CN113385220A - Preparation method of catalyst for preparing pyridine and picoline by methanol and ammonia water in one step - Google Patents
Preparation method of catalyst for preparing pyridine and picoline by methanol and ammonia water in one step Download PDFInfo
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- CN113385220A CN113385220A CN202110823746.2A CN202110823746A CN113385220A CN 113385220 A CN113385220 A CN 113385220A CN 202110823746 A CN202110823746 A CN 202110823746A CN 113385220 A CN113385220 A CN 113385220A
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- catalyst
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- molecular sieve
- acid
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 50
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 title claims abstract description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title abstract description 96
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 title abstract description 32
- 235000011114 ammonium hydroxide Nutrition 0.000 title abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 55
- 239000002808 molecular sieve Substances 0.000 claims abstract description 53
- 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 53
- 238000005470 impregnation Methods 0.000 claims abstract description 32
- 239000003513 alkali Substances 0.000 claims abstract description 31
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003446 ligand Substances 0.000 claims abstract description 28
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 21
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 18
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 13
- WVUYYXUATWMVIT-UHFFFAOYSA-N 1-bromo-4-ethoxybenzene Chemical compound CCOC1=CC=C(Br)C=C1 WVUYYXUATWMVIT-UHFFFAOYSA-N 0.000 claims abstract description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 10
- 239000001361 adipic acid Substances 0.000 claims abstract description 9
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 9
- 150000002500 ions Chemical class 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims abstract description 5
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 5
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 73
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 63
- 238000003756 stirring Methods 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 18
- 239000011550 stock solution Substances 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 43
- 239000011259 mixed solution Substances 0.000 description 31
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- 239000007791 liquid phase Substances 0.000 description 16
- 239000002585 base Substances 0.000 description 14
- 238000005303 weighing Methods 0.000 description 13
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 239000012159 carrier gas Substances 0.000 description 8
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 239000002149 hierarchical pore Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 229940044658 gallium nitrate Drugs 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000001384 succinic acid Substances 0.000 description 4
- UJPKMTDFFUTLGM-UHFFFAOYSA-N 1-aminoethanol Chemical compound CC(N)O UJPKMTDFFUTLGM-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000558306 Gynocardia odorata Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- -1 alkyl pyridine Chemical compound 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/655—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/08—Preparation by ring-closure
- C07D213/09—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention relates to a catalyst for preparing pyridine and picoline by a methanol and ammonia water one-step method and a preparation method thereof, the catalyst takes a metal complex solution formed by metal ions and ligands as an impregnation solution to perform impregnation treatment on a ZSM-5 molecular sieve subjected to alkali treatment, and the ligand substances are any one of oxalic acid, malonic acid, succinic acid, adipic acid and 2-methylglutaric acid; the metal ions are any one of Zn, La, Bi, Ga and Cr ions. The catalyst is a ZSM-5 molecular sieve catalyst modified by adopting a low-cost metal complex, is applied to the catalytic reaction of preparing pyridine and picoline by a one-step method of methanol and ammonia water, shows excellent catalytic performance and has stronger application value.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a catalyst for preparing pyridine and picoline by a methanol and ammonia water one-step method and a preparation method thereof.
Background
The pyridine base is an important raw material for fine chemical engineering, and the application range of the pyridine base comprises a plurality of fields of spices, medicines, pesticides, feeds and the like. Pyridine base can be extracted from coal tar, or synthesized by using carbonyl compound (aldehyde or ketone) and ammonia as raw materials.
