modified metal component precursor salt onto a refractory inorganic oxide support;
b) Drying the impregnation mixture obtained in a) at 100-130 ℃;
c) Reducing the solid obtained in b) with hydrogen at 300-600 deg.c to obtain the selective ammonification hydrogenation catalyst.
10. The method for synthesizing cyclohexylimine according to claim 9, characterized in that the structural general formula of the glyoxal monoacetal is:
or alternatively
Wherein A is 1 、A 2 Is a fatty chain with 1-5 carbon atoms, A 5 A carbon chain having 2 to 3 carbon atoms;
the structural general formula of the glyoxal diacetal is as follows:
or alternatively
Wherein A1, A2, A3 and A4 are respectively and independently aliphatic chains with carbon number of 1-5; a5 and A6 are respectively independent carbon chains with 2-3 carbon numbers, and the carbon chains are provided with optional hydroxyl, halogen and alkyl.
11. The process for synthesizing cyclohexylimine according to claim 10, characterized in that the selective ammoniation hydrogenation catalyst contains 10 to 50wt% of active metal Ni,0.01 to 10wt% of Sn, 0 to 2wt% of a second modified metal component and the balance of refractory inorganic oxide support.
12. Process for the synthesis of cyclohexylimine according to claim 11, characterized in that the selective ammoniation hydrogenation catalyst contains from 0.02 to 2% by weight of the second modified metal component.
13. Process for the synthesis of cyclohexylimine according to any of claims 9 to 12, characterized in that the second modified metal component is Pt or Pd.
14. Process for the synthesis of cyclohexylimine according to any of claims 9 to 12, characterized in that the mass ratio of glyoxal, glyoxal monoacetal or glyoxal diacetal to hydrogen, ammonia is: 1:4-100:1.05-20, and reacting for 1-10h in a reaction kettle; or in a fixed bed, with a space velocity of 0.01 to 10h -1 。
15. The process for the synthesis of cyclohexylimine according to claim 14, characterized in that the reaction temperature is 150 to 250 ℃ and the pressure is 1 to 6MPa; the reaction is carried out in a reaction kettle for 2 to 4 hours or in a fixed bed reactor with the airspeed of 0.1 to 5 hours -1 。
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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4461858A (en) * 1980-05-16 1984-07-24 E. I. Du Pont De Nemours And Company Polyvinylalcohol/melamine-formaldehyde interaction products
US6043395A (en) * 1998-06-04 2000-03-28 Bayer Aktiengesellschaft Process for preparing variable mixtures of cyclohexyl-amine and dicyclohexylamine
WO2010012672A2 (en) * 2008-08-01 2010-02-04 Basf Se Method for the production of diamines from lactams
CN103097336A (en) * 2010-09-11 2013-05-08 奥克塞有限公司 Method for producing primary aliphatic amines from aldehydes
CN104262168A (en) * 2014-09-22 2015-01-07 北京旭阳化工技术研究院有限公司 Preparation method of hexamethylenediamine
CN104277018A (en) * 2013-07-02 2015-01-14 中国科学院大连化学物理研究所 Method for preparing 2, 5-dimethylamino furan from 2, 5-diformyl furan
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
CN109647419A (en) * 2018-12-20 2019-04-19 大连理工大学 A kind of rare earth oxide-modified adipic dinitrile hydrogenation preparing hexanediamine high-selectivity catalyst, preparation method and application
CN109651166A (en) * 2017-10-10 2019-04-19 中国石油化工股份有限公司 The method that aniline prepares cyclohexylamine
CN110981705A (en) * 2019-11-12 2020-04-10 万华化学集团股份有限公司 Method for preparing cyclohexane dimethylamine
CN111054432A (en) * 2019-12-16 2020-04-24 中国科学院大连化学物理研究所 Catalyst for preparing hexamethylene diamine and preparation method and application thereof
CN111072489A (en) * 2019-12-16 2020-04-28 中国科学院大连化学物理研究所 Method for preparing hexamethylene diamine from hexamethylene dialdehyde in fixed bed reactor
CN111116377A (en) * 2019-12-16 2020-05-08 中国科学院大连化学物理研究所 Method for preparing hexamethylene diamine

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8293945B2 (en) * 2007-12-21 2012-10-23 Basf Se Method for producing an amine
CN102639231B (en) * 2009-12-03 2014-12-10 巴斯夫欧洲公司 Catalyst and method for producing an amine
US9040451B2 (en) * 2011-11-17 2015-05-26 Basf Se Process for producing Sn-comprising catalysts
EP3634935B1 (en) * 2017-06-09 2022-03-09 Basf Se Process for preparing ethyleneamines

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4461858A (en) * 1980-05-16 1984-07-24 E. I. Du Pont De Nemours And Company Polyvinylalcohol/melamine-formaldehyde interaction products
US6043395A (en) * 1998-06-04 2000-03-28 Bayer Aktiengesellschaft Process for preparing variable mixtures of cyclohexyl-amine and dicyclohexylamine
WO2010012672A2 (en) * 2008-08-01 2010-02-04 Basf Se Method for the production of diamines from lactams
CN103097336A (en) * 2010-09-11 2013-05-08 奥克塞有限公司 Method for producing primary aliphatic amines from aldehydes
CN104277018A (en) * 2013-07-02 2015-01-14 中国科学院大连化学物理研究所 Method for preparing 2, 5-dimethylamino furan from 2, 5-diformyl furan
CN104262168A (en) * 2014-09-22 2015-01-07 北京旭阳化工技术研究院有限公司 Preparation method of hexamethylenediamine
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
CN109651166A (en) * 2017-10-10 2019-04-19 中国石油化工股份有限公司 The method that aniline prepares cyclohexylamine
CN109647419A (en) * 2018-12-20 2019-04-19 大连理工大学 A kind of rare earth oxide-modified adipic dinitrile hydrogenation preparing hexanediamine high-selectivity catalyst, preparation method and application
CN110981705A (en) * 2019-11-12 2020-04-10 万华化学集团股份有限公司 Method for preparing cyclohexane dimethylamine
CN111054432A (en) * 2019-12-16 2020-04-24 中国科学院大连化学物理研究所 Catalyst for preparing hexamethylene diamine and preparation method and application thereof
CN111072489A (en) * 2019-12-16 2020-04-28 中国科学院大连化学物理研究所 Method for preparing hexamethylene diamine from hexamethylene dialdehyde in fixed bed reactor
CN111116377A (en) * 2019-12-16 2020-05-08 中国科学院大连化学物理研究所 Method for preparing hexamethylene diamine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
柯明 ; 张曼曼 ; 胡海强 ; 宋昭峥 ; .六亚甲基亚胺的合成进展.化工科技.2013,(第06期),全文. *

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