CN103804229A - Method for inhibiting degradation of phosphorus containing ligand in process of synthesizing adiponitrile via butadiene method - Google Patents
Method for inhibiting degradation of phosphorus containing ligand in process of synthesizing adiponitrile via butadiene method Download PDFInfo
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- CN103804229A CN103804229A CN201410052747.1A CN201410052747A CN103804229A CN 103804229 A CN103804229 A CN 103804229A CN 201410052747 A CN201410052747 A CN 201410052747A CN 103804229 A CN103804229 A CN 103804229A
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- containing ligand
- phosphorus
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- nickel catalyst
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003446 ligand Substances 0.000 title claims abstract description 54
- 239000011574 phosphorus Substances 0.000 title claims abstract description 54
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 54
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 48
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 230000008569 process Effects 0.000 title claims abstract description 23
- 230000015556 catabolic process Effects 0.000 title abstract description 12
- 238000006731 degradation reaction Methods 0.000 title abstract description 12
- 230000002194 synthesizing effect Effects 0.000 title abstract 3
- 230000002401 inhibitory effect Effects 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000005669 hydrocyanation reaction Methods 0.000 claims abstract description 24
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 18
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 12
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims abstract description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 6
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 14
- 150000007530 organic bases Chemical class 0.000 claims description 13
- UVKXJAUUKPDDNW-NSCUHMNNSA-N (e)-pent-3-enenitrile Chemical compound C\C=C\CC#N UVKXJAUUKPDDNW-NSCUHMNNSA-N 0.000 claims description 12
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 claims description 12
- 239000002841 Lewis acid Substances 0.000 claims description 12
- 150000007517 lewis acids Chemical class 0.000 claims description 12
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 12
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 6
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 5
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000007115 recruitment Effects 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 abstract 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 abstract 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- 230000009466 transformation Effects 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- ISBHMJZRKAFTGE-UHFFFAOYSA-N pent-2-enenitrile Chemical compound CCC=CC#N ISBHMJZRKAFTGE-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 235000019605 sweet taste sensations Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for inhibiting degradation of phosphorus containing ligand in process of synthesizing adiponitrile via a butadiene method, and the method comprises the step of adding organic alkali in isomerization reaction and secondary hydrocyanation reaction, wherein the organic alkali comprises triethylamine, diethylamine, dimethylamine, hexamethylenediamine, pyridine, phenylamine, phenylamine and N,N-dimethylaniline or N,N-diethylaniline. According to the method, organic alkali is added in the isomerization reaction and secondary hydrocyanation reaction, then the degradation of the phosphorus containing ligand in the isomerization reaction and secondary hydrocyanation reaction is effectively inhibited, and the degradation rate of the phosphorus containing ligand is controlled within 5%, so that the magnitude of recruitment of the phosphorus containing ligand is decreased, the separation recovery rate of the zero-valence nickel catalyst and the phosphorus containing ligand is improved at the same time and the raw material cost for synthesizing the adiponitrile via the butadiene method is reduced; and the method provided by the invention does not influence the conversion rate and the selectivity of the isomerization reaction and secondary hydrocyanation reaction.
Description
Technical field
The present invention relates to the production technical field of adiponitrile, relate to a kind of method that suppresses phosphorus-containing ligand degraded in butadiene process Adiponitrile.
Background technology
Adiponitrile molecular formula is CN(CH
2)
4cN, English is abbreviated as ADN, is one of main raw material of producing type material nylon 66, and its proterties is colourless oil liquid, is slightly with sweet taste, toxic and corrodibility, density is 962g/cm
2, 1 ℃ of fusing point, 295 ℃ of boiling points (1atm).In addition, it also has wide application in electronics, light industry and other organic synthesis field.
The synthetic method of adiponitrile is more, and the operational path of producing at present adiponitrile mainly contains two kinds of Electrolytic Dimeric Acrylonitrile method and butadiene processs.Butadiene process Adiponitrile mainly divides hydrocyanation, isomerization, three steps of secondary hydrocyanation, and the reaction equation of these three steps is as follows:
Visible, zero-valent nickel catalyst and phosphorus-containing ligand participate in the three-step reaction of butadiene process Adiponitrile as homogeneous system, and the structural formula of phosphorus-containing ligand mainly contains following four kinds:
But, after isomerization, secondary hydrocyanation reaction finish, through isolating product, when Separation and Recovery zero-valent nickel catalyst and phosphorus-containing ligand carry out recycled, phosphorus-containing ligand degraded in system, degradation rate, 10%～20%, now needs to supplement a certain amount of phosphorus-containing ligand, need to reduce the Separation and Recovery rate of zero-valent nickel catalyst and phosphorus-containing ligand simultaneously, increased the raw materials cost of butadiene process Adiponitrile.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of method that suppresses phosphorus-containing ligand degraded in butadiene process Adiponitrile, can effectively suppress the degraded of phosphorus-containing ligand in isomerization reaction and secondary hydrocyanation reaction, reduce the raw materials cost of butadiene process Adiponitrile.
For achieving the above object, the invention provides following technical scheme:
The invention discloses the method that suppresses phosphorus-containing ligand degraded in the isomerization reaction of butadiene process Adiponitrile, 2-methyl-3-crotononitrile is mixed with zero-valent nickel catalyst, phosphorus-containing ligand, Lewis acid and organic bases, there is isomerization reaction, generate the product that comprises 3 pentene nitrile.
Further, described organic bases is triethylamine, diethylamine, dimethylamine, hexanediamine, pyridine, aniline, quadrol, DMA or N, N-Diethyl Aniline.
Further, described Lewis acid is zinc chloride, aluminum chloride, zinc sulfate, iron protochloride, iron(ic) chloride or tin tetrachloride, and described phosphorus-containing ligand is triphenyl phosphite, tricresyl phosphite o-toluene ester, tricresyl phosphite m-tolyl ester or tri-p-cresyl phosphite.
Further, the mol ratio of described 2-methyl-3-crotononitrile and zero-valent nickel catalyst is 30 ~ 100:1, the mol ratio of phosphorus-containing ligand and zero-valent nickel catalyst is 5 ~ 50:1, and the mol ratio of Lewis acid and zero-valent nickel catalyst is 1 ~ 50:1, and the mol ratio of organic bases and phosphorus-containing ligand is 1:10～100.
Further, the reaction pressure of described isomerization reaction is 0.1 ~ 0.2 Mpa, and temperature of reaction is 80 ~ 110 ℃, insulation reaction 6 ~ 24 hours.
The invention also discloses the method that suppresses phosphorus-containing ligand degraded in the secondary hydrocyanation reaction of butadiene process Adiponitrile, 3 pentene nitrile is mixed with prussic acid, zero-valent nickel catalyst, phosphorus-containing ligand, Lewis acid and organic bases, there is secondary hydrocyanation reaction, generate the product that comprises adiponitrile.
Further, described organic bases is triethylamine, diethylamine, dimethylamine, hexanediamine, pyridine, aniline, quadrol, DMA or N, N-Diethyl Aniline.
Further, described Lewis acid is zinc chloride, aluminum chloride, zinc sulfate, iron protochloride, iron(ic) chloride or tin tetrachloride, and described phosphorus-containing ligand is triphenyl phosphite, tricresyl phosphite o-toluene ester, tricresyl phosphite m-tolyl ester or tri-p-cresyl phosphite.
Further, the mol ratio of described 3 pentene nitrile and zero-valent nickel catalyst is 60 ~ 300:1, the mol ratio of prussic acid and zero-valent nickel catalyst is 30 ~ 100:1, the mol ratio of phosphorus-containing ligand and zero-valent nickel catalyst is 5 ~ 50:1, the mol ratio of Lewis acid and zero-valent nickel catalyst is 1 ~ 10:1, and the mol ratio of organic bases and phosphorus-containing ligand is 1:10～100.
Further, the reaction pressure of described secondary hydrocyanation reaction is 0.2 ~ 0.5 Mpa, and temperature of reaction is 50 ~ 100 ℃, insulation reaction 3 ~ 5 hours.
Beneficial effect of the present invention is:
The present invention by adding organic bases in isomerization reaction and secondary hydrocyanation reaction, effectively suppress the degraded of phosphorus-containing ligand in isomerization reaction and secondary hydrocyanation reaction, phosphorus-containing ligand degradation rate is controlled in 5%, therefore reduced the magnitude of recruitment of phosphorus-containing ligand, can improve the Separation and Recovery rate of zero-valent nickel catalyst and phosphorus-containing ligand simultaneously, reduced the raw materials cost of butadiene process Adiponitrile, and the transformation efficiency of method of the present invention on isomerization reaction and secondary hydrocyanation reaction and selectivity are without impact.
Embodiment
In order to make object of the present invention, technical scheme and beneficial effect clearer, will be described in detail the preferred embodiments of the present invention below.
embodiment 1
2-methyl-3-crotononitrile, tricresyl phosphite o-toluene ester, zero-valent nickel catalyst, aluminum chloride and triethylamine are added in isomerization reactor with the mol ratio of 30:5:1:1:0.5, control reaction pressure is 0.1Mpa, temperature of reaction is 100 ℃, insulation reaction 12 hours; After reaction finishes, isolate product 3 pentene nitrile (3PN) and unreacted 2-methyl-3-crotononitrile (2M3BN) completely.It is that 95%, 3PN selectivity is 95% that high performance liquid chromatography (HPLC) records the transformation efficiency that in system, phosphorus-containing ligand degradation rate is 1.2%, 2M3BN.
embodiment 2
2-methyl-3-crotononitrile, triphenyl phosphite, zero-valent nickel catalyst, zinc chloride and diethylamine are added in isomerization reactor with the mol ratio of 80:10:1:30:0.2, and control reaction pressure is 0.1Mpa, and temperature of reaction is 110 ℃, insulation reaction 12 hours; After reaction finishes, isolate product 3 pentene nitrile (3PN) and unreacted 2-methyl-3-crotononitrile (2M3BN) completely.It is that 96%, 3PN selectivity is 95% that high performance liquid chromatography (HPLC) records the transformation efficiency that in system, phosphorus-containing ligand degradation rate is 2.1%, 2M3BN.
embodiment 3
By 2-methyl-3-crotononitrile, triphenyl phosphite, zero-valent nickel catalyst, zinc sulfate and N, accelerine adds in isomerization reactor with the mol ratio of 100:15:1:50:0.15, control reaction pressure is 0.1Mpa, and temperature of reaction is 100 ℃, insulation reaction 8 hours; After reaction finishes, isolate product 3 pentene nitrile (3PN) and unreacted 2-methyl-3-crotononitrile (2M3BN) completely.It is that 97%, 3PN selectivity is 97% that high performance liquid chromatography (HPLC) records the transformation efficiency that in system, phosphorus-containing ligand degradation rate is 3%, 2M3BN.
embodiment 4
3 pentene nitrile, prussic acid, zero-valent nickel catalyst, tricresyl phosphite m-tolyl ester, iron protochloride and hexanediamine are added in secondary hydrocyanation reaction device with the mol ratio of 60:30:1:5:1:0.5, control reaction pressure is 0.3Mpa, temperature of reaction is 80 ℃, insulation reaction 5 hours; After reaction finishes, obtain adiponitrile product through purifying, purity is greater than 99.5%, and transformation efficiency is 75%, and selectivity is 81%, and it is 2.2% that high performance liquid chromatography (HPLC) records phosphorus-containing ligand degradation rate in system.
embodiment 5
By 3 pentene nitrile, prussic acid, zero-valent nickel catalyst, tricresyl phosphite m-tolyl ester, iron protochloride and N, N-Diethyl Aniline adds in secondary hydrocyanation reaction device with the mol ratio of 150:50:1:10:5:0.2, control reaction pressure is 0.3Mpa, and temperature of reaction is 100 ℃, insulation reaction 3 hours; After reaction finishes, obtain adiponitrile product through purifying, purity is greater than 99.5%, and transformation efficiency is 77%, and selectivity is 78%, and it is 3.0% that high performance liquid chromatography (HPLC) records phosphorus-containing ligand degradation rate in system.
embodiment 6
3 pentene nitrile, prussic acid, zero-valent nickel catalyst, tri-p-cresyl phosphite, tin tetrachloride and pyridine are added in secondary hydrocyanation reaction device with the mol ratio of 300:100:1:15:10:0.15, control reaction pressure is 0.3Mpa, temperature of reaction is 100 ℃, insulation reaction 3 hours; After reaction finishes, obtain adiponitrile product through purifying, purity is greater than 99.5%, and transformation efficiency is 75%, and selectivity is 80%, and it is 3.5% that high performance liquid chromatography (HPLC) records phosphorus-containing ligand degradation rate in system.
Finally explanation is, above preferred embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is described in detail by above preferred embodiment, but those skilled in the art are to be understood that, can make various changes to it in the form and details, and not depart from the claims in the present invention book limited range.
Claims (10)
1. in the isomerization reaction of a butadiene process Adiponitrile, suppress the method for phosphorus-containing ligand degraded, it is characterized in that: 2-methyl-3-crotononitrile is mixed with zero-valent nickel catalyst, phosphorus-containing ligand, Lewis acid and organic bases, there is isomerization reaction, generate the product that comprises 3 pentene nitrile.
2. in the isomerization reaction of butadiene process Adiponitrile according to claim 1, suppress the method for phosphorus-containing ligand degraded, it is characterized in that: described organic bases is triethylamine, diethylamine, dimethylamine, hexanediamine, pyridine, aniline, quadrol, N, accelerine or N, N-Diethyl Aniline.
3. in the isomerization reaction of butadiene process Adiponitrile according to claim 1, suppress the method for phosphorus-containing ligand degraded, it is characterized in that: described Lewis acid is zinc chloride, aluminum chloride, zinc sulfate, iron protochloride, iron(ic) chloride or tin tetrachloride, described phosphorus-containing ligand is triphenyl phosphite, tricresyl phosphite o-toluene ester, tricresyl phosphite m-tolyl ester or tri-p-cresyl phosphite.
4. in the isomerization reaction of butadiene process Adiponitrile according to claim 1, suppress the method for phosphorus-containing ligand degraded, it is characterized in that: the mol ratio of described 2-methyl-3-crotononitrile and zero-valent nickel catalyst is 30 ~ 100:1, the mol ratio of phosphorus-containing ligand and zero-valent nickel catalyst is 5 ~ 50:1, the mol ratio of Lewis acid and zero-valent nickel catalyst is 1 ~ 50:1, and the mol ratio of organic bases and phosphorus-containing ligand is 1:10～100.
5. in the isomerization reaction of butadiene process Adiponitrile according to claim 1, suppress the method for phosphorus-containing ligand degraded, it is characterized in that: the reaction pressure of described isomerization reaction is 0.1 ~ 0.2 Mpa, temperature of reaction is 80 ~ 110 ℃, insulation reaction 6 ~ 24 hours.
6. in the secondary hydrocyanation reaction of a butadiene process Adiponitrile, suppress the method for phosphorus-containing ligand degraded, it is characterized in that: 3 pentene nitrile is mixed with prussic acid, zero-valent nickel catalyst, phosphorus-containing ligand, Lewis acid and organic bases, there is secondary hydrocyanation reaction, generate the product that comprises adiponitrile.
7. in the secondary hydrocyanation reaction of butadiene process Adiponitrile according to claim 6, suppress the method for phosphorus-containing ligand degraded, it is characterized in that: described organic bases is triethylamine, diethylamine, dimethylamine, hexanediamine, pyridine, aniline, quadrol, N, accelerine or N, N-Diethyl Aniline.
8. in the secondary hydrocyanation reaction of butadiene process Adiponitrile according to claim 6, suppress the method for phosphorus-containing ligand degraded, it is characterized in that: described Lewis acid is zinc chloride, aluminum chloride, zinc sulfate, iron protochloride, iron(ic) chloride or tin tetrachloride, described phosphorus-containing ligand is triphenyl phosphite, tricresyl phosphite o-toluene ester, tricresyl phosphite m-tolyl ester or tri-p-cresyl phosphite.
9. in the secondary hydrocyanation reaction of butadiene process Adiponitrile according to claim 6, suppress the method for phosphorus-containing ligand degraded, it is characterized in that: the mol ratio of described 3 pentene nitrile and zero-valent nickel catalyst is 60 ~ 300:1, the mol ratio of prussic acid and zero-valent nickel catalyst is 30 ~ 100:1, the mol ratio of phosphorus-containing ligand and zero-valent nickel catalyst is 5 ~ 50:1, the mol ratio of Lewis acid and zero-valent nickel catalyst is 1 ~ 10:1, and the mol ratio of organic bases and phosphorus-containing ligand is 1:10～100.
10. in the secondary hydrocyanation reaction of butadiene process Adiponitrile according to claim 6, suppress the method for phosphorus-containing ligand degraded, it is characterized in that: the reaction pressure of described secondary hydrocyanation reaction is 0.2 ~ 0.5 Mpa, temperature of reaction is 50 ~ 100 ℃, insulation reaction 3 ~ 5 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023060929A1 (en) * | 2021-10-15 | 2023-04-20 | 浙江大学 | Application of polydentate phosphite ligand in catalytic synthesis of adiponitrile |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3553298A (en) * | 1967-10-20 | 1971-01-05 | Hooker Chemical Corp | Hydrolytic stabilized phosphite esters |
| CN100545147C (en) * | 2004-01-29 | 2009-09-30 | 巴斯福股份公司 | The method for preparing linear pentenenitrile |
| CN100564353C (en) * | 2004-01-29 | 2009-12-02 | 巴斯福股份公司 | The method for preparing adiponitrile by the hydrocyanation 1,3-butadiene |
-
2014
- 2014-02-17 CN CN201410052747.1A patent/CN103804229B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3553298A (en) * | 1967-10-20 | 1971-01-05 | Hooker Chemical Corp | Hydrolytic stabilized phosphite esters |
| CN100545147C (en) * | 2004-01-29 | 2009-09-30 | 巴斯福股份公司 | The method for preparing linear pentenenitrile |
| CN100564353C (en) * | 2004-01-29 | 2009-12-02 | 巴斯福股份公司 | The method for preparing adiponitrile by the hydrocyanation 1,3-butadiene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023060929A1 (en) * | 2021-10-15 | 2023-04-20 | 浙江大学 | Application of polydentate phosphite ligand in catalytic synthesis of adiponitrile |
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