CN107986974B - Method for preparing cyclohexane dimethylamine - Google Patents
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- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
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- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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Abstract
The invention relates to a method for producing cyclohexanedimethanamine by direct amination (reductive amination) of cyclohexanedimethanol, wherein the cyclohexanedimethanol performs reductive amination reaction with ammonia and hydrogen in the presence of a ruthenium catalyst and a modification auxiliary agent to prepare the cyclohexanedimethanamine. The method has the advantages of high conversion rate of raw materials up to more than 99%, high yield of aminated products up to more than 90%, less than 10% of byproducts, simple product separation, no need of recycling unreacted raw materials and intermediates, reduced energy consumption and finally reduced production cost.
Description
Technical Field
The invention relates to a method for producing amine, in particular to a method for producing cyclohexanedimethanamine by directly using a cyclohexanedimethanol amination (reductive amination) method, belonging to the field of chemical raw material manufacturing.
Technical Field
The conventional method for synthesizing cyclohexanedimethanamine is to prepare phthalonitrile by ammoxidation, obtain a xylylenediamine intermediate by hydrogenation of nitrile by using a hydrogenation technology, and further obtain the cyclohexanedimethanamine by further hydrogenation of p-xylylenediamine. The process has long route, more conversion steps and large investment, and relates to safe production with high risk in two-step hydrogenation.
In the published U.S. Pat. No. 5,5371293, 5% ruthenium on carbon or ruthenium on alumina was used as a catalyst to hydrogenate isophthalonitrile to 1, 3-cyclohexanedimethanamine with a yield of only 88%.
In U.S. Pat. No. 4,4070399, 1, 4-cyclohexanedimethanamine was obtained by hydrogenation of terephthalonitrile using a 5% ruthenium-palladium on carbon catalyst, with a maximum yield of 98%. Nitrile raw materials are adopted, so that the raw material cost is high, two-step hydrogenation is needed, and the equipment investment and safety risk are high.
In European patent publication EP0703213, m-xylylenediamine is hydrogenated in a yield of 94% by using a ruthenium, nickel and rhodium (or their compounds) catalyst. M-xylylenediamine is hydrogenated, the diamine is used as the raw material, and only p-phenylene ring is hydrogenated, so that the diamine raw material has high cost and poor economical efficiency. In the U.S. published patent No. US3998881, 1, 3-cyclohexanedimethanamine is obtained by hydrogenating isophthalonitrile with a 5% rhodium alumina catalyst, and the yield after rectification is only 71%.
Chinese published patent CN200980108138.0 discloses a direct amination method of cyclohexanedimethanol; the catalyst adopts Ni, Co, Cu and other transition metals as auxiliary agents, the conversion rate of the raw materials can only reach 60-90 percent, and the separation is difficult because the boiling points of the product and the raw materials are close. And the product selectivity is low, about 70 percent, and a large amount of accompanying byproducts exist.
It is seen that the problems of long process route, low product yield and low selectivity exist in the prior published method for producing cyclohexanedimethanamine, so that a technical scheme which has simple process flow, improves amination yield and reduces byproducts needs to be developed.
Disclosure of Invention
The invention aims to provide a method for preparing cyclohexane dimethylamine, which has the advantages of high conversion rate of raw materials up to more than 99%, amination product yield of more than 90%, less than 10% of by-products, simple product separation, no need of recycling unreacted raw materials and intermediates, reduced energy consumption and finally reduced production cost.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing cyclohexanedimethanamine by direct reductive amination of cyclohexanedimethanol, wherein the cyclohexanedimethanamine is prepared by reductive amination of cyclohexanedimethanol, ammonia and hydrogen in the presence of a ruthenium catalyst and a modification aid.
In the present invention, the cyclohexanedimethanol is a combination of 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, and cis, trans isomers and mixtures thereof.
