CN113248404B - Preparation method of perfluoroalkyl nitrile - Google Patents
Preparation method of perfluoroalkyl nitrile Download PDFInfo
- Publication number
- CN113248404B CN113248404B CN202110426938.XA CN202110426938A CN113248404B CN 113248404 B CN113248404 B CN 113248404B CN 202110426938 A CN202110426938 A CN 202110426938A CN 113248404 B CN113248404 B CN 113248404B
- Authority
- CN
- China
- Prior art keywords
- perfluoroalkyl
- nitrile
- reaction
- methane
- perfluoroalkyl nitrile
- 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.)
- Active
Links
- -1 perfluoroalkyl nitrile Chemical class 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 31
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 238000006297 dehydration reaction Methods 0.000 abstract description 5
- 238000005070 sampling Methods 0.000 description 28
- 239000007789 gas Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 16
- 238000004817 gas chromatography Methods 0.000 description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 7
- 239000012024 dehydrating agents Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002808 molecular sieve Substances 0.000 description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- SFFUEHODRAXXIA-UHFFFAOYSA-N 2,2,2-trifluoroacetonitrile Chemical compound FC(F)(F)C#N SFFUEHODRAXXIA-UHFFFAOYSA-N 0.000 description 6
- AASDJASZOZGYMM-UHFFFAOYSA-N 2,3,3,3-tetrafluoro-2-(trifluoromethyl)propanenitrile Chemical compound FC(F)(F)C(F)(C#N)C(F)(F)F AASDJASZOZGYMM-UHFFFAOYSA-N 0.000 description 6
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- DEYAKVNIRRRJGO-UHFFFAOYSA-N 2,3,3,3-tetrafluoro-2-(trifluoromethyl)propanamide Chemical compound NC(=O)C(F)(C(F)(F)F)C(F)(F)F DEYAKVNIRRRJGO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- NRKYWOKHZRQRJR-UHFFFAOYSA-N 2,2,2-trifluoroacetamide Chemical compound NC(=O)C(F)(F)F NRKYWOKHZRQRJR-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- UAMWCQNANZEBFX-UHFFFAOYSA-N N-fluoro-2-methylpropanamide Chemical compound CC(C(=O)NF)C UAMWCQNANZEBFX-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MTLOQUGSPBVZEO-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanenitrile Chemical group FC(F)(F)C(F)(F)C#N MTLOQUGSPBVZEO-UHFFFAOYSA-N 0.000 description 1
- BOZRBIJGLJJPRF-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluorobutanenitrile Chemical compound FC(F)(F)C(F)(F)C(F)(F)C#N BOZRBIJGLJJPRF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000005431 greenhouse gas Substances 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
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002918 waste heat 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
In order to solve the problems of complex process route and expensive raw materials in the existing method for preparing perfluoroalkyl nitrile by adopting dehydration reaction, the invention provides a preparation method of perfluoroalkyl nitrile, which comprises the following operation steps: takes perfluoroalkyl methane as raw material, and reacts with NH under the catalysis of ammonia oxidation catalyst 3 、O 2 Reacting; the mixture containing perfluoroalkyl nitrile is obtained by reaction, and the mixture is purified to obtain the perfluoroalkyl nitrile. The preparation method provided by the invention can effectively reduce the preparation cost of the existing perfluoroalkyl nitrile and simplify the process flow.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method of perfluoroalkyl nitrile.
Background
Perfluoroalkyl nitriles are a particular class of fine fluorine-containing chemicals. Among the more studied at present are trifluoroacetonitrile, an important intermediate for synthesizing trifluoromethyl nitrogen heterocyclic compounds in the fluorine-containing medicine and pesticide industries, and perfluoroisobutyronitrile (i.e., heptafluoroisobutyronitrile), which is developed as an insulating gas for high-voltage power transmission and transformation systems replacing greenhouse gas SF 6. In particular fields of application, perfluoroalkyl nitriles have their important roles.
The prior synthesis of perfluoroalkyl nitrile generally has two synthesis strategies of fluorination of (less) fluoronitrile raw materials and functional group conversion of perfluorinated compounds with proper framework structures, and the latter is the most in actual synthesis; in particular to a technical method for the main industrial production of trifluoroacetonitrile and perfluoroisobutyronitrile by utilizing perfluoroalkyl amide compounds to carry out dehydration reaction. For example:
campagna et al, tetrahedron Letters 1977 (21), 1813-1816 report a process for converting trifluoroacetamide to trifluoroacetonitrile using trifluoroacetic anhydride/pyridine as a dehydrating agent. Maeshall et al, synthesis Communications 2004,34 (5), 903-907, report a process for converting trifluoroacetamide to trifluoroacetonitrile using triphenylphosphine/carbon tetrachloride as a dehydrating agent. The yield of the trifluoro acetonitrile synthesized by the method can reach 85 percent.
In WO2013/151741, 3M company discloses a process for converting perfluoro isobutyramide to perfluoro isobutyronitrile using trifluoroacetic anhydride/pyridine as a dehydrating agent. The dehydrating agent disclosed in CN201711233637.5, CN201810357666.0 by beijing technology for conversion of perfluoro isobutyramide to perfluoro isobutyronitrile may be trifluoroacetic anhydride, acetic anhydride, thionyl chloride, phosphorus pentoxide, phosphorus oxychloride, with the use of solvents such as pyridine, polyphosphoric acid, carbon tetrachloride, N-dimethylformamide, N-diethylformamide, 1, 4-dioxane, dimethyl sulfoxide or mixtures thereof. The dehydrating agent used in CN201810233636.9 by the national institute of electric and dawn chemical industry, is trifluoroacetic anhydride plus an organic base (preferably pyridine and triethylamine). In CN201811058167.8, a institute of electric and power sciences of guangdong and Shanghai organic chemistry of the national institute of sciences, low-priced phosphorus pentoxide/N, N dimethylformamide is used as a dehydrating agent. The blue sky environment protection adopts p-toluenesulfonyl chloride as a dehydrating agent (matched with an organic solvent) in CN201811578643.9, so that a better yield is obtained.
However, the cost of the dehydration agent is generally high and the dehydration agent cannot be reused, the synthesis of the raw material perfluoroalkyl amide needs a plurality of steps to be completed, the whole process is complex, and the production cost of the perfluoroalkyl nitrile is high, so that the development of a new process method is necessary.
Disclosure of Invention
Aiming at the problems of complex process route and expensive raw materials in the existing method for preparing the perfluoroalkyl nitrile by adopting the dehydration reaction, the invention provides a preparation method of the perfluoroalkyl nitrile.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a preparation method of perfluoroalkyl nitrile, which comprises the following operation steps:
takes perfluoroalkyl methane as raw material, and reacts with NH under the catalysis of ammonia oxidation catalyst 3 、O 2 Reacting;
the mixture containing perfluoroalkyl nitrile is obtained by reaction, and the mixture is purified to obtain the perfluoroalkyl nitrile.
Optionally, the perfluoroalkyl nitrile is represented by structural formula 1:
R-CN
structure 1
Wherein R is selected from linear or branched perfluoroalkyl groups with 1-16 carbon atoms.
Optionally, the perfluoroalkyl nitrile is represented by structural formula 2:
wherein R is 1 、R 2 、R 3 Each independently selected from C n F 2n+1 N is an integer from 0 to 5.
Optionally, the ammoxidation catalyst includes one or more of a V element, an Sb element, and a Mo element.
Optionally, the ammoxidation catalyst comprises V element and Mo element, and optional Te element, nb element, ce element or mixture thereof.
Optionally, the perfluoroalkyl methane is in gas phase with NH 3 、O 2 And (3) reacting.
Alternatively, the reaction is carried out in an ebullated-bed reactor.
Optionally, in the reaction system, perfluoroalkyl methane and NH 3 、O 2 The volume ratio of (2) is 1:0.5-3:2-10.
Alternatively, the reaction temperature of the reaction system is 300-600 ℃.
Optionally, before the reaction, introducing perfluoroalkyl methane and NH 3 、O 2 Preheating to the reaction temperature.
According to the preparation method of the perfluoroalkyl nitrile, perfluoroalkyl methane is adopted as a reaction raw material to carry out ammoxidation reaction, wherein perfluoro on perfluoroalkyl methane is a necessary condition, fluorine on perfluoroalkyl methane is a strong electron withdrawing group, the superstrong stability of perfluoroalkyl part in the ammoxidation reaction process can be effectively ensured, if perfluoroalkyl is replaced by non-fluoroalkyl or partially fluorinated alkyl, the common excessive oxidation problem in the ammoxidation reaction can occur, a large number of side reaction products are generated, and byproducts in the method only find perfluoroalkyl aldehyde and perfluoroalkyl amide which are intermediates of the ammoxidation reaction, so that the product selectivity of the perfluoroalkyl nitrile is higher, and meanwhile, the obtained perfluoroalkyl aldehyde and perfluoroalkyl amide can be separated from the perfluoroalkyl nitrile through simple rectification and unreacted raw material perfluoroalkyl methane and continuously participate in the cyclic reaction to prepare the perfluoroalkyl nitrile without the emission of byproducts.
The perfluoroalkyl nitrile preparation method adopts the raw material perfluoroalkyl methane which has simple structure, easy synthesis and safe physicochemical properties, and simultaneously has NH 3 And O 2 The preparation method of the perfluoroalkyl nitrile provided by the invention can effectively reduce the preparation cost of the traditional perfluoroalkyl nitrile and simplify the process flow.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The embodiment of the invention provides a preparation method of perfluoroalkyl nitrile, which comprises the following operation steps:
takes perfluoroalkyl methane as raw material, and reacts with NH under the catalysis of ammonia oxidation catalyst 3 、O 2 Reacting;
the mixture containing perfluoroalkyl nitrile is obtained by reaction, and the mixture is purified to obtain the perfluoroalkyl nitrile.
According to the preparation method of the perfluoroalkyl nitrile, perfluoroalkyl methane is adopted as a reaction raw material to carry out ammoxidation reaction, wherein perfluoro on perfluoroalkyl methane is a necessary condition, fluorine on perfluoroalkyl methane is a strong electron withdrawing group, the superstrong stability of perfluoroalkyl part in the ammoxidation reaction process can be effectively ensured, if perfluoroalkyl is replaced by non-fluoroalkyl or partially fluorinated alkyl, the common problem of overoxidation in the ammoxidation reaction can occur, a large number of side reaction products are generated, and byproducts in the application only find perfluoroalkyl aldehyde and perfluoroalkyl amide which are intermediates of the ammoxidation reaction, so that the product selectivity of the perfluoroalkyl nitrile is higher, and meanwhile, the obtained perfluoroalkyl aldehyde and perfluoroalkyl amide can be separated from the perfluoroalkyl nitrile through simple rectification and unreacted raw material perfluoroalkyl methane to continuously participate in the circulation reaction to prepare the perfluoroalkyl nitrile, so that the problem of overoxidation is solved, the overall conversion rate is high, and the characteristics of green and environment protection are achieved.
The perfluoroalkyl nitrile preparation method adopts the raw material perfluoroalkyl methane which has simple structure, easy synthesis and safe physicochemical properties, and simultaneously has NH 3 And O 2 The preparation method of the perfluoroalkyl nitrile provided by the invention can effectively reduce the preparation cost of the traditional perfluoroalkyl nitrile and simplify the process flow.
In some embodiments, the perfluoroalkyl nitrile is represented by structural formula 1:
R-CN
structure 1
Wherein R is selected from linear or branched perfluoroalkyl groups with 1-16 carbon atoms.
In a preferred embodiment, the perfluoroalkyl nitrile is represented by structural formula 2:
wherein R is 1 、R 2 、R 3 Each independently selected from C n F 2n+1 N is an integer from 0 to 5.
As an example: when R is 1 ＝R 2 ＝R 3 When=f, the perfluoroalkyl nitrile is selected from trifluoroacetonitrile;
when R is 1 ＝CF 3 ，R 2 ＝R 3 When=f, the perfluoroalkyl nitrile is selected from pentafluoropropionitrile;
when R is 1 ＝CF 2 CF 3 ，R 2 ＝R 3 When=f, the perfluoroalkyl nitrile is selected from the group consisting of heptafluorobutyronitrile;
when R is 1 ＝R 2 ＝CF 3 ，R 3 When=f, the perfluoroalkyl nitrile is selected from the group consisting of heptafluoroisobutyronitrile.
In some embodiments, the ammoxidation catalyst includes one or more of a V element, a Sb element, and a Mo element.
In some embodiments, the ammoxidation catalyst comprises elemental V and elemental Sb, and optionally elemental Al, elemental W, elemental Mo, or mixtures thereof.
Specifically, the ammoxidation catalyst is selected from VSb 3 Al 2 W 1.5 Mo 0.5 。
In some embodiments, the ammoxidation catalyst comprises V and Mo elements, and optionally Te, nb, ce elements or mixtures thereof.
In a more preferred embodiment, the ammoxidation catalyst is selected from MoV 0.31 Te 0.23 Nb 0.24 Ce 0.05 。
Although different types of ammoxidation catalysts are used for catalyzing the conversion of perfluoroalkyl methane into perfluoroalkyl nitrile, the catalytic effects are greatly different, and the yield of the perfluoroalkyl nitrile is affected. When the ammoxidation catalyst includes V element and Mo element, and optionally Te element, nb element, ce element or a mixture thereof, it has a good catalytic effect and can obtain a high yield as compared with other catalysts.
In some embodiments, the reaction system is run at atmospheric or low pressure, and the increase in reaction pressure has no significant effect on the increase in yield.
In some embodiments, the perfluoroalkyl methane is in the gas phase with NH 3 、O 2 And (3) reacting.
Due to NH 3 、O 2 Are all gas-phase substances, and take part in the reaction by taking the perfluoroalkyl methane as gas phase, so that the perfluoroalkyl methane and NH can be effectively improved 3 、O 2 And the reaction efficiency is further improved.
Depending on the difference in the materials of the perfluoroalkyl methane used, the perfluoroalkyl methane may be vaporized by increasing the temperature or decreasing the pressure.
In some embodiments, the reaction is performed in an ebullated bed reactor.
In the reaction, the ammoxidation catalyst may be first set inside the boiling bed reactor and then introduced into gaseous reaction material (e.g. perfluoroalkyl methane, NH) 3 、O 2 ) The flow rate of the reaction raw materials should reach a state that the ammonia oxidation catalyst can reach boiling motion, which is favorable for enabling the ammonia oxidation catalyst to be fully contacted with the reaction raw materials, updating the materials on the surface of the ammonia oxidation catalyst in time, ensuring the catalytic effect and being favorable for removing the reaction heat.
In some embodiments, in the reaction system, the perfluoroalkyl methane, NH 3 、O 2 The volume ratio of (2) is 1:0.5-3:2-10.
In a preferred embodiment, the perfluoroalkyl methane, NH 3 、O 2 The volume ratio of (2) is 1:1-2:4-6.
In some embodiments, the reaction temperature of the reaction system is 300-600 ℃.
In a preferred embodiment, the reaction temperature of the reaction system is 400-500 ℃.
In some embodiments, prior to the reaction, the perfluoroalkyl methane, NH, are introduced 3 、O 2 Preheating to the reaction temperature to obtain perfluoroalkyl methane and NH 3 、O 2 The reaction temperature can be reached faster, and the time consumption of the reaction is shortened.
The invention is further illustrated by the following examples.
Example 1
This example is illustrative of the process for preparing perfluoroalkyl nitriles of the present disclosure, comprising the following steps:
20 g of ammonia oxidation catalyst VSb was charged into a laboratory fluidized bed reactor having an inner diameter of 25mm 3 Al 2 W 1.5 Mo 0.5 Heating to 430 ℃; CF is to be 3 CH 3 、NH 3 、O 2 Respectively gasifying and then respectively passing through a regulating valve, a rotameter and a preheater and then introducing into the reactor; the flow rate of the valve is adjusted to be 2L/min, 3L/min and 5L/min respectively. And (3) connecting the product gas obtained by the reaction with a sampling tee pipe, a collecting bottle and an emptying pipe after passing through a buffer, a heat exchanger (2) and a molecular sieve dryer. After the reaction was stably carried out for 1 hour, sampling was carried out for gas chromatography, sampling was carried out every 15 minutes, sampling was carried out 10 times continuously, and the results were averaged. The result of the gas chromatography analysis is that the product gas contains CF 3 CH 3 、CF 3 CN、CF 3 CHO、CF 3 CONH 2 58.6%, 33.5%, 4.1% and 3.8% respectively. From the chromatographic analysis results, CF was found 3 CH 3 Conversion of 41.4%, CF 3 CN selectivity of 80.9%, CF 3 The single pass yield of CN was 33.5%.
Example 2
This example is illustrative of the process for preparing perfluoroalkyl nitriles of the present disclosure, comprising the following steps:
20 g of ammonia oxidation catalyst MoV was charged into a laboratory fluidized bed reactor having an inner diameter of 25mm 0.31 Te 0.23 Nb 0.24 Ce 0.05 Heating to 450 ℃; CF is to be 3 CH 3 、NH 3 、O 2 Respectively gasifying and then respectively passing through a regulating valve, a rotameter and a preheater and then introducing into the reactor; the flow rate of the valve is adjusted to be 2L/min, 3L/min and 5L/min respectively. And (3) connecting the product gas obtained by the reaction with a sampling tee pipe, a collecting bottle and an emptying pipe after passing through a buffer, a heat exchanger (2) and a molecular sieve dryer. After the reaction was stably carried out for 1 hour, sampling was carried out for gas chromatography, sampling was carried out every 15 minutes, sampling was carried out 10 times continuously, and the results were averaged. The result of the gas chromatography analysis is that the product gas contains CF 3 CH 3 、CF 3 CN、CF 3 CHO、CF 3 CONH 2 37.8%, 56.5%, 3.5% and 2.2%, respectively. From the chromatographic analysis results, CF was found 3 CH 3 Conversion was 62.2%, CF 3 CN selectivity of 90.8％，CF 3 The single pass yield of CN was 56.5%.
Example 3
This example is illustrative of the process for preparing perfluoroalkyl nitriles of the present disclosure, comprising the following steps:
20 g of ammonia oxidation catalyst VSb was charged into a laboratory fluidized bed reactor having an inner diameter of 25mm 3 Al 2 W 1.5 Mo 0.5 Heating to 430 ℃; CF is to be 3 CF 2 CH 3 、NH 3 、O 2 Respectively gasifying and then respectively passing through a regulating valve, a rotameter and a preheater and then introducing into the reactor; the flow rate of the valve is adjusted to be 2L/min, 3L/min and 5L/min respectively. And (3) connecting the product gas obtained by the reaction with a sampling tee pipe, a collecting bottle and an emptying pipe after passing through a buffer, a heat exchanger (2) and a molecular sieve dryer. After the reaction was stably carried out for 1 hour, sampling was carried out for gas chromatography, sampling was carried out every 15 minutes, sampling was carried out 10 times continuously, and the results were averaged. The result of the gas chromatography analysis is that the product gas contains CF 3 CF 2 CH 3 、CF 3 CF 2 CN、CF 3 CF 2 CHO、CF 3 CF 2 CONH 2 61.2%, 34.4%, 2.1% and 2.3% respectively. From the chromatographic analysis results, CF was found 3 CF 2 CH 3 Conversion was 38.8%, CF 3 CF 2 CN selectivity of 88.7%, CF 3 CF 2 The single pass yield of CN was 34.4%.
Example 4
This example is illustrative of the process for preparing perfluoroalkyl nitriles of the present disclosure, comprising the following steps:
20 g of ammonia oxidation catalyst MoV was charged into a laboratory fluidized bed reactor having an inner diameter of 25mm 0.31 Te 0.23 Nb 0.24 Ce 0.05 Heating to 450 ℃; CF is to be 3 CF 2 CH 3 、NH 3 、O 2 Respectively gasifying and then respectively passing through a regulating valve, a rotameter and a preheater and then introducing into the reactor; the flow rate of the valve is adjusted to be 2L/min, 3L/min and 5L/min respectively. The product gas obtained by the reaction is passed through a buffer and is exchangedAnd the heater (x 2) and the molecular sieve dryer are connected with a sampling three-way pipe, a collecting bottle and an emptying pipe. After the reaction was stably carried out for 1 hour, sampling was carried out for gas chromatography, sampling was carried out every 15 minutes, sampling was carried out 10 times continuously, and the results were averaged. The result of the gas chromatography analysis is that the product gas contains CF 3 CF 2 CH 3 、CF 3 CF 2 CN、CF 3 CF 2 CHO、CF 3 CF 2 CONH 2 39.1%, 55.7%, 3.3% and 1.9%, respectively. From the chromatographic analysis results, CF was found 3 CF 2 CH 3 Conversion was 60.9%, CF 3 CF 2 CN selectivity 91.5%, CF 3 CF 2 The single pass yield of CN was 55.7%.
Example 5
This example is illustrative of the process for preparing perfluoroalkyl nitriles of the present disclosure, comprising the following steps:
20 g of ammonia oxidation catalyst VSb was charged into a laboratory fluidized bed reactor having an inner diameter of 25mm 3 Al 2 W 1.5 Mo 0.5 Heating to 410 ℃; will (CF) 3 ) 2 CFCH 3 、NH 3 、O 2 Respectively gasifying and then respectively passing through a regulating valve, a rotameter and a preheater and then introducing into the reactor; the flow rate of the valve is adjusted to be 2L/min, 3L/min and 5L/min respectively. And (3) connecting the product gas obtained by the reaction with a sampling tee pipe, a collecting bottle and an emptying pipe after passing through a buffer, a heat exchanger (2) and a molecular sieve dryer. After the reaction was stably carried out for 1 hour, sampling was carried out for gas chromatography, sampling was carried out every 15 minutes, sampling was carried out 10 times continuously, and the results were averaged. The result of the gas chromatography analysis is that the product gas contains (CF 3 ) 2 CFCH 3 、(CF 3 ) 2 CFCN、(CF 3 ) 2 CFCHO、(CF 3 ) 2 CFCONH 2 65.9%, 28.7%, 2.3% and 3.1% respectively. From the chromatographic analysis results (CF) 3 ) 2 CFCH 3 The conversion was 34.1% (CF) 3 ) 2 CFCN selectivity was 84.1% (CF) 3 ) 2 The single pass yield of CFCN was 28.7%.
Example 6
This example is illustrative of the process for preparing perfluoroalkyl nitriles of the present disclosure, comprising the following steps:
20 g of ammonia oxidation catalyst MoV was charged into a laboratory fluidized bed reactor having an inner diameter of 25mm 0.31 Te 0.23 Nb 0.24 Ce 0.05 Heating to 440 ℃; will (CF) 3 ) 2 CFCH 3 、NH 3 、O 2 Respectively gasifying and then respectively passing through a regulating valve, a rotameter and a preheater and then introducing into the reactor; the flow rate of the valve is adjusted to be 2L/min, 3L/min and 5L/min respectively. And (3) connecting the product gas obtained by the reaction with a sampling tee pipe, a collecting bottle and an emptying pipe after passing through a buffer, a heat exchanger (2) and a molecular sieve dryer. After the reaction was stably carried out for 1 hour, sampling was carried out for gas chromatography, sampling was carried out every 15 minutes, sampling was carried out 10 times continuously, and the results were averaged. The result of the gas chromatography analysis is that the product gas contains (CF 3 ) 2 CFCH 3 、(CF3) 2 CFCN、(CF 3 ) 2 CFCHO、(CF 3 ) 2 CFCONH 2 45.4%, 50.3%, 1.8% and 2.5% respectively. From the chromatographic analysis results (CF) 3 ) 2 CFCH 3 The conversion was 54.6% (CF) 3 ) 2 CFCN selectivity was 92.1% (CF) 3 ) 2 The single pass yield of CFCN was 50.3%.
Example 7
This example is illustrative of the process for preparing perfluoroalkyl nitriles of the present disclosure, comprising the following steps:
15 kg of ammonia oxidation catalyst MoV was charged into a pilot fluidized bed reactor having an inner diameter of 40cm 0.31 Te 0.23 Nb 0.24 Ce 0.05 Heating to 440 ℃; will (CF) 3 ) 2 CFCH 3 、NH 3 、O 2 Respectively gasifying and then respectively passing through a regulating valve, a rotameter and a preheater and then introducing into the reactor; the valve is regulated to make the flow rates of 1500L/min, 2250L/min and 3750L/min respectively. The product gas obtained by the reaction is connected with a buffer, a waste heat recoverer, a plate heat exchanger (2 in series) and a molecular sieve dryerA gas receiving warehouse, a gas compressor, a condenser and a liquid collecting tank. After the reaction was stably carried out for 2 hours, gas chromatography was performed by sampling from a sampling port in front of a liquid collecting tank, sampling was performed every 30 minutes, sampling was performed 6 times continuously, and the results were averaged. The result of the gas chromatography analysis is that the product gas contains (CF 3 ) 2 CFCH 3 、(CF 3 ) 2 CFCN、(CF 3 ) 2 CFCHO、(CF 3 ) 2 CFCONH 2 48.8%, 47.6%, 1.5% and 2.1% respectively. From the chromatographic analysis results (CF) 3 ) 2 CFCH 3 The conversion was 51.2% (CF) 3 ) 2 CFCN selectivity was 93.0% (CF) 3 ) 2 The once-through yield of CFCN was 47.6%.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (5)
1. A method for preparing perfluoroalkyl nitrile, which is characterized by comprising the following operation steps:
takes perfluoroalkyl methane as raw material, and reacts with NH under the catalysis of ammonia oxidation catalyst 3 、O 2 Reacting at 300-600deg.C with ammonia oxidation catalyst selected from MoV 0.31 Te 0.23 Nb 0.24 Ce 0.05 ；
Obtaining a mixture containing perfluoroalkyl nitrile through reaction, and purifying the mixture to obtain perfluoroalkyl nitrile, wherein the perfluoroalkyl nitrile is shown as a structural formula 2:
wherein R is 1 、R 2 、R 3 Each independently selected from C n F 2n+1 N is an integer from 0 to 5.
2. According to claimThe process for producing a perfluoroalkyl nitrile according to claim 1, wherein the perfluoroalkyl methane is in a gas phase with NH 3 、O 2 And (3) reacting.
3. The process for producing a perfluoroalkyl nitrile according to claim 1, wherein the reaction is carried out in an ebullated-bed reactor.
4. A process for producing a perfluoroalkyl nitrile according to claim 2 or 3, characterized in that, in the reaction system, a perfluoroalkyl methane, NH 3 、O 2 The volume ratio of (2) is 1:0.5-3:2-10.
5. The process for producing a perfluoroalkyl nitrile according to claim 1, wherein the introduced perfluoroalkyl methane and NH are reacted with each other 3 、O 2 Preheating to the reaction temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110426938.XA CN113248404B (en) | 2021-04-20 | 2021-04-20 | Preparation method of perfluoroalkyl nitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110426938.XA CN113248404B (en) | 2021-04-20 | 2021-04-20 | Preparation method of perfluoroalkyl nitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113248404A CN113248404A (en) | 2021-08-13 |
| CN113248404B true CN113248404B (en) | 2024-01-05 |
Family
ID=77221194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110426938.XA Active CN113248404B (en) | 2021-04-20 | 2021-04-20 | Preparation method of perfluoroalkyl nitrile |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113248404B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664696A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing cyanobenzene |
| CN109320436A (en) * | 2018-11-20 | 2019-02-12 | 北京宇极科技发展有限公司 | The method that gas phase catalysis prepares perfluor nitrile |
| CN110642750A (en) * | 2019-10-16 | 2020-01-03 | 三明市海斯福化工有限责任公司 | Preparation method of perfluoroalkyl nitrile |
-
2021
- 2021-04-20 CN CN202110426938.XA patent/CN113248404B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664696A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing cyanobenzene |
| CN109320436A (en) * | 2018-11-20 | 2019-02-12 | 北京宇极科技发展有限公司 | The method that gas phase catalysis prepares perfluor nitrile |
| CN110642750A (en) * | 2019-10-16 | 2020-01-03 | 三明市海斯福化工有限责任公司 | Preparation method of perfluoroalkyl nitrile |
Non-Patent Citations (1)
| Title |
|---|
| 《化学百科全书》编辑委员会.《化学百科全书》.化学工业出版社,1997,第302-304页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113248404A (en) | 2021-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109320436B (en) | Method for preparing perfluoronitrile by gas phase catalysis | |
| CN111825568A (en) | Synthesis method of perfluoroisobutyronitrile | |
| CN112624911A (en) | 2-chloro-3-fluoro-4- (trifluoromethyl) benzaldehyde and synthetic method thereof | |
| CN111848444A (en) | Synthesis method of perfluoroisobutyronitrile | |
| CN108069831A (en) | A kind of method for synthesizing 2,3- dimethyl -4- fluorophenols | |
| CN114085163B (en) | Method for synthesizing 2, 3-tetrafluoro-2- (trifluoromethyl) propionitrile by gas phase catalytic fluorination | |
| CN113248404B (en) | Preparation method of perfluoroalkyl nitrile | |
| CN102746190A (en) | Preparation method of trifluoroacetonitrile | |
| JP2019513838A (en) | Method of preparing 1,2-dichlorohexafluorocyclopentene | |
| CN111269129B (en) | Method for preparing 5,5 '-disubstituted-2, 2' -diaminobiphenyl and hydrochloride thereof by continuous flow oxidation coupling method | |
| CN114057605B (en) | Method for producing nitrile by gas phase dehydration | |
| CN111389424A (en) | Catalyst, preparation method and application in hexafluoropropylene oligomerization reaction | |
| CN114634397B (en) | Method for preparing hexafluoropropylene dimer by gas phase method | |
| CN108084001A (en) | A kind of synthetic method of improved 1- acetyl-1-chlorcyclopropanes | |
| CN113683530B (en) | Method for preparing heptafluoroisobutyronitrile by gas phase hydrocyanation | |
| CN116239496A (en) | Method for continuously preparing heptafluoroisobutyronitrile | |
| CN107082737B (en) | Method for simultaneously preparing dichlorohexachlorocyclopentene isomers | |
| CN113292392B (en) | Rearrangement reaction between saturated hydrochlorofluorocarbons and method for preparing fluoroalcohol by using rearrangement reaction | |
| CN113511954B (en) | Continuous flow preparation method of 1,2, 3-trichloropropane | |
| CN109651266A (en) | A kind of preparation method of herbicide terbacil | |
| CN112250622B (en) | Preparation method of 4-fluoropyridine-2-amine | |
| CN114671781B (en) | Method for converting arylbenzylamine into arylnitrile compound | |
| CN110407676B (en) | Synthetic method and application of diphenylethanedione compound | |
| CN103641692A (en) | Preparation of novel fluorine-containing bisphenol compound | |
| CN104030907B (en) | A kind of liquid phase oxidation prepares the method for 2-bromine Fluorenone |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |