CN103664691B - Prepare the method for adiponitrile - Google Patents
Prepare the method for adiponitrile Download PDFInfo
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- CN103664691B CN103664691B CN201310749806.6A CN201310749806A CN103664691B CN 103664691 B CN103664691 B CN 103664691B CN 201310749806 A CN201310749806 A CN 201310749806A CN 103664691 B CN103664691 B CN 103664691B
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- adiponitrile
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- 238000000034 method Methods 0.000 title claims abstract description 57
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 title claims abstract description 45
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims abstract description 129
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 116
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000005669 hydrocyanation reaction Methods 0.000 claims abstract description 73
- 239000000203 mixture Substances 0.000 claims abstract description 58
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 58
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003446 ligand Substances 0.000 claims abstract description 40
- UVKXJAUUKPDDNW-NSCUHMNNSA-N (e)-pent-3-enenitrile Chemical compound C\C=C\CC#N UVKXJAUUKPDDNW-NSCUHMNNSA-N 0.000 claims abstract description 38
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 230000000694 effects Effects 0.000 claims abstract description 6
- 239000002841 Lewis acid Substances 0.000 claims abstract description 5
- 150000007517 lewis acids Chemical group 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 18
- 238000005516 engineering process Methods 0.000 claims description 10
- -1 phosphinic acid ester Chemical class 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 7
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 150000003003 phosphines Chemical class 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 abstract description 22
- 239000006227 byproduct Substances 0.000 abstract description 18
- 238000006317 isomerization reaction Methods 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000000470 constituent Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- ISBHMJZRKAFTGE-UHFFFAOYSA-N pent-2-enenitrile Chemical compound CCC=CC#N ISBHMJZRKAFTGE-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- FDLFMPKQBNPIER-UHFFFAOYSA-N 1-methyl-3-(3-methylphenoxy)benzene Chemical compound CC1=CC=CC(OC=2C=C(C)C=CC=2)=C1 FDLFMPKQBNPIER-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- FEVFLQDDNUQKRY-UHFFFAOYSA-N tris(4-methylphenyl) phosphite Chemical compound C1=CC(C)=CC=C1OP(OC=1C=CC(C)=CC=1)OC1=CC=C(C)C=C1 FEVFLQDDNUQKRY-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method preparing adiponitrile, the method comprises: make divinyl and the first prussic acid, under the effect of catalyzer, the first hydrocyanation reaction occur, to obtain the first mixture; First separation is carried out to each component of the first mixture, to obtain the second mixture, residue divinyl and residue the first prussic acid respectively; In the second mixture, add promotor, and pass into the second prussic acid, to obtain the 3rd mixture containing adiponitrile; Second separation is carried out to the 3rd mixture, to obtain adiponitrile, residue 3 pentene nitrile respectively, to remain the second prussic acid, reacted catalyzer and reacted promotor, wherein, described catalyzer is the title complex that monodentate phosphine ligand, bidentate phosphine ligands and zero-valent nickel form, and described promotor is Lewis acid.Utilize the method to prepare adiponitrile, by product is few, and without the need to carrying out 2M3BN isomerization reaction, technique is simple, and cost is low, yield is high, good product quality, economic environmental protection.
Description
Technical field
The present invention relates to chemical field, in particular to the preparation method of adiponitrile.
Background technology
Divinyl hydrocyanation adiponitrile technique is that du pont company succeeds in developing at 20 century 70s and is applied to industrial production.At present, divinyl hydrocyanation adiponitrile mainly adopts monodentate phosphine-zero valent nickel complex to be catalyzer, mainly comprise following three reactions steps (Ma Yuan, Yu Baowei, Zhang Haiyan, adiponitrile production technology compares, Henan chemical industry, 24th volume (8) in 2007,4-6, is incorporated to herein in full by referring to by it):
First, there is hydrocyanation reaction in divinyl (BD) and prussic acid (HCN) under monodentate phosphine-zero-valent nickel complexes catalysis, generates straight chain product 3 pentene nitrile (3PN) and branched byproduct 2-methyl-3-crotononitrile (2M3BN); Then, there is isomerization reaction in 2M3BN, generates 3-PN; Finally, there is hydrocyanation reaction in 3PN and prussic acid (HCN), obtains target product adiponitrile (ADN).The technique of this divinyl hydrocyanation adiponitrile, be the most mature and reliable of current technique, cost is lower, of reduced contamination, quality product and the higher adiponitrile preparation technology of yield.
But the method preparing adiponitrile of present stage still haves much room for improvement.
Summary of the invention
The present invention completes based on the following discovery of contriver:
Contriver finds, current divinyl hydrocyanation adiponitrile technique (as previously mentioned), carry out in hydrocyanation reaction process at divinyl and prussic acid, generate more by product 2M3BN because adopting monodentate phosphine-zero valent nickel complex catalyzer, 2M3BN:3PN maintains between 1.5:1 ~ 1:2.5.And due to 2M3BN can with prussic acid generation hydrocyanation reaction, obtain by product 2-methyl cellosolve acetate glutaronitrile, thus reduce the yield of target product ADN.And then in order to improve productive rate, this by product must be carried out isomerization reaction so that 2M3BN is changed into 3PN, then obtaining more target product AND by 3PN is carried out hydrocyanation reaction.But, the separation of 2M3BN and the production cost needed for isomerization reaction and facility investment expense very high; And the high temperature demands of the separation of 2M3BN and isomerization reaction and longer high-temperature residence time, can cause that the catalyzer of thermo-sensitivity dissociates, inactivation, thus the consumption of catalyzer and the cost of catalyst regeneration can be increased.Therefore, whole process costs is high, yield is low, complex process.
The present invention is intended at least to solve one of technical problem existed in prior art.For this reason, one object of the present invention be to propose that a kind of technique is simple, cost is low, yield is high, good product quality, less energy consumption, economic environmental protection the method preparing adiponitrile.
According to an aspect of the present invention, the invention provides a kind of method preparing adiponitrile.According to embodiments of the invention, the method comprises the following steps: make divinyl and the first prussic acid, under the effect of catalyzer, the first hydrocyanation reaction occur, to obtain the first mixture containing 3 pentene nitrile; First separation is carried out to each component of described first mixture, to obtain the second mixture, residue divinyl and residue the first prussic acid respectively; In described second mixture, add promotor, and pass into the second prussic acid, to make the 3 pentene nitrile in described second mixture and described second prussic acid that the second hydrocyanation reaction occur, obtain the 3rd mixture containing adiponitrile; And the second separation is carried out to described 3rd mixture, to obtain adiponitrile, residue 3 pentene nitrile respectively, to remain the second prussic acid, reacted catalyzer and reacted promotor, wherein, described catalyzer is the title complex that monodentate phosphine ligand, bidentate phosphine ligands and zero-valent nickel form, and described promotor is Lewis acid.
Contriver is surprised to find, utilize method of the present invention can prepare quality efficiently good, the adiponitrile that purity is high, and, the method adopts monodentate phosphine ligand, the title complex that bidentate phosphine ligands and zero-valent nickel form is catalyzer, with divinyl and prussic acid for adiponitrile prepared by raw material, divinyl and prussic acid react the branched by-product 2M3BN generated significantly to be reduced, the yield of 3PN significantly rises, ratio 2M3BN:3PN between the two can reach more than 1:25, thus without the need to carrying out isomerization reaction, and this incites somebody to action simplification of flowsheet greatly, reduce production cost and facility investment expense.Namely relative to prior art, method of the present invention is without the need to carrying out the step of isomerization reaction by 2-methyl-3-crotononitrile (2M3BN), technique is simple to operation, and cost is low, less investment, yield are high, good product quality, less energy consumption, economic environmental protection.
