A method for continuously producing an amine compound

Abstract

The application discloses a method for continuously preparing amine compounds by one-step reaction with acid / ester, an ammonia source and hydrogen as raw materials, a catalyst used in the method and a preparation method and application of the catalyst. According to the method, the catalyst is first loaded into a reactor, hydrogen is introduced into the reactor, and the catalyst is activated by being heated to 200-500 DEG C for 1-6 hours; after the activation is completed, the reaction temperature is adjusted to a target reaction temperature of 200-500 DEG C, and the pressure of the reaction system is adjusted to 0.1-5 MPa; the reaction raw materials, i.e., acid / ester and the ammonia source, are continuously added into the reactor to perform the reaction; after the raw materials contact the catalyst bed, the raw materials are separated from the reactor under the driving of gas, enter a condenser and a gas-liquid separator, and then enter a product storage tank, and the tail gas is exhausted. According to the method, the production energy consumption can be effectively reduced, the production cost is reduced, and industrial production can be easily realized.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of chemical synthesis, in particular, to a method for continuously preparing amine compounds by one-step reaction using acid / ester, ammonia source and hydrogen as raw materials, a catalyst used in the method and a preparation method and use thereof. BACKGROUND

[0002] Aliphatic amines are important intermediates in organic synthesis and have a wide range of applications in many fields. Cyclohexanedimethylamine is a cycloaliphatic amine, which is a colorless transparent liquid. It is an excellent epoxy resin curing agent with wide application, excellent yellowing resistance, good toughness and fast curing speed. It can be used in epoxy curing agents, floor paint, especially for occasions with high color stability requirements, civil engineering adhesives, polyamides and polyurethane chain extension. Its characteristics are fast curing at room temperature, low color, excellent yellowing resistance, excellent chemical resistance and operability in humid environments. 1,10-decanediamine is a white or light yellow crystal, which is easily soluble in ethanol, flammable at high temperature and open flame, and releases toxic gases when decomposed at high temperature. It is widely used in the synthesis of long-chain polyamides such as polyamide 1010, polyamide 10T, polyamide 10I and polyamide 1012.

[0003] At present, the main method for synthesizing aliphatic amines is hydrogenation reaction from nitrile raw materials. Cyclohexanedimethylamine is mainly prepared by hydrogenation reaction of the corresponding benzenedicarbonitrile, and chain aliphatic amines such as 1,10-decanediamine are mainly prepared by hydrogenation of 1,10-decanedinitrile, while 1,10-decanedinitrile is prepared by heating reaction of 1,10-decanedioic acid in the presence of ammonia and catalyst. The main method is a multi-step batch process, which is complex and has low production efficiency. SUMMARY

[0004] Technical problem

[0005] One object of the present application is to provide a method for preparing amine compounds by one-step continuous reaction using acid / ester, ammonia source and hydrogen as raw materials. The method according to the present application has excellent catalytic activity and target selectivity.

[0006] Another object of the present application is to provide a catalyst used in the preparation method.

[0007] Another object of the present application is to provide the use of the catalyst in the method for preparing amine compounds by one-step continuous reaction.

[0008] Another object of the present application is to provide a preparation method of the catalyst.

[0009] Technical scheme

[0010] According to one aspect of the present application, a method for preparing an amine compound by one-step continuous reaction using acid / ester, ammonia source, and hydrogen as raw materials is provided, and the method is performed as follows:

[0011] First, the catalyst is loaded into the reactor, hydrogen is introduced into the reactor, and the catalyst is activated at 200-500°C for 1-6 hours. After the activation is completed, the reaction temperature is adjusted to the target reaction temperature of 200-500°C, and the reaction system pressure is adjusted to 0.1-5 MPa. The raw materials, acid / ester and ammonia source, are continuously added to the reactor for reaction. After the raw materials contact with the catalyst bed, they are separated from the reactor under the driving of gas, enter the condenser and gas-liquid separator, and then enter the product storage tank, and the tail gas is exhausted.

[0012] Preferably, when the acid / ester and ammonia source are solids, they are added by a solid feeder, and a check valve is installed at the lower part of the solid feeder. When the acid / ester and ammonia source are liquids, the raw materials are pumped into the reaction system by a feed pump. The liquid ammonia is pumped into the reactor by a plunger pump, and the gaseous raw material (such as hydrogen) is introduced into the reactor by a mass flow controller.

[0013] Preferably, the fixed bed reactor is generally loaded with 3-10 g of catalyst, and the fluidized bed reactor is generally loaded with about 100 g of catalyst.

[0014] Preferably, if high-pressure reaction is required, the reactor pressure is increased by a back pressure valve, otherwise the normal pressure hydrogen atmosphere is maintained.

[0015] Preferably, in the method for preparing an amine compound according to the present application, the acid / ester raw material is selected from the following reaction substances of structural formula.

[0016]

[0017] wherein R, R1, and R2 are each independently selected from hydrogen, C1-C6 alkyl, halogen-substituted C1-6 alkyl, hydroxyl-substituted C1-6 alkyl, and amine-substituted C1-6 alkyl.

