CN111662211A - Method for synthesizing adiponitrile - Google Patents
Method for synthesizing adiponitrile Download PDFInfo
- Publication number
- CN111662211A CN111662211A CN201910175210.7A CN201910175210A CN111662211A CN 111662211 A CN111662211 A CN 111662211A CN 201910175210 A CN201910175210 A CN 201910175210A CN 111662211 A CN111662211 A CN 111662211A
- Authority
- CN
- China
- Prior art keywords
- adiponitrile
- raw materials
- hexane
- synthesizing
- oxygen
- 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
Links
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 11
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 11
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 10
- 238000000889 atomisation Methods 0.000 claims description 5
- 230000002572 peristaltic effect Effects 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 238000005669 hydrocyanation reaction Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of chemical synthesis, and particularly relates to a method for synthesizing adiponitrile, which synthesizes the adiponitrile in a fluidized bed at the temperature of 100 ℃ and 200 ℃ by taking normal hexane and ammonia gas as raw materials, oxygen as an oxidant and V-Cr-P-O/SiO2 as a catalyst. The method for preparing adiponitrile has the advantages of cheap raw materials and good economic effect; the synthetic method has the advantages of non-toxic raw materials and high safety; the reaction temperature is low, the requirement on equipment is not high, and the equipment investment cost is low; and the synthesis method does not need a solvent and has high yield.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a method for synthesizing adiponitrile.
Background
Adiponitrile (ADN) is a very important organic chemical intermediate, mainly used for preparing nylon-66. The industrial synthesis of adiponitrile mainly includes butadiene hydrocyanation, adipic acid ammoniation dehydration and acrylonitrile electrolytic dimerization. Among the three methods, the butadiene hydrocyanation method has a complex process, consumes a large amount of chlorine and hydrocyanic acid, and causes high production cost and high risk; the adipic acid ammoniation method needs expensive raw material adipic acid and higher reaction temperature, and the reaction process generates solid waste; the acrylonitrile electrolytic dimerization method has high requirements on equipment, needs to consume a large amount of electric energy, and has expensive raw materials and small profit space. Therefore, there is a need to develop new adiponitrile synthesis methods.
Disclosure of Invention
The invention aims to provide a method for synthesizing adiponitrile.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for synthesizing adiponitrile takes normal hexane and ammonia gas as raw materials, oxygen as an oxidant and V-Cr-P-O/SiO2 as a catalyst, and synthesizes the adiponitrile in a fluidized bed at the temperature of 100-200 ℃.
N-hexane: oxygen: the volume ratio of ammonia gas is 1: 10-30: 2 to 5.
The ratio of the molar amount of the V-Cr-P-O/SiO2 catalyst to the volume of the n-hexane is 0.02-0.06 mol/L.
The operating parameters of the fluidized bed were: fluidizing gas inlet velocity: 100-; inlet air temperature of the fluidizing gas: 100-200 ℃; flow rate of the peristaltic pump: 100-500 ml/h; the air pressure for spray atomization is 0.15-4 BAR; the amount of the sprayed sample is 50-400 g/time.
Compared with the prior art, the invention has the beneficial effects that:
(1) the synthetic method has cheap raw materials and good economic effect;
(2) the synthetic method has the advantages that the raw materials are nontoxic and high in safety;
(3) the synthesis method has low reaction temperature, low requirement on equipment and low equipment investment cost;
(4) the synthesis method of the invention does not need solvent and has high yield.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the following preferred embodiments.
Example 1: a process for synthesizing adiponitrile features that n-hexane and ammonia gas as raw materials, oxygen as oxidant and V-Cr-P-O/SiO2 as catalyst are used to synthesize adiponitrile in fluidized bed at 150 deg.C. N-hexane: oxygen: the volume ratio of ammonia gas is 1: 20: 3.5. the ratio of the molar amount of the V-Cr-P-O/SiO2 catalyst to the volume of n-hexane is 0.04 mol/L. After 24 hours of reaction, the yield is 90 percent, and the purity can reach 96 percent.
The operating parameters of the fluidized bed were: fluidizing gas inlet velocity: 100-; inlet air temperature of the fluidizing gas: 150 ℃; flow rate of the peristaltic pump: 100-500 ml/h; the air pressure for spray atomization is 0.15-4 BAR; the amount of the sprayed sample is 50-400 g/time.
Example 2A synthesis of adiponitrile using n-hexane and ammonia as raw materials, oxygen as oxidant, V-Cr-P-O/SiO2 as catalyst, in a 100 ℃ fluidized bed. N-hexane: oxygen: the volume ratio of ammonia gas is 1: 10: 2. the ratio of the molar amount of the V-Cr-P-O/SiO2 catalyst to the volume of n-hexane is 0.02 mol/L. After 24 hours of reaction, the yield is 82%, and the purity can reach 94%.
The operating parameters of the fluidized bed were: fluidizing gas inlet velocity: 100-; inlet air temperature of the fluidizing gas: 100 ℃; flow rate of the peristaltic pump: 100-500 ml/h; the air pressure for spray atomization is 0.15-4 BAR; the amount of the sprayed sample is 50-400 g/time.
Example 3A synthesis of adiponitrile using n-hexane and ammonia as raw materials, oxygen as oxidant, V-Cr-P-O/SiO2 as catalyst, in a fluidized bed at 200 ℃. N-hexane: oxygen: the volume ratio of ammonia gas is 1: 30: 5. the ratio of the molar amount of the V-Cr-P-O/SiO2 catalyst to the volume of n-hexane was 0.06 mol/L. After 24h of reaction, the yield is 92%, and the purity can reach 85%.
The operating parameters of the fluidized bed were: fluidizing gas inlet velocity: 100-; inlet air temperature of the fluidizing gas: 200 ℃; flow rate of the peristaltic pump: 100-500 ml/h; the air pressure for spray atomization is 0.15-4 BAR; the amount of the sprayed sample is 50-400 g/time.
The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.
Claims (4)
1. A method for synthesizing adiponitrile is characterized in that adiponitrile is synthesized in a fluidized bed at 200 ℃ and 100 ℃ by taking normal hexane and ammonia gas as raw materials, oxygen as an oxidant and V-Cr-P-O/SiO2 as a catalyst.
2. The method of synthesizing adiponitrile according to claim 1, wherein the ratio of n-hexane: oxygen: the volume ratio of ammonia gas is 1: 10-30: 2 to 5.
3. The method for synthesizing adiponitrile according to claim 1, wherein the ratio of the molar amount of the V-Cr-P-O/SiO2 catalyst to the volume of n-hexane is 0.02-0.06 mol/L.
4. The process for the synthesis of adiponitrile according to claim 1, wherein the parameters of use of the fluidized bed are: fluidizing gas inlet velocity: 100-; inlet air temperature of the fluidizing gas: 100-200 ℃; flow rate of the peristaltic pump: 100-500 ml/h; the air pressure for spray atomization is 0.15-4 BAR; the amount of the sprayed sample is 50-400 g/time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910175210.7A CN111662211A (en) | 2019-03-08 | 2019-03-08 | Method for synthesizing adiponitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910175210.7A CN111662211A (en) | 2019-03-08 | 2019-03-08 | Method for synthesizing adiponitrile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111662211A true CN111662211A (en) | 2020-09-15 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910175210.7A Pending CN111662211A (en) | 2019-03-08 | 2019-03-08 | Method for synthesizing adiponitrile |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111662211A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3959339A (en) * | 1973-06-05 | 1976-05-25 | Mitsubishi Gas Chemical Company, Inc. | Process for producing aromatic nitriles |
| CN105017070A (en) * | 2014-04-23 | 2015-11-04 | 中国科学院大连化学物理研究所 | Method for preparing adiponitrile by catalytic conversion of 1,6-hexanediol |
-
2019
- 2019-03-08 CN CN201910175210.7A patent/CN111662211A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3959339A (en) * | 1973-06-05 | 1976-05-25 | Mitsubishi Gas Chemical Company, Inc. | Process for producing aromatic nitriles |
| CN105017070A (en) * | 2014-04-23 | 2015-11-04 | 中国科学院大连化学物理研究所 | Method for preparing adiponitrile by catalytic conversion of 1,6-hexanediol |
Non-Patent Citations (2)
| Title |
|---|
| REDDY, B. MAHIPAL ET AL.: "One-step synthesis of adiponitrile by catalytic ammoxidation over antimony-vanadium phosphorus oxide/γ-alumina catalyst", 《JOURNAL OF THE CHEMICAL SOCIETY, CHEMICAL COMMUNICATIONS》 * |
| 马玉龙等: "V-Cr-P-O/SiO2高分散催化剂催化甲基吡啶氨氧化反应", 《石油化工》 * |
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| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200915 |
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