In addition, following additional technical characteristic can also be had according to the method preparing adiponitrile of the embodiment of the present invention:
According to embodiments of the invention, in the catalyst, the mol ratio of described monodentate phosphine ligand and described bidentate phosphine ligands and described zero-valent nickel is (4 ~ 10): (1 ~ 8): 1, preferably (5 ~ 7): (2 ~ 5): 1.Thus, the complex-catalyzed performance that monodentate phosphine ligand, bidentate phosphine ligands and zero-valent nickel form is good, and namely catalyzer is to the excellent catalytic effect of the first hydrocyanation reaction of divinyl and prussic acid, and by product is few.Wherein, according to some embodiments of the present invention, described monodentate phosphine ligand from least one of phosphine class, phosphorous acid esters, phosphiinic acid ester and phosphinic acid ester, preferred phosphorous acid esters, more preferably tricresyl phosphite.According to embodiments of the invention, described bidentate phosphine ligands is from least one of phosphine class, phosphorous acid esters, phosphiinic acid ester and phosphinic acid ester, and preferred phosphorous acid esters, more preferably containing the phosphorous acid aromatic hydrocarbons ester class that ortho position replaces.According to embodiments of the invention, described promotor is for being selected from triphenyl-boron, ZnCl
2, FeCl
2, ZnBr
2, SnCl
2and SnBr
2in at least one, preferred triphenyl-boron and ZnCl
2.According to some embodiments of the present invention, the mol ratio of described promotor and described zero-valent nickel is 1:0.5-2.Thus, the second hydrocyanation reaction efficiency is high, and namely 3 pentene nitrile and described second prussic acid can fully react.
According to some embodiments of the present invention, in 60-120 degree Celsius of preferred 70-100 degree Celsius, carry out described first hydrocyanation reaction 4-6 hour under the condition of the preferred 1.0-1.8MPa of 0.5-2.5MPa.
According to embodiments of the invention, in 60-120 degree Celsius of preferred 80-100 degree Celsius, carry out described second hydrocyanation reaction 4-6 hour under the condition of the preferred 0.15-0.35MPa of 0.1-0.5MPa.
According to embodiments of the invention, utilize distillation technology to carry out described first and be separated, utilize rectifying and abstraction technique to carry out described second and be separated.Particularly, utilize the difference of each component boiling point, adopt distillation technology to carry out described first and be separated; Utilize the difference of the difference of each component boiling point and each component solubleness in a solvent, adopt rectifying to carry out described second with abstraction technique and be separated.
According to embodiments of the invention, described residue divinyl and described residue first prussic acid are returned for described first hydrocyanation reaction.
According to embodiments of the invention, described residue 3 pentene nitrile, described residue second prussic acid and described reacted promotor are returned for described second hydrocyanation reaction, described reacted catalyzer is returned for described first hydrocyanation reaction.
According to embodiments of the invention, any one that be selected from tank reactor, multi-continuous stirred tank reactor and tubular reactor is utilized to carry out described first hydrocyanation reaction and described second hydrocyanation reaction.
Additional aspect of the present invention and advantage will part provide in the following description, and part will become obvious from the following description, or be recognized by practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage will become obvious and easy understand from accompanying drawing below combining to the description of embodiment, wherein:
Fig. 1 shows the schematic flow sheet of the method preparing adiponitrile according to an embodiment of the invention;
Fig. 2 shows according to one embodiment of the invention, prepares the schematic flow sheet of the general method of adiponitrile.
Embodiment
Be described below in detail embodiments of the invention, the example of described embodiment is shown in the drawings.Being exemplary below by the embodiment be described with reference to the drawings, only for explaining the present invention, and can not limitation of the present invention being interpreted as.
It should be noted that, term " first ", " second " only for describing object, and can not be interpreted as instruction or hint relative importance or imply the quantity indicating indicated technical characteristic.Thus, be limited with " first ", the feature of " second " can express or impliedly comprise one or more these features.Further, in describing the invention, except as otherwise noted, the implication of " multiple " is two or more.
As previously mentioned, according to an aspect of the present invention, the invention provides a kind of method preparing adiponitrile.Contriver finds, utilize method of the present invention can prepare quality efficiently good, the adiponitrile that purity is high, and, the method adopts monodentate phosphine ligand, the title complex that bidentate phosphine ligands and zero-valent nickel form is catalyzer, with divinyl and prussic acid for adiponitrile prepared by raw material, divinyl and prussic acid react the branched by-product 2M3BN generated significantly to be reduced, the yield of 3PN significantly rises, ratio 2M3BN:3PN between the two can reach more than 1:25, thus without the need to carrying out isomerization reaction, and this incites somebody to action simplification of flowsheet greatly, reduce production cost and facility investment expense.Namely relative to prior art, method of the present invention is without the need to carrying out the step of isomerization reaction by 2-methyl-3-crotononitrile (2M3BN), technique is simple to operation, and cost is low, less investment, yield are high, good product quality, less energy consumption, economic environmental protection.
Below in conjunction with Fig. 1, the method preparing adiponitrile of the present invention is described in detail.Particularly, according to embodiments of the invention, with reference to Fig. 1, the method comprises the following steps:
S100: the first hydrocyanation reaction
Make divinyl and the first prussic acid, under the effect of catalyzer, the first hydrocyanation reaction occur, to obtain the first mixture containing 3 pentene nitrile, wherein, described catalyzer is the title complex that monodentate phosphine ligand, bidentate phosphine ligands and zero-valent nickel form.
Wherein, according to embodiments of the invention, in the catalyst, the ratio of described monodentate phosphine ligand and described bidentate phosphine ligands and described zero-valent nickel is not particularly limited, according to concrete examples more of the present invention, the mol ratio of described monodentate phosphine ligand and described bidentate phosphine ligands and described zero-valent nickel is (4 ~ 10): (1 ~ 8): 1, preferably (5 ~ 7): (2 ~ 5): 1.Thus, the complex-catalyzed performance that monodentate phosphine ligand, bidentate phosphine ligands and zero-valent nickel form is good, and namely catalyzer is to the excellent catalytic effect of the first hydrocyanation reaction of divinyl and prussic acid, and by product is few.Wherein, the concrete kind of described monodentate phosphine ligand and bidentate phosphine ligands is also not particularly limited, as long as the compound that three is formed Butadiene and prussic acid the first hydrocyanation reaction can occur effectively.According to some embodiments of the present invention, described monodentate phosphine ligand from least one of phosphine class, phosphorous acid esters, phosphiinic acid ester and phosphinic acid ester, preferred phosphorous acid esters, more preferably tricresyl phosphite.According to embodiments of the invention, described bidentate phosphine ligands is from least one of phosphine class, phosphorous acid esters, phosphiinic acid ester and phosphinic acid ester, preferred phosphorous acid esters, more preferably containing the phosphorous acid aromatic hydrocarbons ester class that ortho position replaces, the such as compound shown in formula I, II, III:
In addition, according to preferred embodiments more of the present invention, catalyzer of the present invention is monodentate phosphine ligand tricresyl phosphite, the phosphorous acid aromatic hydrocarbons ester class of bidentate phosphine ligands containing ortho position replacement and the title complex of zero-valent nickel composition.
According to embodiments of the invention, the equipment that the first hydrocyanation reaction adopts and required reaction conditions are not particularly limited, as long as can ensure that divinyl and the first prussic acid fully react, and by product less.According to some embodiments of the present invention, in 60-120 degree Celsius of preferred 70-100 degree Celsius, carry out described first hydrocyanation reaction 4-6 hour under the condition of the preferred 1.0-1.8MPa of 0.5-2.5MPa.According to other embodiments of the present invention, any one that be selected from tank reactor, multi-continuous stirred tank reactor and tubular reactor is utilized to carry out described first hydrocyanation reaction.Thereby, it is possible to make divinyl and the first prussic acid fully react, by product is few.
S200: the first is separated
First separation is carried out to each component of described first mixture, to obtain the second mixture, residue divinyl and residue the first prussic acid respectively.
It should be noted that, the main component of described first mixture is: 3 pentene nitrile, catalyzer, residue divinyl, remain the first prussic acid and a small amount of by product.Wherein, 3 pentene nitrile and catalyzer are the reaction raw materials of follow-up generation object product adiponitrile, and remain divinyl and residue the first prussic acid can be recovered utilization, thus, in order to ensure carrying out smoothly of subsequent reactions, and residue reaction raw materials is made full use of, need the 3 pentene nitrile in the first mixture and catalyzer, with residue divinyl with remain the first prussic acid and be effectively separated.According to embodiments of the invention, based on the difference of each component boiling point in the first mixture, adopt general chemical industry distillation technique, by containing the light constituent of divinyl and Microamounts of Hydrogen cyanic acid in the first mixture, rectifying separation effectively can be carried out with the heavy constituent (i.e. the second mixture) containing 3 pentene nitrile and catalyzer.According to embodiments of the invention, utilize distillation technology to carry out described first and be separated.According to concrete examples more of the present invention, adopt rectifying tower to carry out described rectifying, the plate tower number of described rectifying tower is 20 ~ 50, tower top pressure is 0.02 ~ 0.10MPa, tower reactor pressure is 0.01 ~ 0.2MPa, and the temperature of tower top is-20 ~ 0 degree Celsius, and bottom temperature is 100 ~ 140 degrees Celsius.Thus, separation efficiency is high, effective.
Further, according to embodiments of the invention, described residue divinyl and described residue first prussic acid are returned for described first hydrocyanation reaction, namely contain the light constituent of divinyl and Microamounts of Hydrogen cyanic acid by the raw material returned as the first hydrocyanation reaction; Containing heavy constituent i.e. second mixture of 3 pentene nitrile and catalyzer by as the raw material of the second hydrocyanation reaction and catalyzer.Thereby, it is possible to make full use of surplus stock, science environmental protection, economically feasible, and the carrying out needing reaction after being conducive to.
S300: the second hydrocyanation reaction
Promotor is added in described second mixture, and pass into the second prussic acid, to make the 3 pentene nitrile in described second mixture and described second prussic acid that the second hydrocyanation reaction occur, obtain the 3rd mixture containing adiponitrile, wherein, described promotor is Lewis acid.
According to embodiments of the invention, the lewis acidic concrete kind that described promotor adopts also is not particularly limited.According to concrete examples more of the present invention, described promotor is for being selected from triphenyl-boron, ZnCl
2, FeCl
2, ZnBr
2, SnCl
2and SnBr
2in at least one, preferred triphenyl-boron and ZnCl
2.According to some embodiments of the present invention, the mol ratio of described promotor and described zero-valent nickel is 1:0.5-2.
Thus, the second hydrocyanation reaction efficiency is high, and namely 3 pentene nitrile and described second prussic acid can fully react.
According to embodiments of the invention, the equipment that the second hydrocyanation reaction adopts and required reaction conditions are also not particularly limited, as long as can ensure that 3 pentene nitrile and the second prussic acid fully react.According to embodiments of the invention, in 60-120 degree Celsius of preferred 80-100 degree Celsius, carry out described second hydrocyanation reaction 4-6 hour under the condition of the preferred 0.15-0.35MPa of 0.1-0.5MPa.According to other embodiments of the present invention, any one that be selected from tank reactor, multi-continuous stirred tank reactor and tubular reactor is utilized to carry out described second hydrocyanation reaction.Thereby, it is possible to make 3 pentene nitrile and the second prussic acid fully react, by product is few.
S400: the second is separated
Second separation is carried out to described 3rd mixture, so as to obtain respectively adiponitrile, residue 3 pentene nitrile, remain the second prussic acid, described catalyzer and described promotor.
It should be noted that, the main component of described 3rd mixture is: adiponitrile, residue 3 pentene nitrile, remain the second prussic acid, catalyzer, promotor and a small amount of by product.Wherein, product for the purpose of adiponitrile, and remain 3 pentene nitrile, remain the second prussic acid, reacted catalyzer and the equal recoverable of promotor, thus, in order to purified product, and reaction raw materials is reclaimed, to make full use of, realize the object of energy-conserving and environment-protective, need to be separated each component in the 3rd mixture, and remove by product.According to embodiments of the invention, based on each component boiling point and deliquescent difference in the 3rd mixture, general chemical industry distillation and abstraction technique is adopted (such as to can refer to the method in CN200580003700.5, be incorporated in full herein by referring to by it), each component in the 3rd mixture can be separated effectively.
According to embodiments of the invention, described residue 3 pentene nitrile, described residue second prussic acid and reacted promotor are returned for described second hydrocyanation reaction, reacted catalyzer is returned for described first hydrocyanation reaction.
Below in conjunction with embodiment, the solution of the present invention is made an explanation.It will be understood to those of skill in the art that the following examples only for illustration of the present invention, and should not be considered as limiting scope of the present invention.Unreceipted concrete technology or condition in embodiment, according to the technology described by the document in this area or condition or carry out according to product description.Agents useful for same or the unreceipted production firm person of instrument, being can by the conventional products of commercial acquisition.
General method:
With reference to Fig. 2, the method preparing adiponitrile of the following embodiment of the present invention, generally has following flow process:
A) hydrocyanation I: divinyl and prussic acid, under the effect of catalyzer, hydrocyanation reaction is occurred, obtains the mixture 1 containing 3 pentene nitrile, and wherein said catalyzer is the title complex that monodentate phosphine ligand, bidentate phosphine ligands and zero-valent nickel form.
B) be separated I: described mixture 1 is carried out rectifying separation, obtain the mixture 2 as heavy constituent and the divinyl as light constituent and prussic acid, described mixture 2 is containing 3 pentene nitrile and described catalyzer.And isolated divinyl and prussic acid are returned the raw material as hydrocyanation I; Divinyl and prussic acid will be removed, and containing the mixture 2 of 3 pentene nitrile and catalyzer as the raw material of hydrocyanation II and catalyzer.
C) hydrocyanation II: the 3 pentene nitrile in mixture 2 is under the effect of catalyzer and promotor, and with prussic acid generation hydrocyanation reaction, obtain the mixture 3 containing adiponitrile, wherein said promotor is Lewis acid.
D) product separation II: with distillation technology, each component in mixture 3 is separated by extraction, and the raw material isolated 3 pentene nitrile, prussic acid and catalyzer returned as divinyl hydrocyanation reaction and catalyzer; Then adiponitrile product is obtained after being removed by by product.
Embodiment 1:
A) hydrocyanation I: the title complex that monodentate phosphine (tricresyl phosphite m-tolyl ester) and bidentate phosphine (compound shown in formula I) and zero-valent nickel formed is (in the title complex that monodentate phosphine and bidentate phosphine and zero-valent nickel form, monodentate phosphine: bidentate phosphine: the mol ratio of zero-valent nickel is 6:2:1), HCN(prussic acid) and BD(divinyl) in molar ratio for 6:115:165 drops in tank reactor, control temperature of reaction is 100 DEG C, pressure is 1.0MPa, reaction stop is 4 hours, to obtain the mixture 1 containing 3 pentene nitrile.
B) I is separated: introduced by the mixture 1 of gained and be separated I(rectifying tower).This rectifying tower adopts stage number to be the rectifying tower of 50, and wherein, the tower top pressure of rectifying tower is 0.05MPa, and tower reactor pressure is 0.06MPa, and the temperature of tower top is 40 degrees Celsius, and bottom temperature is 135 degrees Celsius.Containing 3 pentene nitrile, a small amount of by product and catalyzer in the tower reactor heavy constituent mixture 2 of rectifying tower.Containing the light constituent such as unreacted raw material divinyl and prussic acid in the column overhead light constituent of rectifying tower, this light constituent is returned to hydrocyanation reaction device, as the raw material of hydrocyanation reaction.
C) hydrocyanation II: introduce in the tank reactor of hydrocyanation II by above-mentioned heavy constituent mixture 2, carries out further 3 pentene nitrile hydrocyanation reaction.
Then, in this tank reactor, be that 1:0.5 adds promotor ZnCl by promotor and zero-valent nickel mol ratio
2, be that 115:6 adds prussic acid according to the mol ratio of prussic acid and zero-valent nickel, control that temperature of reaction is 80 DEG C, pressure is 0.1MPa, reaction stop is 6 hours, so that from obtaining mixture 3.
D) product separation II: output mixture 3 from the tank reactor of hydrocyanation II, through multiple rectifying and extracting and separating operation, makes each component be separated.Concrete grammar refers to CN200580003700.5, and at this, description is omitted.And the raw material isolated 3 pentene nitrile, prussic acid and catalyzer returned as divinyl hydrocyanation reaction and catalyzer; Then adiponitrile product is obtained after solvent and by product being removed.
Finally, through detecting, in the present embodiment, the total recovery through this reaction process gained divinyl is greater than 83.9%, and product adiponitrile purity is 99.5%.
Embodiment 2:
A) hydrocyanation I: the title complex that monodentate phosphine (tricresyl phosphite o-toluene ester) and bidentate phosphine (compound shown in formula II) and zero-valent nickel formed is (in the title complex that monodentate phosphine and bidentate phosphine and zero-valent nickel form, monodentate phosphine: bidentate phosphine: the mol ratio of zero-valent nickel is 5:5:1), HCN and BD be in molar ratio for 6:115:165 drops in tank reactor, control temperature of reaction is 70 DEG C, pressure is 1.8MPa, reaction stop is 4 hours, to obtain the mixture 1 containing 3 pentene nitrile.
B) I is separated:
Identical with embodiment 1.
C) hydrocyanation II: introduce in the tank reactor of hydrocyanation II by above-mentioned heavy constituent mixture 2, carries out further 3 pentene nitrile hydrocyanation reaction.
Then, to in this tank reactor, be that 1:2 adds promotor triphenyl-boron by promotor and zero-valent nickel mol ratio, be that 115:6 adds prussic acid according to the mol ratio of prussic acid and zero-valent nickel, control temperature of reaction is 100 DEG C, pressure is 0.35MPa, reaction stop is 4 hours, so that from obtaining mixture 3.
D) product separation II:
Identical with embodiment 1.
Finally, through detecting, in the present embodiment, the total recovery through this reaction process gained divinyl is greater than 83.5%, and product adiponitrile purity is 99.6%.
Embodiment 3:
A) hydrocyanation I: the title complex that monodentate phosphine (tri-p-cresyl phosphite) and bidentate phosphine (compound shown in formula III) and zero-valent nickel formed is (in the title complex that monodentate phosphine and bidentate phosphine and zero-valent nickel form, monodentate phosphine: bidentate phosphine: the mol ratio of zero-valent nickel is 7:2:1), HCN and BD be in molar ratio for 6:115:165 drops in tank reactor, control temperature of reaction is 90 DEG C, pressure is 1.8MPa, reaction stop is 4 hours, to obtain the mixture 1 containing 3 pentene nitrile.
B) I is separated:
Identical with embodiment 1.
C) hydrocyanation II: introduce in the tank reactor of hydrocyanation II by above-mentioned heavy constituent mixture 2, carries out further 3 pentene nitrile hydrocyanation reaction.
Then, in this tank reactor, be that 1:1 adds promotor ZnCl by promotor and zero-valent nickel mol ratio
2, be that 115:6 adds prussic acid according to the mol ratio of prussic acid and zero-valent nickel, it is 80 DEG C, pressure 0.1MPa that temperature of reaction controls, and reaction stop is 5 hours, so that from obtaining mixture 3.
D) product separation II:
Identical with embodiment 1.
Finally, through detecting, in the present embodiment, the total recovery through this reaction process gained divinyl is greater than 80.5%, and product adiponitrile purity is 99.4%.
In the description of this specification sheets, specific features, structure, material or feature that the description of reference term " embodiment ", " some embodiments ", " example ", " concrete example " or " some examples " etc. means to describe in conjunction with this embodiment or example are contained at least one embodiment of the present invention or example.In this manual, identical embodiment or example are not necessarily referred to the schematic representation of above-mentioned term.And the specific features of description, structure, material or feature can combine in an appropriate manner in any one or more embodiment or example.
Although illustrate and describe embodiments of the invention, those having ordinary skill in the art will appreciate that: can carry out multiple change, amendment, replacement and modification to these embodiments when not departing from principle of the present invention and aim, scope of the present invention is by claim and equivalents thereof.
Claims (18)
1. prepare a method for adiponitrile, it is characterized in that, comprise the following steps:
Make divinyl and the first prussic acid, under the effect of catalyzer, the first hydrocyanation reaction occur, to obtain the first mixture containing 3 pentene nitrile;
First separation is carried out to each component of described first mixture, to obtain the second mixture, residue divinyl and residue the first prussic acid respectively;
In described second mixture, add promotor, and pass into the second prussic acid, to make the 3 pentene nitrile in described second mixture and described second prussic acid that the second hydrocyanation reaction occur, obtain the 3rd mixture containing adiponitrile; And
Second separation is carried out to described 3rd mixture, so as to obtain respectively adiponitrile, residue 3 pentene nitrile, remain the second prussic acid, reacted catalyzer and reacted promotor,
Wherein, described catalyzer is the title complex that monodentate phosphine ligand, bidentate phosphine ligands and zero-valent nickel form, and described promotor is Lewis acid,
In the catalyst, the mol ratio of described monodentate phosphine ligand and described bidentate phosphine ligands and described zero-valent nickel is (5 ~ 7): (2 ~ 5): 1.
2. method according to claim 1, is characterized in that, described monodentate phosphine ligand is from least one of phosphine class, phosphorous acid esters, phosphiinic acid ester and phosphinic acid ester.
3. method according to claim 2, is characterized in that, described monodentate phosphine ligand is phosphorous acid esters.
4. method according to claim 3, is characterized in that, described monodentate phosphine ligand is tricresyl phosphite.
5. method according to claim 1, is characterized in that, described bidentate phosphine ligands is from least one of phosphine class, phosphorous acid esters, phosphiinic acid ester and phosphinic acid ester.
6. method according to claim 5, is characterized in that, described bidentate phosphine ligands is phosphorous acid esters.
7. method according to claim 6, is characterized in that, described bidentate phosphine ligands is the phosphorous acid aromatic hydrocarbons ester class replaced containing ortho position.
8. method according to claim 1, is characterized in that, described promotor is for being selected from triphenyl-boron, ZnCl
2, FeCl
2, ZnBr
2, SnCl
2and SnBr
2in at least one.
9. method according to claim 8, is characterized in that, described promotor is triphenyl-boron and ZnCl
2.
10. method according to claim 1, is characterized in that, the mol ratio of described promotor and described zero-valent nickel is 1:0.5-2.
11. methods according to claim 1, is characterized in that, in 60-120 degree Celsius, carry out described first hydrocyanation reaction under the condition of 0.5-2.5MPa.
12. methods according to claim 11, is characterized in that, in 70-100 degree Celsius, carry out described first hydrocyanation reaction under the condition of 1.0-1.8MPa.
13. methods according to claim 1, is characterized in that, in 60-120 degree Celsius, carry out described second hydrocyanation reaction under the condition of 0.1-0.5MPa.
14. methods according to claim 13, is characterized in that, in 80-100 degree Celsius, carry out described second hydrocyanation reaction under the condition of 0.15-0.35MPa.
15. methods according to claim 1, is characterized in that, utilize distillation technology to carry out described first and are separated, utilize rectifying and abstraction technique to carry out described second and be separated.
16. methods according to claim 1, is characterized in that, return described residue divinyl and described residue first prussic acid for described first hydrocyanation reaction.
17. methods according to claim 1, it is characterized in that, described residue 3 pentene nitrile, described residue second prussic acid and described reacted promotor are returned for described second hydrocyanation reaction, described reacted catalyzer is returned for described first hydrocyanation reaction.
18. methods according to claim 1, is characterized in that, utilize any one that be selected from tank reactor, multi-continuous stirred tank reactor and tubular reactor to carry out described first hydrocyanation reaction and described second hydrocyanation reaction.
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| CN105017073A (en) * | 2015-07-20 | 2015-11-04 | 重庆中平紫光科技发展有限公司 | Recycle method of hydrocyanation catalyst for butadiene-based synthesis of adiponitrile |
| CN105130845B (en) * | 2015-07-20 | 2017-05-10 | 重庆中平紫光科技发展有限公司 | Method of inhibiting degradation of zero-valent nickel in synthesis of adiponitrile through butadiene method |
| CN106975519B (en) * | 2015-09-23 | 2021-09-07 | 英威达纺织（英国）有限公司 | Method for preparing a catalyst system for hydrocyanation and isomerization |
| CN108640854A (en) * | 2018-04-28 | 2018-10-12 | 山东豪迈化工技术有限公司 | A kind of synthetic method of adiponitrile |
| CN111892514A (en) * | 2020-08-13 | 2020-11-06 | 阳泉煤业（集团）有限责任公司 | Method for preparing adiponitrile by direct hydrocyanation of butadiene |
| CN113372239A (en) * | 2021-07-21 | 2021-09-10 | 青岛普泰克化工有限公司 | Method for preparing C5 monoalkene nitrile by reacting 1, 3-butadiene with hydrogen cyanide |
| CN113912516B (en) * | 2021-10-15 | 2023-06-27 | 浙江新和成股份有限公司 | Application of multidentate phosphite ligand in catalytic synthesis of adiponitrile |
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