[0018] Preferably, R, R1, and R2 are each independently selected from hydrogen, C1-C4 alkyl, halogen-substituted C1-4 alkyl, hydroxyl-substituted C1-4 alkyl, and amine-substituted C1-4 alkyl.

[0019] Preferably, R, R1, and R2 are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl.

[0020] Preferably, the halogen is selected from fluorine atom, chlorine atom, and bromine atom.

[0021] n is an integer between 2 and 15, for example n can be an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15; preferably n is an integer between 2 and 10; more preferably n is an integer between 2 and 6. Preferably, the reactor in the method for preparing amine compounds is selected from any one of a continuous stirred tank reactor, a plug flow reactor, a fixed bed reactor and a fluidized bed reactor or can be a mixed reactor connected with two or more of these reactors. Preferably, it is a fixed bed reactor or a fluidized bed reactor.

[0022] Preferably, the catalyst can be in the form of a strip, a column, a sheet or a particle.

[0023] Preferably, the temperature in the method for preparing amine compounds is preferably 250°C to 400°C.

[0024] Preferably, the reaction pressure in the method for preparing amine compounds is 0.1 MPa to 5 MPa, preferably 0.1 MPa to 3 MPa.

[0025] Preferably, in the method for preparing amine compounds, the ammonia source comprises one or more of ammonia, urea, ammonium carbonate, ammonium bicarbonate.

[0026] Preferably, in the method for preparing amine compounds, the molar ratio of the acid / ester to the ammonia source is 1:4 to 1:30, preferably 1:5 to 1:20.

[0027] Preferably, in the method for preparing amine compounds, the molar ratio of the acid / ester to hydrogen is 1:4 to 1:40, preferably 1:4 to 1:20.

[0028] Preferably, the acid / ester can be reacted in the presence or absence of a solvent, and the solvent is one or more selected from acetonitrile, 1,4-dioxane, methanol, ethanol, preferably acetonitrile, methanol, ethanol.

[0029] Preferably, the method for preparing amine compounds can be carried out at a reaction space velocity of 0.05 h -1 ~ 5 h -1 , preferably 0.03 h -1 ~ 3 h -1 .

[0030] Preferably, the activation step of the catalyst is carried out as follows: before the reaction, the reactor loaded with the catalyst is heated to an activation temperature of 300°C to 500°C and maintained for 2 to 5 h; preferably, the activation temperature can be 300°C to 400°C.

[0031] Preferably, the method for preparing amine compounds further comprises post-reaction treatment. Specifically, after condensation and gas-liquid separation, the reaction product is subjected to rectification. The condensation, gas-liquid separation and rectification are methods and conditions for separating amine compounds that are conventional in the art, and will not be described here in detail.

[0032] The catalyst in the method for preparing amine compounds according to the present application comprises a carrier and an active component, wherein:

[0033] The carrier comprises one or more selected from γ-Al2O3, SiO2, ZrO2, TiO2, HZSM5, SAPO-34, HY, Hβ and HMOR, preferably γ-Al2O3, SiO2, HZSM5, HY, Hβ; more preferably γ-Al2O3, SiO2, HZSM5, Hβ.

[0034] The active component comprises one or more metal elements selected from platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), nickel (Ni) and cobalt (Co).

[0035] According to an embodiment of the present application, in the catalyst, the mass ratio of the metal element in the active component to the carrier is (0.1-20):100, preferably (0.5-10):100, and more preferably (1.0-10):100. If the ratio is lower than this range, the catalyst activity is insufficient, and the conversion rate of the raw material is not high; if the ratio is higher than this range, the production cost of the catalyst is increased, and the selectivity of the product can be reduced.

[0036] Preferably, the active component comprises one or more metal elements selected from platinum (Pt), palladium (Pd), nickel (Ni) and cobalt (Co).

[0037] Preferably, the catalyst is prepared as follows:

[0038] (1) The carrier is immersed in an equal volume of an aqueous solution of an active component precursor, and then is left to stand and dried;

[0039] (2) The product obtained in step (1) is calcined in an air atmosphere at 250-300°C for 2-5h;

[0040] (3) The product obtained in step (2) is reduced in a hydrogen atmosphere at 250-400°C for 2-4h.

[0041] Preferably, the active component precursor comprises one or more of nitrates, chlorides (chloro complexes) and acetates of Pt, Pd, Ru, Rh, Ni and Co.

[0042] Preferably, in step (1), the concentration of the active component precursor aqueous solution is 0.005 mol / L to 0.1 mol / L.

[0043] Preferably, in step (1), the standing time is 2 h to 5 h.

[0044] Preferably, in step (1), the drying temperature is 110°C to 150°C and the drying time is 5 h to 10 h.

[0045] Preferably, the preparation method of the catalyst further comprises pretreatment of the carrier. Preferably, before step (1), the carrier is calcined in an air atmosphere at 200°C to 400°C for 2 h to 5 h.

