CN107413372A - 生产卤代芳腈的流化床催化剂及其使用方法 - Google Patents
生产卤代芳腈的流化床催化剂及其使用方法 Download PDFInfo
- Publication number
- CN107413372A CN107413372A CN201710531530.2A CN201710531530A CN107413372A CN 107413372 A CN107413372 A CN 107413372A CN 201710531530 A CN201710531530 A CN 201710531530A CN 107413372 A CN107413372 A CN 107413372A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- aromatic nitrile
- nitrile halide
- span
- halide
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 116
- -1 aromatic nitrile halide Chemical class 0.000 title claims abstract description 44
- 239000012530 fluid Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002808 molecular sieve Substances 0.000 claims abstract description 17
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 8
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 3
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 3
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 3
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 3
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 3
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 claims abstract 2
- 238000002441 X-ray diffraction Methods 0.000 claims description 18
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- NHWQMJMIYICNBP-UHFFFAOYSA-N 2-chlorobenzonitrile Chemical compound ClC1=CC=CC=C1C#N NHWQMJMIYICNBP-UHFFFAOYSA-N 0.000 claims description 4
- XUHFBOUSHUEAQZ-UHFFFAOYSA-N bromobenzyl cyanide Chemical compound N#CC(Br)C1=CC=CC=C1 XUHFBOUSHUEAQZ-UHFFFAOYSA-N 0.000 claims description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- IAQRNDXVYOQXLS-UHFFFAOYSA-N 2,3-dibromobenzonitrile Chemical compound BrC1=CC=CC(C#N)=C1Br IAQRNDXVYOQXLS-UHFFFAOYSA-N 0.000 claims description 2
- OHDYZVVLNPXKDX-UHFFFAOYSA-N 2,3-dichlorobenzonitrile Chemical compound ClC1=CC=CC(C#N)=C1Cl OHDYZVVLNPXKDX-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- 150000001342 alkaline earth metals Chemical class 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 26
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- 239000011259 mixed solution Substances 0.000 description 19
- 230000000694 effects Effects 0.000 description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 13
- 239000011651 chromium Substances 0.000 description 13
- 150000002825 nitriles Chemical class 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 235000006408 oxalic acid Nutrition 0.000 description 12
- 238000007493 shaping process Methods 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 10
- GJNGXPDXRVXSEH-UHFFFAOYSA-N 4-chlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C=C1 GJNGXPDXRVXSEH-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 229910052720 vanadium Inorganic materials 0.000 description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 235000021384 green leafy vegetables Nutrition 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000005243 fluidization Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011268 mixed slurry Substances 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229910004605 CdOx Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 1
- OSOUNOBYRMOXQQ-UHFFFAOYSA-N 1-chloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1 OSOUNOBYRMOXQQ-UHFFFAOYSA-N 0.000 description 1
- ZPUMMRQAZXRERX-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid;vanadium Chemical compound [V].OC(=O)C(O)C(O)C(O)=O ZPUMMRQAZXRERX-UHFFFAOYSA-N 0.000 description 1
- 241001347978 Major minor Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical class [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 229920006391 phthalonitrile polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000009491 slugging Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7015—CHA-type, e.g. Chabazite, LZ-218
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/001—Calcining
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/28—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing six-membered aromatic rings, e.g. styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种生产卤代芳腈的流化床催化剂及其使用方法。主要解决以往技术中催化剂的卤代芳烃转化率偏低或卤代芳腈选择性偏低的问题。本发明通过采用分子组成为VPaCrbAcMdOx的活性组分,与氧化硅或分子筛载体组合而形成催化剂,其中,A选自碱金属或碱土金属;M选自Ti、Zr、Hf、La、Ce、Nb、Cr、Mo、W、Co、Zn、Fe、Ni、B、Sb、Bi、As、Ga、Ge、Sn、In中的至少一种的技术方案,提升了催化剂的卤代芳腈活性选择性,有效的解决了该技术问题,可用于一系列卤代芳腈产品的工业化生产。
Description
技术领域
本发明涉及一种生产卤代芳腈的流化床催化剂及其使用方法。
背景技术
卤代芳腈是芳腈化合物中的重要一类,可用于生产医药、农药、染料等,是重要的精细化学品。如邻氯苯甲腈经硝化氨解反应可制得多用途偶氮分散染料的重要中间体2-氰基-4-硝苯胺;与卤代苯合成联苯化合物用于制备非肽型抗血管紧张素,还可制备多种消炎杀菌药物;对氯苯甲腈、对溴苯甲腈也常被用做医药和农药中间体等。
