CN109096184A - A kind of preparation method of pyridine carboxylic acid class compound - Google Patents
A kind of preparation method of pyridine carboxylic acid class compound Download PDFInfo
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- CN109096184A CN109096184A CN201811016586.5A CN201811016586A CN109096184A CN 109096184 A CN109096184 A CN 109096184A CN 201811016586 A CN201811016586 A CN 201811016586A CN 109096184 A CN109096184 A CN 109096184A
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- class compound
- carboxylic acid
- pyridine carboxylic
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- -1 pyridine carboxylic acid class compound Chemical class 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 50
- 230000003647 oxidation Effects 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 239000012528 membrane Substances 0.000 claims abstract description 35
- 239000002002 slurry Substances 0.000 claims abstract description 24
- 230000001590 oxidative effect Effects 0.000 claims abstract description 23
- 239000007800 oxidant agent Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 239000000706 filtrate Substances 0.000 claims abstract description 13
- 230000001681 protective effect Effects 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 16
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 claims description 16
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 13
- 229960003512 nicotinic acid Drugs 0.000 claims description 13
- 235000001968 nicotinic acid Nutrition 0.000 claims description 13
- 239000011664 nicotinic acid Substances 0.000 claims description 13
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000004615 ingredient Substances 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N Picolinic acid Natural products OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 11
- 238000000926 separation method Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000012805 post-processing Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 238000009295 crossflow filtration Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 210000005036 nerve Anatomy 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical compound CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 description 1
- NYYAUGSBUVAOHW-UHFFFAOYSA-N 2-methyl-1h-pyrrole;pyridine Chemical compound CC1=CC=CN1.C1=CC=NC=C1 NYYAUGSBUVAOHW-UHFFFAOYSA-N 0.000 description 1
- 206010002091 Anaesthesia Diseases 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229930003270 Vitamin B Natural products 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000001949 anaesthesia Methods 0.000 description 1
- 230000037005 anaesthesia Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229940072185 drug for treatment of tuberculosis Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229960003350 isoniazid Drugs 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000005152 nicotinamide Nutrition 0.000 description 1
- 239000011570 nicotinamide Substances 0.000 description 1
- 229960003966 nicotinamide Drugs 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- IBBMAWULFFBRKK-UHFFFAOYSA-N picolinamide Chemical compound NC(=O)C1=CC=CC=N1 IBBMAWULFFBRKK-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- AKGNIBXGIPMDLE-UHFFFAOYSA-N pyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC=C1.OC(=O)C1=CC=NC=C1 AKGNIBXGIPMDLE-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 235000019156 vitamin B Nutrition 0.000 description 1
- 239000011720 vitamin B Substances 0.000 description 1
Classifications
-
- 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
- C07D213/60—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 with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
-
- 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
- C07D213/60—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 with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
-
- 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
- C07D213/60—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 with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
- C07D213/807—Processes of preparation by oxidation of pyridines or condensed pyridines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The present invention provides a kind of preparation methods of pyridine carboxylic acid class compound, comprising the following steps: picoline class compound, gaseous oxidant and protective gas are carried out pressurized, heated processing, until reaction temperature and reaction pressure by (1) pretreatment of raw material respectively；(2) catalytic oxidation will be respectively fed to carry out catalytic oxidation in the slurry bed system oxidation system equipped with catalyst by pretreated raw material in step (1), generate the reaction solution of pyridine carboxylic acid class compound；(3) UF membrane separates the reaction solution of pyridine carboxylic acid class compound obtained in step (2) by inoranic membrane, obtains pyridine carboxylic acid class compound filtrate.Preparation method of the invention has many advantages, such as that technical conditions are mild, easy to operate, high-efficient, cost of material is low, yield is high, low energy consumption, generates in preparation process without harmful exhaust and waste liquid, it can be widely applied to the industrial production of pyridine carboxylic acid class compound, there are good economical, societal benefits.
Description
Technical field
The present invention relates to a kind of preparation methods of organic matter, and in particular to a kind of preparation side of pyridine carboxylic acid class compound
Method.
Background technique
2- pyridine carboxylic acid, niacin (acidum nicotinicum) or isonicotinic acid (Isonicotinic acid) are among important organic synthesis
Body.Wherein, 2- pyridine carboxylic acid can be used for preparing Carbocainum drug and nerve drug, inhibit and local anaesthesia side in nerve
Face is widely used, it can also be used to synthesize 2- pyridine carboxylic acid salt and herbicide etc.；Niacin is vitamin B indispensable in human body3,
The drug that niacin is produced as intermediate is also used for synthesis niacinamide, Buddhist nun gram stops, niacin triazine, herbicide up to as many as tens kinds
With agrochemical；Isonicotinic acid is also used for synthesizing amide, hydrazides, esters etc. and spreads out mainly for the preparation of anti-tuberculosis drugs isoniazid
Biology.
Currently, the synthetic method of pyridine carboxylic acid class compound mainly has: chemical reagent oxidizing process, ammonia oxidation, gas phase are urged
Change oxidizing process and electrochemical oxidation process.
Chemical reagent oxidizing process is the method for earliest pyridine synthesis formic acid, is with potassium permanganate, nitric acid, ozone etc. for oxygen
Agent, the pyridine synthesis formic acid such as direct oxidation picoline, ethylpyridine.This method oxidizer is big, at high cost, and produces
Process can generate a large amount of waste liquids, and environmental pollution is serious, not meet the requirement of Green Chemistry and clean manufacturing.
Ammonia oxidation is one of the important method of industrial production pyridine carboxylic acid, is first by alkyl pyridine 300 ~ 450
DEG C when become steam, then mixed with ammonia, vapor, air or oxygen, catalysis oxidation generates itrile group pyridine, then by hydrolysis,
Obtain pyridine carboxamide and pyridine carboxylic acid.This method reaction temperature is high, and energy consumption is big, and reaction is not easy to control, and catalyst pair
Material purity requires high.
Catalytic gas phase oxidation method is using air or oxygen-enriched air as oxidant, under the effect of the catalyst, by methyl pyrrole
Pyridine is oxidized to pyridine carboxylic acid.For this method compared with ammonia oxidation, reaction temperature is low, and energy consumption is few, convenient for control, but is catalyzed
Agent is high to the purity requirement of raw material, and is easy to produce tar and toxic gas.
Electrochemical oxidation process be using electronics as reagent, by reactant on the electrode electronics gain and loss realize organic compound
A kind of new technology of object synthesis.The problems such as there are technical difficulty height for this method, and production control is stringent, at high cost, and yield is low, because
And experimental stage is remained at present.
By above-mentioned analysis it is found that the synthesis process of existing pyridine carboxylic acid is complex, condition is harsh, cost compared with
Height, production capacity is lower, and pollutant discharge amount is big.As pyridine carboxylic acid class compound is in medicine, chemical industry, food and production and living
Dosage gradually increases, develop it is a kind of it is at low cost, yield is high, the synthetic method right and wrong of environmentally protective pyridine carboxylic acid class compound
It is often necessary.
Summary of the invention
It is an object of the invention to provide a kind of preparation methods of pyridine carboxylic acid class compound, to solve existing preparation method
Complex process, at high cost, heavy-polluted problem.
The object of the present invention is achieved like this:
A kind of preparation method of pyridine carboxylic acid class compound, comprising the following steps:
(1) pretreatment of raw material carries out picoline class compound, gaseous oxidant and protective gas at pressurized, heated respectively
Reason, until reaction temperature and reaction pressure；
(2) catalytic oxidation is aoxidized the slurry bed system equipped with catalyst is respectively fed to by pretreated raw material in step (1)
Catalytic oxidation is carried out in reaction system, generates the reaction solution of pyridine carboxylic acid class compound；
(3) reaction solution of pyridine carboxylic acid class compound obtained in step (2) is separated by inoranic membrane, is obtained by UF membrane
It is post-treated to obtain pyridine carboxylic acid class compound to pyridine carboxylic acid class compound filtrate；Catalyst is trapped in slurry by inoranic membrane
Subsequent reaction is continued to participate in bed oxidation system.
The picoline class compound is 2- picoline, 3- picoline or 4- picoline, pyridine first obtained
Acids product mutually should be 2- pyridine carboxylic acid, niacin or isonicotinic acid.
The gaseous oxidant is pure oxygen, ozone or prepares one or more of air, the gaseous oxidant be with
When air processed, the mass content for preparing oxygen in air is 5% ~ 90%, preferably 10% ~ 50%.
The protective gas is nitrogen or recycled offgas, and the recycled offgas is after reaction carries out a period of time, from slurry
The tail gas (being largely nitrogen, prepare air containing minute quantity) being discharged in bed oxidation reactor.
During the catalytic oxidation of the step (2), controls and risen in picoline class compound and gaseous oxidant
The molar ratio of the ingredient of oxidation is 1: 0.05 ~ 5, and the mass concentration of catalyst is 1% ~ 8%, and reaction temperature is 150 ~ 330 DEG C,
Reaction pressure is 1.0 ~ 3.0MPa, and the residence time is 15 ~ 90min.Preferably, in the step (2), picoline class compound
Molar ratio with the ingredient for playing oxidation in gaseous oxidant is 1:0.1 ~ 2；The mass concentration of catalyst is 3% ~ 5%；Reaction
Temperature is 160 ~ 280 DEG C, and reaction pressure is 1.5 ~ 2.5MPa, and the residence time is 15 ~ 60min.
Inoranic membrane in the step (3) is arranged in slurry bed system oxidation reactor and/or setting is anti-in slurry bed system oxidation
The outer circulating tube road outside device is answered, the inoranic membrane is metal film or ceramic membrane.
As shown in Fig. 2, slurry bed system oxidation system used in the present invention includes slurry bed system oxidation reactor and follows outside
Endless tube road is equipped with the import of picoline class compound, protective gas import and offgas outlet at the top of reactor, in reactor
It is interior to be equipped with material distributor, blender and built-in membrane filter, the material outlet of reactor bottom end by pipeline successively with circulation
Pump, the first condenser, external membrane filter, static mixer, pre-reactor and the second condenser are connected, and the second condenser goes out
Material mouth is connected by pipeline with the recycle stock import of reactor head.Each segment pipe and circulating pump, the first condenser, external film
Filter, static mixer, pre-reactor, the second condenser collectively constitute external circulation line.Built-in film filtering in reactor
Device and the external membrane filter of outer circulating tube road can be arranged simultaneously, can also select a setting.
When built-in membrane filter is only arranged, catalyst, methyl-pyridyl compound, protective gas are added into reactor,
Turn on agitator and circulating pump establish circulation, gaseous oxidant are passed through into static mixer, in pre-reactor, methyl pyrrole
Acridine compound is aoxidized by gaseous oxidant in the presence of a catalyst, and the upper half in reactor, reaction terminates, and obtains pyridine first
Acid compound reaction solution.The lower half in reactor, pyridine carboxylic acid compound reaction solution are separated through built-in membrane filter, exudation
The discharge of pyridine carboxylic acid compound filtrate, catalyst are trapped in reactor, via the recycle stock outlet of reactor bottom, are followed
Ring pump, the first condenser are mixed with the gaseous oxidant being continuously passed through in static mixer, by pre-reactor, the second condensation
Device and pipeline are carried out continuously back to realization circular response in reactor and separation.
When external membrane filter is only arranged, pyridine carboxylic acid class compound reaction solution via reactor bottom recycle stock
Enter external membrane filter after outlet, circulating pump, the first condenser to be separated by filtration, the pyridine carboxylic acid compound filtrate row of exudation
Out, catalyst slurry is trapped and is entered in static mixer with to recycle logistics mode and mixed with gaseous oxidant, by pre- anti-
Device, the second condenser and pipeline is answered to be carried out continuously back to realization circular response in reactor and separation.
When built-in membrane filter and external membrane filter are arranged simultaneously, the pyridine carboxylic acid class compound that is obtained in reactor
Reaction solution is divided into two parts, respectively by built-in membrane filter and external membrane filter, realizes circular response and separation.
The preparation method of pyridine carboxylic acid class compound provided by the invention, specifically with picoline class compound and gas
Oxidant is raw material, and using slurry bed process, in the presence of a catalyst, pyrrole is made in a step catalysis oxidation picoline class compound
Pyridine formic acid compound, then by the separation of membrane separation technique progress reaction solution, catalyst retention is continued in the reaction system
Oxidation reaction is participated in, process flow diagram of the invention is shown in Fig. 1.
Compared with prior art, the present invention have raw material is easy to get, is at low cost, yield is high, easy to operate, process flow is short,
Continuously, there are good realistic meaning and economical, societal benefits in the advantages that environmentally protective.The invention avoids strong corrosive oxygen
The use of agent, is conducive to clean manufacturing；The present invention uses paste state bed reactor, and reactant is big, mixed with catalyst contact area
It closes uniformly, reaction temperature is low, and reaction system temperature is uniform, eliminates reaction hot spot, reduces the generation of high temperature side reaction；This hair
It is bright to couple reaction process with separation process, it is separated at once after reaction, substantially increases production efficiency, using film point
Catalyst is trapped in reactor from technology, avoids the loss of catalyst.
Detailed description of the invention
Fig. 1 is process flow diagram of the invention.
Fig. 2 is the structural schematic diagram of slurry bed system oxidation system.
In figure, 1, material distributor, 2, blender, 3, reactor, 4, built-in membrane filter, 5, circulating pump, 6, first is cold
Condenser, 7, external membrane filter, 8, static mixer, 9, pre-reactor, the 10, second condenser.
Specific embodiment
Below with reference to embodiment, the present invention is further elaborated, the process being not described in detail in the following embodiments and
Method is conventional method well known in the art, and raw materials used or reagent is unless otherwise stated commercially available product in embodiment, can be led to
Commercial channel is crossed to buy.
The preparation method of pyridine carboxylic acid class compound provided by the invention, comprising the following steps:
Catalyst, picoline class compound are added into paste state bed reactor, and is passed through protective gas, turn on agitator and follows
Ring pump, establishes circulation, is then passed through gaseous oxidant into static mixing gas, in pre-reactor, picoline class compound
It is aoxidized in the presence of a catalyst by gaseous oxidant, in reactor, reaction terminates, and obtains pyridine carboxylic acid compound reaction solution.
Wherein, picoline class compound, protective gas and gaseous oxidant are the raw materials being pretreated to reaction temperature and pressure,
The molar ratio that the ingredient of oxidation is played in picoline class compound and gaseous oxidant is 1: 0.05 ~ 5, and catalyst can be catalyzed
It aoxidizes picoline class compound and generates pyridine carboxylic acid class compound, the mass concentration of catalyst is 1% ~ 8%, anti-in reactor
Answering temperature is 150 ~ 330 DEG C, and reaction pressure is 1.0 ~ 3.0MPa, and the residence time is 15 ~ 90min.
The obtained built-in membrane filter in the reacted device of pyridine carboxylic acid class compound reaction solution is filtered separation, catalysis
Agent is trapped in reactor, and per-meate side obtains pyridine carboxylic acid class compound filtrate；
Alternatively, obtained pyridine carboxylic acid class compound reaction solution is carried out through recycling in the external membrane filter being pumped into outside reactor
It is separated by filtration, catalyst slurry is trapped and is added in the reaction of raw material after logistics mode participates in recycling, and per-meate side obtains
Pyridine carboxylic acid class compound filtrate；
Film in membrane filter is metal film or ceramic membrane, and separate mode is dead-end filtration or cross-flow filtration.
The post-processing such as pyridine carboxylic acid class compound concentrating filter liquor, purification, obtains pyridine carboxylic acid class compound.
Embodiment 1
(1) pretreatment of raw material
It is 160 DEG C that 2- picoline, which is carried out heating pressurized treatments to temperature, pressure 1.5MPa；
Air is configured to the preparation air that oxygen quality content is 20%, is 1.5 using carrying out being compressed to pressure after filter
Then MPa is preheated to 160 DEG C；
It is 1.5 MPa that nitrogen, which is compressed to pressure, is then preheated to 160 DEG C of temperature.
(2) oxidation reaction
It will be continuously sent into equipped with catalysis respectively in step (1) by pretreated 2- picoline, preparation air, nitrogen
Catalytic oxidation is carried out in the slurry bed system oxidation system of agent, generates the reaction solution of 2- pyridine carboxylic acid.In reaction process, control
Reaction temperature processed is 160 DEG C, and pressure is 1.5 MPa, and the residence time is 30 min, 2- picoline and preparation ambient oxygen partial
The molar ratio of son is 1: 0.5, and the mass concentration of catalyst is that 3%(needs to be added into reaction kettle in due course according to catalyst consumption
Catalyst).
(3) UF membrane
By the reaction solution of 2- pyridine carboxylic acid obtained in step (2) pass through the metal film that is arranged in slurry bed system oxidation reactor into
The separation of row dead-end filtration, obtains 2- pyridine carboxylic acid filtrate, catalyst is then trapped in reaction system, continues to participate in subsequent urge
Oxidation.
The postprocessing working procedures such as the concentrated again, purification of gained filtrate, finally obtain 2- pyridine carboxylic acid, 2- picoline conversion ratio
Reach 95%, 97% is selectively reached to product 2- pyridine carboxylic acid.
Embodiment 2
(1) pretreatment of raw material
It is 170 DEG C that 3- picoline, which is carried out heating pressurized treatments to temperature, pressure 1.6MPa；
Air is configured to the preparation air that oxygen quality content is 30%, is 1.6 using carrying out being compressed to pressure after filter
Then MPa is preheated to 170 DEG C；
It is 1.6MPa that nitrogen or recycled offgas, which are compressed to pressure, is then preheated to 170 DEG C of temperature.Reaction starting uses nitrogen
It (is largely nitrogen to the tail gas being discharged in slurry bed system oxidation reactor after reacting and carrying out a period of time as protective gas
Gas prepares air containing minute quantity) it is recycled, i.e., heating pressurized treatments are carried out to reaction temperature and pressure to recycled offgas
Power.
(2) oxidation reaction
Pretreated 3- picoline will be passed through in step (1), prepare air, nitrogen (or recycled offgas) respectively continuously
It is sent into the slurry bed system oxidation system equipped with catalyst and carries out catalytic oxidation, generate the reaction solution of niacin.It reacted
Cheng Zhong, controlling reaction temperature is 170 DEG C, and pressure is 1.6 MPa, and the residence time is 45 min, 3- picoline and preparation air
The molar ratio of middle oxygen molecule is 1: 0.5, and the mass concentration of catalyst is that 3%(is needed according to catalyst consumption, in due course to reaction
Catalyst is added in kettle).
(3) UF membrane
The reaction solution of niacin obtained in step (2) is passed through to the metal being arranged on slurry bed system oxidation reactor outer circulating tube road
Film carries out cross-flow filtration separation, obtains niacin filtrate, catalyst is then trapped in reaction system, continues to participate in subsequent catalysis
Oxidation reaction.
The postprocessing working procedures such as gained filtrate is concentrated again, purification, obtain niacin, and 3- picoline conversion ratio reaches 96%, right
Product niacin selectively reaches 98%.
Embodiment 3
(1) pretreatment of raw material
It is 180 DEG C that 4- picoline, which is carried out heating pressurized treatments to temperature, pressure 1.8MPa；
Air is configured to the preparation air that oxygen quality content is 25%, using being compressed after filter, until pressure is 1.8
Then MPa is preheated to 180 DEG C；
It is 1.8MPa that nitrogen, which is compressed to pressure, is then preheated to 180 DEG C of temperature.
(2) oxidation reaction
It will be continuously sent into equipped with catalysis respectively in step (1) by pretreated 4- picoline, preparation air, nitrogen
Catalytic oxidation is carried out in the slurry bed system oxidation system of agent, generates the reaction solution of isonicotinic acid.In reaction process, control is anti-
Answering temperature is 180 DEG C, and pressure is 1.8 MPa, and the residence time is 50 min, 4- picoline and preparation ambient oxygen partial
Molar ratio is 1: 0.6, and the mass concentration of catalyst is that 3%(needs to add catalysis into reaction kettle in due course according to catalyst consumption
Agent).
(3) UF membrane
By a part in the reaction solution of isonicotinic acid obtained in step (2) by being arranged in outside slurry bed system oxidation reactor
Metal film carries out cross-flow filtration separation, and another part passes through the metal film being arranged in inside slurry bed system oxidation reactor and carries out dead end
Filtering, obtains isonicotinic acid filtrate, catalyst is then trapped in reaction system, continues to participate in subsequent catalytic oxidation.
The postprocessing working procedures such as the concentrated again, purification of gained filtrate, obtain isonicotinic acid, and 4- picoline conversion ratio reaches 95%,
97% is selectively reached to product isonicotinic acid.
Embodiment 4
Raw material is 3- picoline, and reaction temperature is 160 DEG C, and reaction pressure is 1.5 MPa, and the residence time is 45 min, 3- first
Yl pyridines and the molar ratio for preparing ambient oxygen partial are 1: 0.1, and the mass concentration of catalyst is 3%, other conditions and operation
It is same as Example 2.
3- picoline conversion ratio reaches 97%, selectively reaches 97% to product niacin.
Embodiment 5
Raw material is 3- picoline, and reaction temperature is 280 DEG C, and reaction pressure is 2.5 MPa, and the residence time is 15 min, 3- first
Yl pyridines and the molar ratio for preparing ambient oxygen partial are 1: 2, and the mass concentration of catalyst is 3%, and other conditions and operation are equal
It is same as Example 2.
3- picoline conversion ratio reaches 96%, selectively reaches 98% to product niacin.
Claims (10)
1. a kind of preparation method of pyridine carboxylic acid class compound, which comprises the following steps:
(1) pretreatment of raw material carries out picoline class compound, gaseous oxidant and protective gas at pressurized, heated respectively
Reason, until reaction temperature and reaction pressure；
(2) catalytic oxidation is aoxidized the slurry bed system equipped with catalyst is respectively fed to by pretreated raw material in step (1)
Catalytic oxidation is carried out in reaction system, generates the reaction solution of pyridine carboxylic acid class compound；
(3) reaction solution of pyridine carboxylic acid class compound obtained in step (2) is separated by inoranic membrane, is obtained by UF membrane
It is post-treated to obtain pyridine carboxylic acid class compound to pyridine carboxylic acid class compound filtrate；Catalyst is trapped in slurry bed system by inoranic membrane
Subsequent reaction is continued to participate in oxidation system.
2. the preparation method of pyridine carboxylic acid class compound according to claim 1, which is characterized in that the gaseous oxidant
For one or more of pure oxygen, ozone or preparation air, the mass content for preparing oxygen in air is 5% ~ 90%.
3. the preparation method of pyridine carboxylic acid class compound according to claim 2, which is characterized in that in the preparation air
The mass fraction of oxygen is 10% ~ 50%.
4. the preparation method of pyridine carboxylic acid class compound according to claim 1, which is characterized in that the protective gas is
The recycled offgas that nitrogen or catalytic oxidation process generate.
5. the preparation method of pyridine carboxylic acid class compound according to claim 1, which is characterized in that the step (2)
During catalytic oxidation, the molar ratio of the ingredient of oxidation is played in control picoline class compound and gaseous oxidant
It is 1: 0.05 ~ 5, the mass concentration of catalyst is 1% ~ 8%, and reaction temperature is 150 ~ 330 DEG C, and reaction pressure is 1.0 ~ 3.0MPa,
Residence time is 15 ~ 90min.
6. the preparation method of pyridine carboxylic acid class compound according to claim 5, which is characterized in that in the step (2),
The molar ratio that the ingredient of oxidation is played in picoline class compound and gaseous oxidant is 1: 0.1 ~ 2.
7. the preparation method of pyridine carboxylic acid class compound according to claim 5, which is characterized in that in the step (2),
The mass concentration of catalyst is 3% ~ 5%.
8. the preparation method of pyridine carboxylic acid class compound according to claim 5, which is characterized in that in the step (2),
Reaction temperature is 160 ~ 280 DEG C, and reaction pressure is 1.5 ~ 2.5MPa, and the residence time is 15 ~ 60min.
9. the preparation method of pyridine carboxylic acid class compound according to claim 1, which is characterized in that in the step (3)
Inoranic membrane be arranged in slurry bed system oxidation reactor and/or be arranged on the outer circulating tube road outside slurry bed system oxidation reactor,
The inoranic membrane is metal film or ceramic membrane.
10. the preparation method of pyridine carboxylic acid class compound according to claim 1, which is characterized in that the picoline
Class compound is 2- picoline, 3- picoline or 4- picoline, and pyridine carboxylic acid class compound obtained mutually should be 2- pyrrole
Pyridine formic acid, niacin or isonicotinic acid.
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