[0046] According to another aspect of the application, there is provided use of the catalyst in the method for preparing amine compounds from acid / ester, ammonia source and hydrogen gas through one-step continuous reaction.

[0047] Advantages

[0048] The method for one-step continuous synthesis of amine compounds from acid / ester, ammonia source and hydrogen gas provided by the present application can effectively reduce energy consumption and production cost, and is easy to realize industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0049] Figure 1 Schematic diagram of a synthesis reaction device for synthesizing amine compounds according to an embodiment of the present application.

[0050] Figure 2 Gas chromatogram of a reaction product according to Reaction Example 1 of the present application. DETAILED DESCRIPTION

[0051] Hereinafter, preferred embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. Before the description, it should be understood that the term used in the specification and the appended claims should not be construed as limited to a general and dictionary meaning, but interpreted based on the meaning and concepts of the present application under the principle that the inventor is allowed to define the terms appropriately for best explaining the present application. Therefore, the description herein merely describes preferred embodiments of the present application, but it is not intended to limit the scope of the present application, and it should be understood that other equivalents and modifications can be made thereto without departing from the spirit and scope of the present application.

[0052] The following examples are merely set forth as examples of embodiments of the present application and should not be construed as limiting the present application in any way. It will be appreciated by persons skilled in the art that modifications can be made to the present application without departing from the spirit and scope of the present application.

[0053] Preparation of amine compounds

[0054] In the method for preparing amine compounds according to this application, amine compounds are obtained through a one-step ammoniation, dehydration, and hydrogenation reaction using an acid / ester, an ammonia source, and hydrogen. The product obtained after post-processing is filtered through a 0.22 μm filter membrane and analyzed by gas chromatography (GC). Qualitative analysis of the low-boiling-point product is performed by GC-MS and comparison with the GC retention time of the standard, confirming that the reaction product is mainly an amine compound. Quantitative determination of the product is performed using a Shimadzu-GC 2020 gas chromatograph, and quantitative analysis is performed by comparing the retention time with the standard and the peak area. The relevant calculation formulas are as follows:

[0055]

[0056]

[0057]

[0058]

[0059]

[0060] The feed rate of acid / ester is expressed in g / min, and the amount of catalyst is expressed in g.

[0061] like Figure 1 The diagram shows a schematic of an apparatus for synthesizing amine compounds according to one embodiment of this application. The reactor is filled with a catalyst for preparing amine compounds according to this application. First, a carrier gas is introduced into the reaction tube at a controlled flow rate using a mass flow controller to create a carrier gas atmosphere. A heating furnace can then be used to activate the catalyst. Next, while maintaining the temperature of the reaction tube, an acid / ester is fed into the reaction tube via a feed pump / feeder, an ammonia source (solid ammonia source is fed into the reaction tube via a feeder) is fed into the reaction tube via a mass flow controller, and hydrogen is fed into the reaction tube via a mass flow controller. Under the carrier gas atmosphere and with the catalyst catalyzing, the reaction produces a product containing amine compounds. After condensation and gas-liquid separation, the amine compounds can be collected.

[0062] According to this application, the catalyst is applied to the process of preparing amine compounds using acids / esters, ammonia sources, and hydrogen as raw materials. The method for preparing amine compounds provided by this application uses readily available raw materials, has a more environmentally friendly route, is simple in process, highly efficient, and can be used for continuous production.

[0063] Unless otherwise specified, all raw materials used in this application are commercially available, and all methods and equipment used are conventional methods and equipment in the field.

[0064] In the following examples, 1,4-dimethyl cyclohexanedicarboxylate, 1,4-cyclohexanedicarboxylic acid, 1,3-dimethyl cyclohexanedicarboxylate, 1,2-dimethyl cyclohexanedicarboxylate, 1,2-dimethyl cyclopentanedicarboxylate, 1,3-dimethyl cyclopentanedicarboxylate, dimethyl sebacate, dimethyl adipate, methyl 2-methoxyacetate, cobalt nitrate, nickel nitrate, urea, ammonium carbonate, ammonium bicarbonate were purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.; chloroplatinic acid, palladium nitrate, ruthenium chloride were purchased from Xi'an Kailixin Material Co., Ltd., SiO2was purchased from Qingdao Haoyang Chemical Co., Ltd., Hβ, HZSM5were purchased from Tianjin Nanhua Catalyst Co., Ltd., high-purity nitrogen, high-purity helium, high-purity hydrogen, air were purchased from Qingdao Dehai Weiye Technology Co., Ltd.

[0065] Preparation of the catalyst

[0066] Preparation Example 1

[0067] The catalyst for preparing amine compounds was prepared by a method comprising the following steps:

[0068] (i) Pretreatment of the carrier: 50 g of γ-Al2O3was calcined at 300°C for 5 h in an air atmosphere;

[0069] (ii) The pretreated carrier obtained in step (i) was impregnated with an aqueous nickel nitrate solution with a concentration of 0.1 mol / L at an equal volume, and was left to stand for 5 h, and then was dried at 120°C for 10 h;

[0070] (iii) The product obtained in step (ii) was calcined at 300°C for 5 h in an air atmosphere;

[0071] (iv) The product obtained in step (iii) was reduced at 400°C for 4 h in a hydrogen atmosphere, wherein the hydrogen flow rate was 50 mL / min; thus, catalyst 1 was prepared.

[0072] Preparation Example 2

[0073] The catalyst for preparing amine compounds was prepared by a method comprising the following steps:

[0074] (i) Pretreatment of the carrier: 50 g of HZSM5was calcined at 300°C for 5 h in an air atmosphere;

[0075] (ii) The pretreated carrier obtained in step (i) was impregnated with an aqueous cobalt nitrate solution with a concentration of 0.05 mol / L at an equal volume, and was left to stand for 5 h, and then was dried at 120°C for 10 h;

[0076] (iii) The product obtained in step (ii) was calcined at 350°C for 5 h in an air atmosphere;

[0077] (iv) reduction of the product of step (iii) in a hydrogen atmosphere at 400°C for 4h, wherein the hydrogen flow rate is 50 mL / min; thereby producing catalyst 2.

[0078] Preparation Example 3

[0079] A catalyst for preparing an amine compound was prepared by a method comprising the following steps:

[0080] (i) Pretreatment of the support: calcination of 50 g of Hβ in an air atmosphere at 300°C for 5h;

[0081] (ii) The pretreated support from step (i) was impregnated with an aqueous solution of chloroplatinic acid having a concentration of 0.01 mol / L in an equal volume, left to stand for 5h, and then dried at 120°C for 10h;

[0082] (iii) Calcination of the product of step (ii) in an air atmosphere at 300°C for 5h;

[0083] (iv) Reduction of the product of step (iii) in a hydrogen atmosphere at 350°C for 4h, wherein the hydrogen flow rate is 50 mL / min; thereby producing catalyst 3.

[0084] Preparation Example 4

[0085] A catalyst for preparing an amine compound was prepared by a method comprising the following steps:

[0086] (i) Pretreatment of the support: calcination of 50 g of SiO2 in an air atmosphere at 300°C for 5h;

[0087] (ii) The pretreated support from step (i) was impregnated with an aqueous solution of palladium nitrate having a concentration of 0.01 mol / L in an equal volume, left to stand for 5h, and then dried at 120°C for 10h;

[0088] (iii) Calcination of the product of step (ii) in an air atmosphere at 300°C for 5h;

[0089] (iv) Reduction of the product of step (iii) in a hydrogen atmosphere at 350°C for 4h, wherein the hydrogen flow rate is 50 mL / min; thereby producing catalyst 4.

[0090] Preparation Example 5

[0091] A catalyst for preparing an amine compound was prepared by a method comprising the following steps:

[0092] (i) Pretreatment of the support: calcination of 50 g of SiO2 in an air atmosphere at 300°C for 5h;

[0093] (ii) the pretreated support obtained in step (i) was impregnated with an equal volume of a 0.1 mol / L aqueous solution of nickel nitrate, left to stand for 5 h, and then dried at 120°C for 10 h;

[0094] (iii) the product obtained in step (ii) was calcined in an air atmosphere at 300°C for 5 h;

[0095] (iv) the product obtained in step (iii) was reduced in a hydrogen atmosphere at 350°C for 4 h, with a hydrogen flow rate of 50 mL / min; thus obtaining catalyst 5.

[0096] Preparation Example 6

[0097] A catalyst for preparing amine compounds was prepared by a process comprising the following steps:

[0098] (i) pretreatment of the support: 50 g of ZnO was calcined in an air atmosphere at 300°C for 5 h;

[0099] (ii) the pretreated support obtained in step (i) was impregnated with an equal volume of a 0.05 mol / L aqueous solution of nickel nitrate, left to stand for 5 h, and then dried at 120°C for 10 h;

[0100] (iii) the product obtained in step (ii) was calcined in an air atmosphere at 300°C for 5 h;

[0101] (iv) the product obtained in step (iii) was reduced in a hydrogen atmosphere at 350°C for 4 h, with a hydrogen flow rate of 50 mL / min; thus obtaining catalyst 6.

[0102] Reaction Example 1

[0103] 1,4-Cyclohexanedimethylamine was prepared by the following steps:

[0104] (a) 5 g of the shaped catalyst 1 in Preparation Example 1 was added to a fixed bed reactor, heated to 300°C under a hydrogen atmosphere for 3 h for activation, then cooled to 300°C, and the system back pressure was adjusted to 2 MPa; and

[0105] (b) 1,4-cyclohexanedimethyl acid dimethyl ester was passed into the fixed bed reactor at a reaction temperature of 300°C and a pressure of 2 MPa at a space velocity of 0.6 h -1 Liquid ammonia was pumped into the reactor at a molar ratio of 10:1 (1,4-cyclohexanedimethyl acid dimethyl ester: ammonia) for reaction, and the molar ratio of hydrogen to 1,4-cyclohexanedimethyl acid dimethyl ester was 20:1.

[0106] The reaction product was subjected to condensation and gas-liquid separation and then subjected to GC detection. The results showed that the conversion rate of 1,4-cyclohexane dimethyl ester was 99.3%, and the selectivity of 1,4-cyclohexane dimethyl amine was 93.4%. Figure 2 A gas chromatogram of the reaction product according to Reaction Example 1 of the present application.

[0107] Reaction Example 2

[0108] 1,3-cyclohexane dimethyl amine was prepared by the following steps:

[0109] (a) 5 g of the shaped catalyst 2 in Preparation Example 2 was added to a fixed bed reactor, heated to 400°C under a hydrogen atmosphere for 3 h for activation, then cooled to 300°C, and the system back pressure was adjusted to 2 MPa; and

[0110] (b) 1,3-cyclohexane dimethyl ester was passed into the fixed bed reactor at a space velocity of 0.3 h -1 -1 at a reaction temperature of 300°C and a pressure of 2 MPa, liquid ammonia was pumped into the reactor for reaction at a molar ratio (1,3-cyclohexane dimethyl ester: ammonia) of 10:1, and the molar ratio of hydrogen to 1,3-cyclohexane dimethyl ester was 10:1.

[0111] The reaction product was subjected to condensation and gas-liquid separation and then subjected to GC detection. The results showed that the conversion rate of 1,3-cyclohexane dimethyl ester was 99.2%, and the selectivity of 1,3-cyclohexane dimethyl amine was 95.2%.

[0112] Reaction Example 3

[0113] The method for preparing 1,2-cyclohexane dimethyl amine according to the present application was carried out by the following steps:

[0114] (a) 5 g of the shaped catalyst 3 in Preparation Example 3 was added to a fixed bed reactor, heated to 400°C under a hydrogen atmosphere for 3 h for activation, then cooled to 300°C, and the system back pressure was adjusted to 2 MPa; and

[0115] (b) 1,2-cyclohexane dimethyl ester was passed into the fixed bed reactor at a space velocity of 0.5 h -1 -1 at a reaction temperature of 350°C and a pressure of 1 atm, liquid ammonia was pumped into the reactor for reaction at a molar ratio (1,2-cyclohexane dimethyl ester: ammonia) of 20:1, and the molar ratio of hydrogen to 1,2-cyclohexane dimethyl ester was 20:1.

[0116] The reaction product was subjected to condensation and gas-liquid separation and then subjected to GC detection. The results showed that the conversion rate of 1,2-cyclohexane dimethyl ester was 99.4%, and the selectivity of 1,2-cyclohexane dimethyl amine was 94.6%.

[0117] Reaction Example 4

[0118] The method for preparing 1,2-cyclopentanedimethylamine is as follows:

[0119] (a) 5 g of the shaped catalyst 4 in Preparation Example 4 was added to a fixed bed reactor, heated to 400°C under a hydrogen atmosphere for 3 h for activation, then cooled to 330°C, and the system back pressure was adjusted to 3 MPa; and

[0120] (b) dimethyl 1,2-cyclopentanedicarboxylate was passed into the fixed bed reactor at a space velocity of 0.3 h -1 -1 at a reaction temperature of 330°C and normal pressure, liquid ammonia was pumped into the reactor for reaction at a molar ratio (dimethyl 1,2-cyclopentanedicarboxylate: ammonia) of 10:1, and the molar ratio of hydrogen to dimethyl 1,2-cyclopentanedicarboxylate was 20:1.

[0121] The reaction product was subjected to condensation and gas-liquid separation, and then was detected by GC, and the results showed that the conversion rate of dimethyl 1,2-cyclopentanedicarboxylate was 99.3%, and the selectivity of 1,2-cyclopentanedimethylamine was 95.1%.

[0122] Reaction Example 5

[0123] The method for preparing 1,3-cyclopentanedimethylamine is as follows:

[0124] (a) 5 g of the shaped catalyst 5 in Preparation Example 5 was added to a fixed bed reactor, heated to 400°C under a hydrogen atmosphere for 3 h for activation, then cooled to 330°C, and the system back pressure was adjusted to 1 MPa; and

[0125] (b) dimethyl 1,3-cyclopentanedicarboxylate was passed into the fixed bed reactor at a space velocity of 0.3 h -1 -1 at a reaction temperature of 330°C and normal pressure, liquid ammonia was pumped into the reactor for reaction at a molar ratio (dimethyl 1,3-cyclopentanedicarboxylate: ammonia) of 10:1, and the molar ratio of hydrogen to dimethyl 1,3-cyclopentanedicarboxylate was 20:1.

[0126] The reaction product was subjected to condensation and gas-liquid separation, and then was detected by GC, and the results showed that the conversion rate of dimethyl 1,3-cyclopentanedicarboxylate was 99.0%, and the selectivity of 1,3-cyclopentanedimethylamine was 95.9%.