芳腈的生产有化学合成、气相氨氧化等方法,其中将芳烃、氨与空气经气相氨氧化反应一步合成芳腈,流程短,污染少,是目前芳腈生产的主要方法。该反应的特点是主副反应都是强放热反应过程。因而,催化剂活性组分及形式的选择和相应反应器的选择就显得至关重要。流化床具有传热传质效率高、易于大型化等优点,但对催化剂物理化学性能和反应器中流态化质量控制尤其是催化剂有较高要求。卤代芳腈作为芳腈中的一类,同样符合上述特点。
在芳烃氨氧化制芳腈的流化床催化剂中,钒系氧化物催化剂是最为有效的催化体系,如V-P、V-Cr等催化体系,通常以氧化铝、碳化硅、氧化硅为载体,制备成不同粒度的球形颗粒在流化床反应器中应用。早期的催化剂通常以简单组成的V-P-O、V-Cr-O等氧化物体系作为催化剂,普遍存在芳腈选择性较低的问题。近年的生产芳腈流化床催化剂,大多采用多组分钒系氧化物催化剂,一定程度上提高了芳腈的选择性。但芳腈催化剂的开发大多针对间苯二甲腈、对苯二甲腈等芳腈化合物,而对卤代芳腈涉及较少。CN1782330中公开了一种制备邻氯苯甲腈的流化床催化剂,以VCraBbXcYdZeOf/SiO2作为催化剂;CN1223579公开了一种制对氯苯甲腈的流化床催化剂,采用组成为VCraAbBcCdOx/SiO2作为催化剂;CN1252043公开了一种制备对溴苯甲腈的方法,使用活性组成为VCraAbBcCdOx的负载催化剂。以上这些流化床催化剂均采用V-Cr系氧化物,同时添加多种组分和二氧化硅载体,以实现卤代芳腈的生产。但是,由于卤代芳烃本身固有的结构特点,与甲苯、二甲苯等芳烃相比,其分子中卤代基团的存在,使α位C-H键的活化更为困难,因此其氨氧化过程中对催化剂的活化能力要求更高。上述所有文献报道的这些催化剂,通常存在催化卤代芳烃氨氧化活性较低的问题,而为了提升活性而提升温度或提高催化剂中V含量后,催化剂的选择性则会出现显著下降。进一步改进生产卤代芳腈的活性选择性是催化剂改进的重要问题。
发明内容
本发明所要解决的技术问题是克服以往技术中催化剂在卤代芳烃氨氧化活性较高时芳腈选择性偏低、催化剂成本高的问题,提供一种新的用于氨氧化制备卤代芳腈的催化剂。该催化剂具有更环保、成本相对低廉、生产卤代芳腈兼具较高活性与选择性,且适用于流化床操作的特点。
为解决上述技术问题,本发明采用的技术方案如下:
一种生产卤代芳腈的流化床催化剂,包括活性组分和载体;活性组分为以原子比计如下组成的组合物:
VPaCrbAcMdOx
式中:A选自碱金属或碱土金属元素中的至少一种;
M选自Ti、Zr、Hf、La、Ce、Nb、Cr、Mo、W、Co、Zn、Fe、Ni、B、Sb、As、Ga、Ge、Sn、In中的至少一种;
其中a的取值范围为0~1.5;b的取值范围为0.1~1;c的取值范围为0.01~0.5;d的取值范围为0~1;x为满足催化剂中各元素化合价所需的氧原子数。
上述技术方案中,优选的a的取值范围不为0。
上述技术方案中,优选的,a的取值范围为0.5~1.5;更优选的,a的取值范围为0.5~1.0。
上述技术方案中,优选的,b的取值范围为0.1~0.7,更优选的,b的取值范围为0.1~0.6。
上述技术方案中,优选的,c的取值范围为0.01~0.5,优选的,c的取值范围为0.01~0.3,更优选的,c的取值范围为0.01~0.2。
上述技术方案中,优选的,d的取值范围为0.01~0.5。
上述技术方案中,优选的,催化剂还含有选自Se和/或Te,其与V的摩尔比为0.01~0.2。
上述技术方案中,优选的,Se和/或Te组分与V的摩尔比为0.02~0.1。
上述技术方案中,五氧化二钒、磷酸及通式A、M各元素对应氧化物是本发明催化剂活性组分的起始原料,也可以选择经适当方法可制得氧化物的其它化合物为本发明催化剂组份的原料。例如:
钒原料:偏钒酸铵、硫酸钒、有机酸钒如草酸钒或酒石酸钒;
磷原料:五氧化二磷、磷钼酸、磷钨酸;
A、M原料:硝酸盐或可溶性的盐。
上述技术方案中,A通常为选自于碱金属和碱土金属元素中的至少一种。更优选的,选自碱金属元素中的至少一种。
上述技术方案中,催化剂组成中的载体含量以重量百分比计为20~70%。更优选的,载体含量为30%~60%。
上述技术方案中,载体优选为SSZ-13分子筛。
上述技术方案中,载体优选为SSZ-13分子筛和氧化硅复合载体。
上述技术方案中,复合载体中SSZ-13分子筛和氧化硅的比例为(1:9)~(9:1);更优选比例为(1:4)~(4:1)。
上述技术方案中,与常见的卤代芳烃氨氧化催化剂不同,载体使用分子筛材料。所述的分子筛载体优选为纯硅分子筛;纯硅分子筛优选自MCM-41、MCM-48、SBA-1、SBA-2、SBA-15、SBA-16、MSU、HMS中的至少一种。
上述技术方案中的催化剂可通过混浆法或浸渍法制备。优选的,使用混浆法制备。
本发明催化剂可形成组合物相结构,其晶相组成可用X射线衍射(XRD)技术进行侦测和定义。符合本发明定义的催化剂,其特征在于催化剂的XRD谱图中归属于V2O5或Cr2O3的主要特征峰和归属于CrVO4的主要衍射特征峰其强度的比值为0~0.5。
符合本发明定义的催化剂,其特征还在于催化剂中应具有CrVO4相,通过本发明的特殊组合和制备方法,可控制其在2θ=27.8±0.5°处衍射峰峰高(I1)和2θ=13.8±0.5°处的衍射峰峰高(I2)比例I1:I2=3.5~6。此时对应的催化剂具有特别良好的催化性能。
上述技术方案中,催化剂制备方法如下:将钒、铬原料溶于酸后与含M原料溶液混合得到混合溶液A,将磷原料、水和载体混合反应制成混合溶液B,混合溶液A和混合溶液B浓缩后得到混合浆料,经干燥焙烧后得到最终催化剂。
优选的,催化剂的制备方法如下:将定量的钒、铬原料溶于加热的酸溶液中,并分别加入除磷原料以外的助催化元素原料并加热搅拌制成混合溶液A;将磷酸水溶液中加入载体并充分加热搅拌制成混合溶液B;将混合溶液A缓慢加入混合溶液B中并进行搅拌浓缩得到一定固含量的混合浆料。将混合浆料通过干燥成型得催化剂前体,将催化剂前体焙烧后得到最终催化剂。
上述技术方案中,优选的,催化剂前体分别在300~350℃预焙烧和500~700℃焙烧活化得最终催化剂。
本发明催化剂可在普通设计的流化床反应器中进行,通常只要保证气流的流态化质量,减少流化过程中“气泡”、“沟流”和“腾涌”等非正常流化现象的产生,同时尽量降低气流返混的程度,以提高反应的选择性。
本发明催化剂可用于生产各种卤代芳腈,包括(邻、间、对)氯苯甲腈、(邻、间、对)溴苯甲腈、二氯苯甲腈、二溴苯甲腈。
本发明催化剂通常在常压下进行反应,也可在加压情况下进行反应,但反应压力提高不利于卤代芳腈产品收率的提高。因此,优选的,反应系统的压力应保持常压或尽量接近于常压。
本发明催化剂在实施例中卤代芳烃的转化率、芳腈的选择性和芳腈收率定义如下:
本发明催化剂实施例考察是在φ38毫米×1800毫米不锈钢流化床反应器中进行,催化剂的加入量600克。
通过本发明所制备的催化剂,通过采用特定的制备方法,具备特定的XRD谱峰,具有更优的氨氧化活性,适用于工业应用;特别是当采用强度和比表面积均较高的纯硅介孔分子筛作为载体,能够显著提升卤代芳烃氨氧化的活性,同时采用本发明的活性组分组成,可在不增加钒含量且降低铬含量的情况下,保持催化剂的高选择性,解决了活性与选择性兼顾的问题,有效提升催化剂的经济性与环保性;此外采用复合载体为催化剂载体,取得了预料不到的技术效果,可明显提高目标产物的选择性。
下面通过实施例对本发明作进一步的阐述,但并不因此而限制本发明范围。
附图说明
图1为本发明优选催化剂的XRD谱图。
图2为对比催化剂的XRD谱图。
具体实施方式
【实施例1】
催化剂制备:
将0.5mol的五氧化二钒与0.3mol三氧化二铬加入加热至85℃的含2mol草酸的50wt%草酸溶液中,充分搅拌反应2h。在保持搅拌的情况下,加入0.02mol五氧化二铌继续反应1h后在溶液中加入0.08mol硝酸钾、含0.1mol钼的磷钼酸和去离子水并搅拌均匀得到溶液A。
将含0.8mol磷酸的20wt%磷酸溶液中加入约200g SBA-15纯硅分子筛后加热搅拌至75℃并持续搅拌2h得混合溶液B。
将溶液A缓慢加入溶液B中,加热搅拌形成稳定混合溶液并浓缩至固含量45%(重量),得粘稠浆料。
将上述浆料在喷雾干燥器中喷雾干燥成形,成形后的催化剂前体于300℃预焙烧2小时,然后在650℃焙烧4.5小时,得催化剂活性组分除O外以原子比组成为:VP0.8Cr0.6K0.08Mo0.1Nb0.04,催化剂XRD谱图见图1。催化剂XRD衍射测试在2θ=27.8°处衍射峰峰高(I1)和2θ=13.8°处的衍射峰峰高(I2)比例I1:I2=4.56。
将催化剂用于对氯甲苯氨氧化制对氯苯甲腈:
反应工艺条件:对氯甲苯∶氨∶空气=1∶4∶35(摩尔)
负荷0.06h-1(WWH)
反应压力0.1MPa(表压)
反应温度420℃
结果:对氯甲苯转化率98.3%
对氯苯甲腈选择性93.7%
对氯苯甲腈收率92.1%
【实施例2-16】
采用与实施例1相同的制备方法,但调整各组分加入量,得不同含量组成的催化剂,采用与实施例1相同的评价条件进行对氯甲苯氨氧化反应,评价结果见表1。
【实施例17】
催化剂制备:
将0.5mol的五氧化二钒与0.3mol三氧化二铬加入加热至85℃的含2mol草酸的50wt%草酸溶液中,充分搅拌反应2h得到溶液A。
将含0.8mol磷酸的20wt%磷酸溶液中加入约200g SBA-15纯硅分子筛后加热搅拌至75℃并持续搅拌2h得混合溶液B。
将溶液A缓慢加入溶液B中,加热搅拌形成稳定混合溶液并浓缩至固含量45%(重量),得粘稠浆料。
将上述浆料在喷雾干燥器中喷雾干燥成形,成形后的催化剂前体于300℃预焙烧2小时,然后在650℃焙烧4.5小时,得催化剂活性组分除O外以原子比组成为:VP0.8Cr0.6,催化剂XRD谱图见图1。催化剂XRD衍射测试在2θ=27.8°处衍射峰峰高(I1)和2θ=13.8°处的衍射峰峰高(I2)比例I1:I2=3.90。
将催化剂用于对氯甲苯氨氧化制对氯苯甲腈:
反应工艺条件同实施例1,评价结果见表1。
【实施例18】
催化剂制备:
将0.5mol的五氧化二钒与0.3mol三氧化二铬加入加热至85℃的含2mol草酸的50wt%草酸溶液中,充分搅拌反应2h得到溶液A。
将含0.8mol磷酸的20wt%磷酸溶液中加入约200gSSZ-13分子筛后加热搅拌至75℃并持续搅拌2h得混合溶液B。
将溶液A缓慢加入溶液B中,加热搅拌形成稳定混合溶液并浓缩至固含量45%(重量),得粘稠浆料。
将上述浆料在喷雾干燥器中喷雾干燥成形,成形后的催化剂前体于300℃预焙烧2小时,然后在650℃焙烧4.5小时,得催化剂活性组分除O外以原子比组成为:VP0.8Cr0.6,催化剂XRD谱图见图1。催化剂XRD衍射测试在2θ=27.8°处衍射峰峰高(I1)和2θ=13.8°处的衍射峰峰高(I2)比例I1:I2=4.16。
将催化剂用于对氯甲苯氨氧化制对氯苯甲腈:
反应工艺条件同实施例1,评价结果见表1。
【实施例19】
催化剂制备:
将0.5mol的五氧化二钒与0.3mol三氧化二铬加入加热至85℃的含2mol草酸的50wt%草酸溶液中,充分搅拌反应2h得到溶液A。
将含0.8mol磷酸的20wt%磷酸溶液中加入50gSSZ-13分子筛、150克氧化硅后加热搅拌至75℃并持续搅拌2h得混合溶液B。
将溶液A缓慢加入溶液B中,加热搅拌形成稳定混合溶液并浓缩至固含量45%(重量),得粘稠浆料。
将上述浆料在喷雾干燥器中喷雾干燥成形,成形后的催化剂前体于300℃预焙烧2小时,然后在650℃焙烧4.5小时,得催化剂活性组分除O外以原子比组成为:VP0.8Cr0.6,催化剂XRD谱图见图1。催化剂XRD衍射测试在2θ=27.8°处衍射峰峰高(I1)和2θ=13.8°处的衍射峰峰高(I2)比例I1:I2=4.30。
将催化剂用于对氯甲苯氨氧化制对氯苯甲腈:
反应工艺条件同实施例1,评价结果见表1。
【实施例20】
催化剂制备:
将0.5mol的五氧化二钒与0.3mol三氧化二铬加入加热至85℃的含2mol草酸的50wt%草酸溶液中,充分搅拌反应2h得到溶液A。
将含0.8mol磷酸的20wt%磷酸溶液中加入150gSSZ-13分子筛、50克氧化硅后加热搅拌至75℃并持续搅拌2h得混合溶液B。
将溶液A缓慢加入溶液B中,加热搅拌形成稳定混合溶液并浓缩至固含量45%(重量),得粘稠浆料。
将上述浆料在喷雾干燥器中喷雾干燥成形,成形后的催化剂前体于300℃预焙烧2小时,然后在650℃焙烧4.5小时,得催化剂活性组分除O外以原子比组成为:VP0.8Cr0.6,催化剂XRD谱图见图1。催化剂XRD衍射测试在2θ=27.8°处衍射峰峰高(I1)和2θ=13.8°处的衍射峰峰高(I2)比例I1:I2=4.27。
将催化剂用于对氯甲苯氨氧化制对氯苯甲腈:
反应工艺条件同实施例1,评价结果见表1。
【对比例1】
将0.5mol的五氧化二钒加入含2mol草酸的50wt%草酸溶液中,充分搅拌,反应2h得含钒溶液。在保持搅拌的状态下顺序加入含0.8mol磷酸的85wt%磷酸,0.08mol的硝酸钾、含0.1mol钼的磷钼酸、0.6mol硝酸铬、0.04mol草酸铌铵和去离子水,并将计量的SBA-15纯硅分子筛在搅拌下慢慢加到上述溶液中,搅拌成稳定混合溶液后并加热蒸发至固含量45%(重量),得粘稠浆料。
将上述浆料在喷雾干燥器中喷雾干燥成形,成形后的催化剂前体于300℃预焙烧2小时,然后在650℃焙烧4.5小时,得催化剂活性组分除O外以原子比组成为:VP0.8Cr0.6K0.08Mo0.1Nb0.04。催化剂XRD谱图见图2。催化剂XRD衍射测试在2θ=27.8°处衍射峰峰高(I1)和2θ=13.8°处的衍射峰峰高(I2)比例I1:I2=3.34。
【对比例2】
采用与对比例1相同的制备方法,但减少权利要求中的某些组分,更换载体,所得催化剂采用与实施例1相同的评价条件进行对氯甲苯氨氧化反应,评价结果见表1。
【对比例3】
采用与实施例13相同的催化剂组成,但调整加料顺序,且催化剂不经预焙烧而直接焙烧。
表1
【实施例21-26】
使用实施例1方法制备催化剂,将催化剂分别用于不同卤代芳腈的氨氧化反应,
反应工艺条件为:
邻氯甲苯∶氨∶空气=1∶4~6∶20~40(摩尔)
负荷0.05~0.06h-1(WWH)
反应压力0.1MPa(表压)
反应温度415~425℃
考评结果如表2所示。
表2
实施例 | 反应原料 | 原料转化率% | 芳腈选择性mol% |
21 | 对氯甲苯 | 98.3 | 93.7 |
22 | 邻氯甲苯 | 98.0 | 90.4 |
23 | 间氯甲苯 | 98.2 | 91.5 |
24 | 对溴甲苯 | 98.5 | 88.7 |
25 | 2,6-二氯甲苯 | 97.9 | 87.5 |
26 | 3,4-二氯甲苯 | 98.2 | 88.2 |
Claims (12)
1.一种生产卤代芳腈的流化床催化剂,包括活性组分和载体;活性组分为以原子比计如下组成的组合物:
VPaCrbAcMdOx
式中:A选自碱金属或碱土金属元素中的至少一种;
M选自Ti、Zr、Hf、La、Ce、Nb、Cr、Mo、W、Co、Zn、Fe、Ni、B、Sb、Bi、As、Ga、Ge、Sn、In中的至少一种;
其中a的取值范围为0~1.5;b的取值范围为0.1~1;c的取值范围为0~0.5;d的取值范围为0~1;x为满足催化剂中各元素化合价所需的氧原子数;
载体为氧化硅或分子筛。
2.如权利要求1所述的生产卤代芳腈的流化床催化剂,其特征在于催化剂的XRD谱图中V2O5或Cr2O3和CrVO4的主要衍射特征峰强度的比例为0~0.5。
3.如权利要求1所述的生产卤代芳腈的流化床催化剂,其特征在于催化剂的XRD衍射图谱中,在2θ=27.8±0.5°处衍射峰峰高(I1)和2θ=13.8±0.5°处的衍射峰峰高(I2)比例I1:I2=3.5~6。
4.如权利要求1所述的生产卤代芳腈的流化床催化剂,其特征在于a的取值范围为0.5~1.5;和/或c的取值范围为0.01~0.5。
5.如权利要求1所述的生产卤代芳腈的流化床催化剂,其特征在于A选自碱金属元素中的至少一种。
6.如权利要求1所述的生产卤代芳腈的流化床催化剂,其特征在于a的取值范围为0.5~1;和/或b的取值范围为0.1~0.7;和/或c的取值范围为0.01~0.3;和/或d的取值范围为0.01~0.5。
7.如权利要求1所述的生产卤代芳腈的流化床催化剂,其特征在于载体在催化剂中以重量计含量为20%~70%。
8.如权利要求1所述的生产卤代芳腈的流化床催化剂,其特征在于载体为分子筛。
9.如权利要求8所述的生产卤代芳腈的流化床催化剂,其特征在于载体选自纯硅分子筛。
10.如权利要求9所述的生产卤代芳腈的流化床催化剂,其特征在于纯硅分子筛选自MCM-41、MCM-48、SBA-1、SBA-2、SBA-15、SBA-16、MSU、HMS中的一种或至少一种。
11.一种生产卤代芳腈的方法,卤代芳烃与权利要求1~10任一项所述催化剂接触反应得到卤代芳腈。
12.如权利要求11所述的生产卤代芳腈的方法,其特征在于所述卤代芳腈选自(邻、间、对)氯苯甲腈、(邻、间、对)溴苯甲腈、二氯苯甲腈、二溴苯甲腈中的一种或至少一种。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710531530.2A CN107413372B (zh) | 2017-07-03 | 2017-07-03 | 生产卤代芳腈的流化床催化剂及其使用方法 |
PCT/CN2018/093041 WO2019007239A1 (zh) | 2017-07-03 | 2018-06-27 | 适用于卤代芳腈生产的流化床催化剂、其制备及应用 |
EP18827532.5A EP3650120A4 (en) | 2017-07-03 | 2018-06-27 | FLUIDIZED BED CATALYST APPLICABLE TO THE PRODUCTION OF HALOARYLNITRILE, ITS PREPARATION AND APPLICATION |
JP2020500036A JP7113066B2 (ja) | 2017-07-03 | 2018-06-27 | ハロゲン化芳香族ニトリルの調製に適した流動床触媒、その調製および用途 |
US16/624,945 US10894247B2 (en) | 2017-07-03 | 2018-06-27 | Fluidized-bed catalyst suitable for the production of halogenated aromatic nitriles, its preparation and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710531530.2A CN107413372B (zh) | 2017-07-03 | 2017-07-03 | 生产卤代芳腈的流化床催化剂及其使用方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107413372A true CN107413372A (zh) | 2017-12-01 |
CN107413372B CN107413372B (zh) | 2020-06-09 |
Family
ID=60427801
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710531530.2A Active CN107413372B (zh) | 2017-07-03 | 2017-07-03 | 生产卤代芳腈的流化床催化剂及其使用方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US10894247B2 (zh) |
EP (1) | EP3650120A4 (zh) |
JP (1) | JP7113066B2 (zh) |
CN (1) | CN107413372B (zh) |
WO (1) | WO2019007239A1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019007239A1 (zh) * | 2017-07-03 | 2019-01-10 | 中国石油化工股份有限公司 | 适用于卤代芳腈生产的流化床催化剂、其制备及应用 |
CN113248355A (zh) * | 2021-07-07 | 2021-08-13 | 山东国邦药业有限公司 | 一种对氯苯甲醛的制备方法 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102519507B1 (ko) * | 2019-09-30 | 2023-04-07 | 주식회사 엘지화학 | 프로필렌의 암모산화용 촉매, 이의 제조 방법, 및 이를 이용한 프로필렌의 암모산화 방법 |
CN113304764B (zh) * | 2021-05-08 | 2023-09-26 | 大连和源化学科技开发有限公司 | 一种用于乙酸甲酯氨化脱水制乙腈的催化剂及其制备方法 |
CN115518688B (zh) * | 2021-06-24 | 2024-01-26 | 中国石油化工股份有限公司 | 一种用于生产2,6-二氯苯甲腈的催化剂及其制备方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1230464A (zh) * | 1998-03-30 | 1999-10-06 | 中国石油化工总公司 | 用于制备卤代芳腈的流化床催化剂 |
CN1230465A (zh) * | 1998-03-30 | 1999-10-06 | 中国石油化工总公司 | 制备卤代芳腈的流化床催化剂 |
CN1443752A (zh) * | 2002-03-13 | 2003-09-24 | 中国石油化工股份有限公司 | 用于制备邻氯苯甲腈的流化床催化剂 |
CN1490080A (zh) * | 2002-10-16 | 2004-04-21 | 中国石油化工股份有限公司 | 用于芳烃氨氧化的流化床催化剂 |
CN103896807A (zh) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | 用于氨氧化制备对苯二甲腈的方法 |
CN106268890A (zh) * | 2016-08-05 | 2017-01-04 | 中国石油化工股份有限公司 | 芳烃氨氧化流化床催化剂、制备方法和用途 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0525367A1 (en) * | 1991-07-10 | 1993-02-03 | Mitsubishi Gas Chemical Company, Inc. | Catalyst and process for producing nitrile compounds |
JP3156734B2 (ja) * | 1991-07-10 | 2001-04-16 | 三菱瓦斯化学株式会社 | ニトリル化合物の製造法および製造用触媒 |
EP1113001B1 (en) * | 1999-12-27 | 2008-11-05 | Mitsubishi Gas Chemical Company, Inc. | Process for producing nitrile compounds |
JP4380866B2 (ja) * | 1999-12-27 | 2009-12-09 | 三菱瓦斯化学株式会社 | ニトリル化合物の製造法 |
WO2002016031A2 (en) * | 2000-08-21 | 2002-02-28 | Showa Denko K. K. | Catalyst for ammoxidation and method for producing nitrile compound using the catalyst |
CN1223579C (zh) | 2002-11-13 | 2005-10-19 | 中国石油化工股份有限公司 | 用于制备对氯苯甲腈的方法 |
CN1252043C (zh) | 2004-02-18 | 2006-04-19 | 中国石油化工股份有限公司 | 用于制备对溴苯甲腈的方法 |
CN106362760B (zh) * | 2016-08-05 | 2018-11-20 | 中国石油化工股份有限公司 | 芳烃氨氧化催化剂、制备方法及其使用方法 |
CN107413372B (zh) * | 2017-07-03 | 2020-06-09 | 中国石油化工股份有限公司 | 生产卤代芳腈的流化床催化剂及其使用方法 |
-
2017
- 2017-07-03 CN CN201710531530.2A patent/CN107413372B/zh active Active
-
2018
- 2018-06-27 WO PCT/CN2018/093041 patent/WO2019007239A1/zh unknown
- 2018-06-27 JP JP2020500036A patent/JP7113066B2/ja active Active
- 2018-06-27 US US16/624,945 patent/US10894247B2/en active Active
- 2018-06-27 EP EP18827532.5A patent/EP3650120A4/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1230464A (zh) * | 1998-03-30 | 1999-10-06 | 中国石油化工总公司 | 用于制备卤代芳腈的流化床催化剂 |
CN1230465A (zh) * | 1998-03-30 | 1999-10-06 | 中国石油化工总公司 | 制备卤代芳腈的流化床催化剂 |
CN1443752A (zh) * | 2002-03-13 | 2003-09-24 | 中国石油化工股份有限公司 | 用于制备邻氯苯甲腈的流化床催化剂 |
CN1490080A (zh) * | 2002-10-16 | 2004-04-21 | 中国石油化工股份有限公司 | 用于芳烃氨氧化的流化床催化剂 |
CN103896807A (zh) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | 用于氨氧化制备对苯二甲腈的方法 |
CN106268890A (zh) * | 2016-08-05 | 2017-01-04 | 中国石油化工股份有限公司 | 芳烃氨氧化流化床催化剂、制备方法和用途 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019007239A1 (zh) * | 2017-07-03 | 2019-01-10 | 中国石油化工股份有限公司 | 适用于卤代芳腈生产的流化床催化剂、其制备及应用 |
US10894247B2 (en) | 2017-07-03 | 2021-01-19 | China Petroleum & Chemical Corporation | Fluidized-bed catalyst suitable for the production of halogenated aromatic nitriles, its preparation and application thereof |
CN113248355A (zh) * | 2021-07-07 | 2021-08-13 | 山东国邦药业有限公司 | 一种对氯苯甲醛的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
EP3650120A1 (en) | 2020-05-13 |
JP7113066B2 (ja) | 2022-08-04 |
US20200139356A1 (en) | 2020-05-07 |
CN107413372B (zh) | 2020-06-09 |
JP2020527450A (ja) | 2020-09-10 |
EP3650120A4 (en) | 2021-04-07 |
WO2019007239A1 (zh) | 2019-01-10 |
US10894247B2 (en) | 2021-01-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107413372A (zh) | 生产卤代芳腈的流化床催化剂及其使用方法 | |
CN102451702B (zh) | 丙烯醛氧化制丙烯酸催化剂及其制备方法 | |
CN106268890B (zh) | 芳烃氨氧化流化床催化剂、制备方法和用途 | |
JP5458088B2 (ja) | ナノ結晶ビスマス−モリブデン混合酸化物の製造方法 | |
CN111097468B (zh) | 烷基吡啶氨氧化催化剂及其制备方法 | |
CN100566829C (zh) | 氨氧化法制丙烯腈催化剂 | |
CN103896807A (zh) | 用于氨氧化制备对苯二甲腈的方法 | |
CN102371156A (zh) | 氨氧化制不饱和腈流化床催化剂及其制备方法 | |
JP2000005603A (ja) | 不飽和ニトリル製造用触媒組成物 | |
CN101992091A (zh) | 氨氧化制不饱和腈流化床催化剂及其制备方法 | |
CN107282062A (zh) | 丙烯氨氧化制丙烯腈的催化剂及其制备方法 | |
CN105195165B (zh) | 一种烯烃氨氧化制不饱和腈的流化床催化剂及其制备方法 | |
CN111097464B (zh) | 钒系催化剂及其制备方法 | |
CN103664696A (zh) | 用于制备苯甲腈的方法 | |
CN107282060A (zh) | 氨氧化工艺丙烯腈催化剂 | |
CN107282063A (zh) | 丙烯氨氧化法丙烯腈催化剂 | |
CN107413371A (zh) | 用于生产卤代芳腈的流化床催化剂及其用途 | |
CN115518688B (zh) | 一种用于生产2,6-二氯苯甲腈的催化剂及其制备方法 | |
CN104549350B (zh) | 丙烯酸催化剂及其制备方法 | |
CN103769128B (zh) | 氨氧化制不饱和腈流化床催化剂的制备方法 | |
JP7459589B2 (ja) | アクリル酸合成用触媒の製造方法 | |
CN112624940B (zh) | 一种制备间苯二甲腈的方法 | |
CN102372650B (zh) | 氨氧化制不饱和腈的方法 | |
CN103539701A (zh) | 用于氨氧化制备邻氯苯甲腈的方法 | |
CN113797946A (zh) | 芳烃氨氧化催化剂及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |