CN113372239A - Method for preparing C5 monoalkene nitrile by reacting 1, 3-butadiene with hydrogen cyanide - Google Patents

Method for preparing C5 monoalkene nitrile by reacting 1, 3-butadiene with hydrogen cyanide Download PDF

Info

Publication number
CN113372239A
CN113372239A CN202110827478.1A CN202110827478A CN113372239A CN 113372239 A CN113372239 A CN 113372239A CN 202110827478 A CN202110827478 A CN 202110827478A CN 113372239 A CN113372239 A CN 113372239A
Authority
CN
China
Prior art keywords
catalyst
stream
nitrile
phosphorus
reaction
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
CN202110827478.1A
Other languages
Chinese (zh)
Inventor
王治邦
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.)
Qingdao Putec Chemical Co ltd
Original Assignee
Qingdao Putec Chemical 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 Qingdao Putec Chemical Co ltd filed Critical Qingdao Putec Chemical Co ltd
Priority to CN202110827478.1A priority Critical patent/CN113372239A/en
Publication of CN113372239A publication Critical patent/CN113372239A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • 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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
    • 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
    • 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
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a method for preparing C5 monoalkene nitrile by direct hydrocyanation reaction of 1, 3-butadiene and hydrogen cyanide in the presence of Ni (0) -phosphorus complex catalyst. The catalyst required for the reaction is a complex catalyst of Ni (0) with a phosphorus ligand consisting of a monodentate multidentate phosphite or phosphinite ligand and mixtures thereof. The reactor adopts a mode of a continuous stirred tank type or a loop reactor, 1, 3-butadiene and hydrogen cyanide are subjected to high-selectivity addition reaction to generate C5 monoalkene nitrile, wherein the ratio of linear nitrile to branched nitrile is obviously higher than that of the prior art under the catalyst system and the reaction process conditions of the invention, so that the continuous isomerization and separation processes for the subsequent production of adiponitrile are saved. The present invention also includes a continuous process for separating the desired product C5 monoalkene nitrile from the hydrocyanation reaction mixture, separating the catalyst, unreacted starting materials, and recycling them to the reactor.

Description

Method for preparing C5 monoalkene nitrile by reacting 1, 3-butadiene with hydrogen cyanide
Technical Field
The invention relates to the field of chemical industry, in particular to a method for preparing adiponitrile by hydrocyanation reaction of olefin, which is an important intermediate for producing nylon 66 and hexamethylene diisocyanate in polyurethane industry.
Background
Adiponitrile is an important intermediate for producing nylon 66 and hexamethylene diisocyanate in the polyurethane industry, and the industrially mainstream adiponitrile production process is prepared from 1, 3-butadiene and hydrogen cyanide through hydrocyanation. The technology was successfully developed by DuPont in the last 60 th century, and the production process includes the addition reaction of one molecule of butadiene and one molecule of hydrogen cyanide to produce C5 monoalkene nitrile, including isomers of 3-pentenenitrile and 2-methyl-3-butenenitrile, and the addition reaction of a small amount of butadiene to two molecules of hydrogen cyanide to produce C6 dinitrile, such as adiponitrile and 2-methylglutaronitrile. In order to obtain more adiponitrile as a target product, the generated 2-methyl-3-butenenitrile needs to generate 3-pentenenitrile through isomerization reaction, and the generated 3-pentenenitrile is further converted into adiponitrile by one molecule of hydrogen cyanide. The process has long route, more process equipment and high energy consumption, and the reaction product of the first-step addition needs to be separated to obtain 2-methyl-3-butenenitrile, and then the 2-methyl-3-butenenitrile is converted into 3-pentenenitrile through isomerization reaction.
The technology adopts a novel monodentate and multidentate phosphorus mixed ligand to react with zero-valent nickel to prepare the novel nickel (0) -phosphorus complex catalyst, the catalyst can obviously improve the yield of C5 monoalkene nitrile generated in the addition reaction of butadiene and hydrogen cyanide, and the ratio of the generated linear chain and branched chain C5 monoalkene nitrile is more than 20, which is obviously higher than that of the prior art, and can obviously reduce the processing amount and energy consumption of an isomerization unit.
Disclosure of Invention
The object of the present invention is to provide a process for preparing C5 monoalkenenitriles by reacting 1, 3-butadiene with hydrogen cyanide in the presence of a zero-valent nickel-phosphorus complex catalyst, the C5 monoalkenenitriles formed being able to be reacted further by addition reaction with hydrogen cyanide to form adiponitrile.
The phosphorus-containing ligand in the catalyst is a mixed ligand of monodentate and multidentate phosphinite or phosphite. Wherein the monodentate phosphorus ligand has the structure P (X)1R1）(X2R2)（X3R3). Wherein R is1、R2、R3Is phenyl or phenyl with substituent on side chain. R1、R2、R3If the substituted phenyl is substituted, the substituent on the phenyl can be mono-substituted or di-substituted methyl, ethyl, isopropyl or tertiary butyl, and the position of the substituent can be at three positions of ortho, meta and para of a benzene ring at the position of the PXR bond.
X1、X2、X3Is oxygen or a single bond, satisfies X1、X2、X3Simultaneously oxygen or one oxygen and the other two single bonds.
In a preferred embodiment if X1、X2、X3One of which is oxygen and the other two of which are single bonds, to form a compound of the structure P (OR)1)(R2)(R3) Or P (R)1)(OR2)(R3) Or P (R)1)( R2)(OR3) The phosphinate ester of (1).
In another preferred embodiment, the group X1、X2、X3At the same time as oxygen, the structure P (OR) is formed1)(OR2)(OR3) Phosphite esters of (a).
R1、R2、R3Which may be the same or different, in a preferred embodiment R1、R2And R3Is a group selected from phenyl, tolyl, isopropylphenyl and tert-butylphenyl, and the position of the substituent may be at three positions, i.e., o-, m-and p-positions, of the POR bond. Radical R1、R2And R3Up to two are phenyl groups, in another preferred embodiment the group R1、R2And R3Up to two are o-isopropylphenyl, and in another preferred embodiment the group R1、R2And R3And a maximum of two are o-tolyl groups.
Phosphites can be obtained by the following process:
(a) reacting phosphorus trichloride with a compound selected from R1OH、R2OH and R3Reacting OH with an alcohol or a mixture thereof to obtain a dihalophosphite,
(b) reacting said phosphorodichloridate with a compound selected from the group consisting of R1OH、R2OH and R3Reaction of an OH alcohol or mixture thereof to give a monohalophosphorous diester, and
(c) reacting said monohalophosphorous diester with a compound selected from R1OH、R2OH and R3Reaction of OH with an alcohol OR mixture thereof to give P (OR)1)(OR2)(OR3) Phosphite esters of (a).
The above reaction may be carried out in three steps as described above, or may be carried out in any combination of two or three steps.
Bidentate phosphorus ligands are
Figure 197212DEST_PATH_IMAGE001
X11、X12、X13、X21、X22、X23Each independently oxygen or a single bond.
R11、R12、R21、R22The substituent is methyl, ethyl, isopropyl or tertiary butyl. The number of the substituent groups can be 1-2, the position of the substituent groups can be at three positions of ortho, meta and para of the RXP bond connected with the position of the benzene ring R, R is11、R12、R21、R22May be the same or different.
Y is biphenyl or binaphthyl with substituent on the side chain of aromatic ring, and the substituent can be methyl, ethyl, isopropyl or tert-butyl. The number of the substituent groups can be 1-3, and the position of the substituent groups is in three positions of ortho, meta and para of the position of the YXP bond connecting aromatic ring Y.
X11、X12、X13、X21、X22、X23The requirement is that both phosphorus ligands on the resulting bidentate phosphorus ligand are simultaneously phosphinite or phosphite ligands.
In a preferred embodiment X11、X12、X21、X22Each is a single bond, X13、X23Is oxygen, thereby making X11、X12And X13The surrounding phosphorus atom becomes the central atom of the phosphinic acid ester, with X being present21、X22And X23The surrounding phosphorus atom becomes the central atom of the phosphinate.
In another preferred embodiment X11、X12、X13、X21、X22、X23Each being oxygen. At this time, X11、X12And X13The surrounding phosphorus atom becomes the central atom of the phosphite ester, and X is simultaneously bonded to the phosphite ester21、X22And X23Surrounded phosphorus atomThe atom is the central atom of the phosphite.
The bidentate phosphinite ligands described above can be prepared by reacting a diaryl phosphonium chloride with dihydroxybiphenyl or binaphthyl.
The bidentate phosphite ligands described above may be prepared by reacting monohalophosphites with dihydroxybiphenyl or binaphthyl.
In a preferred embodiment of the process according to the invention, the phosphorus ligand and/or the free phosphorus ligand of the nickel (0) -phosphorus complex is selected from phosphite ligands or phosphinite ligands, the above-described binding of zero-valent nickel to the ligand being carried out in the presence or absence of a solvent.
In a preferred embodiment, the zero-valent nickel and the above-described ligand are combined in the absence of a solvent, and the nickel (0) -phosphorus complex catalyst formed is present in excess of the ligand.
In another preferred embodiment the above-described nickel (0) -phosphorus complex catalyst is dissolved in a suitable solvent to form a homogeneous metal complex catalyst. In general, the solvents used are hydrocarbons, such as benzene, toluene, xylene, cumene, trimethylbenzene or nitriles, such as acetonitrile, 3-pentenenitrile, adiponitrile, methylglutaronitrile, ethers, such as diethyl ether, isopropyl ether, methyl tert-butyl ether, tetrahydrofuran, etc.
According to some embodiments of the invention, the molar ratio of monodentate phosphorus, bidentate phosphorus, zero-valent nickel catalyst in the catalyst is monodentate phosphorus: bidentate phosphorus: zero-valent nickel = (5-30): (1-10): 1. wherein the monodentate phosphorus and multidentate phosphorus ligands are preferably selected from the group consisting of phosphinites, phosphites and combinations thereof.
The hydrocyanation reaction may be carried out in the presence or absence of a solvent which is inert, i.e., does not react with the catalyst and reactants, and is liquid at the reaction temperature and pressure. The solvent used may be the same as or different from the catalyst solvent, and in general, the solvent used is a hydrocarbon such as benzene, toluene, xylene, cumene, trimethylbenzene, or a nitrile such as acetonitrile, 3-pentenenitrile, adiponitrile, methylglutaronitrile, an ether such as diethyl ether, isopropyl ether, methyl tert-butyl ether, tetrahydrofuran, anisole, ethylene glycol diethyl ether, or the like.
ButadieneThe hydrocyanation reaction can be carried out in a continuous stirred tank type or a loop reactor, and the reaction temperature is controlled to be 50-250 DEGoAnd C, controlling the retention time to be 1-8 hours.
According to some embodiments of the present invention, a process for preparing C5 monoalkene nitriles by reacting butadiene with hydrogen cyanide comprises the following process steps:
(a) reacting 1, 3-butadiene with hydrogen cyanide under catalysis of the above-described nickel (0) -phosphorus complex catalyst to obtain a first stream comprising C5 monoalkenenitrile, catalyst, 1, 3-butadiene, hydrogen cyanide,
(b) distilling the first stream of the reaction product mixture in a rectification column T1 to obtain a second stream containing butadiene and hydrogen cyanide as light-end products and a third stream containing C5 monoalkene nitrile, catalyst as heavy-end products, returning the second stream to the catalytic reaction unit,
(c) the third stream is distilled in a rectification column T2 to obtain a fourth stream as light components, i.e.the desired product C5 monoalkenenitrile, and a fifth stream containing the catalyst as heavy components, which is returned to the reaction unit.
In some embodiments of the invention, the number of the plates of the rectifying tower T1 is 15-50, the absolute pressure of the tower top is 0.01-0.15 MPa, and the temperature of the tower top is-10-30oC, the temperature of the tower kettle is 100-160 DEGoC。
The number of tower plates of the rectifying tower T2 is 15-50, the absolute pressure of the tower top is 0.02-0.15 MPa, and the temperature of the tower top is 90-120oC, the temperature of the tower kettle is 110-160 DEGoC
A process for preparing C5 monoalkene nitriles by direct hydrocyanation of 1, 3-butadiene, which can also employ another preferred process step:
(a) reacting 1, 3-butadiene with hydrogen cyanide catalyzed by the zero-valent nickel-phosphorus complex catalyst to produce a first stream of reaction products comprising C5 monoalkene nitrile, catalyst, 1, 3-butadiene, hydrogen cyanide,
(b) introducing the first stream of reaction products into a rectification column T3, obtaining a sixth stream from rectification column T3 as a light fraction, containing butadiene, hydrocyanic acid, C5 monoalkene nitrile and a seventh stream as a heavy fraction, containing catalyst, returning it to the catalytic reaction unit,
(C) distilling the sixth stream in a rectification T4 to obtain an eighth stream containing butadiene, hydrocyanic acid, branched C5 nitrile, and a ninth stream containing the desired product C5 monoalkene nitrile as heavies in the column as light components, and returning the eighth stream to the catalytic reaction unit.
In some examples of the invention, the number of plates of the rectifying tower T3 is 15-50, the absolute pressure of the tower top is 0.02-0.15 MPa, and the temperature of the tower top is 0-60 MPaoC, the temperature of the tower kettle is 100-180 DEGoC；
The number of tower plates of the rectifying tower T4 is 15-50, the absolute pressure of the tower top is 0.02-0.15 MPa, the absolute pressure of the tower kettle is 0.02-0.15 MPa, and the temperature of the tower top is-10-60oC, the temperature of the tower kettle is 100-180 DEGoC 。
According to the method for preparing the C5 monoalkene nitrile by hydrocyanating the butadiene, the complex catalyst consisting of the mixed ligand of the monodentate phosphorus and the bidentate phosphorus and the nickel (0) is adopted, the catalytic system is stable, the efficiency is higher, the yield of the C5 monoalkene nitrile generated by the addition of the butadiene and the hydrogen cyanide is over 90 percent, the yield of the directly-connected C5 monoalkene nitrile in the generated product is greatly improved, the yields of the branched C5 monoalkene nitrile, the methylglutaronitrile and the adiponitrile are greatly reduced, the processing amount and the energy consumption of an isomerization unit can be obviously reduced, the isomerization unit can be selected to be saved according to the process requirements, the subsequent addition reaction is directly carried out on the branched C5 monoalkene nitrile, the methylglutaronitrile and the like to generate the adiponitrile, the process flow is greatly simplified, and the investment cost is saved.
Drawings
FIG. 1 is a schematic diagram of the process flow for the preparation of C5 monoalkene nitrile by reacting butadiene with hydrogen cyanide in example 1 of the present invention.
FIG. 2 is a schematic diagram of the process flow for the preparation of C5 monoalkene nitrile by reacting butadiene with hydrogen cyanide in example 2 of the present invention.
In order to more fully understand the technical contents of the present invention, the technical solutions of the present invention will be further described and illustrated with reference to the following specific embodiments.
Example 1
Mono-dentate phosphorus P (O-phenyl)1.0(O-m-tolyl)1.0(O-p-tolyl)1.0And a complex catalyst consisting of bidentate phosphorus ligand A and zero-valent nickel, HCN and BD are put into a continuous stirring tank type reactor according to the molar ratio of 1: 110: 115 (wherein, the molar ratio of monodentate phosphine to bidentate phosphine to zero-valent nickel is 10:3: 1), and the reaction temperature is controlled to be 120oAnd C, the reaction residence time is 5 hours, and a first flow of the reaction product mixture is obtained.
Figure 613150DEST_PATH_IMAGE002
Ligand A
The first material flow enters a rectifying tower T1 for rectification, the rectifying tower T1 adopts a rectifying tower with 15 trays, wherein the absolute pressure of the operation of the rectifying tower is 0.08MPa, and the temperature of the top of the tower is 8oC, the tower kettle temperature is 130 DEGoC. The light component fraction taken out of the rectifying tower T1 is a second material flow containing butadiene and hydrogen cyanide, and the second material flow is returned to the catalytic reaction unit for continuous reaction. The heavy component obtained from the bottom of the rectifying tower is divided into a third material flow containing C5 monoalkene nitrile and catalyst.
Introducing the third stream into a rectifying tower T2 for rectification, wherein the rectifying tower T2 adopts a rectifying tower with the tower number of 35, the absolute pressure of the rectifying tower T2 is 0.04MPa, and the tower top temperature is 105 MPaoC, the tower kettle temperature is 121oC, the light fraction obtained from the second rectification column T2 is divided into a fourth stream containing the desired product, C5 monoalkene nitrile, and the recombinant fraction is divided into a fifth stream containing the catalyst, which is returned to the catalytic reaction unit.
The butadiene is processed by the hydrocyanation reaction and the separation procedure, the total yield of the C5-monoalkene nitrile is more than 90.2 percent, wherein the ratio of the linear chain and the branched chain C5 monoalkene nitrile is 23, the purity of the linear chain C5 monoalkene nitrile is 94.7 percent, and the butadiene can be used as a raw material for preparing adiponitrile by the next reaction with the hydrogen cyanide.
Example 2
Reacting monodentate phosphorus P (O-isopropylphenyl)0.6(O-m-methylphenyl)1.6(O-p-methylphenyl)0..8And bidentate phosphorus ligands B withThe complex consisting of zero-valent nickel, HCN and BD are put into a continuous stirred tank reactor according to the mol ratio of 1: 110: 115 (wherein, the mol ratio of monodentate phosphine to bidentate phosphine to zero-valent nickel is 8:2: 1), and the reaction temperature is controlled to be 120oAnd C, the reaction residence time is 5 hours, and a first flow of the reaction product mixture is obtained.
Figure 349024DEST_PATH_IMAGE003
Ligand B
Rectifying the first material flow in a rectifying tower T3, wherein the rectifying tower T3 adopts a rectifying tower with 35 trays, the absolute pressure of the top of the rectifying tower is 0.05MPa, the absolute pressure of the bottom of the rectifying tower is 0.06MPa, and the temperature of the top of the rectifying tower is 30 DEG CoC, the tower kettle temperature is 128oC; a sixth stream comprising butadiene, hydrogen cyanide and C5 monoalkene nitrile is obtained at the top of the rectification column T3. As bottom heavies of the rectification column T3, a fifth stream comprising catalyst is obtained, which is returned to the hydrocyanation reactor for use as catalyst.
Pumping the sixth material flow into a rectifying tower T4 by a pump, wherein the rectifying tower T4 adopts a rectifying tower with 40 trays, the pressure at the top of the rectifying tower is 0.03MPa, the pressure at the bottom of the rectifying tower is 0.04MPa, and the temperature at the top of the rectifying tower is-2oC, the tower kettle temperature is 106oC; a seventh stream of light components is obtained in a rectification column T4, which contains butadiene and hydrocyanic acid and is returned to the hydrocyanation reactor, and an eighth stream of the heavy components fraction of rectification column T4 is the desired product C5 monoalkenenitrile.
In this example, butadiene and hydrogen cyanide were subjected to catalytic reaction and separation procedures to obtain C5-monoalkene nitriles in a total yield of greater than 92.0%, with a linear to branched C5 monoalkene nitrile ratio of 22 and a linear C5 monoalkene nitrile purity of 94.1%, which could be used as a starting material for the next hydrocyanation reaction to adiponitrile.
Example 3
Adding monodentate phosphorus P (O-O-tolyl)1.0(O-m-tolyl)1.0(O-p-tolyl)1.0And a complex of bidentate phosphorus ligand C and zero-valent nickel, HCN and BD in a molar ratio of 1: 100: 110 (Wherein, monodentate phosphine: bidentate phosphine: the mol ratio of the zero-valent nickel is 8:2: 1) is put into a continuous stirred tank reactor, and the reaction temperature is controlled to be 120oAnd C, the reaction residence time is 5 hours, and a first flow of the reaction product mixture is obtained.
Figure 892132DEST_PATH_IMAGE004
Ligand C
Rectifying the first material flow in a rectifying tower T3, wherein the rectifying tower T3 adopts a rectifying tower with 35 trays, the absolute pressure of the top of the rectifying tower is 0.04MPa, the absolute pressure of the bottom of the rectifying tower is 0.05MPa, and the temperature of the top of the rectifying tower is 24 MPaoC, the tower kettle temperature is 121oC; a sixth stream comprising butadiene, hydrogen cyanide and C5 monoalkene nitrile is obtained at the top of the rectification column T3. As bottom heavies of the rectification column T3, a fifth stream comprising catalyst is obtained, which is returned to the hydrocyanation reactor for use as catalyst.
Pumping the sixth material flow into a rectifying tower T4 by a pump, wherein the rectifying tower T4 adopts a rectifying tower with 40 trays, the pressure at the top of the rectifying tower is 0.03MPa, the pressure at the bottom of the rectifying tower is 0.04MPa, and the temperature at the top of the rectifying tower is-2oC, the tower kettle temperature is 106oC; a seventh stream of light components is obtained in a rectification column T4, which contains butadiene and hydrocyanic acid and is returned to the hydrocyanation reactor, and an eighth stream of the heavy components fraction of rectification column T4 is the desired product C5 monoalkenenitrile.
In this example, butadiene and hydrogen cyanide were subjected to catalytic reaction and separation procedures to obtain C5-monoalkene nitriles in an overall yield of greater than 90.6%, with a ratio of linear to branched C5 monoalkene nitriles of 21 and a purity of 93.5% for linear C5 monoalkene nitriles, which could be used as a feedstock for the next addition with hydrogen cyanide to adiponitrile.
The embodiments described above are only individual embodiments of the invention, not all embodiments, and do not limit the scope of the invention in any way. All other implementations made by those skilled in the art without any inventive step are included in the scope of the present invention.

Claims (9)

1. A process for preparing C5 monoalkene nitriles by reacting 1, 3-butadiene with hydrogen cyanide, characterized in that the following reaction and separation process steps are employed:
(a) 1, 3-butadiene is reacted with hydrogen cyanide in the presence of a nickel (0) -phosphorus complex catalyst to form a first stream of a reaction product mixture containing C5 monoalkenenitrile, the catalyst being a complex of Ni (0) and a phosphorus ligand, the phosphorus ligand being a mixed ligand of monodentate and bidentate phosphite or phosphinite ligands, the reaction temperature being controlled in the range from 50 to 250%oC, the molar ratio of the butadiene, the hydrogen cyanide and the nickel (0) -phosphorus complex catalyst is (50-200): 1,
(b) the first stream of the reaction product mixture is separated to provide the product C5 monoalkenenitrile.
2. The catalyst of claim 1, wherein: the monodentate phosphorus ligand has the structure P (X)1R1）(X2R2)（X3R3），X1、X2、X3Is oxygen or a single bond, satisfies X1、X2、X3Simultaneously oxygen or one oxygen and the other two single bonds, R1、R2、R3The substituent on the phenyl can be mono-substituted or di-substituted methyl, ethyl, isopropyl and tert-butyl, the number of the substituent is 1-3, the position of the substituent can be at three positions of ortho, meta and para of a benzene ring at the position of PXR bond connection R, R is phenyl or substituted phenyl, and R is a phenyl group1、R2、R3May be the same or different, and the phosphinate or phosphite so formed may be symmetrical and asymmetrical.
3. The catalyst of claim 1, wherein: bidentate phosphorus ligands are
Figure 637982DEST_PATH_IMAGE001
X11、X12、X13、X21、X22、X23Each independently is oxygen or a single bond, R11、R12、R21、R22The substituent group can be methyl, ethyl, isopropyl and tert-butyl, the number of the substituent groups can be 1-2, the position of the substituent group can be connected with three positions of ortho, meta and para of the R position of the benzene ring in RXP bond, R is11、R12、R21、R22Y is biphenyl or binaphthyl with substituent on the side chain of aromatic ring, the above substituent can be methyl, ethyl, isopropyl, tert-butyl, the number of the substituent can be 1-3, the substituent position is at three positions of ortho, meta and para of the aromatic ring connected with Y position by YXP bond, X is identical or different11、X12、X13、X21、X22、X23The requirement that the two phosphorus ligands on the resulting bidentate phosphine ligand are simultaneously phosphinite or phosphite ligands, R on the flanking units on both sides of the central unit of the bidentate phosphorus ligand11、R12、R21、R22The groups may be the same or different, such that the flanking units on both sides have symmetry or asymmetry.
4. The catalyst of claim 1, wherein: the nickel (0) -phosphorus complex catalyst is obtained by reacting a monodentate phosphorus-containing and multidentate phosphorus ligand with nickel (0), and the catalyst can be prepared in the presence or absence of a solvent, wherein the ratio of nickel (0), the monodentate phosphorus ligand and the multidentate phosphorus ligand is 1 (5-30) to (1-10), and the monodentate phosphorus and the multidentate phosphorus ligand are excessive.
5. The catalyst of claim 1, wherein: the nickel (0-phosphorus complex catalyst preparation can be carried out in the presence of a solvent, and generally, the solvent used is a hydrocarbon such as benzene, toluene, xylene, cumene, trimethylbenzene, a nitrile such as acetonitrile, 3-pentenenitrile, methylglutaronitrile, adiponitrile, an ether such as diethyl ether, isopropyl ether, methyl tert-butyl ether, tetrahydrofuran, anisole, ethylene glycol diethyl ether or the like.
6. The process for producing a C5 olefinic nitrile according to claim 1, wherein: by adjusting the composition of the catalyst and the reaction process conditions in the reaction unit, the yield of the C5 monoalkene nitrile from butadiene is above 90%, and the ratio of the linear and branched isomers in the C5 monoalkene nitrile is above 20.
7. The process for preparing C5 olefinic nitrile according to claim 1, wherein the following separation procedure is used:
(a) distilling the first stream of the reaction product mixture in a rectifying column T1 to obtain a second stream containing butadiene and hydrogen cyanide as light-end products and a third stream containing C5 monoalkene nitrile, catalyst as heavy-end products, returning the second stream to the catalytic reaction unit,
(b) the third stream is distilled in a rectification column T2 to obtain a fourth stream as light components, i.e. the desired product C5 monoalkenenitrile, and a fifth stream containing the catalyst as heavy components, which is returned to the catalytic reaction unit.
8. The process according to claim 1 for preparing C5 olefinic nitrile, wherein the following separation steps are also used:
(a) introducing said first stream of reaction products into a rectification column T3, obtaining a sixth stream comprising butadiene, hydrocyanic acid, C5 monoalkene nitrile and a seventh stream comprising catalyst as heavy components, as light components fraction, in a rectification column T3, which is returned to the reaction unit,
(b) distilling the sixth stream in a rectification T4 to obtain an eighth stream as light components, which contains butadiene, hydrocyanic acid, a small amount of branched C5 nitrile, and a ninth stream as heavy components in the column bottom, which contains the desired product C5 monoalkene nitrile, and returning the eighth stream to the reaction unit.
9. The process for producing C5 olefinic nitrile according to claim 1, wherein: the C5 monoalkene nitrile obtained by the reaction and separation process can be used as a raw material for preparing adiponitrile by carrying out secondary addition reaction with hydrogen cyanide.
CN202110827478.1A 2021-07-21 2021-07-21 Method for preparing C5 monoalkene nitrile by reacting 1, 3-butadiene with hydrogen cyanide Pending CN113372239A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110827478.1A CN113372239A (en) 2021-07-21 2021-07-21 Method for preparing C5 monoalkene nitrile by reacting 1, 3-butadiene with hydrogen cyanide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110827478.1A CN113372239A (en) 2021-07-21 2021-07-21 Method for preparing C5 monoalkene nitrile by reacting 1, 3-butadiene with hydrogen cyanide

Publications (1)

Publication Number Publication Date
CN113372239A true CN113372239A (en) 2021-09-10

Family

ID=77582656

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110827478.1A Pending CN113372239A (en) 2021-07-21 2021-07-21 Method for preparing C5 monoalkene nitrile by reacting 1, 3-butadiene with hydrogen cyanide

Country Status (1)

Country Link
CN (1) CN113372239A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113416152A (en) * 2021-08-02 2021-09-21 青岛普泰克化工有限公司 Method for preparing adiponitrile by reacting linear C5 monoalkene nitrile with hydrogen cyanide
WO2023060929A1 (en) * 2021-10-15 2023-04-20 浙江大学 Application of polydentate phosphite ligand in catalytic synthesis of adiponitrile

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1745062A (en) * 2002-12-23 2006-03-08 罗狄亚聚酰胺中间体公司 Process of synthesis of compounds having nitrile functions from ethylenically unsaturated compounds
CN101484416A (en) * 2006-07-14 2009-07-15 因温斯特技术公司 Hydrocyanation process with reduced yield losses
CN101489992A (en) * 2006-07-14 2009-07-22 因温斯特技术公司 Process for making 3-pentenenitrile by hydrocyanation of butadiene
CN103012197A (en) * 2012-12-18 2013-04-03 安徽省安庆市曙光化工股份有限公司 Preparation method of 3-pentenenitrile and preparation method of adiponitrile
CN103664691A (en) * 2013-12-27 2014-03-26 安徽省安庆市曙光化工股份有限公司 Method for preparing adiponitrile
CN103732323A (en) * 2011-06-10 2014-04-16 因温斯特技术公司 Nickel form for preparation of catalytic nickel-ligand complexes

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1745062A (en) * 2002-12-23 2006-03-08 罗狄亚聚酰胺中间体公司 Process of synthesis of compounds having nitrile functions from ethylenically unsaturated compounds
CN101484416A (en) * 2006-07-14 2009-07-15 因温斯特技术公司 Hydrocyanation process with reduced yield losses
CN101489992A (en) * 2006-07-14 2009-07-22 因温斯特技术公司 Process for making 3-pentenenitrile by hydrocyanation of butadiene
CN103732323A (en) * 2011-06-10 2014-04-16 因温斯特技术公司 Nickel form for preparation of catalytic nickel-ligand complexes
CN103012197A (en) * 2012-12-18 2013-04-03 安徽省安庆市曙光化工股份有限公司 Preparation method of 3-pentenenitrile and preparation method of adiponitrile
CN103664691A (en) * 2013-12-27 2014-03-26 安徽省安庆市曙光化工股份有限公司 Method for preparing adiponitrile

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113416152A (en) * 2021-08-02 2021-09-21 青岛普泰克化工有限公司 Method for preparing adiponitrile by reacting linear C5 monoalkene nitrile with hydrogen cyanide
WO2023060929A1 (en) * 2021-10-15 2023-04-20 浙江大学 Application of polydentate phosphite ligand in catalytic synthesis of adiponitrile

Similar Documents

Publication Publication Date Title
EP2044007B1 (en) Process for making 3-pentenenitrile by hydrocyanation of butadiene
EP2046729B1 (en) Hydrocyanation process with reduced yield losses
CN101479236B (en) Process for making 3-pentenenitrile by hydrocyanation of butadiene
KR101152563B1 (en) Method for producing linear pentenenitrile
US7709675B2 (en) Continuous method for the production of linear pentene nitriles
US8278474B2 (en) Method for the separation of pentenenitrile isomers
US7919646B2 (en) Hydrocyanation of 2-pentenenitrile
CN113372239A (en) Method for preparing C5 monoalkene nitrile by reacting 1, 3-butadiene with hydrogen cyanide
WO1999006359A1 (en) Improved hydrocyanation process
JP2009543881A (en) Hydrocyanation with reduced yield loss
CA2640958A1 (en) Improved process for producing nickel(0)-phosphorus ligand complexes
EP2229354B1 (en) Process for making and refining 3-pentenenitrile, and for refining 2-methyl-3-butenenitrile
CN113416152A (en) Method for preparing adiponitrile by reacting linear C5 monoalkene nitrile with hydrogen cyanide
KR20150021545A (en) Stable ligand mixtures and processes for making same
WO2023228077A1 (en) Multidentate phosphite ligands, catalytic compositions containing such ligands, and catalytic processes utilizing such catalytic compositions
CN109651195A (en) The method of 2- allyl acetonitrile isomerization reaction generation 3 pentene nitrile
WO2024028718A1 (en) Bidfntate phosphite ligands. catalytic compositions containing such ligands. and catalytic processes utilizing such catalytic compositions
WO2024028717A1 (en) Arsenic-containing ligands, catalytic compositions containing such ligands, and catalytic processes utilizing such catalytic compositions
WO2024028722A1 (en) Bidentate phosphite ligands, catalytic compositions containing such ligands, and catalytic processes utilizing such catalytic compositions
CN109721508A (en) A method of preparing 3 pentene nitrile

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