[0127] Reaction Example 6

[0128] The method for preparing 1,4-cyclohexanedimethylamine is as follows:

[0129] (a) 100 g of the catalyst 6 in Preparation Example 6 was added to a fluidized bed reactor, heated to 400°C under a hydrogen atmosphere for 3 h for activation, then cooled to 330°C; and

[0130] (b) at a reaction temperature of 330 °C and a pressure of 0.1 MPa, decanoic acid was passed into the fluidized bed reactor at a space velocity of 0.2 h -1 The urea was added into the reactor by a solid feeder at a molar ratio of 10:1 (diethyl 1,4-cyclohexanedicarboxylate: urea) and the molar ratio of hydrogen to diethyl 1,4-cyclohexanedicarboxylate was 20:1.

[0131] The reaction product was subjected to condensation and gas-liquid separation and then was detected by GC. The results showed that the conversion rate of diethyl 1,4-cyclohexanedicarboxylate was 99.5% and the selectivity of 1,4-cyclohexanedimethylamine was 93.3%.

[0132] Reaction Example 7

[0133] The method for preparing 2-methoxyethylamine was as follows:

[0134] (a) 5 g of the shaped catalyst 1 in Preparation Example 1 was added into a fixed bed reactor, was heated to 400 °C under a hydrogen atmosphere for 3 h for activation, then was cooled to 330 °C, and the system back pressure was adjusted to 3 MPa; and

[0135] (b) at a reaction temperature of 330 °C and normal pressure, methyl 2-methoxyacetate was passed into the fixed bed reactor at a space velocity of 0.3 h -1 The liquid ammonia was pumped into the reactor at a molar ratio of 10:1 (methyl 2-methoxyacetate: ammonia) and the molar ratio of hydrogen to methyl 2-methoxyacetate was 20:1.

[0136] The reaction product was subjected to condensation and gas-liquid separation and then was detected by GC. The results showed that the conversion rate of methyl 2-methoxyacetate was 99.3% and the selectivity of 2-methoxyethylamine was 95.1%.

[0137] Reaction Example 8

[0138] The method for preparing decanediamine was as follows:

[0139] (a) 100 g of the catalyst 6 in Preparation Example 6 was added into a fluidized bed reactor, was heated to 400 °C under a hydrogen atmosphere for 3 h for activation, then was cooled to 330 °C; and

[0140] (b) at a reaction temperature of 330 °C and a pressure of 0.1 MPa, decanedioic acid was passed into the fluidized bed reactor at a space velocity of 0.2 h -1 The ammonium carbonate was added into the reactor by a solid feeder at a molar ratio of 10:1 (decanedioic acid: ammonium carbonate) and the molar ratio of hydrogen to decanedioic acid was 10:1.

[0141] The reaction product was condensed and gas-liquid separated, and then subjected to chromatographic detection. The results showed that the conversion rate of sebacic acid was 99.0%, and the selectivity of decanediamine was 93.7%.

[0142] Reaction Example 9

[0143] The method for preparing hexanediamine was prepared by the following steps:

[0144] (a) 100 g of catalyst 6 in Preparation Example 6 was added to a fluidized bed reactor, and heated to 400°C under a hydrogen atmosphere for 3 h for activation, and then cooled to 330°C; and

[0145] (b) at a reaction temperature of 330°C and a pressure of 0.1-0.2 MPa, sebacic acid was passed into the fluidized bed reactor at a space velocity of 0.2 h -1 -1, and ammonia was added to the reactor through a solid feeder at a molar ratio (sebacic acid:ammonia) of 10:1, and the molar ratio of hydrogen to sebacic acid was 10:1.

[0146] The reaction product was condensed and gas-liquid separated, and then subjected to chromatographic detection. The results showed that the conversion rate of sebacic acid was 99.0%, and the selectivity of decanediamine was 93.7%.

[0147] Reaction Example 10

[0148] The method for preparing pentanediamine was prepared by the following steps:

[0149] (a) 100 g of catalyst 6 in Preparation Example 6 was added to a fluidized bed reactor, and heated to 400°C under a hydrogen atmosphere for 3 h for activation, and then cooled to 350°C; and

[0150] (b) at a reaction temperature of 350°C and a pressure of 0.1 MPa, glutaric acid was passed into the fluidized bed reactor at a space velocity of 0.4 h -1 -1, and ammonia was added to the reactor through a mass flow controller at a molar ratio (glutaric acid:ammonia) of 10:1, and the molar ratio of hydrogen to glutaric acid was 10:1.

[0151] The reaction product was condensed and gas-liquid separated, and then subjected to chromatographic detection. The results showed that the conversion rate of sebacic acid was 99.0%, and the selectivity of decanediamine was 93.7%.

[0152] Reaction Example 11

[0153] The method for preparing octanediamine was prepared by the following steps:

[0154] (a) 100 g of catalyst 6 in Preparation Example 6 was added to a fluidized bed reactor, and heated to 400°C under a hydrogen atmosphere for 3 h for activation, and then cooled to 330°C; and

[0155] (b) at a reaction temperature of 330°C and a pressure of 0.1-0.2 MPa, octandioic acid was passed into the fluidized bed reactor at a space velocity of 0.2 h -1 The reaction was carried out by feeding ammonium bicarbonate into the reactor through a solid feeder at a molar ratio (ammonium bicarbonate: octandioic acid) of 10:1, and the molar ratio of hydrogen to octandioic acid was 10:1.

[0156] The reaction product was subjected to condensation and gas-liquid separation, and then was detected by chromatography. The results showed that the conversion rate of octandioic acid was 99.5%, and the selectivity of octanediamine was 91.8%.

[0157] Reaction Example 12

[0158] The method for preparing n-hexylamine was prepared by the following steps:

[0159] (a) 5 g of the shaped catalyst 5 in Preparation Example 5 was added into a fixed bed reactor, and was heated to 400°C under a hydrogen atmosphere for 3 h for activation, and then was cooled to 330°C, and the system back pressure was adjusted to 1 MPa; and

[0160] (b) at a reaction temperature of 330°C and normal pressure, methyl hexanoate was passed into the fixed bed reactor at a space velocity of 0.3 h -1 The reaction was carried out by feeding liquid ammonia into the reactor at a molar ratio (methyl hexanoate: ammonia) of 10:1, and the molar ratio of hydrogen to methyl hexanoate was 10:1.

[0161] The reaction product was subjected to condensation and gas-liquid separation, and then was detected by GC. The results showed that the conversion rate of methyl hexanoate was 99.9%, and the selectivity of hexylamine was 94.9%.

[0162] The above examples are only used to illustrate the technical solutions of the present application, but not to limit it. Although the present application has been described in detail with reference to the foregoing examples, it should be understood by those skilled in the art that the technical solutions recorded in the foregoing examples can be modified, or some or all of the technical features can be replaced by equivalents, without departing from the spirit and essence defined in the claims of the present application. These modifications or replacements are still within the scope defined by the claims of the present application.

Claims

1. A method for preparing an amine compound by one-step continuous reaction using acid / ester, ammonia source and hydrogen as raw materials, the method being performed as follows: first, loading a catalyst into a reactor, introducing hydrogen into the reactor, and activating the catalyst at 200-500 ℃ for 1-6 h, then adjusting the reaction temperature to a target reaction temperature of 200-500 ℃ and adjusting the reaction system pressure to 0.1-5 MPa; continuously adding acid / ester and ammonia source into the reactor to perform the reaction, and after the raw materials contact with the catalyst bed, they are driven by gas to leave the reactor, enter a condenser and a gas-liquid separator, and then enter a product storage tank, and the tail gas is exhausted. In the method, the catalyst comprises a carrier and an active component, the carrier comprises one or more selected from γ-Al 2 O 3, SiO 2, ZrO 2, TiO 2, HZSM-5, HY, Hβ and HMOR, and the active component comprises one or more metal elements selected from platinum (Pt), palladium (Pd), nickel (Ni) and cobalt (Co); the mass ratio of the metal elements in the active component to the carrier is (0.1-20): 100; the acid / ester raw material is selected from the following reaction substances of the following structural formula: wherein R, R 1 and R 2 are each independently selected from hydrogen, C 1-C 6 alkyl, halogen-substituted C 1-6 alkyl, hydroxyl-substituted C 1-6 alkyl and amine-substituted C 1-6 alkyl, and n is an integer between 2 and 15; the ammonia source comprises one or more of ammonia, urea, ammonium carbonate and ammonium bicarbonate. 2.The method for preparing an amine compound according to claim 1, wherein in the acid / ester raw material, R, R 1 and R 2 are each independently selected from hydrogen, C 1-C 4 alkyl, halogen-substituted C 1-4 alkyl, hydroxyl-substituted C 1-4 alkyl and amine-substituted C 1-4 alkyl. in the acid / ester raw material, R, R 1 and R 2 are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.

3. The method of claim 1, wherein the amine compound is prepared by the reaction of the compound of formula (2) with the compound of formula (3) in the presence of a base. in the acid / ester raw material, the halogen is selected from fluorine atom, chlorine atom and bromine atom.

4. The method of claim 1, wherein the amine compound is prepared by the reaction of the compound of formula (2) with the compound of formula (3) in the presence of a base. in the acid / ester raw material, n is an integer between 2 and 10.

5. The method of claim 1, wherein the amine compound is prepared by the reaction of the compound of formula (2) with the compound of formula (3) in the presence of a base. in the acid / ester raw material, n is an integer between 2 and 6.

6. The method of claim 1, wherein the amine compound is prepared by the reaction of the compound of formula (2) with the compound of formula (3) in the presence of a base. 7.The method for preparing an amine compound according to claim 1, wherein when the acid / ester and the ammonia source are solid, they are added by a solid feeder, and a non-return valve is installed at the lower part of the solid feeder; when the acid / ester and the ammonia source are liquid, they are pumped into the reaction system by a feed pump, wherein liquid ammonia is pumped into the reactor by a plunger pump, and hydrogen is introduced into the reactor by a mass flow controller. the reactor in the method for preparing an amine compound is selected from any one of a continuous stirred tank reactor, a plug flow reactor, a fixed bed reactor and a fluidized bed reactor, or is a mixed reactor connected by two or more of these reactors.

8. The method for preparing amine compounds according to claim 1, characterized in that, the reactor in the method for preparing an amine compound is a fixed bed reactor or a fluidized bed reactor.

9. The method of claim 8, wherein the amine compound is prepared by the reaction of the compound of formula (2) with the compound of formula (3) in the presence of a base. the fixed bed reactor is loaded with 3-10 g of catalyst, and the fluidized bed reactor is loaded with 100 g of catalyst.

10. The method of claim 9, wherein the amine compound is prepared by the reaction of the compound of formula (2) with the compound of formula (3) in the presence of a base. ​ 11. The method for preparing amine compounds according to claim 1, characterized in that, The high-pressure reaction is carried out by increasing the pressure of the reactor through a back pressure valve, otherwise maintaining a normal pressure hydrogen atmosphere.

12. The method for preparing amine compounds according to claim 1, characterized in that, The catalyst is in the form of a strip, a column, a sheet or a particle.

13. The method for preparing amine compounds according to claim 1, characterized in that, The temperature of the method for preparing the amine compound is 250-400 DEG C.

14. The method for preparing amine compounds according to claim 1, characterized in that, The reaction pressure of the method for preparing the amine compound is 0.1-3 MPa.

15. The method for preparing amine compounds according to claim 1, characterized in that, In the method for preparing the amine compound, the molar ratio of the acid / ester to the ammonia source is 1:4-1:

30.

16. The method for preparing amine compounds according to claim 1, characterized in that, In the method for preparing the amine compound, the molar ratio of the acid / ester to the hydrogen is 1:4-1:

40.

17. The method for preparing amine compounds according to claim 1, characterized in that, The acid / ester is reacted in the presence or absence of a solvent selected from one or more of acetonitrile, 1,4-dioxane, methanol and ethanol.

18. The method for preparing amine compounds according to claim 1, characterized in that, The method for preparing the amine compound is carried out at a reaction space velocity of 0.05 h -1 ~ 5 h -1 .

19. The method for preparing amine compounds according to claim 1, characterized in that, The catalyst is activated by heating the reactor loaded with the catalyst to an activation temperature of 300-500 DEG C and maintaining for 2-5 h.

20. The method of claim 1, wherein, In the method for preparing the amine compound, the molar ratio of the acid / ester to the ammonia source is 1:5-1:

20.

21. The method for preparing amine compounds according to claim 1, characterized in that, In the method for preparing the amine compound, the molar ratio of the acid / ester to the hydrogen is 1:4-1:

20.

22. The method for preparing amine compounds according to claim 1, characterized in that, The acid / ester is reacted in the presence or absence of a solvent selected from acetonitrile, methanol and ethanol.

23. The method for preparing amine compounds according to claim 11, characterized in that, The method for preparing the amine compound is carried out at a reaction space velocity of 0.03 h -1 ~ 3 h -1 .

24. The method for preparing amine compounds according to claim 11, characterized in that, The activation temperature is 300-400 DEG C.

25. The method for preparing amine compounds according to claim 1, characterized in that, The catalyst comprises a carrier and an active component, and the carrier is gamma-Al2O3, SiO2, HZSM5, HY or Hbeta.

26. The method of claim 1, wherein the amine compound is prepared by the method of claim 1. The catalyst comprises a carrier and an active component, and the carrier is gamma-Al2O3, SiO2, HZSM5 or Hbeta.

27. The method for preparing amine compounds according to claim 1, characterized in that, The mass ratio of the metal element in the active component to the carrier is (0.5-10):

100.

28. The method for preparing amine compounds according to claim 1, characterized in that, The mass ratio of the metal element in the active component to the carrier is (1.0-10):

100.

29. The method for preparing amine compounds according to claim 1, characterized in that, The catalyst is prepared as follows: (1) the carrier is impregnated with an active component precursor aqueous solution in an equal volume, and then is left to stand and dried; (2) the product obtained in step (1) is calcined in an air atmosphere at 250-300 DEG C for 2-5 h; (3) the product obtained in step (2) is reduced in a hydrogen atmosphere at 250-400 DEG C for 2-4 h.

30. The method of claim 29, wherein the amine compound is prepared by the process of claim 28. 30 The active component precursor comprises one or more of nitrate, chloride and acetate of Pt, Pd, Ni and Co; In step (1), the concentration of the active component precursor aqueous solution is 0.005-0.1 mol / L; In step (1), the standing time is 2-5 h; In step (1), the drying temperature is 110-150 DEG C and the drying time is 5-10 h; The preparation method of the catalyst further comprises pretreatment of the carrier: before step (1), the carrier is calcined in an air atmosphere at 200-400 DEG C for 2-5 h.

31. Use of the catalyst in the method for preparing the amine compound according to claim 1 in a method for preparing an amine compound by one-step continuous reaction from an acid / ester, an ammonia source and hydrogen.

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