In the present invention, the ammonia is NH3。
In the invention, the ruthenium catalyst comprises an active component ruthenium, a carrier and an optional auxiliary agent, wherein the content of Ru is 0.5-10 wt% and 1-5 wt% of the active component based on the total weight of the catalyst; the auxiliary elements are one or two or more of Cr, V, Zn, Fe, Co, Cu, Mo and Sn; preferably, Cr and Cu are compounded, wherein the mass ratio of Cr to Cu is 5: 1-1: 5; the preferred mass ratio is 2: 1-1: 2; the content of Cr and Cu is preferably 0.5 wt% to 2 wt%; the balance being carriers. The carrier is one or two or more of activated carbon, alumina, silica and zirconia.
In the invention, the modifying auxiliary agent is quaternary ammonium base with a general formula [ R1R2R3R4N]+(OH)-Wherein R is1、R2、R3、R4Is an alkane group of C1-C4, wherein R1、R2、R3、R4May be the same or different. Preferably, the modifying assistant is added in the form of an aqueous solution at a concentration of 1 wt% to 60 wt%, preferably 5 wt% to 15 wt%, and the modifier is used in an amount of 0.1 wt% to 10 wt%, preferably 0.5 wt% to 3 wt%, based on the weight of cyclohexanedimethanol. The addition of the modification auxiliary agent is used for reducing secondary amine (including intermolecular and intramolecular) byproducts in the reductive amination process and ensuring the selectivity of primary amine main products.
The catalyst of the present invention is suitable for the direct reductive amination of cyclohexanedimethanol, particularly 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, and combinations of cis, trans isomers and mixtures thereof.
In the research process of applying the catalyst system to reductive amination reaction, the active metal component Ru shows excellent activity to the reductive amination reaction of cyclohexane dimethanol, particularly to 1, 3-cyclohexane dimethanol, 1, 4-cyclohexane dimethanol, and the combination of cis-isomer, trans-isomer and mixture thereof as raw materials for reductive amination; however, when the content of incorporated Ru in the catalyst is below 0.5 wt%, there is a significant decrease in catalyst selectivity during reductive amination; when the content of Ru is higher than 10 wt%, the increase of the content of Ru does not contribute to the improvement of the activity and selectivity of the catalyst, and even increases by-products, so that the content of Ru in the catalyst is controlled to be 0.5 wt% -10 wt%, preferably 1 wt% -5 wt%.
In the invention, the catalyst auxiliary element is added to improve the toxicity resistance and carbon deposition resistance of the catalyst and prolong the service life of the catalyst.
The preparation method of the catalyst adopts an impregnation method well known in the industry, and uses metal solution to impregnate the carrier to obtain a catalyst precursor; and drying and roasting the catalyst precursor to obtain the catalyst. For specific operations, reference is made to the methods described in Chinese patent application Nos. CN201310449697.6 and CN 201510671624.0.
The method for producing cyclohexanedimethanamine according to the present invention may be carried out either batchwise or continuously, preferably continuously. The continuous process for preparing cyclohexanedimethanamine can be carried out in the form of a liquid phase reaction in a tubular reactor or in the form of a gas phase reaction.
In the present invention, the molar ratio of ammonia to cyclohexanedimethanol is from 1 to 50, preferably from 2 to 10. The molar ratio of hydrogen to cyclohexanedimethanol is from 0.01 to 1, preferably from 0.05 to 0.5. The catalyst space velocity is from 0.01 to 1kg of cyclohexanedimethanol per liter of catalyst per hour, preferably from 0.1 to 0.5kg of cyclohexanedimethanol per liter of catalyst per hour. The amount of the batch process catalyst is 0.5 to 15 wt%, preferably 1 to 5 wt%, based on the mass of the raw material cyclohexanedimethanol.
In the invention, the reaction temperature of the reductive amination reaction is 150-250 ℃, preferably 170-230 ℃; the reaction pressure (absolute pressure) is 1MPa to 30MPa, preferably 3MPa to 15 MPa.
In the present invention, a solvent may or may not be used in the reductive amination process, and the solvent includes, but is not limited to, water, benzene, cyclohexane, toluene, diethyl ether, THF (tetrahydrofuran), MTBE (methyl tert-butyl ether), and other ethers and hydrocarbons. The present invention is preferably carried out without the use of a solvent.
According to the method, the cyclohexanedimethanamine, in particular the 1, 3-cyclohexanedimethanol, the 1, 4-cyclohexanedimethanol and the combination of cis-isomer, trans-isomer and mixture thereof are prepared by the method, the yield of the cyclohexanedimethanamine product can reach 90-95%, and the conversion rate of raw materials can reach 99-100%.
The invention has the beneficial effects that:
compared with the prior amination catalyst with high metal content such as Ni, Co and the like, the active component Ru obviously improves the reaction activity of unit catalyst mass, the selectivity to target amination products and the conversion rate of raw materials.
The addition of an auxiliary element, particularly a proper amount (0.5 wt% -2 wt%) of a compound (5: 1-1: 5) of Cu and Cr is effective in improving the toxicity resistance and carbon deposition resistance of the catalyst and prolonging the service life of the catalyst.
The modified auxiliary agent can improve the acidity of the catalytic surface, reduce the generation of secondary amine byproducts and high polymers in the reaction process, and improve the selectivity of primary amination products.
Compared with the prior direct amination technology, the invention has high conversion rate of raw materials, the yield of aminated products is more than 90%, secondary amine and high polymer byproducts can be effectively reduced by less than 10% due to the use of the modification auxiliary agent, the subsequent products are simple to separate, unreacted raw materials and intermediates are not required to be recycled, the energy consumption is reduced, and the production cost is finally reduced.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the examples listed, and it should also include equivalent modifications and variations to the technical solutions defined in the claims appended to the present application.
Gas chromatograph: shimadzu GC-2014(FID) detector, SE-30 capillary column
The sample inlet is 270 ℃, and the detector is 270 ℃; temperature rising procedure: the temperature is kept constant at 70 ℃ for 1min, and then the temperature is increased to 240 ℃ at the speed of 40 ℃/min and kept for 5 min.
In the embodiment, the reductive amination reactor is a batch kettle type reactor or a fixed bed reactor,
liquid ammonia, hydrogen: vanhua chemical group, Inc.;
1, 3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol: tuo's chemical Unoxol Diol series
Alumina powder: zibo Zi Sheng AlMg Co., Ltd 4010-1 series;
tetramethylammonium hydroxide (analytical grade): chinese medicine reagent
Tetrabutylammonium hydroxide (analytically pure): chinese medicine reagent
Example 1
93.2g of alumina powder was dried at 120 ℃ for 12 hours, poured into 90ml of a nitrate-impregnated solution containing 5g of Ru, 0.3g of Cu, 0.5g of Cr and 1g of Mo, and thoroughly mixed at room temperature for 2 hours. The above catalyst precursor was dried at 100 ℃ for 8 hours, calcined at 400 ℃ for 4 hours, and cooled to obtain catalyst 1, which was analyzed by ICP, and contained 5% Ru, 0.3% Cu, 0.5% Cr, and 1% Mo.
Example 2
97.7g of a zirconium dioxide spherical support having a diameter of 2mm were dried at 120 ℃ for 12 hours, poured into 100ml of a nitrate-impregnated solution containing 1gRu, 0.5g of Cr, 0.1g of 0.1g V, 0.4g of Fe, 0.1g of Co, 0.1g of Cu and 0.1g of Sn, and thoroughly mixed at room temperature for 2 hours. The catalyst precursor was dried at 120 ℃ for 4 hours, calcined at 475 ℃ for 12 hours, and then cooled to obtain catalyst 2. ICP analysis of this material gave 1% Ru, 0.5% Cr, 0.1% V, 0.4% Fe, 0.1% Co, 0.1% Cu and 0.1% Sn.
Example 3
88g of a spherical silica carrier having a diameter of 2mm was dried at 100 ℃ for 24 hours, and 90 g was poured into ml of a nitrate-impregnated solution containing 10gRu, 0.2g of Cr, 0.4g of Zn, 0.1g of Co, 1g of Cu and 0.3g of Mo, and thoroughly mixed at room temperature for 2 hours. The catalyst precursor was dried at 60 ℃ for 24 hours under vacuum, calcined at 300 ℃ for 18 hours, and then cooled to obtain catalyst 3. By ICP analysis, 10% Ru, 0.2% Cr, 0.4% Zn, 0.1% Co, 1% Cu and 0.3% Mo were present.
Example 4
98.2g of a silica-containing alumina clover type extrudate support having a diameter of 3mm, containing 5% silicon, were dried at 110 ℃ for 10h and then poured into 100ml of a nitrate impregnation solution containing 0.5g of Ru, 0.5g of Cr, 0.1g of 0.1g V, 0.4g of Fe, 0.1g of Co, 0.1g of Cu and 0.1g of Sn and mixed thoroughly at room temperature for 2 h. The catalyst precursor was dried at 110 ℃ for 6 hours under vacuum, calcined at 350 ℃ for 6 hours, and then cooled to obtain catalyst 4. ICP analysis of this material gave 0.5% Ru, 0.5% Cr, 0.1% V, 0.4% Fe, 0.1% Co, 0.1% Cu and 0.1% Sn.
Example 5
Amination of 1, 3-cyclohexanedimethanol
In a 1.5L autoclave were placed 10g of catalyst 1, 200g of 1, 3-cyclohexanedimethanol, 200g of liquid ammonia, 13g of 15% [ (CH3)4N]Filling 3.5NL hydrogen into OH (tetramethylammonium hydroxide) solution, reacting at 180 ℃ under the reaction pressure of about 15MPa for 5h, distilling the reactant to remove excessive ammonia and water after the reaction is stopped, and analyzing by gas chromatography to find out 1, 3-cyclohexanedimethanol, 93 wt% of 1, 3-cyclohexanedimethylamine and intramolecular secondary amine (3-azabicyclo [3.3.1 ]]Nonane) 5 wt%, intermolecular secondary amine (bis ((3-aminomethylcyclohexyl) methyl) amine) and its high polymer 2 wt%, conversion of the raw material 100%, amination product yield 93%.
Example 6
Amination of 1, 4-cyclohexanedimethanol
A1.5L autoclave was charged with 10g of catalyst 1, 200g of 1, 4-cyclohexanedimethanol, 200g of liquid ammonia, 10g of 10% [ (C)4H9)4N]OH (tetrabutylammonium hydroxide) solution is filled with 20NL hydrogen, reaction pressure is about 20MPa at 220 ℃, reaction is carried out for 3.5h, after the reaction is stopped, excessive ammonia and water are removed by distillation of reactants, gas chromatography analysis is carried out, 1, 4-cyclohexanedimethanol is not detected, 95 wt% of 1, 4-cyclohexanedimethylamine and intramolecular secondary amine (3-azabicyclo [3.2.2]]Nonane) 3 wt%, intermolecular secondary amine (bis ((4-aminomethylcyclohexyl) methyl) amine) and its polymer 2 wt%, conversion of the raw material 100%, amination product yield 95%.
Comparative example 1 (No modifier)
Amination of 1, 4-cyclohexanedimethanol
10g of catalyst 1, 200g of 1, 4-cyclohexanedimethanol and 200g of liquid ammonia are placed in a 1.5L autoclave, 20NL of hydrogen is charged, the reaction pressure is about 20MPa at 220 ℃, the reaction is carried out for 3.5h, after the reaction is stopped, the reactants are distilled to remove the excessive ammonia and water, and by using gas chromatography analysis, about 7% of 1, 4-cyclohexanedimethanol, 82% of 1, 4-cyclohexanedimethanamine, 8% of intramolecular secondary amine (3-azabicyclo [3.2.2] nonane), 3% of intermolecular secondary amine (bis ((4-aminomethylcyclohexyl) methyl) amine) and high polymer thereof, the conversion rate of raw materials is 93%, and the yield of aminated products is 82%.
Example 7
Amination of 1, 4-cyclohexanedimethanol
Filling 30ml of catalyst 2 in a fixed bed reactor, reducing the catalyst 2 by using hydrogen at the temperature of 250 ℃ for 24 hours, reducing the temperature to 225 ℃ after the reduction is finished, increasing the system pressure to 18MPa and starting feeding, using dioxane as a solvent, ensuring that the concentration of 1, 4-cyclohexanedimethanol is 30 wt%, and adding 15% [ (CH)3)4N]OH solution, [ (CH)3)4N]The OH amount is 10 wt% of the weight of the 1, 4-cyclohexanedimethanol, and the feeding volume space velocity of the 1, 4-cyclohexanedimethanol is 0.1kg/Lcat-1Liquid ammonia/1, 4-cyclohexanedimethanol molar ratio of 30:1, hydrogen/1, 4-cyclohexanedimethanol molar ratio of 0.05:1, reactants were distilled to remove excess ammonia, dioxane solvent and water, 1, 4-cyclohexanedimethanol was not detected using gas chromatography, 1, 4-cyclohexanedimethanamine was 94 wt%, intramolecular secondary amine (3-azabicyclo [3.2.2] intramolecular secondary amine)]Nonane) 5 wt%, intermolecular secondary amine (bis ((4-aminomethylcyclohexyl) methyl) amine) and high polymer 1 wt%, conversion of raw material 100%, amination product yield 94%. After 100h, sampling and analyzing, the result is unchanged, the conversion rate of the raw material is 100 percent, and the yield of the aminated product is 94 percent.
Example 8
Amination of 1, 4-cyclohexanedimethanol
Filling 30ml of catalyst 3 in a fixed bed reactor, reducing the catalyst by using hydrogen at the temperature of 250 ℃ for 24 hours, reducing the temperature to 150 ℃ after the reduction is finished, increasing the system pressure to 5MPa and starting feeding, using cyclohexane as a solvent, wherein the concentration of 1, 4-cyclohexanedimethanol is 20 wt%, and addingTo which 20% [ (C) was added4H9)4N]OH solution, [ (C)4H9)4N]The OH dosage is 10 wt% of the weight of the 1, 4-cyclohexanedimethanol, and the space velocity of the 1, 4-cyclohexanedimethanol is 0.5kg/Lcat-1Liquid ammonia/1, 4-cyclohexanedimethanol molar ratio of 5:1, hydrogen/1, 4-cyclohexanedimethanol molar ratio of 0.1:1, reactants were distilled to remove excess ammonia, cyclohexane solvent and water, 1, 4-cyclohexanedimethanol was not detected using gas chromatography, 1, 4-cyclohexanedimethanamine was 96 wt%, intramolecular secondary amine (3-azabicyclo [3.2.2]]Nonane) 2 wt%, intermolecular secondary amine (bis ((4-aminomethylcyclohexyl) methyl) amine) and high polymer 2 wt%, conversion of raw material 100%, amination product yield 96%. After 100h, sampling and analyzing, the result is unchanged, the conversion rate of the raw material is 100 percent, and the yield of the aminated product is 96 percent.
Example 9
Amination of 1, 3-cyclohexanedimethanol
Filling 30ml of catalyst 4 in a fixed bed reactor, reducing the catalyst 4 by using hydrogen at the temperature of 250 ℃ for 24 hours, reducing the temperature to 150 ℃ after the reduction is finished, increasing the system pressure to 30MPa, starting feeding, using no solvent and simultaneously adding 3% [ (C)3H7)4N]OH solution, [ (C)3H7)4N]The OH dosage is 0.5 weight percent of the weight of the 1, 3-cyclohexanedimethanol, and the space velocity of the 1, 3-cyclohexanedimethanol is 1kg/Lcat-1Liquid ammonia/1, 3-cyclohexanedimethanol molar ratio of 50:1, hydrogen/1, 3-cyclohexanedimethanol molar ratio of 1:1, the reactants were distilled to remove excess ammonia and water, 1, 3-cyclohexanedimethanol was not detected using gas chromatography, 92 wt% of 1, 3-cyclohexanedimethylamine, intramolecular secondary amine (3-azabicyclo [3.3.1 ] dimethyl amine)]4 wt% of nonane), 4 wt% of intermolecular secondary amine (bis ((3-aminomethylcyclohexyl) methyl) amine) and a polymer thereof, 100% of conversion of raw materials, and 92% of yield of aminated products. After 100h, sampling and analyzing, the result is unchanged, the conversion rate of the raw material is 100 percent, and the yield of the aminated product is 92 percent.
Comparative example 2
Amination of 1, 4-cyclohexanedimethanol
A fixed bed reactor was charged with 30ml of a commercially available charge5wt％Ru/Al2O3The catalyst (Zhuangxinwan Feng) is reduced by hydrogen at the temperature of 250 ℃ for 24 hours, after the reduction is finished, the temperature is reduced to 220 ℃, the system pressure is increased to 15MPa and the feeding is started, THF is used as a solvent, the concentration of 1, 4-cyclohexanedimethanol is 25 wt%, and the space velocity of 1, 4-cyclohexanedimethanol is 0.3kg/lcat.h-1Liquid ammonia/1, 4-cyclohexanedimethanol molar ratio of 15:1, hydrogen/1, 4-cyclohexanedimethanol molar ratio of 0.2:1, reactants were distilled to remove excess ammonia, THF solvent and water, and using gas chromatography analysis 17 wt% of 1, 4-cyclohexanedimethanol remains, 56 wt% of 1, 4-cyclohexanedimethanamine, intramolecular secondary amine (3-azabicyclo [3.2.2] intramolecular secondary amine)]Nonane) 19 wt%, intermolecular secondary amine (bis ((4-aminomethylcyclohexyl) methyl) amine) and high polymer 8 wt%, conversion of raw material 83%, amination product yield 56%. After 100h, sampling and analyzing, the conversion rate of the raw material is reduced to 71 percent, and the yield of the aminated product is 45 percent.
Claims (16)
1. A method for preparing cyclohexane dimethylamine is characterized in that cyclohexane dimethylamine is prepared by the reductive amination reaction of cyclohexane dimethanol, ammonia and hydrogen in the presence of ruthenium catalyst and modification auxiliary agent; the ruthenium catalyst comprises the following components: the content of the active component Ru is 0.5 wt% -10 wt%; one or more of the auxiliary elements Cr, V, Zn, Fe, Co, Cu, Mo and Sn, the content of which is 0 to 5 percent by weight; and a carrier; the modifying assistant is quaternary ammonium base with the general formula of [ R1R2R3R4N]+(OH)-Wherein R is1、R2、R3、R4Identical or different, respectively C1-C4 alkane radicals; the reaction temperature of the reductive amination reaction is 150-250 ℃; the absolute pressure of the reaction is 1MPa-30 MPa.
2. The method of claim 1, wherein the cyclohexanedimethanol is one or more of 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, and the cis and trans isomers thereof, and the ammonia is NH3。
3. The method of claim 1, wherein the active ingredient Ru is present in an amount of 1 wt% to 5 wt%.
4. The method according to claim 1, wherein the auxiliary element is a compound of Cr and Cu, and the mass ratio of the compound of Cr and Cu is 5: 1-1: 5.
5. The method of claim 4, wherein the Cr and Cu content is 0.5 wt% to 2 wt%.
6. The method of claim 1, wherein the support is a mixture of one or more of activated carbon, alumina, silica, and zirconia.
7. The method of claim 1, wherein the modifier additive is added as an aqueous solution at a concentration of 1 wt% to 60 wt%, and the modifier additive is present in an amount of 0.1 wt% to 10 wt% based on the weight of cyclohexanedimethanol.
8. The method of claim 7, wherein the concentration of the modifier additive is 5 wt% to 15 wt% and the modifier additive is present in an amount of 0.5 wt% to 3 wt% based on the weight of cyclohexanedimethanol.
9. The process of any one of claims 1-8, wherein the molar ratio of ammonia to cyclohexanedimethanol is from 1 to 50; the molar ratio of hydrogen to cyclohexanedimethanol is from 0.01 to 1.
10. The process of claim 9, wherein the molar ratio of ammonia to cyclohexanedimethanol is from 2 to 10; the molar ratio of hydrogen to cyclohexanedimethanol is from 0.05 to 0.5.
11. The process of any one of claims 1 to 8 wherein, when the reductive amination process is a batch process, the catalyst is used in an amount of from 0.5 to 15 wt.%, based on the mass of the starting cyclohexanedimethanol; when a continuous process is adopted, the space velocity of the catalyst is 0.01-1kg of cyclohexanedimethanol/Lcat/h.
12. The method of claim 11 wherein, when the reductive amination process is a batch process, the catalyst is used in an amount of 1 to 5 weight percent, based on the mass of the starting cyclohexanedimethanol; when a continuous process is adopted, the space velocity of the catalyst is 0.1-0.5kg of cyclohexanedimethanol/Lcat/h.
13. The process of claim 1, wherein the reductive amination reaction is carried out at a temperature of from 170 ℃ to 230 ℃; the absolute pressure of the reaction is 3MPa-15 MPa.
14. The process according to any one of claims 1 to 8, wherein the reductive amination reaction is carried out with or without a solvent, said solvent being one or more of water, hydrocarbons and ethers.
15. The method of claim 14, wherein said reductive amination is carried out without the use of a solvent.
16. The method of claim 14, wherein the solvent is one or more of water, benzene, cyclohexane, toluene, diethyl ether, THF, and MTBE.
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| CN111195523B (en) * | 2018-11-16 | 2022-02-15 | 中国科学院大连化学物理研究所 | Catalyst for producing amine by hydrogenation of cyanogen compounds, preparation method and application thereof |
| CN110105223A (en) * | 2019-05-15 | 2019-08-09 | 常州大学 | A kind of method that continuity method prepares 1,3- hexamethylene dimethylamine |
| CN110496613B (en) * | 2019-09-11 | 2022-04-22 | 万华化学集团股份有限公司 | Hydrogenation catalyst, preparation method thereof and method for preparing o-diaminomethylcyclohexane |
| CN110981705B (en) * | 2019-11-12 | 2022-08-05 | 万华化学集团股份有限公司 | Method for preparing cyclohexane dimethylamine |
| CN112300006A (en) * | 2020-11-25 | 2021-02-02 | 淄博正大聚氨酯有限公司 | Method for preparing 1, 4-cyclohexyl dimethylamine by using hydroamination method |
| CN113461543B (en) * | 2021-07-27 | 2024-02-02 | 万华化学集团股份有限公司 | Rectification and purification method of 1, 3-cyclohexanediamine crude product |
| CN115304488A (en) * | 2022-08-26 | 2022-11-08 | 中南大学 | Synthetic method of cyclohexylmethylamine and derivatives thereof |
| CN117964498A (en) * | 2024-04-02 | 2024-05-03 | 鞍山七彩化学股份有限公司 | Method for preparing rich trans-1, 4-cyclohexanedimethylamine |
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