CN117586130A - Preparation method of hexamethylenediamine - Google Patents

Preparation method of hexamethylenediamine Download PDF

Info

Publication number
CN117586130A
CN117586130A CN202311363527.6A CN202311363527A CN117586130A CN 117586130 A CN117586130 A CN 117586130A CN 202311363527 A CN202311363527 A CN 202311363527A CN 117586130 A CN117586130 A CN 117586130A
Authority
CN
China
Prior art keywords
catalyst
hexamethylenediamine
reaction
hydrogenation
adiponitrile
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202311363527.6A
Other languages
Chinese (zh)
Inventor
张立娟
刘晓龙
张聪颖
郭凤娇
姜瑞航
刘帅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wanhua Chemical Group Co Ltd
Original Assignee
Wanhua Chemical Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wanhua Chemical Group Co Ltd filed Critical Wanhua Chemical Group Co Ltd
Priority to CN202311363527.6A priority Critical patent/CN117586130A/en
Publication of CN117586130A publication Critical patent/CN117586130A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
    • C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J25/00—Catalysts of the Raney type
    • B01J25/02—Raney nickel
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
    • B01J31/0248—Nitriles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a preparation method of hexamethylenediamine, which comprises the following steps: 1) Pretreatment of the catalyst: mixing a hydrogenation catalyst and a modifier, and treating for 0.5-2h in a nitrogen atmosphere to obtain a modified catalyst; 2) Hydrogenation reaction: adiponitrile is hydrogenated in the presence of a modified catalyst to hexamethylenediamine. The method for preparing hexamethylenediamine has the advantages of good catalyst stability, high product yield and low DCH (dedicated channel) production amount, and can avoid the problems of frequent device shutdown and the like without introducing inorganic alkali.

