CN106000375B - A kind of method that Ti-Si composite oxide and its catalysis prepare 3- picolines - Google Patents
A kind of method that Ti-Si composite oxide and its catalysis prepare 3- picolines Download PDFInfo
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- CN106000375B CN106000375B CN201610459713.3A CN201610459713A CN106000375B CN 106000375 B CN106000375 B CN 106000375B CN 201610459713 A CN201610459713 A CN 201610459713A CN 106000375 B CN106000375 B CN 106000375B
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- picolines
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- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 229910004339 Ti-Si Inorganic materials 0.000 title claims abstract description 54
- 229910010978 Ti—Si Inorganic materials 0.000 title claims abstract description 54
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical class CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 27
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 26
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 23
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229960003868 paraldehyde Drugs 0.000 claims abstract description 19
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 11
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229960004011 methenamine Drugs 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 53
- 239000010936 titanium Substances 0.000 claims description 44
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 38
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 33
- 229910052719 titanium Inorganic materials 0.000 claims description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 32
- 229910052710 silicon Inorganic materials 0.000 claims description 32
- 239000010703 silicon Substances 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000011833 salt mixture Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 9
- 239000000284 extract Substances 0.000 claims description 8
- 239000008213 purified water Substances 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 229960004756 ethanol Drugs 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000011017 operating method Methods 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 11
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical class CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- 238000007086 side reaction Methods 0.000 abstract 1
- 239000011949 solid catalyst Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- -1 diethyl acetate ammonium Chemical compound 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VWDWKYIASSYTQR-YTBWXGASSA-N sodium;dioxido(oxo)azanium Chemical compound [Na+].[O-][15N+]([O-])=O VWDWKYIASSYTQR-YTBWXGASSA-N 0.000 description 2
- FEKWWZCCJDUWLY-UHFFFAOYSA-N 3-methyl-1h-pyrrole Chemical class CC=1C=CNC=1 FEKWWZCCJDUWLY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- GKKDCARASOJPNG-UHFFFAOYSA-N metaldehyde Chemical compound CC1OC(C)OC(C)OC(C)O1 GKKDCARASOJPNG-UHFFFAOYSA-N 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 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
- 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
- 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
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- C07D213/10—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles from acetaldehyde or cyclic polymers thereof
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of method that Ti-Si composite oxide and its catalysis prepare 3 picolines, using para-acetaldehyde, methenamine as raw material, under Ti-Si composite oxide catalytic action, reacted under 200~270 DEG C and 3.5~10.0Mpa of process conditions, directly filtered after material cooling after completion of the reaction, the solid catalyst layer of gained carries out repeating to apply mechanically, and the fluid product layer of gained obtains 3 picolines after extracting, distilling.Ti-Si composite oxide provided by the invention has bigger serface and very high thermal stability, advantageously reduces the generation of side reaction, can prepare 3 picolines with efficient catalytic, 3 picoline yield significantly improve.This technique effect is related with the weight ratio of ammonium nitrate and ammonium hydrogen carbonate in Ti-Si composite oxide preparation method, and the weight ratio of ammonium nitrate and ammonium hydrogen carbonate is 6~8:When 1, Ti-Si composite oxide catalytic efficiency highest.
Description
Technical field
The invention belongs to medicinal chemistry art, is related to a kind of Ti-Si composite oxide and its catalysis prepares 3- picolines
Method.
Background technology
The preparation method of 3- picolines is mainly the following：(1) vapor phase method：Using formaldehyde, acetaldehyde, ammonia as raw material, lead to
The mixture that fixed bed reactors directly generate several pyridines is crossed, by isolated 3- picolines；(2) liquid phase method：With three
Metacetaldehyde, methenamine are raw material, and under the action of ammonium dibasic phosphate solution, 3- picolines are obtained through high-temperature high-voltage reaction；
(3) liquid phase method：Using para-acetaldehyde, methenamine as raw material, under the action of ionic liquid (diethyl acetate ammonium etc.), through high temperature
Reaction under high pressure obtains 3- picolines.
Above-mentioned several preparation methods all Shortcomings：The problem of method (1) is low there are yield, and accessory substance is more；Method (2)
Conversion ratio yield increases, but using ammonium dibasic phosphate solution as catalyst, there are problems that low yield；Method (3) intermediate ion
Liquid is unstable at this point in the reaction, also result in recycled hardly possible, it is of high cost the problem of, industrial metaplasia has not yet been formed at present
Production.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of being suitable for industrialized production, with trimerization
Acetaldehyde, methenamine are raw material, and under Ti-Si composite oxide catalytic action, 3- picolines are prepared by high-temperature high-voltage reaction
Method.
The above-mentioned purpose of the present invention is achieved by following technical solution：
A kind of Ti-Si composite oxide of high catalytic activity, is made by the steps and forms：
Step S1, silicon solution is mixed and made into by the raw material of following parts by weight：Silicon source, 20~30 parts；Surfactant, 5~
15 parts；Deionized water, 60~80 parts；
Step S2, titanium solution is mixed and made into by the raw material of following parts by weight：Titanium source, 20~30 parts；Deionized water, 60~80
Part；
Step S3, titanium solution is added slowly in silicon solution, and 50~70 DEG C of stirrings 1~2 obtain titanium silicon mixed solution when small；
Step S4, the salt-mixture of ammonium nitrate and ammonium hydrogen carbonate is added to above-mentioned titanium silicon mixed solution；Every 100 parts by weight
Add 7~9 parts of the salt-mixture in titanium silicon mixed solution, the weight ratio of ammonium nitrate and ammonium hydrogen carbonate is 6~8:1；
Step S5, step S4 resulting solutions are spray-dried, spray dryer nozzle temperature 180~220 DEG C it
Between, outlet temperature is between 80~120 DEG C；
Step S6, by step S5 products therefroms when 550~650 DEG C of roastings 1.5~2.5 are small, lives up to the high catalysis
The Ti-Si composite oxide of property；Ti/Si molar ratios are 0.5~5 in Ti-Si composite oxide:1.
Further, in step S1, the silicon source is waterglass, the one or more in sodium metasilicate, Ludox.
Further, in step S1, surfactant is Tween-80, Arlacel-20, polyvinylpyrrolidone, polyethylene
One or more in alcohol, cetyl trimethylammonium bromide.
Further, in step S2, the titanium source is titanyl sulfate, metatitanic acid, titanium tetrachloride, titanium tetrabromide, tetrafluoride
One or more in titanium, Titanium Nitrate.
Further, in step S4,8 parts of the salt-mixture, nitric acid are added in the titanium silicon mixed solution of every 100 parts by weight
The weight ratio of ammonium and ammonium hydrogen carbonate is 7:1.
Further, in step S6, Ti/Si molar ratios are 1~4 in the Ti-Si composite oxide:1.
A kind of method for preparing 3- picolines using the catalysis of above-mentioned Ti-Si composite oxide, including following operating procedure：
Step S1, weighs Ti-Si composite oxide and pours into autoclave, adds purified water and ethanol, covers tightly reaction
Kettle, sets 200~270 DEG C of reaction temperature, starts to warm up while stirring；
Step S2, weigh para-acetaldehyde, methenamine, ethanol and purified water be uniformly mixed it is spare, as muddiness need to be filtered first；
Step S3, when reactor temperature is raised to design temperature, opens feed pump, mixing prepared by addition step S2
Material, make charging interior completion when 1~5 is small, reaction pressure is maintained between 3.5~10.0Mpa, after charging keep the temperature 15~
25min；
Step S4, after insulation, reaction kettle leads to cooling water temperature, treats that temperature in the kettle drops to 35~45 DEG C, extracts reaction solution
Filtering, solids are applied mechanically for lower batch reaction, and filtrate is extracted with dichloromethane；
Step S5, takes step S4 lower floors extract, and the dichloromethane and ethanol of recycling are applied mechanically for lower batch reaction, under remaining
Layer extract air-distillation, the cut between 130~180 DEG C of jointing temp is up to 3- picolines.
Further, the molar ratio of para-acetaldehyde and methenamine is 0.5~10:Between 1, para-acetaldehyde and titanium silicon are compound
The weight ratio of oxide is 0.2~10:Between 1.
Further, the molar ratio of para-acetaldehyde and methenamine is 1~4:Between 1, para-acetaldehyde and titanium silicon composite oxygen
The weight ratio of compound is 0.5~5:Between 1.
Further, in step S3, charging rate is adjusted, makes charging interior completion when 1.5~3.5 is small.
Advantages of the present invention：
1st, Ti-Si composite oxide catalytic performance provided by the invention is high, and preparation method is simply easily operated；
2nd, provided by the invention utilize makes the method simple possible that Ti-Si composite oxide catalysis prepares 3- picolines by oneself,
3- picoline yield is more than 95%, significant effect.
Embodiment
The essentiality content of the present invention is further illustrated with reference to embodiment, but present invention protection model is not limited with this
Enclose.Although being explained in detail with reference to preferred embodiment to the present invention, it will be understood by those of ordinary skill in the art that, can be right
Technical scheme technical scheme is modified or replaced equivalently, without departing from the spirit and scope of technical solution of the present invention.
In following embodiments, silicon source uses sodium metasilicate, and waterglass or Ludox can also be used to substitute；Surfactant uses
Polyvinylpyrrolidone, can also use Tween-80, Arlacel-20, polyvinyl alcohol, cetyl trimethylammonium bromide；Titanium source uses
Titanium Nitrate, can also use titanyl sulfate, metatitanic acid, titanium tetrachloride, titanium tetrabromide or titanium tetrafluoride.
Embodiment 1：The preparation and catalysis of Ti-Si composite oxide prepare 3- picolines
Step S1, silicon solution is mixed and made into by the raw material of following parts by weight：Silicon source, 25 parts；Surfactant, 10 parts；Go
Ionized water, 70 parts；
Step S2, titanium solution is mixed and made into by the raw material of following parts by weight：Titanium source, 25 parts；Deionized water, 70 parts；
Step S3, titanium solution is added slowly in silicon solution, and 60 DEG C of stirrings 1.5 obtain titanium silicon mixed solution when small；
Step S4, the salt-mixture of ammonium nitrate and ammonium hydrogen carbonate is added to above-mentioned titanium silicon mixed solution；Every 100 parts by weight
Add 8 parts of the salt-mixture in titanium silicon mixed solution, the weight ratio of ammonium nitrate and ammonium hydrogen carbonate is 7:1；
Step S5, step S4 resulting solutions are spray-dried, and spray dryer nozzle temperature is at 200 DEG C, outlet temperature
Degree is at 100 DEG C；
Step S6, it is compound up to the titanium silicon of the high catalytic activity by step S5 products therefroms when 600 DEG C of roastings 2 are small
Oxide；Ti/Si molar ratios are 3 in Ti-Si composite oxide:1.
The effect that 3- picolines are prepared using Ti-Si composite oxide catalysis is shown in embodiment 8.
Embodiment 2：The preparation and catalysis of Ti-Si composite oxide prepare 3- picolines
Step S1, silicon solution is mixed and made into by the raw material of following parts by weight：Silicon source, 20 parts；Surfactant, 5 parts；Go from
Sub- water, 60 parts；
Step S2, titanium solution is mixed and made into by the raw material of following parts by weight：Titanium source, 20 parts；Deionized water, 60 parts；
Step S3, titanium solution is added slowly in silicon solution, and 50 DEG C of stirrings 2 obtain titanium silicon mixed solution when small；
Step S4, the salt-mixture of ammonium nitrate and ammonium hydrogen carbonate is added to above-mentioned titanium silicon mixed solution；Every 100 parts by weight
Add 7 parts of the salt-mixture in titanium silicon mixed solution, the weight ratio of ammonium nitrate and ammonium hydrogen carbonate is 6:1；
Step S5, step S4 resulting solutions are spray-dried, and spray dryer nozzle temperature is at 180 DEG C, outlet temperature
Degree is at 80 DEG C；
Step S6, by step S5 products therefroms when 550 DEG C of roastings 2.5 are small, is answered up to the titanium silicon of the high catalytic activity
Close oxide；Ti/Si molar ratios are 0.5 in Ti-Si composite oxide:1.
The effect that 3- picolines are prepared using Ti-Si composite oxide catalysis is shown in embodiment 8.
Embodiment 3：The preparation and catalysis of Ti-Si composite oxide prepare 3- picolines
Step S1, silicon solution is mixed and made into by the raw material of following parts by weight：Silicon source, 30 parts；Surfactant, 15 parts；Go
Ionized water, 80 parts；
Step S2, titanium solution is mixed and made into by the raw material of following parts by weight：Titanium source, 30 parts；Deionized water, 80 parts；
Step S3, titanium solution is added slowly in silicon solution, and 70 DEG C of stirrings 1 obtain titanium silicon mixed solution when small；
Step S4, the salt-mixture of ammonium nitrate and ammonium hydrogen carbonate is added to above-mentioned titanium silicon mixed solution；Every 100 parts by weight
Add 9 parts of the salt-mixture in titanium silicon mixed solution, the weight ratio of ammonium nitrate and ammonium hydrogen carbonate is 8:1；
Step S5, step S4 resulting solutions are spray-dried, and spray dryer nozzle temperature is at 220 DEG C, outlet temperature
Degree is at 120 DEG C；
Step S6, by step S5 products therefroms when 650 DEG C of roastings 1.5 are small, is answered up to the titanium silicon of the high catalytic activity
Close oxide；Ti/Si molar ratios are 5 in Ti-Si composite oxide:1.
The effect that 3- picolines are prepared using Ti-Si composite oxide catalysis is shown in embodiment 8.
Embodiment 4：The preparation and catalysis of Ti-Si composite oxide prepare 3- picolines
Step S1, silicon solution is mixed and made into by the raw material of following parts by weight：Silicon source, 25 parts；Surfactant, 10 parts；Go
Ionized water, 70 parts；
Step S2, titanium solution is mixed and made into by the raw material of following parts by weight：Titanium source, 25 parts；Deionized water, 70 parts；
Step S3, titanium solution is added slowly in silicon solution, and 60 DEG C of stirrings 1.5 obtain titanium silicon mixed solution when small；
Step S4, the salt-mixture of ammonium nitrate and ammonium hydrogen carbonate is added to above-mentioned titanium silicon mixed solution；Every 100 parts by weight
Add 8 parts of the salt-mixture in titanium silicon mixed solution, the weight ratio of ammonium nitrate and ammonium hydrogen carbonate is 6:1；
Step S5, step S4 resulting solutions are spray-dried, and spray dryer nozzle temperature is at 200 DEG C, outlet temperature
Degree is at 100 DEG C；
Step S6, it is compound up to the titanium silicon of the high catalytic activity by step S5 products therefroms when 600 DEG C of roastings 2 are small
Oxide；Ti/Si molar ratios are 3 in Ti-Si composite oxide:1.
The effect that 3- picolines are prepared using Ti-Si composite oxide catalysis is shown in embodiment 8.
Embodiment 5：The preparation and catalysis of Ti-Si composite oxide prepare 3- picolines
Step S1, silicon solution is mixed and made into by the raw material of following parts by weight：Silicon source, 25 parts；Surfactant, 10 parts；Go
Ionized water, 70 parts；
Step S2, titanium solution is mixed and made into by the raw material of following parts by weight：Titanium source, 25 parts；Deionized water, 70 parts；
Step S3, titanium solution is added slowly in silicon solution, and 60 DEG C of stirrings 1.5 obtain titanium silicon mixed solution when small；
Step S4, the salt-mixture of ammonium nitrate and ammonium hydrogen carbonate is added to above-mentioned titanium silicon mixed solution；Every 100 parts by weight
Add 8 parts of the salt-mixture in titanium silicon mixed solution, the weight ratio of ammonium nitrate and ammonium hydrogen carbonate is 8:1；
Step S5, step S4 resulting solutions are spray-dried, and spray dryer nozzle temperature is at 200 DEG C, outlet temperature
Degree is at 100 DEG C；
Step S6, it is compound up to the titanium silicon of the high catalytic activity by step S5 products therefroms when 600 DEG C of roastings 2 are small
Oxide；Ti/Si molar ratios are 3 in Ti-Si composite oxide:1.
The effect that 3- picolines are prepared using Ti-Si composite oxide catalysis is shown in embodiment 8.
Embodiment 6：The weight ratio of comparative example, ammonium nitrate and ammonium hydrogen carbonate is 5:1
Step S1, silicon solution is mixed and made into by the raw material of following parts by weight：Silicon source, 25 parts；Surfactant, 10 parts；Go
Ionized water, 70 parts；
Step S2, titanium solution is mixed and made into by the raw material of following parts by weight：Titanium source, 25 parts；Deionized water, 70 parts；
Step S3, titanium solution is added slowly in silicon solution, and 60 DEG C of stirrings 1.5 obtain titanium silicon mixed solution when small；
Step S4, the salt-mixture of ammonium nitrate and ammonium hydrogen carbonate is added to above-mentioned titanium silicon mixed solution；Every 100 parts by weight
Add 8 parts of the salt-mixture in titanium silicon mixed solution, the weight ratio of ammonium nitrate and ammonium hydrogen carbonate is 5:1；
Step S5, step S4 resulting solutions are spray-dried, and spray dryer nozzle temperature is at 200 DEG C, outlet temperature
Degree is at 100 DEG C；
Step S6, it is compound up to the titanium silicon of the high catalytic activity by step S5 products therefroms when 600 DEG C of roastings 2 are small
Oxide；Ti/Si molar ratios are 3 in Ti-Si composite oxide:1.
The effect that 3- picolines are prepared using Ti-Si composite oxide catalysis is shown in embodiment 8.
Embodiment 7：The weight ratio of comparative example, ammonium nitrate and ammonium hydrogen carbonate is 9:1
Step S1, silicon solution is mixed and made into by the raw material of following parts by weight：Silicon source, 25 parts；Surfactant, 10 parts；Go
Ionized water, 70 parts；
Step S2, titanium solution is mixed and made into by the raw material of following parts by weight：Titanium source, 25 parts；Deionized water, 70 parts；
Step S3, titanium solution is added slowly in silicon solution, and 60 DEG C of stirrings 1.5 obtain titanium silicon mixed solution when small；
Step S4, the salt-mixture of ammonium nitrate and ammonium hydrogen carbonate is added to above-mentioned titanium silicon mixed solution；Every 100 parts by weight
Add 8 parts of the salt-mixture in titanium silicon mixed solution, the weight ratio of ammonium nitrate and ammonium hydrogen carbonate is 9:1；
Step S5, step S4 resulting solutions are spray-dried, and spray dryer nozzle temperature is at 200 DEG C, outlet temperature
Degree is at 100 DEG C；
Step S6, it is compound up to the titanium silicon of the high catalytic activity by step S5 products therefroms when 600 DEG C of roastings 2 are small
Oxide；Ti/Si molar ratios are 3 in Ti-Si composite oxide:1.
The effect that 3- picolines are prepared using Ti-Si composite oxide catalysis is shown in embodiment 8.
Embodiment 8：Catalysis prepares the effect example of 3- picolines
The Ti-Si composite oxide catalysis prepared respectively using embodiment 1~7 prepares 3- picolines, passes through 3- methyl pyrroles
The catalytic activity height of Ti-Si composite oxide prepared by the yield comparing embodiment 1~7 of pyridine.Preparation method is catalyzed including as follows
Step：
Step S1, weighs Ti-Si composite oxide and pours into autoclave, adds appropriate purified water and ethanol, covers tightly anti-
Kettle is answered, 200~270 DEG C of reaction temperature is set, starts to warm up while stirring；
Step S2, weigh para-acetaldehyde, methenamine, ethanol in proper amount and purified water be uniformly mixed it is spare, as muddiness needs elder generation
Filtering；
Step S3, when reactor temperature is raised to design temperature, opens feed pump, mixing prepared by addition step S2
Material, makes charging interior completion when 3 is small, reaction pressure is maintained between 3.5~4.5Mpa, and 20min is kept the temperature after charging；
Step S4, after insulation, reaction kettle leads to cooling water temperature, treats that temperature in the kettle drops to 40 DEG C, extracts reaction solution filtering,
Solids is applied mechanically for lower batch reaction, and filtrate is extracted with dichloromethane；
Step S5, takes step S4 lower floors extract, and the dichloromethane and ethanol of recycling are applied mechanically for lower batch reaction, under remaining
Layer extract air-distillation, the cut between 130~180 DEG C of jointing temp is up to 3- picolines.
Wherein, the molar ratio of para-acetaldehyde and methenamine is 2.5:1, para-acetaldehyde and Ti-Si composite oxide weight ratio
For 3:1.
1~7 Ti-Si composite oxide of embodiment is catalyzed the yield such as following table for preparing 3- picolines：
| 3- picolines yield (%) | |
| Embodiment 1 | 96.8 |
| Embodiment 2 | 95.1 |
| Embodiment 3 | 95.5 |
| Embodiment 4 | 95.2 |
| Embodiment 5 | 95.7 |
| Embodiment 6 | 65.8 |
| Embodiment 7 | 66.4 |
Catalysis is prepared in the method for 3- picolines, and the molar ratio of para-acetaldehyde and methenamine can be 0.5~10:1
Between, the weight ratio of para-acetaldehyde and Ti-Si composite oxide can be 0.2~10:Between 1, preferably para-acetaldehyde and Wu Luotuo
The molar ratio of product is 1~4:Between 1, the weight ratio of para-acetaldehyde and Ti-Si composite oxide is 0.5~5:Between 1.Step S3
Middle charging is interior when 1.5~3.5 is small to be completed.
The above results show that Ti-Si composite oxide provided by the invention can prepare 3- picolines, 3- with efficient catalytic
Picoline yield significantly improves, this and the weight ratio of ammonium nitrate and ammonium hydrogen carbonate in Ti-Si composite oxide preparation method
Related, the weight ratio of ammonium nitrate and ammonium hydrogen carbonate is 6~8:When 1, Ti-Si composite oxide catalysis prepares 3- picolines
Efficiency highest.
The effect of above-described embodiment indicates that the essentiality content of the present invention, but the protection of the present invention is not limited with this
Scope.It will be understood by those of ordinary skill in the art that can to technical scheme technical scheme is modified or replaced equivalently,
Without departing from the essence and protection domain of technical solution of the present invention.
Claims (7)
1. a kind of Ti-Si composite oxide, it is characterised in that be made by the steps and form：
Step S1, silicon solution is mixed and made into by the raw material of following parts by weight：Silicon source, 20 ~ 30 parts；Surfactant, 5 ~ 15 parts；Go
Ionized water, 60 ~ 80 parts；
Step S2, titanium solution is mixed and made into by the raw material of following parts by weight：Titanium source, 20 ~ 30 parts；Deionized water, 60 ~ 80 parts；
Step S3, titanium solution is added slowly in silicon solution, and 50 ~ 70 DEG C of stirrings 1 ~ 2 obtain titanium silicon mixed solution when small；
Step S4, the salt-mixture of ammonium nitrate and ammonium hydrogen carbonate is added to above-mentioned titanium silicon mixed solution；The titanium silicon of every 100 parts by weight
Add 7 ~ 9 parts of the salt-mixture in mixed solution, the weight ratio of ammonium nitrate and ammonium hydrogen carbonate is 6 ~ 8:1；
Step S5, step S4 resulting solutions is spray-dried, spray dryer nozzle temperature goes out between 180 ~ 220 DEG C
Mouth temperature is between 80 ~ 120 DEG C；
Step S6, by step S5 products therefroms when 550 ~ 650 DEG C of roastings 1.5 ~ 2.5 are small, up to Ti-Si composite oxide；Titanium silicon
Ti/Si molar ratios are 0.5 ~ 5 in composite oxides:1；
Wherein：In step S1, the silicon source is waterglass, the one or more in sodium metasilicate, Ludox；In step S1, surface
Activating agent is Tween-80, one kind in Arlacel-20, polyvinylpyrrolidone, polyvinyl alcohol, cetyl trimethylammonium bromide
It is or a variety of；In step S2, the titanium source is titanyl sulfate, in metatitanic acid, titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride, Titanium Nitrate
One or more.
2. Ti-Si composite oxide according to claim 1, it is characterised in that：In step S4, the titanium of every 100 parts by weight
Add 8 parts of the salt-mixture in silicon mixed solution, the weight ratio of ammonium nitrate and ammonium hydrogen carbonate is 7:1.
3. Ti-Si composite oxide according to claim 1, it is characterised in that：In step S6, the titanium silicon combined oxidation
Ti/Si molar ratios are 1 ~ 4 in thing:1.
4. the method that one kind prepares 3- picolines using any Ti-Si composite oxide catalysis of claim 1 ~ 3, its
It is characterized in that, including following operating procedure：
Step S1, weighs Ti-Si composite oxide and pours into autoclave, adds purified water and ethanol, covers tightly reaction kettle, if
Determine 200 ~ 270 DEG C of reaction temperature, start to warm up while stirring；
Step S2, weigh para-acetaldehyde, methenamine, ethanol and purified water be uniformly mixed it is spare, as muddiness need to be filtered first；
Step S3, when reactor temperature is raised to design temperature, opens feed pump, mixture prepared by addition step S2, makes
The interior completion when 1 ~ 5 is small is fed, reaction pressure is maintained between 3.5 ~ 10.0Mpa, and 15 ~ 25min is kept the temperature after charging；
Step S4, after insulation, reaction kettle leads to cooling water temperature, treats that temperature in the kettle drops to 35 ~ 45 DEG C, extracts reaction solution filtering,
Solids is applied mechanically for lower batch reaction, and filtrate is extracted with dichloromethane；
Step S5, takes step S4 lower floors extract, and the dichloromethane and ethanol of recycling are applied mechanically for lower batch reaction, remaining lower floor's extraction
Take liquid air-distillation, the cut between 130 ~ 180 DEG C of jointing temp is up to 3- picolines.
5. according to claim 4 be catalyzed the method for preparing 3- picolines, it is characterised in that：Para-acetaldehyde and Wu Luotuo
The molar ratio of product is 0.5 ~ 10:Between 1, the weight ratio of para-acetaldehyde and Ti-Si composite oxide is 0.2 ~ 10:Between 1.
6. according to claim 5 be catalyzed the method for preparing 3- picolines, it is characterised in that：Para-acetaldehyde and Wu Luotuo
The molar ratio of product is 1 ~ 4:Between 1, the weight ratio of para-acetaldehyde and Ti-Si composite oxide is 0.5 ~ 5:Between 1.
7. according to claim 4 be catalyzed the method for preparing 3- picolines, it is characterised in that：In step S3, adjust into
Expect speed, make charging interior completion when 1.5 ~ 3.5 is small.
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| CN1406210A (en) * | 2000-03-02 | 2003-03-26 | 德古萨股份公司 | Method for the production of a titanium-containing zeolite |
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