CN114426502B - Process for the preparation of nitriles - Google Patents
Process for the preparation of nitriles Download PDFInfo
- Publication number
- CN114426502B CN114426502B CN202011092867.6A CN202011092867A CN114426502B CN 114426502 B CN114426502 B CN 114426502B CN 202011092867 A CN202011092867 A CN 202011092867A CN 114426502 B CN114426502 B CN 114426502B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- reaction
- acid
- aldehyde
- chloride
- 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
- 238000000034 method Methods 0.000 title claims abstract description 29
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- -1 aldehyde compounds Chemical class 0.000 claims abstract description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 16
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims description 60
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 26
- 239000002808 molecular sieve Substances 0.000 claims description 25
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 15
- 239000002608 ionic liquid Substances 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 150000008282 halocarbons Chemical class 0.000 claims description 8
- 150000002430 hydrocarbons Chemical group 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 6
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 238000003912 environmental pollution Methods 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 22
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 239000007791 liquid phase Substances 0.000 description 11
- 150000001299 aldehydes Chemical class 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- NZPJVXJPYFQGGW-UHFFFAOYSA-N C(=O)C=O.C(COCCO)O Chemical compound C(=O)C=O.C(COCCO)O NZPJVXJPYFQGGW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 2
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- DGJMPUGMZIKDRO-UHFFFAOYSA-N cyanoacetamide Chemical compound NC(=O)CC#N DGJMPUGMZIKDRO-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- CBPYOHALYYGNOE-UHFFFAOYSA-M potassium;3,5-dinitrobenzoate Chemical compound [K+].[O-]C(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 CBPYOHALYYGNOE-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of nitrile, which comprises the following steps: mixing and heating aldehyde compounds, ammonia, an oxidant, a catalyst and an accelerator, and reacting to obtain nitrile; wherein the aldehyde compound is selected from aldehyde, acetal or a combination thereof, and the promoter is metal chloride. The method can effectively catalyze aldehyde and/or acetal to generate nitrile, has simple preparation process, low cost and little environmental pollution, is suitable for industrial production, greatly improves the selectivity and yield of the obtained product, and has good industrial application prospect.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a preparation method of nitrile.
Background
Nitrile compounds are important organic intermediates widely used in the manufacture of pharmaceuticals, synthetic fibers and plastics, and also in the industries of electroplating, quenching of steel, mineral separation and the like. Classical methods for synthesizing nitriles include substitution of halogenated hydrocarbons, dehydration of amides, ammoxidation of olefins, and the like.
The substitution reaction of halohydrocarbon is a main method for synthesizing nitrile compounds, cyanide substitution is the most common reaction, and after the substitution reaction, a carbon atom is added to a carbon chain, which is one of methods for increasing the carbon chain in organic synthesis. The general formula of the substitution reaction is shown in the following formula (I):
R-X+NaCN→R-CN+Na-X (I)
for example, benzyl cyanide is synthesized by using the reaction. Patent CN105218401B reports a method for synthesizing benzyl cyanide by a continuous method, using benzyl chloride and sodium cyanide as raw materials. Sodium cyanide is extremely toxic and has high cost. Amide dehydration is also a common method for synthesizing nitriles, which mainly uses amide compounds to lose one molecule of water under the condition of dehydrating agent or high temperature catalysis to obtain corresponding nitriles, for example, malononitrile which is an important pesticide intermediate is produced through amide dehydration. In addition, adipoamide can be dehydrated at high temperature under the action of a catalyst to obtain adiponitrile. The general formula of the reaction is shown in the following formula (II):
patent CN1451649a discloses a process for producing malononitrile. Cyanoacetamide is used as a raw material, anhydrous aluminum trichloride, diethylamine hydrochloride and pyridine are used as a composite catalyst, and phosphorus oxychloride is used as a dehydrating agent to synthesize malononitrile. The ammoxidation of olefin is carried out by reacting carbonyl-containing compound (such as aldehyde and ketone) with hydrocyanic acid under certain condition to obtain cyanohydrin compound, which has the following formula (III):
however, these methods have certain drawbacks. For example, cyano groups substituted with halogen are primary by hydrocyanic acid or potassium cyanideThe material has extremely high toxicity and can produce serious environmental pollution; the amide dehydration requires high temperature, high energy consumption and poor product selectivity; high temperatures are required for olefin ammoxidation, and less versatility is achieved, some require the use of iodine (I 2 ) As an oxidizing agent, the cost is high and the pollution is serious.
Therefore, there is a need to develop a more efficient synthesis method of nitrile compounds to solve various problems in the prior art.
It is noted that the information disclosed in the foregoing background section is only for enhancement of understanding of the background of the invention and therefore it may contain information that does not form the prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to overcome at least one defect of the prior art, and provides a preparation method of nitrile, which aims to solve the problems of high production cost, poor product selectivity, environmental pollution and the like of the existing nitrile compounds in the synthesis process.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a preparation method of nitrile, which comprises the following steps: mixing and heating aldehyde compounds, ammonia, an oxidant, a catalyst and an accelerator, and reacting to obtain nitrile; wherein the aldehyde compound is selected from aldehyde, acetal or a combination thereof, and the promoter is metal chloride.
According to one embodiment of the invention, the aldehyde is selected from one or more of the following compounds: r is R 1 -CHO、CHO-R 1 -CHO; wherein R is 1 Selected from C 2-20 Hydrocarbon groups or halogenated hydrocarbons.
According to one embodiment of the invention, the acetals are selected from one or more of the following compounds:
wherein R is 2 Selected from C 2-20 Is a hydrocarbon or halogenated hydrocarbon of A 1 、A 2 、A 3 、A 4 Each independently selected from C 1-5 Alkyl of A 5 、A 6 Each independently selected from C 2-4 Is a hydrocarbon group.
According to one embodiment of the invention, the oxidizing agent is selected from one or more of periodic acid, sodium periodate, potassium persulfate, sodium persulfate and hydrogen peroxide, preferably potassium periodate and/or hydrogen peroxide.
According to one embodiment of the invention, the promoter is selected from one or more of lithium chloride, aluminum chloride, manganese chloride, iron chloride, cobalt chloride, molybdenum chloride, ruthenium chloride, cerium chloride, lanthanum chloride, copper chloride, chromium chloride and chromia chloride, preferably cerium chloride and/or lanthanum chloride; the usage amount of the accelerator is 1% -20% of the molar amount of the aldehyde compound.
According to one embodiment of the invention, the catalyst is a titanium silicalite, wherein the titanium silicalite is a titanium silicalite raw powder or a shaped titanium silicalite, and the titanium silicalite is selected from one or more of TS-1, TS-2, ti-ZSM-5, ti-ZSM-12, ti-ZSM-48, ti-beta, ti-MCM-41 and Ti-MOR.
According to one embodiment of the invention, the method further comprises filtering the product after the reaction to separate out the titanium silicalite molecular sieve; the separated titanium-silicon molecular sieve is washed and dried, and then heated to 120-600 ℃, preferably 200-500 ℃ in nitrogen atmosphere with 5-50% of oxygen content by volume to obtain the regenerated molecular sieve.
According to one embodiment of the invention, the catalyst is used in an amount of 0.01% to 10%, preferably 1% to 5% by mass of the aldehyde compound.
According to one embodiment of the invention, the reaction is carried out in a solvent selected from one or more of methanol, ethanol, isopropanol, chloroform, dichloroethane, benzene and toluene, preferably one or more of methanol and ethanol.
According to one embodiment of the invention, the reaction is carried out in an imidazole-based ionic liquid of the formula:
wherein R is 3 、R 4 Each independently selected from C 1-4 X is selected from halogen, BF or straight chain alkyl or branched chain alkyl 4 Or PF (physical pattern) 4 。
According to one embodiment of the invention, further comprising adding an acid to the reaction, the acid being selected from one or more of hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid and p-phenylsulfonic acid.
According to one embodiment of the invention, the temperature of the reaction is 50 to 200 ℃, preferably 70 to 150 ℃; the pressure is 0.1MPa to 10MPa, preferably 0.1MPa to 1MPa.
According to the technical scheme, the beneficial effects of the invention are as follows:
the invention provides a new preparation method of nitrile, which can effectively catalyze aldehyde and/or acetal to form nitrile by adopting specific accelerator and catalyst and matching with corresponding reaction conditions and oxidant, has simple process, low cost and little environmental pollution, is suitable for industrial production, and greatly improves the selectivity and yield of the obtained product, thereby having good industrial application prospect.
Drawings
The following drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain the invention, without limitation to the invention.
FIG. 1 is a chromatogram of valeronitrile as the product obtained in example 1.
Detailed Description
The following provides various embodiments or examples to enable those skilled in the art to practice the invention as described herein. These are, of course, merely examples and are not intended to limit the invention from that described. The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and should be considered as specifically disclosed herein.
The invention provides a preparation method of nitrile, which comprises the following steps: mixing and heating aldehyde compounds, ammonia, an oxidant, a catalyst and an accelerator, and reacting to obtain nitrile; wherein the aldehyde compound is selected from aldehyde, acetal or a combination thereof, and the promoter is metal chloride.
According to the present invention, the existing methods for synthesizing nitrile compounds include substitution reaction of halogenated hydrocarbon, dehydration of amide, ammoxidation of olefin, etc. However, these methods have more or less one or more drawbacks such as environmental pollution, high energy consumption, poor product selectivity, etc. Therefore, the inventor of the invention discovers that the aldehyde and/or acetal can be effectively catalyzed to form nitrile by adopting a proper catalyst and a specific accelerator and matching corresponding reaction conditions and oxidants, and the method can remarkably improve the reaction conversion rate and the selectivity of the product, and has simple process, low cost, little environmental pollution and good industrial application prospect.
The process for producing the nitrile of the present invention is specifically described below.
First, an aldehyde compound is provided as a reactant. Wherein, as previously mentioned, the aldehyde compound may be an aldehyde, an acetal, or a combination thereof.
In some embodiments, the aldehyde is selected from one or more of the following compounds: r is R 1 -CHO、CHO-R 1 -CHO; wherein R is 1 Selected from C 2-20 Hydrocarbon groups or halogenated hydrocarbons. For example, n-valeraldehyde, glyoxal, glutaraldehyde, and the like.
In some embodiments, the acetal is selected from one or more of the following compounds:
wherein R is 2 Selected from C 2-20 Is a hydrocarbon or halogenated hydrocarbon of A 1 、A 2 、A 3 、A 4 Each independently selected from C 1-5 Alkyl of A 5 、A 6 Each independently selected from C 2-4 Is a hydrocarbon group. For example, glycerol acetal of n-valeraldehyde, diethylene glycol glyoxal, mono-1, 3-propanediol glyoxal, and the like.
Next, the aldehyde compound, ammonia, an oxidizing agent, a catalyst and a promoter are mixed.
Wherein the ammonia is generally ammonia gas, and the oxidant is selected from one or more of periodic acid, sodium periodate, potassium persulfate, sodium persulfate and hydrogen peroxide, preferably potassium periodate and/or hydrogen peroxide. The amount of the oxidant is 1.05-2 times of the stoichiometric ratio, namely, a small excess of the oxidant is adopted in actual use. Too much oxidant can cause the reactants to oxidize excessively, while insufficient oxidant can reduce the conversion of the reactants.
The promoter is one or more selected from lithium chloride, aluminum chloride, manganese chloride, ferric chloride, cobalt chloride, molybdenum chloride, ruthenium chloride, cerium chloride, lanthanum chloride, copper chloride, chromium chloride and chromia chloride, preferably cerium chloride and/or lanthanum chloride. The hydroxylamine intermediate generated by oxide and ammonia can be stabilized to a certain extent by adopting the accelerator, and the hydroxylamine intermediate has a certain dehydration effect, so that the generation of target products is promoted. The accelerator is not particularly limited, and is preferably used in an amount of 1 to 20% by mole, more preferably 1 to 10% by mole, for example, 1%, 2%, 5%, 7%, 8%, 10% by mole, of the aldehyde compound. This is because too much accelerator results in the formation of secondary amines as by-products, while too little accelerator is not significant.
In some embodiments, the foregoing catalyst is a titanium silicalite, wherein the titanium silicalite may be a titanium silicalite raw powder or a shaped titanium silicalite, the titanium silicalite being selected from one or more of TS-1, TS-2, ti-ZSM-5, ti-ZSM-12, ti-ZSM-48, ti-beta, ti-MCM-41, and Ti-MOR. When the titanium-silicon molecular sieve is selected as the catalyst, the titanium-silicon molecular sieve can be recovered and regenerated after the reaction is finished. Specifically, the method comprises the following steps: after the reaction is finished, the molecular sieve is separated by filtration, and is subjected to washing, drying and regeneration, wherein the regeneration temperature is 120-600 ℃, preferably 200-500 ℃, for example 200 ℃, 300 ℃, 350 ℃, 400 ℃, 420 ℃, 480 ℃, 500 ℃, and the like, and the regeneration atmosphere is nitrogen with 5-50% of volume oxygen content, for example 5%, 15%, 20%, 24%, 30%, 35%, 40%, and the like.
In some embodiments, the catalyst is used in an amount of 0.01% to 10% by mass of the aldehyde compound, for example, 0.01%, 0.05%, 0.1%, 0.8%, 1%, 3%, 6%, 8%, etc., preferably 1% to 5%.
According to the present invention, in some embodiments, the foregoing reaction is performed in a solvent, wherein the solvent is selected from one or more of methanol, ethanol, isopropanol, chloroform, dichloroethane, benzene and toluene, preferably one or more of methanol and ethanol.
Furthermore, in some embodiments, the reaction may also be carried out in an imidazole-based ionic liquid of the formula:
wherein R is 3 、R 4 Each independently selected from C 1-4 X is selected from halogen, BF or straight chain alkyl or branched chain alkyl 4 Or PF (physical pattern) 4 . For example, [ BIMIN ]]Cl (R above) 3 ＝CH 3 -，R 4 ＝n-C 4 H 9 -，X＝Cl - )、[BIMIN]PF 6 (above R) 3 ＝CH 3 -，R 4 ＝n-C 4 H 9 -，X＝PF 6 - )。
The imidazole ionic liquid is adopted to replace the solvent, so that the generation of exertive organic matters can be avoided, and the dosage of the imidazole ionic liquid is 1-20 times of the weight of aldehyde compounds.
In some embodiments, the invention further comprises adding an acid to the reaction system, the acid selected from one or more of hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, and p-phenylsulfonic acid. The addition of acid can further reduce the usage amount of the accelerator, and the usage amount of the acid is 0.1-0.5% of the molar amount of aldehydes.
Finally, after the reactants are mixed and placed in a reaction kettle, the reaction system is heated, the reaction temperature is controlled to be 50-200 ℃, the reaction pressure is controlled to be 0.1-10 MPa, and the nitrile is obtained after a certain time of reaction.
The reaction temperature is preferably 70℃to 150℃such as 70℃80℃85℃90℃100℃120℃140℃150℃and the reaction pressure is preferably 0.1MPa to 1MPa such as 0.1MPa, 0.3MPa, 0.5MPa, 0.6MPa, 0.8MPa, 1MPa and the like. Wherein the "pressure" of the reaction according to the invention means the gauge pressure, i.e. the number by which the total absolute pressure exceeds the ambient atmospheric pressure.
In conclusion, the method can effectively catalyze aldehyde or acetal to form nitrile by adopting specific accelerators and catalysts and matching corresponding reaction conditions and oxidants, has simple process, low cost and small environmental pollution, is suitable for industrial production, and has good industrial application prospect, and the selectivity and yield of the obtained product are greatly improved.
The invention will be further illustrated by the following examples, but the invention is not limited thereby. The reagents, materials, etc. used in the present invention are commercially available unless otherwise specified. Furthermore, the reactions in the examples below were all carried out in 500ml autoclaves, involving pressures of gauge pressure.
Example 1
2g of n-valeraldehyde, 0.1g of TS-1 molecular sieve raw powder, 10ml of ethanol, 5.2g of 30% hydrogen peroxide by mass fraction and 0.1g of cerium chloride are weighed, and after being added into a reaction kettle, the mixture is replaced by 1.0MPa nitrogen for 3 times, and 2g of ammonia gas is filled. Raising the temperature to 90 ℃ for reaction for 3 hours, and then cooling to room temperature to obtain the valeronitrile.
FIG. 1 is a chromatogram of valeronitrile obtained as a product in example 1, and it can be seen from FIG. 1 that valeronitrile was successfully prepared by the method of example 1. The liquid phase was analyzed for valeronitrile content and the results are shown in Table 1.
Example 2
2g of n-valeraldehyde, 0.1g of TS-2 molecular sieve raw powder, 10ml of ethanol, 20.0g of potassium periodate and 0.05g of lanthanum chloride are weighed, and after the mixture is added into a reaction kettle, nitrogen with the pressure of 1.0MPa is used for replacing 3 times, and ammonia gas is filled into the mixture for 2g. Raising the temperature to 95 ℃ for reaction for 3 hours, and then cooling to room temperature to obtain the valeronitrile. The liquid phase was analyzed for valeronitrile content and the results are shown in Table 1.
Example 3
3.2g of ethylene glycol acetal of n-valeraldehyde, 0.1g of TS-1 molecular sieve raw powder, 10ml of ethanol are weighed, 20.0g of potassium periodate and 0.05g of cerium chloride are added, after the mixture is added into a reaction kettle, nitrogen with the pressure of 1.0MPa is used for replacing 3 times, and 2g of ammonia gas is filled. Raising the temperature to 100 ℃ for reaction for 3 hours, and then cooling to room temperature to obtain the valeronitrile. The liquid phase was analyzed for valeronitrile content and the results are shown in Table 1.
Example 4
2g of n-valeraldehyde, 0.1g of Ti-beta molecular sieve raw powder and 10ml of ionic liquid [ BIMIN ] Cl are weighed, 20.0g of potassium persulfate and 0.05g of chromium chloride are added, after the mixture is added into a reaction kettle, nitrogen with the pressure of 1.0MPa is used for 3 times, and ammonia gas with the pressure of 2.5g is filled. Raising the temperature to 70 ℃ for reaction for 3 hours, and then cooling to room temperature to obtain the valeronitrile. The liquid phase was analyzed for valeronitrile content and the results are shown in Table 1.
Example 5
2g of n-valeraldehyde, 0.1g of Ti-beta molecular sieve raw powder and 10ml of ionic liquid [ BIMIN ] are weighed]PF 6 5.2g of 30% hydrogen peroxide by mass fraction and 0.05g of chromium chloride are added, and after the mixture is added into a reaction kettle, nitrogen with the pressure of 1.0MPa is used for replacing 3 times, and 3.0g of ammonia gas is filled. Raising the temperature to 75 ℃ for reaction for 3 hours, and then cooling to room temperature to obtain the valeronitrile. The liquid phase was analyzed for valeronitrile content and the results are shown in Table 1.
Example 6
2g of glycerol acetal of n-valeraldehyde, 0.1g of Ti-beta molecular sieve raw powder and 10ml of ionic liquid [ BIMIN ] are weighed]PF 6 5.2g of 30% hydrogen peroxide by mass fraction and 0.05g of chromium chloride are added, and after the mixture is added into a reaction kettle, nitrogen with the pressure of 1.0MPa is used for replacing 3 times, and 3.0g of ammonia gas is filled. Raising the temperature to 75 ℃ for reaction for 3 hours, and then cooling to room temperature to obtain the valeronitrile. The liquid phase was analyzed for valeronitrile content and the results are shown in Table 1.
Example 7
4g of diethylene glycol glyoxal, 0.1g of Ti-MCM-41 raw powder and 10ml of ionic liquid [ BIMIN ] Cl are weighed, 5.2g of 30% hydrogen peroxide by mass fraction and 0.1g of chromium chloride are added into a reaction kettle, and then the mixture is replaced by 1.0MPa nitrogen for 3 times. 10g of ammonia gas is filled, after the temperature is raised to 90 ℃, the reaction is carried out for 5 hours, and the temperature is reduced to room temperature, thus obtaining adiponitrile. The liquid phase was analyzed for adiponitrile content and the results are shown in Table 1.
Example 8
3g of 1, 3-propanediol hexadialdehyde, 0.1g of TS-1 molecular sieve raw powder, 20ml of methanol are weighed, 4.2g of 30% hydrogen peroxide by mass fraction and 0.05g of chromium chloride are added into a reaction kettle, and then the mixture is replaced by 1.0MPa nitrogen for 3 times. 15g of ammonia gas is filled, and after the temperature is raised to 70 ℃, the reaction is carried out for 12 hours, the temperature is reduced to room temperature, and adiponitrile is obtained. The liquid phase was analyzed for adiponitrile content and the results are shown in Table 1.
Example 9
3g of 1, 3-propanediol hexadialdehyde, 0.1g of TS-2 molecular sieve raw powder and 10ml of ionic liquid [ BIMIN ] Cl are weighed, 4.2g of 30% hydrogen peroxide by mass fraction and 0.05g of chromium chloride are added into a reaction kettle, and the mixture is replaced by nitrogen under the pressure of 1.0MPa for 3 times. 15g of ammonia gas is filled, and after the temperature is raised to 75 ℃, the reaction is carried out for 12 hours, the temperature is reduced to room temperature, and adiponitrile is obtained. The liquid phase was analyzed for adiponitrile content and the results are shown in Table 1.
Example 10
2g of n-valeraldehyde, 0.1g of TS-1 molecular sieve raw powder and 10ml of ethanol are weighed, 5.2g of 30% hydrogen peroxide by mass fraction, 0.02g of cerium chloride and 0.01g of phosphoric acid are added into a reaction kettle, and after the reaction kettle is added into the reaction kettle, nitrogen with the pressure of 1.0MPa is used for replacing 3 times, and ammonia gas is filled into the reaction kettle for 2g. Raising the temperature to 90 ℃ for reaction for 3 hours, and then cooling to room temperature to obtain the valeronitrile.
Comparative example 1
2g of n-valeraldehyde (M=86), 0.1g of TS-1 molecular sieve raw powder and 20ml of ethanol are weighed, 10.0g of potassium periodate (M=230) is added, after the mixture is added into a reaction kettle, nitrogen with the pressure of 1.0MPa is used for replacing 3 times, and ammonia gas is filled into the mixture for 2g. Raising the temperature to 120 ℃ for reaction for 2 hours, and then cooling to room temperature to obtain the valeronitrile. The liquid phase was analyzed for valeronitrile content and the results are shown in Table 1.
Comparative example 2
2g of n-valeraldehyde is weighed, 0.1g of Ti-beta molecular sieve raw powder is contained, the average grain diameter of the catalyst is 75 microns, 20ml of dichloroethane is added, 5.2g of 30% hydrogen peroxide by mass fraction is added into a reaction kettle, nitrogen with the pressure of 1.0MPa is used for replacing 3 times, and 2g of ammonia gas is filled. Raising the temperature to 100 ℃ for reaction for 3 hours, and then cooling to room temperature to obtain the valeronitrile. The liquid phase was analyzed for valeronitrile content and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1 above, the present invention can effectively improve the selectivity and yield of nitrile by using the promoter, which can be more than 80%. In contrast, the reaction may not be performed without the addition of the accelerator, or the conversion may be low. In addition, by comparison, the use of an imidazole-based ionic liquid as a solvent can avoid the use of volatile organic solvents in precursors that achieve similar results. In addition, the addition of acid to the reaction system can reduce the use of accelerators and thus reduce costs.
It will be appreciated by persons skilled in the art that the embodiments described herein are merely exemplary and that various other alternatives, modifications and improvements may be made within the scope of the invention. Thus, the present invention is not limited to the above-described embodiments, but only by the claims.
Claims (10)
1. A process for producing a nitrile, comprising: mixing and heating aldehyde compounds, ammonia, an oxidant, a catalyst and a promoter, and reacting to obtain the nitrile; wherein the aldehyde compound is selected from aldehyde, acetal or a combination thereof, and the promoter is metal chloride;
the metal chloride is one or more selected from cerium chloride, lanthanum chloride and chromium chloride, and the using amount of the accelerator is 1-20% of the molar amount of the aldehyde compound;
the catalyst is a titanium silicalite molecular sieve, wherein the titanium silicalite molecular sieve is titanium silicalite molecular sieve raw powder or formed titanium silicalite molecular sieve, and the titanium silicalite molecular sieve is selected from one or more of TS-1, TS-2, ti-ZSM-5, ti-ZSM-12, ti-ZSM-48, ti-beta, ti-MCM-41 and Ti-MOR.
2. According toThe method of claim 1, wherein the aldehyde is selected from one or more of the following compounds: r is R 1 -CHO、CHO-R 1 -CHO; wherein R is 1 Selected from C 2-20 Hydrocarbon groups or halogenated hydrocarbons.
3. The method of claim 1, wherein the acetal is selected from one or more of the following compounds:
wherein R is 2 Selected from C 2-20 Is a hydrocarbon or halogenated hydrocarbon of A 1 、A 2 、A 3 、A 4 Each independently selected from C 1-5 Alkyl of A 5 、A 6 Each independently selected from C 2-4 Alkylene groups of (a).
4. The preparation method according to claim 1, wherein the oxidizing agent is one or more selected from the group consisting of periodic acid, sodium periodate, potassium persulfate, sodium persulfate, and hydrogen peroxide.
5. The method of claim 1, further comprising filtering the reacted product to isolate the titanium silicalite molecular sieve; and (3) washing and drying the separated titanium-silicon molecular sieve, and heating to 120-600 ℃ in a nitrogen atmosphere with the volume oxygen content of 5-50% to obtain the regenerated molecular sieve.
6. The preparation method according to claim 1, wherein the catalyst is used in an amount of 0.01 to 10% by mass of the aldehyde compound.
7. The method of claim 1, wherein the reaction is performed in a solvent selected from one or more of methanol, ethanol, isopropanol, chloroform, dichloroethane, benzene, and toluene.
8. The preparation method according to claim 1, wherein the reaction is carried out in an imidazole-based ionic liquid represented by the following formula:
wherein R is 3 、R 4 Each independently selected from C 1-4 X is selected from halogen, BF or straight chain alkyl or branched chain alkyl 4 Or PF (physical pattern) 4 。
9. The method of claim 1, further comprising adding an acid to the reaction, the acid selected from one or more of hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, and p-phenylsulfonic acid.
10. The method according to claim 1, wherein the reaction temperature is 50 to 200 ℃ and the pressure is 0.1 to 10MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011092867.6A CN114426502B (en) | 2020-10-13 | 2020-10-13 | Process for the preparation of nitriles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011092867.6A CN114426502B (en) | 2020-10-13 | 2020-10-13 | Process for the preparation of nitriles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114426502A CN114426502A (en) | 2022-05-03 |
| CN114426502B true CN114426502B (en) | 2024-02-09 |
Family
ID=81309117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011092867.6A Active CN114426502B (en) | 2020-10-13 | 2020-10-13 | Process for the preparation of nitriles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114426502B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117431276A (en) * | 2023-09-27 | 2024-01-23 | 江苏维尤纳特精细化工有限公司 | Dinitrile refining method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR800000424B1 (en) * | 1975-07-19 | 1980-05-26 | 셔만 죠셉 케머 | Oxidation catalysts |
| JPH0327350A (en) * | 1989-05-01 | 1991-02-05 | Boc Group Inc:The | Manufacture of nitriles |
| JP2004161703A (en) * | 2002-11-14 | 2004-06-10 | Central Glass Co Ltd | Method for producing 2-fluoro-4-(trifluoromethyl) benzonitrile |
| CN108675942A (en) * | 2018-06-19 | 2018-10-19 | 杭州盛漫生物科技有限公司 | A kind of preparation method of aromatic nitrile compounds |
| CN109336923A (en) * | 2018-11-05 | 2019-02-15 | 南京红太阳生物化学有限责任公司 | A method of alpha-aminonitriles are synthesized using mesoporous molecular sieve catalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0500617A (en) * | 2004-03-10 | 2005-12-06 | Rohm & Haas | Processes for converting alkanes to their corresponding unsaturated carboxylic acid esters, for converting an alkane to its corresponding products and for producing unsaturated carboxylic acids or unsaturated nitriles |
| EP2465842A1 (en) * | 2010-12-17 | 2012-06-20 | Sika Technology AG | Amines with secondary aliphatic amines |
-
2020
- 2020-10-13 CN CN202011092867.6A patent/CN114426502B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR800000424B1 (en) * | 1975-07-19 | 1980-05-26 | 셔만 죠셉 케머 | Oxidation catalysts |
| JPH0327350A (en) * | 1989-05-01 | 1991-02-05 | Boc Group Inc:The | Manufacture of nitriles |
| JP2004161703A (en) * | 2002-11-14 | 2004-06-10 | Central Glass Co Ltd | Method for producing 2-fluoro-4-(trifluoromethyl) benzonitrile |
| CN108675942A (en) * | 2018-06-19 | 2018-10-19 | 杭州盛漫生物科技有限公司 | A kind of preparation method of aromatic nitrile compounds |
| CN109336923A (en) * | 2018-11-05 | 2019-02-15 | 南京红太阳生物化学有限责任公司 | A method of alpha-aminonitriles are synthesized using mesoporous molecular sieve catalyst |
Non-Patent Citations (2)
| Title |
|---|
| Heterogeneously Catalyzed Synthesis of Primary Amides Directly from Primary Alcohols and Aqueous Ammonia;Kazuya Yamaguchi et al.;《Angew. Chem. Int. Ed.》;第51卷;第544-547页 * |
| 液相贝克曼重排反应催化剂的研究进展;陈茗 等;《广州化工》;第45卷(第21期);第1-5页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114426502A (en) | 2022-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2018253450B2 (en) | Method for preparing azoxystrobin intermediates | |
| EP1395547B1 (en) | Copper-catalyzed vapor phase hydrocyanation of diolefinic compounds | |
| CN114426502B (en) | Process for the preparation of nitriles | |
| CN111097421A (en) | Supported metal catalyst and method for preparing primary amine by catalyzing aldehyde compound by using same | |
| CN101234965B (en) | Method for producing dialkyl carbonate | |
| Kurokawa et al. | Solid base-catalyzed reaction of nitriles with methanol to form α, β-unsaturated nitriles I. Conversion and selectivity | |
| CN114933532B (en) | Method for continuously synthesizing 2-n-butyl acetoacetic acid ethyl ester by fixed bed | |
| WO2014067242A1 (en) | Method of preparing n1-(2-aminoethyl)-1,2-ethylenediamine | |
| CN109438402B (en) | Benzofuranone derivatives and synthesis method thereof | |
| US6093847A (en) | Process for the preparation of ibuprofen | |
| CN114426503B (en) | Process for producing dinitrile compound | |
| CN111974442B (en) | Catalyst for producing acrylic acid and methyl acrylate, and preparation method and application thereof | |
| CN101343213B (en) | Allyl ether series compound and preparation thereof | |
| Zhang et al. | Aerobic alcohol ammoxidation catalyzed by copper (I)/amino acid: a scalable protocol to nitriles | |
| US8269036B2 (en) | Processes for producing an oxalate by coupling of CO | |
| CN113735738B (en) | Method for preparing anisic nitrile | |
| CN113845442B (en) | Method for preparing p-bromobenzonitrile | |
| CN115417781B (en) | Method for preparing chlorantraniliprole intermediate K amine | |
| CN115232086B (en) | Preparation method of 4-benzyl-2 (3H) -oxazolone | |
| CN102659624A (en) | Method for preparing cyanophenyl compound | |
| Dornan et al. | Green oxidative synthesis of nitriles | |
| CN107602337B (en) | Preparation method of 1,4-dicyano-2-butene | |
| CN102358715B (en) | Method for synthesizing aromatic nitrile with arylboronic acid | |
| CN110922285B (en) | Method for preparing aryl primary amide by metal catalysis one-pot method | |
| CN116283661A (en) | 2, 3-difluoro-6- (trifluoromethyl) -benzonitrile compound and preparation method thereof |
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 |