Description

Preparation method of hexamethylenediamine
Technical Field
The invention relates to a preparation method, in particular to a preparation method of hexamethylenediamine.
Background
Hexamethylenediamine is an important chemical raw material and is mainly used for producing nylon 66, HDI (1, 6-hexamethylene diisocyanate) and the like. The current industrial production method of hexamethylenediamine mainly comprises a high-pressure method and a low-pressure method.
The low-pressure method has mild process conditions and high safety, and is adopted by most manufacturers at home and abroad. The process generally adopts nickel or cobalt catalysts, and the nickel catalysts are low in price compared with cobalt catalysts, but as reported in the document Deactivation of nitrile hydrogenation catalysts: new mechanistic insight from a nylon recycle process, inorganic bases such as NaOH, KOH and the like are required to be added as cocatalysts when the nickel catalysts are used, otherwise, the nickel catalysts are deactivated rapidly. However, the serious defect is that in the post-treatment process, along with the removal of moisture, inorganic alkali is separated out and attached to the inner wall of a process pipeline and a rectifying tower tray, and the water distillation is required to be stopped periodically for removing the alkali, so that the operation of the device is affected.
To address this problem, patent CN108084035A and CN109647419A disclose rare earth metal oxide and alkaline earth metal oxide modified Ni/Al 2 O 3 The catalyst is used for adiponitrile hydrogenation reaction, and inorganic base promoter can be avoided from the source, but the yield of hexamethylenediamine is low. Patent CN116178174a discloses a low energy consumption method for purifying hexamethylenediamine, which uses ionic liquid to extract hexamethylenediamine from an aqueous phase containing alkali before rectification treatment, thereby achieving the purpose of removing alkali and avoiding a series of problems of subsequent rectification treatment. But the ionic liquid preparation and treatment processes are complex.
Another significant problem in the process of preparing hexamethylenediamine by hydrogenation of adiponitrile is the production of the byproduct 1, 2-cyclohexanediamine (DCH), which has very close boiling points to the product hexamethylenediamine, and is difficult to separate, resulting in problems of high energy consumption and product loss for refining.
Patent CN115335356a discloses a process for the hydrogenation of adiponitrile with raney nickel as catalyst and KOH and basic compounds (including alkaline hydroxides, alkaline earth metal hydroxides and ammonium hydroxide) as promoters, CN115298161a discloses the use of CO or CO in a liquid medium 2 A method for modifying Raney nickel catalysts. Both methods can reduce the generation of DCH to a certain extent, but have limited effect, and the content of DCH is still up to more than 1000 ppm; and using CO or CO 2 After modification, the activity of the catalyst is significantly reduced.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of hexamethylenediamine. The method for preparing hexamethylenediamine has the advantages of good catalyst stability, high product yield and low DCH (dedicated channel) production amount, and can avoid the problems of frequent device shutdown and the like without introducing inorganic alkali.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a process for the preparation of hexamethylenediamine comprising the steps of:
1) Pretreatment of the catalyst: mixing a hydrogenation catalyst and a modifier, and treating for 0.5-2h in a nitrogen atmosphere to obtain a modified catalyst;
2) Hydrogenation reaction: hydrogenating adiponitrile in the presence of a modified catalyst to produce hexamethylenediamine;
the modifier is water and/or alcohol with adiponitrile content of 50-200 ppm;
preferably, the addition amount of the modifier is 5-50 times of the mass of the hydrogenation catalyst.
It has now surprisingly been found that if the hydrogenation catalyst is pretreated with a modifier containing a trace amount of adiponitrile, the catalyst activity can be maintained to a certain extent, the catalyst steady-state run time is increased, and in particular, the formation of DCH is significantly reduced, which is advantageous for improving the product quality and yield.
As a preferred embodiment, the reaction conditions for the hydrogenation of adiponitrile are: the reaction temperature is 50-100 ℃, preferably 70-90 ℃, and the hydrogen partial pressure in the reaction process is 1-8MPa, preferably 2-5MPa, and the gauge pressure.
As a preferred embodiment, the adiponitrile hydrogenation reaction is carried out in a mixed solvent consisting of liquid ammonia and water; the liquid ammonia and water are used as the mixed solvent to replace the conventional inorganic alkali, so that on one hand, the alkaline environment is maintained, and on the other hand, the product hexamethylenediamine is extracted into the water phase to accelerate the reaction;
preferably, the mass ratio of liquid ammonia to water in the mixed solvent is (3-50): 1, preferably (6-30): 1.
In a preferred embodiment, in step 2), the mass ratio of adiponitrile to the mixed solvent is 1 (1-6), preferably 1 (2-4).
Preferably, the adiponitrile is fed at a flow rate of 0.5 to 20g/g cat H, preferably 0.5-12g/g cat ·h。
As a preferred embodiment, the hydrogenation reaction is carried out in a fluidized bed, a fixed bed or a stirred tank reactor, and optionally, the hydrogenation reaction is carried out in a batch, continuous or semi-continuous reaction mode; the corresponding catalyst feeding modes are all disposable feeding, and the powder catalyst can be selected to be disposable fed or the formed catalyst can be filled into the reactor according to the type of the reactor.
As a preferred embodiment, the hydrogenation catalyst is selected from one or more of raney nickel, supported metallic Ni catalysts.
As a preferred embodiment, the hydrogenation catalyst is SiO prepared by a direct reduction method 2 A supported metallic Ni catalyst;
preferably, in the catalyst, the loading of the metal Ni in the carrier is 20-40wt%.
As a preferred embodiment, the direct reduction method is specifically:
dissolving precursor of Ni metal in water, and adding SiO 2 Carrying out ultrasonic treatment on the carrier for 1-2h at room temperature, filtering and drying to obtain catalyst powder, and optionally preparing a formed body;
preferably, the drying conditions are: drying at 60-100deg.C for 12-24 hr.
In the invention, ni/SiO prepared by a direct reduction method 2 The catalyst can keep the structure of nickel phyllosilicate which can be used as a catalyst anchoring agent to the greatest extent, so that the activity and stability of the catalyst are greatly improved, the stability of the catalyst after long-term use is comprehensively improved by combining the modification treatment of the modifier, the DCH production is reduced, and the product yield and quality are improved.
As a preferred embodiment, the precursor of metallic Ni is one or more of nitrate, sulfate, hydrochloride of Ni.
As a preferred embodiment, the direct reduction process produces SiO 2 The supported metallic Ni catalyst is applied to hydrogenation reaction after hydrogen activation.
The reaction conditions for hydrogen activation may be, for example, that the catalyst is subjected to an activation treatment with pure hydrogen at 300-400℃for 8-12 hours. Since hydrogen activation is a more conventional catalyst activation in the art, it is generally not described in too much detail, and the above is only one of the possible operating conditions provided by the present invention as applicable to the present reaction, but it should not be taken as any limitation of the protection of the present invention.
The hydrogenation method for preparing hexamethylenediamine has the advantages of high catalyst activity, less byproducts, high product selectivity, long catalyst service life and good stability, and is beneficial to prolonging the reaction operation period. Compared with the conventional technology, the scheme avoids using inorganic alkali, solves the problems of complex post-treatment and long shutdown cleaning period in the prior art, and has obvious advantages in application.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
Unless otherwise specified, the raw materials and reagents in the following examples and comparative examples were obtained by commercial purchase.
In the following embodiments, the reaction solution was analyzed by gas chromatography under the following conditions: agilent DB-5 chromatographic column, sample inlet temperature 280 ℃, FID detector temperature 300 ℃, column flow rate 1.5ml/min, hydrogen flow rate 30ml/min, air flow rate 400ml/min, temperature programming mode of 50 ℃ for 2min, temperature 5 ℃/min to 80 ℃, then 15 ℃/min to 280 ℃ for 10min.
The hydrogenation catalyst provided in the following preparation examples was activated uniformly in a hydrogen atmosphere at 350 ℃ for 10 hours before being used in hydrogenation reaction.
[ preparation example 1 ]
Preparation of hydrogenation catalyst C1:
14.9g of Ni (NO 3 ) 2 ·6H 2 O was dissolved in 20.0g deionized water and 10.0g SiO was weighed out 2 Carrier addition solutionIn the liquid. And carrying out ultrasonic treatment on the solution mixture for 2 hours at room temperature, carrying out suction filtration, and then drying in an oven at 80 ℃ for 12 hours to obtain the hydrogenation catalyst C1.
[ preparation example 2 ]
Preparation of hydrogenation catalyst C2:
9.9g of Ni (NO 3 ) 2 ·6H 2 O was dissolved in 13.4g deionized water and 8.0g SiO was weighed out 2 The carrier is added to the solution. And carrying out ultrasonic treatment on the solution mixture for 1h at room temperature, carrying out suction filtration, and then drying in an oven at 80 ℃ for 24h to obtain the hydrogenation catalyst C2.
[ preparation example 3 ]
Preparation of hydrogenation catalyst C3:
19.8g of Ni (NO) 3 ) 2 ·6H 2 O was dissolved in 26.7g deionized water and 10.0g SiO was weighed out 2 The carrier is added to the solution. And carrying out ultrasonic treatment on the solution mixture for 2 hours at room temperature, carrying out suction filtration, and then drying in an oven at 80 ℃ for 18 hours to obtain the hydrogenation catalyst C3.
[ PREPARATION EXAMPLE 4 ]
Preparation of hydrogenation catalyst C4:
14.9g of Ni (NO 3 ) 2 ·6H 2 O was dissolved in 20.0g deionized water and 10.0g SiO was weighed out 2 The carrier is added to the solution. And (3) carrying out ultrasonic treatment on the solution mixture for 2 hours at room temperature, carrying out suction filtration, then placing the solution mixture in an oven at 80 ℃ for drying for 12 hours, and finally roasting the solution mixture at 550 ℃ for 6 hours to obtain the hydrogenation catalyst C4.
The following examples, comparative examples, are used to prepare hexamethylenediamine:
[ example 1 ]
(1) Catalyst pretreatment
10g of hydrogenation catalyst C1 was added to the reaction vessel, after which 100g of water containing 100ppm of adiponitrile was added, and stirred under nitrogen atmosphere for 1 hour, and the water in the reaction vessel was filtered out to obtain a modified catalyst.
(2) Hydrogenation reaction
12.5g deionized water was added to the above-described catalyst-containing reaction vessel. 3 times with 1MPa nitrogen and 3 times with 1MPa hydrogen, after which 187.5g of liquid ammonia was introduced into the reaction vessel. Stirring is startedThe rotation speed is 1000rpm, a temperature raising program is started, and the temperature in the reaction kettle is raised to 70 ℃. At this time, a hydrogen valve was opened, hydrogen was introduced into the reaction vessel, and the hydrogen partial pressure was adjusted to 3.0MPa. Next, the adiponitrile feed pump and feed line valves were opened, adiponitrile at 6g/g cat H, adding the mixture into a reaction kettle at a flow rate to carry out hydrogenation reaction, and removing reaction heat through water passing through an inner coil in the reaction process. When the adiponitrile feed reached 67g, the feed was stopped and the reaction ended when the hydrogen flow meter indicated 0. Cooling to room temperature, stopping stirring, discharging the reaction kettle to normal pressure, replacing 3 times with 1MPa nitrogen, filtering out materials in the reaction kettle through a bottom inserting pipe with a filter head, sampling and analyzing, and calculating to obtain the hexamethylenediamine with the yield of 99.07% and the DCH content of 0.030%.
(3) Cycle test
And (3) repeating the hydrogenation reaction for 10 times according to the same method in the step (2), and finally sampling and analyzing to obtain the hexamethylenediamine with 98.83% yield and 0.042% DCH content.
[ example 2 ]
(1) Catalyst pretreatment
10g of hydrogenation catalyst C2 was added to the reaction vessel, followed by 300g of water containing 50ppm of adiponitrile, stirred under nitrogen for 2 hours, and the water in the reaction vessel was filtered out to obtain a modified catalyst.
(2) Hydrogenation reaction
6.5g deionized water was added to the above-described catalyst-containing reaction vessel. 3 times with 1MPa nitrogen and 3 times with 1MPa hydrogen, after which 193.5g of liquid ammonia was introduced into the reactor. Stirring is started, the rotating speed is 800rpm, a heating program is started, and the temperature in the reaction kettle is increased to 90 ℃. At this time, a hydrogen valve was opened, hydrogen was introduced into the reaction vessel, and the hydrogen partial pressure was adjusted to 5.0MPa. Next, the adiponitrile feed pump and feed line valves were opened, adiponitrile at 12g/g cat H, adding the mixture into a reaction kettle at a flow rate to carry out hydrogenation reaction, and removing reaction heat through water passing through an inner coil in the reaction process. When the adiponitrile feed reached 100g, the feed was stopped and the reaction was ended when the hydrogen flow meter indicated 0. Cooling to room temperature, stopping stirring, discharging the reaction kettle to normal pressure, and replacing 3 times with 1MPa nitrogen gas to pass through the beltThe materials in the reaction kettle are filtered out by a bottom inserting pipe with a filter head, and the sample analysis is carried out, so that the hexamethylenediamine yield is 99.52% and the DCH content is 0.042%.
(3) Cycle test
And (3) repeating the hydrogenation reaction for 10 times according to the same method in the step (2), and finally sampling and analyzing to obtain the hexamethylenediamine with the yield of 99.18% and the DCH content of 0.031%.
[ example 3 ]
(1) Catalyst pretreatment
10g of hydrogenation catalyst C3 was added to the reaction vessel, then 200g of ethanol containing 200ppm of adiponitrile was added thereto, and the mixture was stirred under nitrogen atmosphere for 1.5 hours, and the ethanol in the reaction vessel was filtered out to obtain a modified catalyst.
(2) Hydrogenation reaction
28.6g of deionized water was added to the above-mentioned reaction vessel containing the catalyst. 3 times with 1MPa nitrogen and 3 times with 1MPa hydrogen, after which 171.4g of liquid ammonia was introduced into the reaction vessel. Stirring is started, the rotating speed is 900rpm, a heating program is started, and the temperature in the reaction kettle is increased to 80 ℃. At this time, a hydrogen valve was opened, hydrogen was introduced into the reaction vessel, and the hydrogen partial pressure was adjusted to 2.0MPa. Next, the adiponitrile feed pump and feed line valves were opened, adiponitrile at 0.5g/g cat H, adding the mixture into a reaction kettle at a flow rate to carry out hydrogenation reaction, and removing reaction heat through water passing through an inner coil in the reaction process. When the adiponitrile feed reached 50g, the feed was stopped and the reaction was ended when the hydrogen flow meter indicated 0. Cooling to room temperature, stopping stirring, discharging the reaction kettle to normal pressure, replacing 3 times with 1MPa nitrogen, filtering out the materials in the reaction kettle through a bottom inserting pipe with a filter head, sampling and analyzing, and calculating to obtain the hexamethylenediamine with 99.15% yield and 0.037% DCH content.