In the patent of the invention in China with the application number of 200910220800.3, a large chemical and physical research institute of Chinese academy of sciences adopts a rare earth modified ZSM-5/ZSM-11 composite molecular sieve, takes titanium dioxide, alumina sol, silica sol and kaolin as adhesives, and prepares a co-crystallized zeolite catalyst through spray forming, and the co-crystallized zeolite catalyst is applied to the ammonia synthesis of pyridine base from formaldehyde and acetaldehyde. An alcohol ammonia process technical route for preparing pyridine alkali by using ethanol/methanol as a carbon source and ammonia water as an ammonia source is researched for years by the chaulmoogra project group of Hunan university. Hydrogen type ZSM-5 is used as a catalyst carrier, a modified catalyst is prepared by using metal salt, the reaction principle of preparing pyridine base by an alcohol ammonia method is explored, and it is found that alcohol in the raw material is firstly oxidized into aldehyde and then reacts with ammonia to generate pyridine and alkyl pyridine. The technical route for producing pyridine base by alcohol ammonia method can avoid the pollution of aldehyde ammonia method to environment and reduce economic cost.
The process for preparing pyridine base by an aldehyde ammonia method is reported in China, but the process for preparing pyridine base by an alcohol ammonia method is only related. The alcohol ammonia method takes ethanol/methanol and ammonia water as raw materials, wherein the alcohol has the advantages of low price, low toxicity, environmental protection and the like, the source is wider, the yield is higher, and the aldehyde is taken as one of the main raw materials of the aldehyde ammonia method, but has the defects of high price, high toxicity, environmental pollution and the like which are not negligible.
Disclosure of Invention
The invention aims to provide a catalyst for preparing pyridine and picoline by a one-step method from methanol and ammonia water and a preparation method thereof, the invention carries out special pretreatment on a modified metal salt solution impregnation liquid, namely, modified metal elements are combined with ligand substances in the modes of electrostatic force, coordination bonds and the like to form stable complex groups with larger effective radius, and the modified metal elements are loaded on the inner surface and the outer surface of a ZSM-5 molecular sieve pore channel by adopting an impregnation method, so that the modified metal elements can be more uniformly dispersed on the inner surface and the outer surface of the ZSM-5 molecular sieve pore channel, and the purposes of low cost, high activity and good coking resistance of the prepared catalyst are achieved. The method effectively solves the problems of high raw material cost, environmental friendliness, low catalyst activity and easy inactivation existing in the conventional industrial production process of pyridine and pyridine base. The invention relates to a green and economic process catalysis technology for preparing pyridine and picoline by one-step catalysis of methanol and ammonia water.
In order to achieve the above purpose, the specific technical scheme of the invention is as follows:
a catalyst for preparing pyridine and picoline takes a metal complex solution formed by modified metal ions and ligands as an impregnation solution to impregnate a ZSM-5 molecular sieve subjected to alkali treatment, wherein the ligand is any one of oxalic acid, malonic acid, succinic acid, adipic acid and 2-methylglutaric acid; the modified metal ions are any one of Zn, La, Bi, Ga and Cr ions.
As a better embodiment in the application, the ZSM-5 molecular sieve is H-type ZSM-5 or Na-type ZSM-5, and the silica-alumina ratio of the ZSM-5 molecular sieve is 50-100.
As a preferred embodiment herein, the alkali is selected from at least one of sodium hydroxide, potassium hydroxide and sodium metaaluminate.
As a preferred embodiment herein, the molar ratio of modifying metal ion to ligand species is from 1:2 to 1: 4.
A preparation method for preparing pyridine and picoline by a methanol and ammonia water one-step method comprises the steps of modifying a ZSM-5 molecular sieve, firstly carrying out alkali treatment on the molecular sieve, then taking a complex solution prepared by modified metal ions and ligand substances as an impregnation solution, carrying out metal element loading modification on the molecular sieve by adopting an impregnation method, and finally obtaining a ZSM-5 molecular sieve catalyst which is uniformly loaded with metal elements and has a multistage pore channel structure, wherein the specific preparation process comprises the following steps:
(1) mixing molecular sieve raw powder ZSM-5 and an aqueous alkali with the concentration of 0.1-0.4 mol/L in a mass ratio of 10 (1-20), stirring for 4-8 hours at a constant temperature of 60 ℃, washing, filtering, drying and roasting to obtain the ZSM-5 molecular sieve with the hierarchical pore structure;
(2) taking a complex solution formed by the modified metal element and the ligand as a stock solution: dropwise adding 0.2mol/L metal salt solution into a ligand substance solution, adjusting the pH of the mixed solution to be 2-4 by using an acid solution, and performing constant volume to obtain a stock solution with the molar ratio of metal ions to ligands being 1: 2-1: 4, wherein the ligand substance is one of oxalic acid, malonic acid, succinic acid, adipic acid and 2-methylglutaric acid; the modified metal element is one of Zn, La, Bi, Ga and Cr; the pH adjusting liquid is selected from one of hydrochloric acid, nitric acid and sulfuric acid;
(3) adding a certain amount of stock solution obtained in the step (2) into the ZSM-5 molecular sieve treated by the alkali liquor in the step (1) by adopting an impregnation method, stirring and impregnating at a low rotating speed for 4-8 hours under the condition of a constant-temperature water bath at the temperature of 60-80 ℃, and drying and roasting to obtain the catalyst with the content of the modified metal elements converted into metal oxides of 1-8 percent in percentage by weight; then grinding, molding and screening the mixture to prepare the modified catalyst.
Compared with the prior art, the invention has the following beneficial effects:
the hierarchical pore molecular sieve ZSM-5 catalyst modified by the metal complex prepared by the method shows more excellent catalytic activity and stability in the catalytic reaction of preparing pyridine and picoline by a one-step method of methanol and ammonia water. The reason is two aspects: on one hand, the ZSM-5 molecular sieve with the hierarchical pore structure obtained by alkali treatment can effectively improve the mass transfer rate and the coking resistance of reactants and products; on the other hand, the method is characterized in that the salt solution impregnation liquid of the modified metal is specially pretreated, namely, a ligand substance is dropwise added into the salt solution of the modified metal to form a stable complex group with a larger effective radius, so that the modified metal elements can be more uniformly dispersed on the inner and outer surfaces of a pore channel of the ZSM-5 molecular sieve, and the catalytic activity of the catalyst is improved.
And secondly, the prepared catalyst has low cost, high activity and good coking resistance.
And (III) the method is environment-friendly and is a green and economic process catalysis technology.
Detailed Description
A preparation method of a catalyst for preparing pyridine and picoline by a methanol and ammonia water one-step method comprises the steps of modifying a ZSM-5 molecular sieve, firstly carrying out alkali treatment on the molecular sieve, then carrying out metal element loading modification on the molecular sieve by using a complex solution prepared by modified metal ions and ligand substances as an impregnation solution by adopting an impregnation method, and finally obtaining the ZSM-5 molecular sieve catalyst with a hierarchical pore structure and uniformly loaded metal elements, wherein the specific preparation process comprises the following steps:
(1) mixing molecular sieve raw powder ZSM-5 and an aqueous alkali with the concentration of 0.1-0.4 mol/L in a mass ratio of 10 (1-20), stirring for 4-8 hours at a constant temperature of 60 ℃, washing, filtering, drying and roasting to obtain the ZSM-5 molecular sieve with the hierarchical pore structure;
(2) preparing a complex solution formed by metal elements and ligands as a stock solution: dropwise adding 0.2mol/L metal salt solution into a ligand substance solution, adjusting the pH of the mixed solution to be 2-4 by using an acid solution, and performing constant volume to obtain a stock solution with the molar ratio of metal ions to ligands being 1: 2-1: 4, wherein the ligand substance is one of oxalic acid, malonic acid, succinic acid, adipic acid and 2-methylglutaric acid; the modified metal element is one of Zn, La, Bi, Ga and Cr; the pH adjusting liquid is selected from one of hydrochloric acid, nitric acid and sulfuric acid;
(3) adding a certain amount of stock solution obtained in the step (2) into the ZSM-5 molecular sieve treated by the alkali liquor in the step (1) by adopting an impregnation method, stirring and impregnating at a low rotating speed for 4-8 hours under the condition of a constant-temperature water bath at the temperature of 60-80 ℃, and drying and roasting to obtain the modified metal element with the load content of 1-8% in percentage by weight of the catalyst; then grinding, molding and screening the mixture to prepare the modified catalyst.
The present invention will be described in further detail with reference to specific examples to better understand the technical solutions and objects of the present invention, but the present invention is not limited thereto.
Example 1
A method for preparing pyridine and picoline by a methanol and ammonia water one-step method comprises the following steps:
(1) weighing a proper amount of sodium hydroxide, dissolving the sodium hydroxide in 500mL of water, and stirring to dissolve the sodium hydroxide to obtain 0.1mol/L sodium hydroxide solution; weighing 10g of ZSM-5 molecular sieve raw powder with the Si/Al molar ratio of 70 in a three-neck flask, adding the prepared sodium hydroxide solution into the three-neck flask, stirring the mixture for 6 hours in a thermostatic water bath at the temperature of 60 ℃, and performing reduced pressure suction filtration, washing, drying and roasting to obtain the ZSM-5 molecular sieve treated by the alkali solution;
(2) dissolving a proper amount of zinc nitrate in 500mL of water, and stirring to dissolve the zinc nitrate to obtain a 0.2mol/L zinc nitrate solution; dissolving a proper amount of 2-methylglutaric acid in 500mL of water, and stirring to dissolve the 2-methylglutaric acid to obtain a 0.6 mol/L2-methylglutaric acid solution; dropwise adding the zinc nitrate solution into a 2-methylglutaric acid solution, adjusting the pH value of the mixed solution to be 2 by using a hydrochloric acid solution, and performing constant volume to obtain a complex stock solution formed by metal ions and ligand substances;
(3) adopting an impregnation method, taking the stock solution in the step (2) as an impregnation solution, taking a ZSM-5 molecular sieve treated by alkali liquor as a carrier, stirring and impregnating for 6 hours at a low rotating speed under the condition of a constant-temperature water bath at 60 ℃, and drying and roasting to obtain a modified catalyst with the modified metal element Zn load content of 4 percent in percentage by weight of the catalyst; the obtained catalyst is molded, ground and sieved to 10-20 meshes, and finally, the catalyst is packaged by a sample bag for standby and is numbered as sample 1.
A fixed bed reactor is adopted, a mixed solution of methanol and ammonia water is introduced into the reactor at a certain flow rate through a micro metering pump, and after the mixed solution is vaporized by a preheating chamber, air at a certain flow rate is used as carrier gas to drive the mixed solution to flow through the prepared catalyst. And fully cooling the mixture by a cold trap at the temperature of 8 ℃ to obtain a liquid-phase product, standing and separating the liquid-phase product to obtain an oil-phase product, wherein the yield of pyridine and picoline products is shown in table 1.
Example 2
A method for preparing pyridine and picoline by a methanol and ammonia water one-step method comprises the following steps:
(1) weighing a proper amount of sodium hydroxide, dissolving the sodium hydroxide in 500mL of water, and stirring to dissolve the sodium hydroxide to obtain 0.2mol/L sodium hydroxide solution; weighing 10g of ZSM-5 molecular sieve raw powder with Si/Al being 58, placing the raw powder into a three-neck flask, adding the prepared sodium hydroxide solution into the three-neck flask, stirring the mixture for 4 hours in a constant-temperature water bath at the temperature of 60 ℃, and performing reduced pressure suction filtration, washing, drying and roasting to obtain the ZSM-5 molecular sieve treated by the alkali solution;
(2) dissolving a proper amount of lanthanum nitrate in 500mL of water, and stirring to dissolve the lanthanum nitrate to obtain a 0.2mol/L lanthanum nitrate solution; weighing a proper amount of oxalic acid, dissolving the oxalic acid in 500mL of water, stirring to dissolve the oxalic acid to obtain 0.4mol/L oxalic acid solution, dropwise adding the lanthanum nitrate solution into the oxalic acid solution, adjusting the pH value of the mixed solution to be 2 by using a sulfuric acid solution, and fixing the volume to obtain complex stock solution formed by metal ions and ligand substances;
(3) adopting an impregnation method, taking the stock solution in the step (2) as an impregnation solution, taking a ZSM-5 molecular sieve treated by alkali liquor as a carrier, stirring and impregnating for 4 hours at a low rotating speed under the condition of a constant-temperature water bath at 60 ℃, and drying and roasting to obtain a modified catalyst with the modified metal element La load content of 3 percent in terms of the weight percent of the catalyst; the resulting catalyst was molded, ground, sieved to 10-20 mesh, and finally packaged with a sample bag for later use, numbered sample 2.
A fixed bed reactor is adopted, a mixed solution of methanol and ammonia water is introduced into the reactor at a certain flow rate through a micro metering pump, and after the mixed solution is vaporized by a preheating chamber, air at a certain flow rate is used as carrier gas to drive the mixed solution to flow through the prepared catalyst. Fully cooling the mixture by a cold trap at the temperature of 8 ℃ to obtain a liquid phase product, standing and separating the liquid phase product to obtain an oil phase product, wherein the yield of pyridine and picoline products is shown in table 1.
Example 3
A method for preparing pyridine and picoline by a methanol and ammonia water one-step method comprises the following steps:
(1) weighing a proper amount of potassium hydroxide, dissolving the potassium hydroxide in 500mL of water, and stirring to dissolve the potassium hydroxide to obtain a 0.3mol/L potassium hydroxide solution; weighing 10g of ZSM-5 molecular sieve raw powder of which the Si/Al is 82, placing the raw powder into a three-neck flask, adding the prepared potassium hydroxide solution into the three-neck flask, stirring for 6 hours in a thermostatic water bath at 60 ℃, and performing reduced pressure suction filtration, washing, drying and roasting to obtain the ZSM-5 molecular sieve treated by the alkali solution;
(2) dissolving a proper amount of gallium nitrate in 500mL of water, and stirring to dissolve the gallium nitrate to obtain a gallium nitrate solution of 0.2 mol/L; dissolving a proper amount of adipic acid in 500mL of water, stirring to dissolve the adipic acid to obtain 0.8mol/L adipic acid solution, dropwise adding the gallium nitrate solution into the adipic acid solution, regulating the pH value of the mixed solution to be 3 by using a hydrochloric acid solution, and performing constant volume to obtain a complex stock solution formed by metal ions and ligand substances;
(3) adopting an impregnation method, taking the stock solution in the step (2) as an impregnation solution, taking a ZSM-5 molecular sieve treated by alkali liquor as a carrier, stirring and impregnating for 7 hours at a low rotating speed under the condition of a constant-temperature water bath at the temperature of 80 ℃, and drying and roasting to obtain a modified catalyst with the modified metal element Ga load content of 1 percent in terms of the weight percent of the catalyst; the resulting catalyst was molded, ground, sieved to 10-20 mesh, and finally packaged with a sample bag for later use, numbered sample 3.
A fixed bed reactor is adopted, a mixed solution of methanol and ammonia water is introduced into the reactor at a certain flow rate through a micro metering pump, and after the mixed solution is vaporized by a preheating chamber, air at a certain flow rate is used as carrier gas to drive the mixed solution to flow through the prepared catalyst. Fully cooling the mixture by a cold trap at the temperature of 8 ℃ to obtain a liquid phase product, standing and separating the liquid phase product to obtain an oil phase product, wherein the yield of pyridine and picoline products is shown in table 1.
Example 4
A method for preparing pyridine and picoline by a methanol and ammonia water one-step method comprises the following steps:
(1) weighing a proper amount of sodium metaaluminate to dissolve in 500mL of water, and stirring to dissolve the sodium metaaluminate to obtain 0.4mol/L sodium metaaluminate solution; weighing 10g of ZSM-5 molecular sieve raw powder with Si/Al being 100, placing the raw powder into a three-neck flask, adding the prepared sodium metaaluminate solution into the three-neck flask, stirring the mixture for 6 hours in a thermostatic water bath at the temperature of 60 ℃, and performing reduced pressure suction filtration, washing, drying and roasting to obtain the ZSM-5 molecular sieve treated by the alkali solution;
(2) dissolving a proper amount of chromium nitrate in 500mL of water, and stirring to dissolve the chromium nitrate to obtain a 0.2mol/L chromium nitrate solution; dissolving a proper amount of succinic acid in 500mL of water, stirring to dissolve the succinic acid to obtain a 0.4mol/L succinic acid solution, dropwise adding the chromium nitrate solution into the succinic acid solution, adjusting the pH value of the mixed solution to 3 by using a nitric acid solution, and fixing the volume to obtain a complex stock solution formed by metal ions and ligand substances;
(3) adopting an impregnation method, taking the stock solution in the step (2) as an impregnation solution, taking a ZSM-5 molecular sieve treated by alkali liquor as a carrier, stirring and impregnating for 8 hours at a low rotating speed under the condition of a constant-temperature water bath at 70 ℃, and drying and roasting to obtain a modified catalyst with the load content of the modified metal element Gr of 4 percent in terms of the weight percent of the catalyst; the resulting catalyst was molded, ground, sieved to 10-20 mesh, and finally packaged with a sample bag for later use, numbered sample 4.
A fixed bed reactor is adopted, a mixed solution of methanol and ammonia water is introduced into the reactor at a certain flow rate through a micro metering pump, and after the mixed solution is vaporized by a preheating chamber, air at a certain flow rate is used as carrier gas to drive the mixed solution to flow through the prepared catalyst. Reacting methanol and ammonia water to generate pyridine base, hydrocarbon products such as low-carbon alkane, low-carbon olefin and aromatic hydrocarbon, amines and the like, fully cooling the obtained product by a cold trap at the temperature of 8 ℃ to obtain a liquid-phase product, standing and separating the liquid-phase product to obtain an oil-phase product, wherein the yield of pyridine and picoline products is shown in table 1.
Example 5
A method for preparing pyridine and picoline by a methanol and ammonia water one-step method comprises the following steps:
adopting an impregnation method, taking a prepared zinc nitrate solution with a certain concentration as an impregnation solution, taking 10g of ZSM-5 molecular sieve raw powder with Si/Al being 70 as a carrier, stirring and impregnating for 6h at a low rotating speed under the condition of a constant-temperature water bath at 60 ℃, and drying and roasting to obtain a modified catalyst with the modified metal element Zn load content of 4 percent in percentage by weight of the catalyst; the resulting catalyst was molded, ground, sieved to 10-20 mesh, and finally packaged with a sample bag for later use, numbered sample 5.
A fixed bed reactor is adopted, a mixed solution of methanol and ammonia water is introduced into the reactor at a certain flow rate through a micro metering pump, and after the mixed solution is vaporized by a preheating chamber, air at a certain flow rate is used as carrier gas to drive the mixed solution to flow through the prepared catalyst. Reacting methanol and ammonia water to generate pyridine base, hydrocarbon products such as low-carbon alkane, low-carbon olefin and aromatic hydrocarbon, amines and the like, fully cooling the obtained product by a cold trap at the temperature of 8 ℃ to obtain a liquid-phase product, standing and separating the liquid-phase product to obtain an oil-phase product, wherein the yield of pyridine and picoline products is shown in table 1.
Example 6
A method for preparing pyridine and picoline by a methanol and ammonia water one-step method comprises the following steps:
(1) weighing a proper amount of sodium hydroxide, dissolving the sodium hydroxide in 500mL of water, and stirring to dissolve the sodium hydroxide to obtain 0.1mol/L sodium hydroxide solution; weighing 10g of ZSM-5 molecular sieve raw powder with Si/Al being 70, placing the raw powder into a three-neck flask, adding the prepared sodium metaaluminate solution into the three-neck flask, stirring the mixture for 6 hours in a thermostatic water bath at the temperature of 60 ℃, and performing reduced pressure suction filtration, washing, drying and roasting to obtain the ZSM-5 molecular sieve treated by the alkali solution;
(3) adopting an impregnation method, taking a prepared zinc nitrate solution with a certain concentration as an impregnation solution, taking a ZSM-5 molecular sieve treated by alkali liquor as a carrier, stirring and impregnating for 6 hours at a low rotating speed under the condition of a constant-temperature water bath at 60 ℃, and drying and roasting to obtain a modified catalyst with the modified metal element Zn load content of 4 percent in percentage by weight of the catalyst; the resulting catalyst was molded, ground, sieved to 10-20 mesh, and finally packaged with a sample bag for later use, numbered sample 6.
A fixed bed reactor is adopted, a mixed solution of methanol and ammonia water is introduced into the reactor at a certain flow rate through a micro metering pump, and after the mixed solution is vaporized by a preheating chamber, air at a certain flow rate is used as carrier gas to drive the mixed solution to flow through the prepared catalyst. Reacting methanol and ammonia water to generate pyridine base, hydrocarbon products such as low-carbon alkane, low-carbon olefin and aromatic hydrocarbon, amines and the like, fully cooling the obtained product by a cold trap at the temperature of 8 ℃ to obtain a liquid-phase product, standing and separating the liquid-phase product to obtain an oil-phase product, wherein the yield of pyridine and picoline products is shown in table 1.
Example 7
A method for preparing pyridine and picoline by a methanol and ammonia water one-step method comprises the following steps:
(1) weighing a proper amount of sodium hydroxide, dissolving the sodium hydroxide in 500mL of water, and stirring to dissolve the sodium hydroxide to obtain 0.1mol/L sodium hydroxide solution; weighing 10g of ZSM-5 molecular sieve raw powder with the Si/Al molar ratio of 70 in a three-neck flask, adding the prepared sodium hydroxide solution into the three-neck flask, stirring the mixture for 6 hours in a thermostatic water bath at the temperature of 60 ℃, and performing reduced pressure suction filtration, washing, drying and roasting to obtain the ZSM-5 molecular sieve treated by the alkali solution;
(2) dissolving a proper amount of copper nitrate in 500mL of water, and stirring to dissolve the copper nitrate to obtain a 0.2mol/L copper nitrate solution; dissolving a proper amount of 2-methylglutaric acid in 500mL of water, and stirring to dissolve the 2-methylglutaric acid to obtain a 0.6 mol/L2-methylglutaric acid solution; dropwise adding the copper nitrate solution into a 2-methylglutaric acid solution, adjusting the pH value of the mixed solution to be 2 by using a hydrochloric acid solution, and performing constant volume to obtain a complex stock solution formed by metal ions and ligand substances;
(3) adopting an impregnation method, taking the stock solution in the step (2) as an impregnation solution, taking a ZSM-5 molecular sieve treated by alkali liquor as a carrier, stirring and impregnating for 6 hours at a low rotating speed under the condition of a constant-temperature water bath at 60 ℃, and drying and roasting to obtain a modified catalyst with the modified metal element Cu load content of 4 percent in terms of the weight percent of the catalyst; the resulting catalyst was molded, ground, sieved to 10-20 mesh, and finally packaged with a sample bag for later use, numbered sample 7.
A fixed bed reactor is adopted, a mixed solution of methanol and ammonia water is introduced into the reactor at a certain flow rate through a micro metering pump, and after the mixed solution is vaporized by a preheating chamber, air at a certain flow rate is used as carrier gas to drive the mixed solution to flow through the prepared catalyst. And fully cooling the mixture by a cold trap at the temperature of 8 ℃ to obtain a liquid-phase product, standing and separating the liquid-phase product to obtain an oil-phase product, wherein the yield of pyridine and picoline products is shown in table 1.
Example 8
One-step preparation of pyridine and picoline from methanol and ammonia water was carried out by using ZSM-5 molecular sieve raw powder having a Si/Al molar ratio of 10g to 70 as a catalyst, and the product was designated as sample 8.
A fixed bed reactor is adopted, a mixed solution of methanol and ammonia water is introduced into the reactor at a certain flow rate through a micro metering pump, and after the mixed solution is vaporized by a preheating chamber, air at a certain flow rate is used as carrier gas to drive the mixed solution to flow through the catalyst. Reacting methanol and ammonia water to generate pyridine base, hydrocarbon products such as low-carbon alkane, low-carbon olefin and aromatic hydrocarbon, amines and the like, fully cooling the obtained product by a cold trap at the temperature of 8 ℃ to obtain a liquid-phase product, standing and separating the liquid-phase product to obtain an oil-phase product, wherein the yield of pyridine and picoline products is shown in table 1.
TABLE 1 yield of pyridine base reaction product in examples
From table 1, it can be found that the yield of pyridine product is very low in the reaction result of sample 8 using ZSM-5 raw powder as a catalyst, while the yield of pyridine and picoline is significantly improved in the reaction results of samples 5 and 6 after alkali treatment and metal ion Zn modification; after the ZSM-5 molecular sieve subjected to alkali treatment is subjected to load modification in a complex ion mode, samples 1, 2, 3 and 4 (respectively modified by Zn, La, Ga and Cr complex ions) show more excellent catalytic effects compared with a conventional modification mode, the yield of pyridine and picoline is greatly improved, and the catalytic effect of a sample 7 modified by Cu complex ions is general; particularly, through comparison of reaction results of samples No. 1, 5 and 6, the best pyridine and picoline yield can be obviously found after the load modification of the Zn complex ion on the base-treated ZSM-5 catalyst. The catalyst prepared by the method takes a stable complex solution formed by active metal ions and ligand substances as an impregnation solution to perform impregnation modification treatment on the ZSM-5 molecular sieve subjected to alkali treatment, so that modified metal elements are more uniformly dispersed on the inner and outer surfaces of a pore channel of the ZSM-5 molecular sieve, and the catalytic activity of the catalyst is improved.
The foregoing basic embodiments of the invention and their various further alternatives can be freely combined to form multiple embodiments, all of which are contemplated and claimed herein. In the scheme of the invention, each selection example can be combined with any other basic example and selection example at will. Numerous combinations will be known to those skilled in the art.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. A catalyst for preparing pyridine and picoline is characterized in that: the catalyst takes a metal complex solution formed by modified metal ions and ligands as an impregnation solution, and the ZSM-5 molecular sieve subjected to alkali treatment is subjected to impregnation treatment, wherein the ligand substance is any one of oxalic acid, malonic acid, succinic acid, adipic acid and 2-methylglutaric acid; the modified metal ions are any one of Zn, La, Bi, Ga and Cr ions.
2. The catalyst of claim 1, wherein: the ZSM-5 molecular sieve is H-type ZSM-5 or Na-type ZSM-5, and the silica-alumina ratio of the ZSM-5 molecular sieve is 50-100.
3. The catalyst of claim 1, wherein: the alkali is at least one selected from sodium hydroxide, potassium hydroxide and sodium metaaluminate.
4. The catalyst of claim 1, wherein: the molar ratio of the modifying metal ion to the ligand species is from 1:2 to 1: 4.
5. A process for preparing a catalyst as claimed in any one of claims 1 to 4, characterized by comprising the steps of:
(1) treating ZSM-5 molecular sieve raw powder with an alkali solution;
(2) preparing a complex solution formed by modified metal ions and ligand substances as a stock solution;
(3) adopting an impregnation method, taking the stock solution as an impregnation solution, and impregnating the ZSM-5 molecular sieve treated by the alkali liquor; then drying, roasting and forming the catalyst to obtain the catalyst.
6. The method of claim 5, wherein: the concentration of the alkali solution in the step (1) is 0.1-0.4 mol/L.
7. The method of claim 5, wherein: the modified metal element loading content is 1-8% by weight of the catalyst.
8. The method of claim 5, wherein: in the process of forming a complex by the metal ions and the ligand in the step (2), the pH of the solution needs to be adjusted to 2-4, and the pH adjusting solution is any one or a mixture of hydrochloric acid, nitric acid and sulfuric acid.
9. The method of claim 5, wherein: and (4) in the dipping process of the modified metal element load in the step (3), the conditions are controlled to be 50-80 ℃ constant-temperature water bath and low-speed stirring dipping for 4-8 hours.
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