CN116120378A - Method for preparing adiponitrile by catalyzing butadiene with ferrocene bidentate phosphine ligand - Google Patents

Method for preparing adiponitrile by catalyzing butadiene with ferrocene bidentate phosphine ligand Download PDF

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CN116120378A
CN116120378A CN202111350443.XA CN202111350443A CN116120378A CN 116120378 A CN116120378 A CN 116120378A CN 202111350443 A CN202111350443 A CN 202111350443A CN 116120378 A CN116120378 A CN 116120378A
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feed liquid
phosphine ligand
butadiene
ferrocene
adiponitrile
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曾伟
滕坤
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Shanghai Institute of Organic Chemistry of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/08—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds
    • C07C253/10—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds to compounds containing carbon-to-carbon double bonds
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/322—Hydrocyanation
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/17—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • 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

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Abstract

The invention discloses a method for preparing adiponitrile by catalyzing butadiene with ferrocene bidentate phosphine ligand. Specifically, the method is completed under the conditions of ferrocene bidentate phosphine ligand, lewis acid auxiliary agent and zero-valent nickel catalytic system by adopting a flow reactor. The method has good selectivity and high conversion rate, and is suitable for industrial production.

Description

Method for preparing adiponitrile by catalyzing butadiene with ferrocene bidentate phosphine ligand
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a method for preparing adiponitrile by catalyzing butadiene with ferrocene bidentate phosphine ligand.
Background
Adiponitrile (molecular formula: NC (CH) 2 ) 4 CN, abbreviated as ADN), a colorless to pale yellow transparent liquid, boiling point 295 ℃, stable in properties, mainly used as an intermediate for manufacturing nylon 66, used as a chromatographic fixing liquid. At present, domestic adiponitrile production technology is monopolized abroad, autonomous production and supply are not realized, and only few well-known large companies in developed countries can produce adiponitrile, including Inward, orchide, basv, germany and Asahi chemical industry.
The synthesis method of adiponitrile is more, and the current process route for producing adiponitrile mainly comprises an acrylonitrile electrolytic dimerization method and a butadiene method. The butadiene method mainly comprises two steps: primary cyanidation and secondary cyanidation.
The main reaction type can be written as:
Figure BDA0003355669430000011
in industrial production, the intermediate 3PN and 2M3BN are separated after the butadiene is first cyanidated, wherein the 2M3BN is isomerized to obtain 3PN, and the product ADN is separated after the 3PN is subjected to the second cyanidation. The unreacted raw materials, the catalyst, the separation and purification intermediates and products are required to be recovered after each cyanidation, and the conversion rate and the selectivity of each cyanidation are low. The conversion rate of butadiene in one-step cyanidation reaction is 70-85% and the selectivity is 60-75%; the conversion rate of the secondary cyanidation is 50-72%, and the selectivity is 70-85%. In addition, the equipment required for the two cyanidation reactions increases the production cost considerably. These reported catalytic systems all have problems of low conversion, low selectivity and unstable catalytic systems, and therefore there is a need to find better catalyst systems.
Disclosure of Invention
The invention aims to provide a catalytic system comprising a ferrocene-containing bidentate phosphine ligand, lewis acid and zero-valent nickel, which is used for catalyzing butadiene to prepare adiponitrile through one-step cyanation.
In a first aspect of the invention, there is provided a ferrocene bidentate phosphine ligand having a structure as shown in formula I or formula II:
Figure BDA0003355669430000021
wherein R is selected from the group consisting of: hydrogen, halogen, substituted or unsubstituted C 1 -C 7 Straight-chain or branched alkyl, substituted or unsubstituted C 1 -C 7 Straight or branched alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl; wherein the substituents are selected from the group consisting of: halogen, C 1 -C 4 Alkyl, diphenyl phosphine substituents.
In another preferred embodiment, R is selected from the group consisting of: hydrogen, chlorine, C 1 -C 4 Straight-chain or branched alkyl, C 1 -C 4 Straight or branched alkoxy, phenyl, benzyl, 2-diphenylphosphinophenyl, or trifluoromethyl.
In another preferred embodiment, R is selected from the group consisting of: hydrogen, methoxy, isopropyl, tert-butyl, benzyl, trifluoromethyl, 2-diphenylphosphinophenyl.
In another preferred embodiment, R is selected from the group consisting of: hydrogen, 2-methoxy, 4-isopropyl, 3-isopropyl, 4-tert-butyl, 4-benzyl, 2-trifluoromethyl, 3- (2-diphenylphosphinophenyl).
In another preferred embodiment, in the structures of formula I and formula II, n is 0, 1 or 2.
In another preferred embodiment, the phosphine ligand is selected from the group consisting of:
Figure BDA0003355669430000022
Figure BDA0003355669430000031
/>
in another preferred embodiment, the phosphine ligand is selected from the group consisting of:
Figure BDA0003355669430000032
in a second aspect of the present invention, there is provided a process for preparing adiponitrile using phosphine ligands described in the first aspect of the present invention for the catalysis of butadiene, comprising the steps of:
Figure BDA0003355669430000033
(a) Providing a feed liquid A, a feed liquid B and a feed liquid C, wherein the feed liquid A is hydrocyanic acid, the feed liquid B is butadiene, and the feed liquid C is a catalyst solution;
wherein the catalyst solution comprises: ferrocene bidentate phosphine ligand, lewis acid auxiliary agent, and zero-valent nickel;
(b) Respectively pumping the feed liquid A and the feed liquid B into a first micro mixer for mixing under the system pressure of 2-6 MPa to obtain a first hot mixed material;
(c) Mixing the first hot mixed material and the feed liquid C in a second micromixer to obtain a second hot mixed material;
(d) Introducing the second hot mixed material into a reactor for reaction, thereby obtaining product feed liquid containing adiponitrile;
(e) And separating unreacted butadiene and hydrocyanic acid in the product feed liquid, and separating the rest materials to obtain adiponitrile.
In another preferred example, the feed liquid B contains nitrogen with the pressure of 0.1-1 MPa.
In another preferred embodiment, the butadiene is in a liquid state.
In another preferred embodiment, in the step (b), the system pressure is regulated by a back pressure valve so that the system pressure reaches a set range.
In another preferred embodiment, the step (b) further includes: the feed liquid A is preheated before being pumped into the first micromixer.
In another preferred embodiment, in said step (b), said preheating is performed using a preheater.
In another preferred embodiment, the step (c) further includes: and preheating the feed liquid C before mixing.
In another preferred embodiment, in said step (c), said preheating is performed using a heat exchanger.
In another preferred embodiment, in step (d), the reactor is a tubular reactor.
In another preferred embodiment, in step (e), the separation treatment is a rectifying column fractional distillation.
In another preferred embodiment, the catalyst solution is ready-to-use.
In another preferred example, the molar ratio of the ferrocene bidentate phosphine ligand, the Lewis acid auxiliary agent and the zero-valent nickel in the catalyst solution is 5-100:0.1-5:1.
In another preferred example, the molar ratio of the ferrocene bidentate phosphine ligand, the Lewis acid auxiliary agent and the zero-valent nickel in the catalyst solution is 8-50:2-5:1.
In another preferred example, the molar ratio of the ferrocene bidentate phosphine ligand, the Lewis acid auxiliary agent and the zero-valent nickel in the catalyst solution is 8-30:2-5:1.
In another preferred embodiment, the lewis acid promoter is selected from the group consisting of: copper chloride, ferric chloride, manganese chloride, titanium trichloride, zinc chloride, zinc bromide, silver acetate, aluminum chloride, or combinations thereof.
In another preferred embodiment, the lewis acid promoter is selected from the group consisting of: silver acetate, zinc chloride, copper chloride, titanium trichloride, zinc bromide, or combinations thereof.
In another preferred embodiment, the molar ratio of butadiene to hydrocyanic acid to zero-valent nickel in the second hot mixture is 50-1000:50-2000:1.
In another preferred example, in the second hot mixed material, the mixing mole ratio of butadiene to hydrocyanic acid to zero-valent nickel is 75-650: 140-1200: 1.
in another preferred embodiment, the molar ratio of butadiene to hydrocyanic acid in the second hot mixture is 0.8-1.2:1-3.
In another preferred example, the sample injection flow rate of the feed liquid A is 0.01-5L/min; the sample injection flow rate of the feed liquid B is 0.01-5L/min; the sample injection flow rate of the feed liquid C is 0.001-0.5L/min.
In another preferred example, the sample injection flow rate of the feed liquid A is 0.2-2L/min, preferably 0.8-0.9L/min.
In another preferred example, the sample injection flow rate of the feed liquid B is 0.01-5L/min, preferably 0.2-2L/min, and more preferably 0.75-0.8L/min.
In another preferred example, the sample injection flow rate of the feed liquid C is 0.02-0.2L/min, preferably 0.08-0.09L/min.
In another preferred embodiment, the reaction temperature is 40 to 180 ℃.
In another preferred embodiment, the reaction temperature is from 90 to 150 ℃, preferably from 100 to 140 ℃.
In another preferred embodiment, the preheating temperature is 40 to 180 ℃.
In another preferred embodiment, the preheating temperature is 90-150 ℃, preferably 100-140 ℃.
In another preferred embodiment, in the step (d), the reaction time is 1 to 60 minutes.
In another preferred embodiment, the reaction time is 30 to 60 minutes, preferably 40 to 55 minutes, more preferably 45 to 50 minutes.
It is understood that within the scope of the present invention, the above-described technical features of the present invention and technical features specifically described below (e.g., in the examples) may be combined with each other to constitute new or preferred technical solutions. And are limited to a space, and are not described in detail herein.
Detailed Description
Through extensive and intensive research, the invention develops a novel method for preparing adiponitrile by catalyzing butadiene with ferrocene bidentate phosphine ligand for the first time through a large number of screening. The invention has simple process flow, high product conversion rate and reduced production energy consumption. On this basis, the present invention has been completed.
The specific embodiments of the present invention are as follows:
step one: the system pressure is back-pressed to 2-6 MPa;
step two: pumping raw material hydrocyanic acid into a microchannel heat exchanger from a storage tank through a feed pump at a certain flow rate, preheating to a specific temperature, and then pumping into a first micromixer;
step three: pumping liquid butadiene containing 0.5MPa nitrogen pressure in raw materials into a first micro mixer through a feed pump from a storage tank at a certain flow rate;
step four: mixing hydrocyanic acid and butadiene in a first micromixer to obtain a first hot mixed material;
step five: pumping the catalyst solution from a storage tank into a micro-channel heat exchanger through a feed pump at a certain flow rate, preheating to a specific temperature to obtain a hot catalyst solution, and pumping into a second micro-mixer;
step six: mixing the first hot mixed material and the hot catalyst solution in a second micromixer, and then entering a tubular reactor to react for a certain time at a specific temperature;
step seven: after the reaction is completed, separating butadiene and hydrocyanic acid which are not reacted completely, and treating the residual materials to obtain the product adiponitrile.
Compared with the prior art, the invention has the advantages that at least:
(1) The method has the advantages that the production procedure is simplified, under the catalysis system of the cyclooctadiene nickel or the nickel-dicyclopentadienyl+Lewis acid+ferrocene bidentate phosphine ligand, the adiponitrile can be successfully prepared by the one-step catalytic reaction of butadiene and hydrocyanic acid, and the intermediate products 3PN and 2M3BN do not need to be separated and isomerized;
(2) The reaction selectivity is high, the selectivity of the adiponitrile product is high and reaches 86% -95%, and the conversion rate is high and reaches 60% -75%;
(3) The catalyst in the reaction has low dosage and high catalytic activity, and can effectively save the production cost in large-scale industrial production;
(4) The production energy consumption is reduced, and the product has high purity and excellent quality.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. Percentages and parts are by weight unless otherwise indicated.
Example 1
Step one: the system pressure is back-pressed to 2MPa;
step two: pumping raw hydrocyanic acid from a storage tank into a micro-channel heat exchanger through a feed pump at a flow rate of 0.87L/min to preheat to 100 ℃, and then pumping into a first micro-mixer;
step three: pumping liquid butadiene containing nitrogen pressure of 0.5MPa in the raw materials into a first micro-mixer from a storage tank at a flow rate of 0.78L/min through a feed pump;
step four: mixing hydrocyanic acid and butadiene in a first micromixer to obtain a first hot mixed material;
step five: phosphine ligand (structural formula I: R is methoxy, para-position, n=1) to silver acetate to zero-valent nickel in a ratio of 10:2:1 to obtain a catalyst system, and pumping the catalyst system into a microchannel heat exchanger from a storage tank at a flow rate of 0.087L/min through a feed pump to preheat to 100 ℃ to obtain a hot catalyst solution;
step six: after the first hot mixed material and the hot catalyst solution are mixed in the second micromixer, the mixture enters a tubular reactor to react for 40min at 100 ℃, and the mixed molar ratio of butadiene to hydrocyanic acid to zero-valent nickel is 155:300:1, a step of;
step seven: after the reaction is completed, separating butadiene and hydrocyanic acid which are not reacted completely, and treating the residual materials to obtain adiponitrile.
In this example, the conversion of the raw material was 75%, the selectivity of the adiponitrile product was 93%, and the crude product was purified by distillation to obtain adiponitrile with a purity of 99.5%.
Examples 2 to 8
The procedure is described in example 1, with reference to the following table for details of ligand structure, composition ratio and environmental conditions and parameters:
Figure BDA0003355669430000071
Figure BDA0003355669430000081
examples 9 to 15
The procedure is described in example 1, with reference to the following table for details of ligand structure, composition ratio and environmental conditions and parameters:
Figure BDA0003355669430000082
Figure BDA0003355669430000091
example 16
Stepwise synthesis of adiponitrile
First cyanation reaction: phosphine ligand (structural formula I: R is methoxy, para position, n=1) to silver acetate to zero-valent nickel in the ratio of 10:2:1, 10g of the catalyst system obtained by mixing the above components in a molar ratio is added into an autoclave at one time, and a cover of the autoclave is closed for sealing; feeding 21g of raw material liquid butadiene, 10g of hydrocyanic acid and 100mL of anhydrous toluene into an autoclave through a metering pump in sequence, and starting stirring after sealing; heating the reaction kettle to 100 ℃ for reaction for 3 hours; and cooling, and detecting through sampling analysis of a sampling tube, wherein the conversion rate of the raw material is 87.6%, and the selectivity of 3PN is 94%.
Second cyanidation: phosphine ligand (structural formula I: R is methoxy, para-position, n=1) to silver acetate to zero-valent nickel in a ratio of 10:2:1, 10g of the catalyst system obtained by mixing the molar ratio is introduced into a reaction kettle for the first cyanidation reaction through a metering pump, then 10g of hydrocyanic acid is introduced into the reaction kettle through the metering pump, and stirring is started; heating the reaction kettle to 100 ℃ for 2 hours; cooling, pumping out residual hydrocyanic acid, and performing reduced pressure distillation and rectification on the reaction liquid to obtain a product.
In the embodiment, the conversion rate of the raw material is 68.2%, the selectivity of the product adiponitrile is 77.1%, and the adiponitrile with the purity of 99.5% is obtained after the crude product is purified by rectification.
Since the catalyst of the present invention can achieve excellent conversion of raw materials in the first step, the reactions of the first and second steps can be completed in the same system. By the above examples, it was found that the one-step synthesis of adiponitrile allows for equivalent or even better conversion of raw materials and selectivity of the product adiponitrile compared to the two-step synthesis of adiponitrile, without purification of intermediates, and with reduced losses; in addition, the method for synthesizing adiponitrile by one step has the advantages of less raw materials and catalysts, lower energy consumption and shorter time.
All documents mentioned in this application are incorporated by reference as if each were individually incorporated by reference. Further, it will be appreciated that various changes and modifications may be made by those skilled in the art after reading the above teachings, and such equivalents are intended to fall within the scope of the claims appended hereto.

Claims (10)

1. A ferrocene bidentate phosphine ligand, which is characterized by having a structure shown in a formula I or a formula II:
Figure FDA0003355669420000011
wherein R is selected from the group consisting of: hydrogen, halogen, substituted or unsubstituted C 1 -C 7 Straight-chain or branched alkyl, substituted or unsubstituted C 1 -C 7 Straight or branched alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl; wherein the substituents are selected from the group consisting of: halogen, C 1 -C 4 Alkyl, diphenyl phosphine substituents.
2. The phosphine ligand of claim 1, wherein R is selected from the group consisting of: hydrogen, chlorine, C 1 -C 4 Straight-chain or branched alkyl, C 1 -C 4 Straight or branched alkoxy, phenyl, benzyl, 2-diphenylphosphinophenyl, or trifluoromethyl.
3. The phosphine ligand of claim 1, wherein R is selected from the group consisting of: hydrogen, methoxy, isopropyl, tert-butyl, benzyl, trifluoromethyl, 2-diphenylphosphinophenyl.
4. A process for preparing adiponitrile using the phosphine ligand-catalyzed butadiene as claimed in claim 1, comprising the steps of:
Figure FDA0003355669420000012
(a) Providing a feed liquid A, a feed liquid B and a feed liquid C, wherein the feed liquid A is hydrocyanic acid, the feed liquid B is butadiene, and the feed liquid C is a catalyst solution;
wherein the catalyst solution comprises: ferrocene bidentate phosphine ligand, lewis acid auxiliary agent, and zero-valent nickel;
(b) Respectively pumping the feed liquid A and the feed liquid B into a first micro mixer for mixing under the system pressure of 2-6 MPa to obtain a first hot mixed material;
(c) Mixing the first hot mixed material and the feed liquid C in a second micromixer to obtain a second hot mixed material;
(d) Introducing the second hot mixed material into a reactor for reaction, thereby obtaining product feed liquid containing adiponitrile;
(e) And separating unreacted butadiene and hydrocyanic acid in the product feed liquid, and separating the rest materials to obtain adiponitrile.
5. The process of claim 4 wherein the molar ratio of ferrocene bidentate phosphine ligand, lewis acid promoter and zero-valent nickel in the catalyst solution is from 5 to 100:0.1 to 5:1.
6. The method of claim 4, wherein the lewis acid promoter is selected from the group consisting of: copper chloride, ferric chloride, manganese chloride, titanium trichloride, zinc chloride, zinc bromide, silver acetate, aluminum chloride, or combinations thereof.
7. The method of claim 4, wherein the molar ratio of butadiene to hydrocyanic acid to zero-valent nickel in the second hot mix is 50-1000:50-2000:1.
8. The method according to claim 4, wherein the sample injection flow rate of the feed liquid A is 0.01-5L/min; the sample injection flow rate of the feed liquid B is 0.01-5L/min; the sample injection flow rate of the feed liquid C is 0.001-0.5L/min.
9. The process of claim 4, wherein the reaction temperature is from 40 to 180 ℃.
10. The method of claim 4, wherein in step (d), the reaction time is 1 to 60 minutes.
CN202111350443.XA 2021-11-15 2021-11-15 Method for preparing adiponitrile by catalyzing butadiene with ferrocene bidentate phosphine ligand Pending CN116120378A (en)

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