(3) Cycle test
And (3) repeating the hydrogenation reaction for 10 times according to the same method in the step (2), and finally sampling and analyzing to obtain the hexamethylenediamine with 98.73% of yield and 0.044% of DCH content.
[ example 4 ]
(1) Catalyst pretreatment
10g of hydrogenation catalyst C4 was added to the reaction vessel, after which 100g of water containing 100ppm of adiponitrile was added, and stirred under nitrogen atmosphere for 1 hour, and the water in the reaction vessel was filtered out to obtain a modified catalyst.
(2) Hydrogenation reaction
12.5g deionized water was added to the above-described catalyst-containing reaction vessel. 3 times with 1MPa nitrogen and 3 times with 1MPa hydrogen, after which 187.5g of liquid ammonia was introduced into the reaction vessel. Stirring is started, the rotating speed is 1000rpm, a heating program is started, and the temperature in the reaction kettle is increased to 70 ℃. At this time, a hydrogen valve was opened, hydrogen was introduced into the reaction vessel, and the hydrogen partial pressure was adjusted to 3.0MPa. Next, the adiponitrile feed pump and feed line valves were opened, adiponitrile at 6g/g cat H, adding the mixture into a reaction kettle at a flow rate to carry out hydrogenation reaction, and removing reaction heat through water passing through an inner coil in the reaction process. When the adiponitrile feed reached 67g, the feed was stopped and the reaction ended when the hydrogen flow meter indicated 0. Cooling to room temperature, stopping stirring, discharging the reaction kettle to normal pressure, replacing 3 times with 1MPa nitrogen, filtering out the materials in the reaction kettle through a bottom inserting pipe with a filter head, sampling and analyzing, and calculating to obtain the hexamethylenediamine with the yield of 95.71% and the DCH content of 0.077%.
(3) Cycle test
And (3) repeating the hydrogenation reaction for 10 times according to the same method in the step (2), and finally sampling and analyzing to obtain the hexamethylenediamine with the yield of 92.26% and the DCH content of 0.18%.
[ example 5 ]
(1) Catalyst pretreatment
10g of Raney nickel catalyst (Jingjiang's Roc catalyst Co., ltd.) was added to the reaction vessel, after which 100g of water containing 100ppm of adiponitrile was added, and the mixture was stirred under nitrogen atmosphere for 1 hour, and the water in the reaction vessel was filtered out to obtain a modified catalyst.
(2) Hydrogenation reaction
12.5g deionized water was added to the above-described catalyst-containing reaction vessel. 3 times with 1MPa nitrogen and 3 times with 1MPa hydrogen, after which 187.5g of liquid ammonia was introduced into the reaction vessel. Stirring is started, the rotating speed is 1000rpm, a heating program is started, and the temperature in the reaction kettle is increased to 70 ℃. At this time, the hydrogen gas is turned onAnd introducing hydrogen into the reaction kettle by a valve, and adjusting the partial pressure of the hydrogen to 3.0MPa. Next, the adiponitrile feed pump and feed line valves were opened, adiponitrile at 6g/g cat H, adding the mixture into a reaction kettle at a flow rate to carry out hydrogenation reaction, and removing reaction heat through water passing through an inner coil in the reaction process. When the adiponitrile feed reached 67g, the feed was stopped and the reaction ended when the hydrogen flow meter indicated 0. Cooling to room temperature, stopping stirring, discharging the reaction kettle to normal pressure, replacing 3 times with 1MPa nitrogen, filtering out materials in the reaction kettle through a bottom inserting pipe with a filter head, sampling and analyzing, and calculating to obtain the hexamethylenediamine with the yield of 96.22% and the DCH content of 0.066%.
(3) Cycle test
And (3) repeating the hydrogenation reaction for 10 times according to the same method in the step (2), and finally sampling and analyzing to obtain the hexamethylenediamine with the yield of 93.28% and the DCH content of 0.14%.
Comparative example 1
The hydrogenation was carried out in the same manner as in example 1 except that 100ppm of water containing adiponitrile was replaced with deionized water in the pretreatment of the catalyst. Sampling analysis after the reaction is finished, and calculating to obtain the hexamethylenediamine with the yield of 93.11% and the DCH content of 0.35%.
And then the hydrogenation reaction is repeatedly carried out for 5 times according to the same method, and finally sampling analysis is carried out, so that the hexamethylenediamine yield is 88.47% and the DCH content is 0.91%.
Comparative example 2
The hydrogenation reaction was carried out in the same manner as in example 1 except that 100ppm of water containing adiponitrile was replaced with 100ppm of water containing liquid ammonia in the pretreatment of the catalyst. Sampling analysis after the reaction is finished, and calculating to obtain the hexamethylenediamine with the yield of 93.81% and the DCH content of 0.33%.
And then the hydrogenation reaction is repeatedly carried out for 5 times according to the same method, and finally sampling analysis is carried out, so that the hexamethylenediamine yield is 89.51% and the DCH content is 0.90%.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.

Claims (10)

1. The preparation method of hexamethylenediamine is characterized by comprising the following steps of:
1) Pretreatment of the catalyst: mixing a hydrogenation catalyst and a modifier, and treating for 0.5-2h in a nitrogen atmosphere to obtain a modified catalyst;
2) Hydrogenation reaction: hydrogenating adiponitrile in the presence of a modified catalyst to produce hexamethylenediamine;
the modifier is water and/or alcohol with adiponitrile content of 50-200 ppm;
preferably, the addition amount of the modifier is 5-50 times of the mass of the hydrogenation catalyst.
2. The process for the preparation of hexamethylenediamine according to claim 1, characterized in that the reaction conditions for the hydrogenation of adiponitrile are: the reaction temperature is 50-100 ℃, preferably 70-90 ℃, and the hydrogen partial pressure in the reaction process is 1-8MPa, preferably 2-5MPa, and the gauge pressure.
3. The method for producing hexamethylenediamine according to claim 1, wherein the adiponitrile hydrogenation reaction is carried out in a mixed solvent composed of liquid ammonia and water;
preferably, the mass ratio of liquid ammonia to water in the mixed solvent is (3-50): 1, preferably (6-30): 1.
4. A process for the preparation of hexamethylenediamine according to any one of claims 1 to 3, characterized in that in step 2) the mass ratio of adiponitrile to mixed solvent is 1 (1-6), preferably 1 (2-4).
Preferably, the adiponitrile is fed at a flow rate of 0.5 to 20g/g cat H, preferably 0.5-12g/g cat ·h。
5. A process for the preparation of hexamethylenediamine according to any one of claims 1 to 3, characterized in that the hydrogenation reaction is carried out in a fluidized bed, a fixed bed or a stirred tank reactor.
6. The method for preparing hexamethylenediamine according to claim 1, wherein the hydrogenation catalyst is one or more selected from Raney nickel and supported metallic Ni catalysts.
7. The method for producing hexamethylenediamine according to claim 6, wherein the hydrogenation catalyst is SiO produced by a direct reduction method 2 A supported metallic Ni catalyst;
preferably, in the catalyst, the loading of the metal Ni in the carrier is 20-40wt%.
8. The method for producing hexamethylenediamine according to claim 7, characterized in that the direct reduction method is specifically:
dissolving precursor of Ni metal in water, and adding SiO 2 Carrying out ultrasonic treatment on the carrier for 1-2h at room temperature, filtering and drying to obtain catalyst powder, and optionally preparing a formed body;
preferably, the drying conditions are: drying at 60-100deg.C for 12-24 hr.
9. The method for producing hexamethylenediamine according to claim 8, wherein the precursor of metallic Ni is one or more of nitrate, sulfate, and hydrochloride of Ni.
10. The method for producing hexamethylenediamine according to any one of claims 7 to 9, characterized in that the direct reduction method produces SiO 2 The supported metallic Ni catalyst is applied to hydrogenation reaction after hydrogen activation.
CN202311363527.6A 2023-10-20 2023-10-20 Preparation method of hexamethylenediamine Pending CN117586130A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311363527.6A CN117586130A (en) 2023-10-20 2023-10-20 Preparation method of hexamethylenediamine

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311363527.6A CN117586130A (en) 2023-10-20 2023-10-20 Preparation method of hexamethylenediamine

Publications (1)

Publication Number Publication Date
CN117586130A true CN117586130A (en) 2024-02-23

Family

ID=89908821

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311363527.6A Pending CN117586130A (en) 2023-10-20 2023-10-20 Preparation method of hexamethylenediamine

Country Status (1)

Country Link
CN (1) CN117586130A (en)

Similar Documents

Publication Publication Date Title
CN108393092B (en) Preparation method of catalyst for preparing secondary amine by nitrile compound hydrogenation, product and application thereof
CZ292717B6 (en) Process for preparing amines and aminonitriles
CN110743544A (en) Palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof
CN109232188B (en) Preparation method of hydrogenated bisphenol A
CN101455963A (en) Catalyst for preparing C2-C3 lower aliphatic amine and production method thereof
CN109174087A (en) A kind of palladium carbon catalyst and the preparation method and application thereof
CN114308035A (en) Hydrogenation catalyst for 1, 4-cyclohexanedicarboxylic acid, preparation method and application thereof
CN108863738A (en) A method of preparing cyclopentanone
CN105061176B (en) A kind of fixed bed synthetic method of 3,3,5 trimethylcyclohexanone
CN112958114A (en) Raney nickel catalyst for hydrogenation of aromatic nitro compound in fixed bed and application thereof
CN110372516B (en) Method for preparing cyclohexylamine
CN117586130A (en) Preparation method of hexamethylenediamine
CN113058608B (en) Catalyst for preparing isopropylbenzene by hydrogenolysis of alpha-dimethyl benzyl alcohol and preparation method thereof
CN102430421B (en) Catalytic agent for synthesizing oxalic ester and preparing method thereof
CN112237946B (en) Terephthalic acid hydrofining reaction and catalyst thereof
CN114054034A (en) Multi-element copper-based non-noble metal hydrogenation catalyst, and preparation method and application thereof
CN103894188A (en) Preparation method for palladium/resin carbon catalyst and application of palladium/resin carbon catalyst
CN114249656A (en) Preparation method of hexamethylene diamine
CN113735688B (en) Recycling method of waste liquid of butanol device
CN115212905A (en) Selective hydrogenation catalyst for alkynol and preparation method and application thereof
CN112138676B (en) Catalyst for preparing o-phenylphenol and preparation method thereof
CN1242972C (en) Catalyst prepared by using M/Mn/Al hydrotalcite as precursor for producing benzyl formaldehyde by gaseous phase hydrogenation of benzoic acid or methoylbenzoatc
CN110743567B (en) Iridium-carbon catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde and preparation method and application thereof
CN113070069A (en) Catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation and preparation method and application thereof
CN111875497B (en) Method for synthesizing ethyl glyoxylate by catalytic hydrogenation of diethyl maleate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination