CN114349661B - Method for preparing alkanedinitrile by liquid phase ammoxidation - Google Patents
Method for preparing alkanedinitrile by liquid phase ammoxidation Download PDFInfo
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- CN114349661B CN114349661B CN202111672097.7A CN202111672097A CN114349661B CN 114349661 B CN114349661 B CN 114349661B CN 202111672097 A CN202111672097 A CN 202111672097A CN 114349661 B CN114349661 B CN 114349661B
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- compound
- vanadium
- catalyst
- dialdehyde
- phosphorus
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- 239000007791 liquid phase Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 239000012071 phase Substances 0.000 claims abstract description 14
- 235000021003 saturated fats Nutrition 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 66
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical compound [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 claims description 31
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical group N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 28
- 229910021529 ammonia Inorganic materials 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 26
- 125000001931 aliphatic group Chemical group 0.000 claims description 22
- -1 succinyl aldehyde Chemical class 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 21
- 238000000926 separation method Methods 0.000 claims description 19
- 150000003682 vanadium compounds Chemical class 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 15
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 claims description 15
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 12
- 229920006395 saturated elastomer Polymers 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 239000012018 catalyst precursor Substances 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 229910052723 transition metal Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 229910052792 caesium Inorganic materials 0.000 claims description 7
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical group [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 16
- 238000007086 side reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical group O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000470 constituent Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000000919 ceramic Chemical group 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 4
- 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 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001869 cobalt compounds Chemical class 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000005078 molybdenum compound Substances 0.000 description 3
- 150000002752 molybdenum compounds Chemical class 0.000 description 3
- 150000002816 nickel compounds Chemical class 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000003839 salts Chemical group 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- ATWLRNODAYAMQS-UHFFFAOYSA-N 1,1-dibromopropane Chemical compound CCC(Br)Br ATWLRNODAYAMQS-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 150000002443 hydroxylamines Chemical class 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 1
- KXNKVYYLWIDVCK-UHFFFAOYSA-N butanedioyl dicyanide Chemical compound N#CC(=O)CCC(=O)C#N KXNKVYYLWIDVCK-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical class [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst for preparing alkanedinitrile by liquid phase ammoxidation. The catalyst has good selectivity and reaction activity and stable performance, and can enable saturated fat dialdehyde to react under the liquid phase condition for a long time. Compared with gas-phase ammoxidation, the preparation method has milder reaction conditions, does not need to be carried out at high temperature, greatly reduces side reactions of raw materials at high temperature, improves the utilization rate and conversion rate of the raw materials, meets the requirements of industrial production, and is beneficial to popularization and application.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing alkyl dinitrile by liquid phase ammoxidation, in particular to a method for preparing succinonitrile and glutaronitrile.
Background
The alkanedinitriles are widely used organic compounds containing cyano groups, are important organic intermediates, and can be directly used as pesticides, fragrances, metal corrosion inhibitors or liquid crystal materials. With the wide application of nitrile compounds, the synthesis method is also widely focused and studied. The main synthesis methods of the nitrile compounds mainly comprise a halohydrocarbon cyanidation method, an ammoxidation method, a carboxynitrile method, an aldehyde nitrile method, an electrolytic synthesis method, an acetonitrile addition method and an acrylonitrile method. Among them, the ammoxidation method is classified into a gas phase ammoxidation method and a liquid phase ammoxidation method.
Succinonitrile is a very important chemical intermediate, and its derivatives have very wide application, for example, butanediamine, which is one of its derivatives, is the basic raw material for producing nylon 45 and the like. The preparation method of aliphatic dinitrile is usually carboxylic acid ammonification method, and the widely used process is that carboxylic acid or its derivative is heated and dissolved in an open system, then ammonia gas is continuously introduced into the solution, so that the system reacts in the presence of phosphoric acid or phosphate and other catalysts, and the process has the problems of higher reaction temperature, longer reaction time, serious side reaction and the like.
Glutaronitrile is an intermediate of bactericide and has very important application value, and is usually obtained by reacting chlorinated hydrocarbon with cyanide, wherein glutaronitrile is usually obtained by reacting dibromopropane with sodium cyanide, dissolving sodium cyanide in water, adding ethanol solution of dibromopropane, cooling, filtering out precipitate, extracting mother liquor with ethyl acetate, washing with water, drying by potassium carbonate, recovering ethyl acetate, decompressing and distilling residues, and collecting fraction of 144-147 ℃ (1.73 kPa), thus obtaining the finished product with the yield of about 80%. However, the process essentially uses sodium cyanide and hydrogen cyanide which are extremely toxic, and has high requirements on the conditions of the whole equipment, and the reaction temperature is usually high, so that side reactions are caused.
Therefore, further research on the preparation method of the alkyl dinitrile is needed, the yield of the product is improved, the generation of byproducts is reduced, and a high-quality product is obtained.
Disclosure of Invention
In order to solve the problems, the invention provides a catalyst for preparing alkyldinitriles by liquid phase ammoxidation and a preparation method of the alkyldinitriles. The method takes saturated dialdehyde as a raw material, adopts a liquid phase ammoxidation method to prepare dinitrile, continuously reacts, avoids high-temperature decomposition of the raw material, reduces coking on the surface of a catalyst, improves the utilization rate of the raw material and the selectivity of the product, prolongs the service life of the catalyst, has simple process flow and low production cost, and is suitable for realizing industrial production. Moreover, the process does not use extremely toxic raw materials such as sodium cyanide, hydrogen cyanide and the like, thereby completing the invention.
The object of the first aspect of the present invention is to provide a catalyst for the preparation of alkanedinitriles by liquid phase ammoxidation. The catalyst is a vanadium-phosphorus catalyst, wherein the catalyst is prepared by dissolving a component element-containing compound in a solution, adding a catalyst carrier, removing the solvent and drying. Calcining the catalyst precursor in the presence of oxygen to obtain the vanadium-phosphorus catalyst.
The molar ratio of the vanadium compound to the phosphorus compound is 1 (0.5-1.5), preferably 1 (0.6-1.3), more preferably 1 (0.7-1.1). Wherein the molar amounts of the vanadium compound and the phosphorus compound are calculated based on the molar amounts of the constituent elements contained therein.
In a preferred embodiment of the present invention, the constituent elements of the vanadium phosphorus catalyst further include a transition metal element and an alkali metal element.
The transition metal element is selected from one or more of titanium, chromium, manganese, iron, cobalt, nickel and palladium, preferably one or more of titanium, chromium, manganese, iron, cobalt and nickel, more preferably one or more of molybdenum, nickel and cobalt, and the component elements of the vanadium-phosphorus catalyst further comprise molybdenum, nickel and cobalt.
The alkali metal element is selected from one or more of potassium, sodium, rubidium and cesium, preferably one or more of potassium, sodium and cesium, more preferably cesium.
The second aspect of the invention aims to provide a preparation method of the vanadium-phosphorus catalyst, which comprises the steps of dissolving a compound containing catalyst component elements in a solution, adding a catalyst carrier, removing the solvent, drying to obtain a catalyst precursor, and calcining in an oxygen atmosphere to obtain the vanadium-phosphorus catalyst.
The object of a third aspect of the present invention is to provide a process for preparing an alkanedinitrile by liquid phase ammoxidation. In the method, saturated aliphatic dialdehyde is used as a raw material, and the raw material is subjected to ammoxidation with an ammonia source and an oxidizing gas in a liquid phase state in the presence of a vanadium-phosphorus catalyst to prepare the alkanedinitrile. The method specifically comprises the following steps:
step 1, respectively preheating saturated aliphatic dialdehyde, an ammonia source and oxidizing gas;
step 2, reacting the preheated saturated aliphatic dialdehyde, an ammonia source and oxidizing gas in the presence of a vanadium-phosphorus catalyst to obtain a mixed reaction phase;
and step 3, carrying out gas-liquid separation on the mixed reaction phase to obtain the alkanedinitrile.
The method for preparing the alkanedinitrile by the vanadium-phosphorus catalyst and the liquid phase ammoxidation has the following beneficial effects:
(1) The vanadium-phosphorus catalyst provided by the invention is used for preparing dinitriles by aiming at saturated aliphatic dialdehyde through liquid-phase ammoxidation, has good selectivity and high activity, can be used for completing the conversion of dinitriles at the temperature of 190-250 ℃, greatly reduces the occurrence of side reactions such as raw material decomposition and the like, and improves the utilization rate of raw materials.
(2) The preparation method of the alkanedinitrile provided by the invention can be carried out in a liquid phase, has mild reaction conditions and simple process, is beneficial to control and is beneficial to popularization and application in actual production.
(3) The preparation method of the invention does not involve the use of cyanide which is a high-toxicity raw material, has relatively low equipment requirement, reduces catalyst coking and greatly reduces production cost.
(4) The separation process of the product of the method for preparing the alkanedinitrile by liquid phase ammoxidation is mainly gas-liquid separation, the separation process is simple and easy to implement, complex equipment and process control are not needed, the obtained product has high yield and low content of byproducts, and the product quality is improved.
Drawings
FIG. 1 shows a succinonitrile gas chromatogram obtained in example 1 of the present invention;
FIG. 2 shows a gas chromatogram of glutaronitrile prepared in example 11 of the present invention.
Detailed Description
The features and advantages of the present invention will become more apparent and evident from the following detailed description of the invention.
The method for preparing the alkanedinitrile by liquid phase ammoxidation provided by the invention takes saturated aliphatic dialdehyde as a raw material, adopts a liquid phase ammoxidation method to continuously react, has relatively mild reaction conditions, reduces high-temperature decomposition of the raw material and surface coking of the catalyst, improves the conversion rate of the process, prolongs the service life of the catalyst, has low production cost, and is suitable for realizing industrial production.
In a first aspect, the present invention provides a catalyst for the preparation of an alkanedinitrile by liquid phase ammoxidation. The catalyst is a vanadium-phosphorus catalyst, wherein the catalyst is prepared by dissolving a component element-containing compound in a solution, adding a catalyst carrier, mixing, and taking out to obtain a catalyst precursor. Calcining the catalyst precursor in the presence of oxygen to obtain the vanadium-phosphorus catalyst.
The molar ratio of the vanadium compound to the phosphorus compound is 1 (0.5-1.5), preferably 1 (0.6-1.3), more preferably 1 (0.7-1.1). Wherein the molar amounts of the vanadium compound and the phosphorus compound are calculated based on the molar amounts of the constituent elements contained therein.
In a preferred embodiment of the present invention, the constituent elements of the vanadium phosphorus catalyst further include a transition metal element and an alkali metal element.
The transition metal element is selected from one or more of titanium, chromium, manganese, iron, cobalt, nickel and palladium, preferably one or more of titanium, chromium, manganese, iron, cobalt and nickel, more preferably one or more of molybdenum, nickel and cobalt, and the component elements of the vanadium-phosphorus catalyst further comprise molybdenum, nickel and cobalt.
In the vanadium-phosphorus catalyst component element compound, the molar ratio of the vanadium compound to the transition metal element-containing compound is 1 (0.1-0.6), preferably 1 (0.15-0.45), and more preferably 1 (0.2-0.3). Wherein the molar amounts of the vanadium compound and the phosphorus compound are calculated based on the molar amounts of the constituent elements contained therein.
Preferably, in the vanadium phosphorus catalyst component element compound, the molar ratio of the molybdenum compound, the nickel compound and the cobalt compound is (0.04-0.17): (0.01-0.09): (0.04-0.18), preferably (0.06-0.15): (0.015-0.07): (0.06-0.15), more preferably (0.08-0.13): (0.02-0.05): (0.08-0.12). Wherein the molar amounts of the molybdenum compound, the nickel compound and the cobalt compound are calculated based on the molar amounts of the constituent elements contained therein.
The alkali metal element is selected from one or more of potassium, sodium, rubidium and cesium, preferably one or more of potassium, sodium and cesium, more preferably cesium.
In the vanadium-phosphorus catalyst component element compound, the molar ratio of the vanadium compound to the alkali metal element compound is 1 (0.01-0.1), preferably 1 (0.025-0.08), and more preferably 1 (0.04-0.06). Wherein the molar amounts of the vanadium compound and the alkali metal compound are calculated based on the molar amounts of the constituent elements contained therein.
The second aspect of the invention provides a preparation method of the vanadium-phosphorus catalyst, which comprises the steps of dissolving a compound containing catalyst component elements in a solution, adding a catalyst carrier, mixing, removing the solvent, drying to obtain a catalyst precursor, and calcining in an atmosphere with oxygen to obtain the vanadium-phosphorus catalyst.
The compound of the catalyst metal component element is salt, metal oxide or acid dissolved in water or acid solution.
The vanadium compound is vanadium oxide such as vanadium pentoxide and vanadium trioxide. The phosphorus compound is a phosphate or phosphoric acid, preferably concentrated phosphoric acid.
The transition metal compound and the alkali metal compound are selected from one or more of salts, metal oxides and acids dissolved in water or an acidic solution.
In a preferred embodiment of the invention, the molybdenum compound is molybdic acid or molybdate, preferably ammonium molybdate and/or sodium molybdate, more preferably ammonium molybdate. The nickel compound is selected from the group consisting of nickel oxides or nickel salts, preferably nickel salts, more preferably nickel chloride. The cobalt compound is selected from oxides or salts of cobalt, preferably cobalt salts, more preferably cobalt chloride or acetate.
The alkali metal compound is selected from alkali metal salts, such as alkali metal nitrate, alkali metal carbonate or alkali metal salt.
The amounts of the vanadium compound, the phosphorus compound, the transition metal compound and the alkali metal compound are specifically as described in the first aspect.
The compound of the catalyst component elements is dissolved in an aqueous solution, preferably an acidic aqueous solution, preferably an organic acid solution, such as oxalic acid solution. The mass concentration of the acidic substance is 10-40%, preferably 20-30%. The molar ratio of the vanadium element to the acid is (0.1-1.0): 2, preferably (0.3-0.8): 2, more preferably (0.5-0.6): 2. The acidic substance is added into the solution, so that the dissolution of the raw materials can be promoted, and the component elements in the catalyst are fully dispersed and contacted.
The catalyst support is selected from molecular sieves, ceramic ring supports or alumina, preferably ceramic ring supports or alumina, more preferably ceramic ring supports.
The calcination is performed in two stages: calcining at 250-450 deg.c for 1.5-6.5 hr and at 300-400 deg.c for 2.5-4.5 hr; the second stage calcination temperature is 500-800 ℃, preferably 600-700 ℃, such as 650 ℃; the calcination time is 5 to 12 hours, preferably 7 to 10 hours. The first stage of calcination is mainly to decompose the metal organic acid salt generated in the preparation of the catalyst at the temperature, the calcination time is to ensure that the organic acid salt in the catalyst can be fully decomposed, and the second stage of calcination is mainly to adjust the valence state of different metal oxides under the high-temperature condition, and the calcination time is to adjust the valence state of the metal element to a stable valence state.
The invention also provides a method for preparing the alkanedinitrile by liquid phase ammoxidation. In the method, saturated aliphatic dialdehyde is used as a raw material, and the raw material is subjected to ammoxidation with an ammonia source and an oxidizing gas in a liquid phase state in the presence of a vanadium-phosphorus catalyst to prepare the alkanedinitrile.
In the present invention, the alkanedinitrile is succinonitrile, glutaronitrile or adiponitrile, preferably succinonitrile or glutaronitrile. The saturated fatty dialdehyde is selected from succinaldehyde, glutaraldehyde or adipaldehyde, preferably succinaldehyde or glutaraldehyde.
The method specifically comprises the following steps:
and step 1, respectively preheating saturated aliphatic dialdehyde, an ammonia source and oxidizing gas.
The ammonia source is selected from ammonia gas, ammonia water or liquid ammonia, preferably ammonia gas. The oxidizing gas is selected from air or oxygen, preferably air.
The preheating temperature of the saturated fatty dialdehyde is lower than the boiling point temperature of the saturated fatty dialdehyde.
In a preferred mode of the invention, the preheating temperature of the saturated fatty dialdehyde is 80-145 ℃, preferably 90-135 ℃, more preferably 95-125 ℃.
Preferably, in the preparation of succinonitrile, the preheating temperature of succinonitrile is 95-145 ℃, preferably 105-135 ℃, more preferably 115-125 ℃; in the preparation of glutaraldehyde, the glutaraldehyde is preheated to a temperature of 80 to 110 ℃, preferably 85 to 105 ℃, more preferably 90 to 98 ℃.
The pressure during preheating is 0.1-4.2MPa, preferably 1.0-3.0MPa.
The preheating temperature of the ammonia source and oxidizing gas is 195-245 ℃, preferably 205-235 ℃, more preferably 215-225 ℃.
In the invention, the saturated fat dialdehyde, the ammonia source and the oxidizing gas are preheated, so that the system can quickly enter a stable reaction stage after entering the reactor, the overall temperature of the reaction system can be controlled, and the conditions that the reaction temperature is too low, the reaction state can not be quickly entered under the process condition, and the reaction is insufficient are avoided.
And step 2, reacting the preheated saturated aliphatic dialdehyde, an ammonia source and oxidizing gas in the presence of a vanadium-phosphorus catalyst to obtain a mixed reaction phase.
The molar ratio of saturated fatty dialdehyde to ammonia source is 1 (2-35), preferably 1 (8-30), more preferably 1 (15-25). The proportion of ammonia is increased, the concentration of ammonia in the reaction system is increased, the contact effect of the catalyst and the aliphatic dialdehyde with the ammonia is enhanced, the ammoxidation reaction is accelerated, and the side reaction caused by insufficient contact is reduced.
The molar ratio of the saturated aliphatic dialdehyde to the oxidizing gas is 1 (15-45), preferably 1 (20-40), more preferably 1 (25-35). When the oxidizing gas is air, oxygen in the air provides an oxygen source for ammoxidation reaction, the ammoxidation reaction of the aliphatic dialdehyde can be promoted by controlling the air proportion in a reasonable range, the oxygen concentration is too high, oxidation side reaction is relatively easy to occur, the oxygen concentration is too low, and the ammoxidation reaction is not completely carried out.
The catalyst has a catalytic treatment capacity of 5-15g of saturated aliphatic dialdehyde, preferably 8-13g of saturated aliphatic dialdehyde, more preferably 10-12g of saturated aliphatic dialdehyde, per 100g of catalyst per hour. The catalyst used in the invention can specifically catalyze saturated aliphatic dialdehyde to carry out ammoxidation to prepare dinitrile, has good selectivity and stable performance, and can stably catalyze the reaction process for a long time.
The residence time of the saturated fatty dialdehyde in the reactor is 6 to 32s, preferably 8 to 26s, more preferably 10 to 20s. The residence time is controlled, so that the aliphatic dialdehyde in the reaction can be completely reacted to generate the corresponding dinitrile, the incomplete reaction can be caused by the too short residence time, the reaction efficiency is lower due to the too long residence time, and meanwhile, side reactions such as excessive oxidation, polymerization and the like can be caused.
The reaction temperature for succinonitrile synthesis is 190-240 ℃, preferably 200-230 ℃, and the reaction pressure is 1.2-4.2 MPa, preferably 1.6-3.0MPa; the reaction temperature for synthesizing glutaronitrile is 180-200 ℃, preferably 185-195 ℃, and the reaction pressure is 1.6-3.0MPa, preferably 1.8-2.8MPa. Because the reaction system is a gas-liquid-solid heterogeneous reaction, the solubility or dispersion effect of ammonia gas and air in saturated fat dialdehyde is increased under the positive pressure condition, and the main purpose is to promote the contact effect of the ammonia gas, the air, the saturated fat dialdehyde and the catalyst.
And step 3, carrying out gas-liquid separation on the mixed reaction phase to obtain the alkanedinitrile.
And (3) introducing the mixed reaction phase obtained in the step (2) into a gas-liquid separator for gas-liquid separation, recycling the gas phase obtained by separation, and separating to obtain the liquid phase which is the alkanedinitrile.
Preferably, after the mixed reaction phase enters the gas-liquid separator, the temperature is reduced, and then the gas-liquid separation is performed. The separation is carried out at 35-75 ℃, preferably 45-75 ℃, more preferably 55-65 ℃. The separation temperature is required to be close to or higher than the melting point of the target product, in order to ensure that the phenomenon of material condensation and pipeline blockage does not occur at the gas-liquid separator, the trapping effect is poor if the trapping temperature is too high, and the product is easy to undergo side reactions, such as polymerization and oxidation, in a trap with continuous high temperature.
The separator is not particularly limited in the invention, and can meet the separation conditions in the invention, and the gas-liquid separation, such as an oil-water separator, can be realized.
The vanadium-phosphorus catalyst provided by the invention can be used for preparing the alkanedinitrile by liquid-phase ammoxidation of saturated aliphatic dialdehyde. Compared with gas phase ammoxidation, the synthesis method has milder reaction conditions, does not need to be carried out at high temperature, greatly reduces side reactions of raw materials at high temperature, and improves the utilization rate and conversion rate of the raw materials. The vanadium-phosphorus catalyst has good selectivity and reaction activity and stable performance, can enable saturated fat dialdehyde to react under the liquid phase condition for a long time, improves the yield of products, meets the requirements of industrial production, and is beneficial to popularization and application.
Examples
Example 1
(1) 58g of vanadium pentoxide was added to a solution composed of 200g of oxalic acid and 600g of water, and stirred for 2 hours. To the above-mentioned mixed solution under stirring was added 6.1g of nickel chloride hexahydrate (NiCl) 2 ·6H 2 O)，125g of ammonium orthomolybdate ((NH) 4 ) 2 MoO 4 ) Stirring for 1 hour, adding 62.8g of phosphoric acid solution (with the concentration of 85.54 wt%) and 4.6g of cesium sulfate, stirring for 2 hours, slowly adding 12.4g of cobalt acetate, stirring for 2 hours, adding 390g of ceramic ring 3X 4mm (manufactured by Jiangxi Hui Co., ltd.), soaking for 24 hours, and taking out to obtain a catalyst precursor. The catalyst precursor is placed in a muffle furnace at 350 ℃ for calcination for 3 hours, then gradually heated to 650 ℃, kept for 8 hours, cooled to room temperature and bottled for standby.
In the preparation of the catalyst, the molar ratio of each element added is V, P, mo, ni, cs, co=1, 0.86, 0.10, 0.04, 0.11.
(2) The raw materials of succinaldehyde, ammonia and air are respectively conveyed into different preheaters for preheating, the preheating temperature of the succinaldehyde is 120 ℃, the preheating temperature of the air and the ammonia is 220 ℃, the preheated succinaldehyde, the ammonia and the air are introduced into a liquid-phase continuous reactor filled with a supported catalyst for reaction, the flow rate of the succinaldehyde is 23.4g/h, and the catalyst loading amount is 213g. The molar ratio of ammonia to succinaldehyde is 20:1, the molar ratio of air to succinaldehyde is 30:1, the reaction temperature is 220 ℃, the reaction pressure is 2.0MPa, and the reaction residence time of succinaldehyde is 13s.
The materials obtained after the reaction enter a gas-liquid separator (an oil-water separator air compressor filter AD 402-04), gas-liquid separation is carried out at 60 ℃, ammonia gas and air obtained by separation are circulated back to a reaction system for continuous reaction, and liquid phase materials are obtained by separation, namely succinonitrile.
The succinonitrile obtained is calculated by gas chromatography analysis: the conversion of succinonitrile was 99.5% and the selectivity of succinonitrile was 98.5%. The gas chromatogram of succinonitrile is shown in FIG. 1.
The catalyst was tested for service life and was considered to be in an inactive state when succinonitrile selectivity was less than 90%. The catalyst in this example had a service life of 3208h.
Example 2
Succinonitrile was prepared as in example 1. The only differences are: the molar ratio of the ammonia gas and the butanedial is 4:1.
Example 3
Succinonitrile was prepared as in example 1. The only differences are: the molar ratio of the ammonia gas and the butanedial is 30:1.
Example 4
Succinonitrile was prepared as in example 1. The only differences are: the reaction was carried out at 190 ℃.
Example 5
Succinonitrile was prepared as in example 1. The only differences are: the reaction was carried out at 240 ℃.
Example 6
Succinonitrile was prepared as in example 1. The only differences are: the reaction was carried out at 3.0MPa.
Example 7
Succinonitrile was prepared as in example 1. The only differences are: the residence time of succinaldehyde was 6s.
Example 8
Succinonitrile was prepared as in example 1. The only differences are: the retention time of succinaldehyde was 18s.
Example 9
Succinonitrile was prepared as in example 1. The only differences are: the residence time of succinaldehyde was 32s.
The conversion of succinonitrile, selectivity to succinonitrile and catalyst operating life in examples 2 to 9 are shown in Table 1:
table 1:
example 11
(1) 58g of vanadium pentoxide was added to a solution composed of 200g of oxalic acid and 600g of water, and stirred for 2 hours. To the above-mentioned mixed solution under stirring was added 4.5g of nickel chloride hexahydrate (NiCl) 2 ·6H 2 O), 13.8g of ammonium orthomolybdate ((NH) 4 ) 2 MoO 4 ) Stirring for 1 hour, adding 66.5g of phosphoric acid solution (concentration 85.54 wt%) and 6.9g of cesium sulfate, stirring for 2 hours, and slowly adding 11.3g of cobalt acetate ((CH) 3 COO) 2 Co), stirring for 2 hours, adding 390g ceramic ring 3X 4mm (manufactured by Jiangxi Huiya), soaking for 24 hours, and taking out to obtain a catalyst precursor. The catalyst precursor is placed in a muffle furnace at 350 ℃ for calcination for 3 hours, then gradually heated to 650 ℃, kept for 8 hours, cooled to room temperature and bottled for standby.
In the preparation of the catalyst, the molar ratio of each element added is V, mo, ni, cs, co=1, 0.91, 0.11, 0.03, 0.06, 0.10.
(2) The glutaraldehyde, ammonia and air are respectively conveyed into different preheaters for preheating, the preheating temperature of glutaraldehyde is 95 ℃, the preheating temperature of air and ammonia is 190 ℃, and the preheated butanedial, ammonia and air are introduced into a liquid-phase continuous reactor filled with a supported catalyst for reaction, wherein the flow rate of glutaraldehyde is 25.2g/h, and the catalyst loading amount is 213g. The molar ratio of ammonia gas to glutaraldehyde is 20:1, the molar ratio of air to glutaraldehyde is 30:1, the reaction temperature is 190 ℃, the reaction pressure is 1.8MPa, and the reaction residence time of glutaraldehyde is 13s.
And (3) feeding the materials obtained after the reaction into a gas-liquid separator, performing gas-liquid separation at 60 ℃, recycling ammonia gas and air obtained by separation into a reaction system, and continuously reacting to obtain the liquid-phase material which is glutaronitrile.
And carrying out gas chromatographic analysis and calculation on the obtained glutaronitrile to obtain the product: glutaraldehyde conversion was 99.7% and glutaronitrile selectivity was 98.7%. The gas chromatogram of glutaronitrile is shown in FIG. 2.
The catalyst was tested for service life and was considered to be in an inactive state when glutaronitrile selectivity was less than 90%. The catalyst in this example had a service life of 3681h.
Comparative example
Succinonitrile was prepared as in example 1, except that: the conversion rate of succinyl aldehyde is 31.7% and the selectivity of succinyl nitrile is 36.9% by taking the 1-sulfobutylpyridine bisulfate ionic liquid hydroxylamine salt with equal mass as a catalyst.
Wherein, the 1-sulfobutylpyridine bisulfate ionic liquid type hydroxylamine salt is as follows:
for a specific preparation method, see example 17 in chinese patent CN103539742 a.
The present invention has been described in detail in connection with the detailed description and/or the exemplary examples and the accompanying drawings, but the description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A method for preparing alkanedinitrile by liquid phase ammoxidation is characterized in that saturated fat dialdehyde is used as a raw material, the raw material is subjected to ammoxidation with an ammonia source and an oxidizing gas in a liquid phase state in the presence of a vanadium-phosphorus catalyst to prepare the alkanedinitrile,
dissolving a compound containing a catalyst component element into a solution, adding a catalyst carrier, and taking out to obtain a catalyst precursor; calcining the catalyst precursor in the presence of oxygen to obtain the vanadium-phosphorus catalyst,
the component elements of the vanadium-phosphorus catalyst also comprise transition metal elements and alkali metal elements;
the transition metal elements are molybdenum, nickel and cobalt;
the alkali metal element is cesium;
the alkane dinitrile is succinonitrile or glutaronitrile; the saturated aliphatic dialdehyde is succinyl aldehyde or glutaraldehyde;
the ammonia source is ammonia gas.
2. The method of claim 1, wherein the step of determining the position of the substrate comprises,
the molar ratio of the vanadium compound to the phosphorus compound is 1 (0.5-1.5), wherein the molar amount of the vanadium compound and the phosphorus compound is calculated by the molar amount of the component elements contained therein;
the molar ratio of the vanadium compound to the transition metal element-containing compound in the vanadium-phosphorus catalyst component element compound is 1 (0.1-0.6), wherein the molar amount of the vanadium compound and the transition metal element-containing compound is calculated by the molar amount of the component element contained therein;
in the vanadium-phosphorus catalyst component element compound, the molar ratio of the vanadium compound to the alkali metal element compound is 1 (0.01-0.1), wherein the molar amount of the vanadium compound and the alkali metal compound is calculated by the molar amount of the component element contained therein.
3. The method of claim 2, wherein the step of determining the position of the substrate comprises,
the molar ratio of the vanadium compound to the phosphorus compound is 1 (0.6-1.3),
in the vanadium-phosphorus catalyst component element compound, the molar ratio of the vanadium compound to the compound containing the transition metal element is 1 (0.15-0.45),
in the vanadium-phosphorus catalyst component element compound, the molar ratio of the vanadium compound to the alkali metal element compound is 1 (0.025-0.08).
4. The method according to claim 1, characterized in that it comprises in particular the following steps:
step 1, respectively preheating saturated aliphatic dialdehyde, an ammonia source and oxidizing gas;
step 2, reacting the preheated saturated aliphatic dialdehyde, an ammonia source and oxidizing gas in the presence of a vanadium-phosphorus catalyst to obtain a mixed reaction phase;
and step 3, carrying out gas-liquid separation on the mixed reaction phase to obtain the alkanedinitrile.
5. The method according to claim 4, wherein in step 1, the preheating temperature of the saturated aliphatic dialdehyde is 80 to 145 ℃; the preheating temperature of the ammonia source and the oxidizing gas is 195-245 ℃.
6. The method according to claim 4, wherein, in step 2,
the mol ratio of the saturated fatty dialdehyde to the ammonia source is 1 (2-35);
the mol ratio of the saturated fatty dialdehyde to the oxidizing gas is 1 (15-45);
the residence time of the saturated fatty dialdehyde in the reactor is 6-32s.
7. The method according to claim 6, wherein, in step 2,
the mol ratio of the saturated fatty dialdehyde to the ammonia source is 1 (8-30);
the mol ratio of the saturated fatty dialdehyde to the oxidizing gas is 1 (20-40);
the residence time of the saturated fatty dialdehyde in the reactor is 8-26s.
8. The method according to claim 4, wherein in the step 2, the reaction temperature for succinonitrile synthesis is 190-240 ℃ and the reaction pressure is 1.2-4.2 MPa; the reaction temperature for synthesizing glutaronitrile is 180-200 ℃, and the reaction pressure is 1.6-3.0MPa.
9. The method according to claim 8, wherein in the step 2, the reaction temperature for succinonitrile synthesis is 200-230 ℃ and the reaction pressure is 1.6-3.0MPa; the reaction temperature for synthesizing glutaronitrile is 185-195 deg.c and the reaction pressure is 1.8-2.8MPa.
10. The process according to claim 4, wherein in step 3, the mixed reaction phase obtained in step 2 is introduced into a gas-liquid separator to perform gas-liquid separation, and the separated gas phase is recovered and reused.
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| CN101774944A (en) * | 2010-02-09 | 2010-07-14 | 南京工业大学 | Acetonitrile production process |
| CN109956889A (en) * | 2017-12-14 | 2019-07-02 | 中国科学院大连化学物理研究所 | A method of catalysis hydroxy aldehyde selection ammoxidation prepares hydroxyl nitrile |
| CN110563554A (en) * | 2019-09-25 | 2019-12-13 | 中国天辰工程有限公司 | Method for producing adiponitrile |
| CN112961075A (en) * | 2021-02-04 | 2021-06-15 | 鞍山七彩化学股份有限公司 | Synthetic method of terephthalonitrile |
| CN114105818A (en) * | 2021-11-11 | 2022-03-01 | 鞍山七彩化学股份有限公司 | Catalyst for catalyzing butyrolactone to obtain succinonitrile and synthesis method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101774944A (en) * | 2010-02-09 | 2010-07-14 | 南京工业大学 | Acetonitrile production process |
| CN109956889A (en) * | 2017-12-14 | 2019-07-02 | 中国科学院大连化学物理研究所 | A method of catalysis hydroxy aldehyde selection ammoxidation prepares hydroxyl nitrile |
| CN110563554A (en) * | 2019-09-25 | 2019-12-13 | 中国天辰工程有限公司 | Method for producing adiponitrile |
| CN112961075A (en) * | 2021-02-04 | 2021-06-15 | 鞍山七彩化学股份有限公司 | Synthetic method of terephthalonitrile |
| CN114105818A (en) * | 2021-11-11 | 2022-03-01 | 鞍山七彩化学股份有限公司 | Catalyst for catalyzing butyrolactone to obtain succinonitrile and synthesis method |
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