CN104496895A - Method for preparing isonicotinic acid by hydrolysis - Google Patents
Method for preparing isonicotinic acid by hydrolysis Download PDFInfo
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- CN104496895A CN104496895A CN201410797446.1A CN201410797446A CN104496895A CN 104496895 A CN104496895 A CN 104496895A CN 201410797446 A CN201410797446 A CN 201410797446A CN 104496895 A CN104496895 A CN 104496895A
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The present invention provides a method for preparing isonicotinic acid by hydrolysis. The method comprises the following preparation steps: 1) hydrolysis reaction: throwing weighed 4-cyanopyridine and sodium hydroxide into a four-opening bottle, weighing a corresponding amount of purified water by using a measuring cylinder and adding the purified water in the four-opening bottle, wherein the mass ratio of 4-cyanopyridine to sodium hydroxide to the purified water is 1: (0.39-0.80): (2-4); starting to stir and heat, starting to time when the temperature rises to 90-115 DEG C, supplementing the purified water in the four-opening bottle according to the original hydrolysis volume in the hydrolysis reaction process to ensure the consistency of the volume, controlling the temperature to 90-115 DEG C, and carrying out the hydrolysis reaction for 1-3 hours to obtain 4-pyridine-sodium formate; 2) decolorizing; 3) crystallizing; 4) separating; 5) drying. The method is few in by-products and high in product purity, and can be used for greatly reducing the energy consumption and greatly improving the process safety while effectively reducing the production cost.
Description
Technical field
The present invention relates to γ-picolinic acid preparing technical field, especially relate to a kind of method that γ-picolinic acid is prepared in hydrolysis.
Background technology
γ-picolinic acid has another name called Isonicotinic acid, is a kind of important medicine intermediate, is mainly used in synthesizing antitubercular agent vazadrine, also for the synthesis of derivatives such as acid amides, hydrazides, ester classes.For a long time, γ-picolinic acid is produced mainly through 4-picoline oxidation style, needs to use the catalyst be made up of multiple compounds, consumes energy high, and pollute large, and product impurities is more, quality is also unstable.By application this patent, significantly can reduce energy consumption, effectively reduce the discharge of pollutent, the quality of product can be effectively controlled simultaneously, drastically reduce the area the impurity contained by product.
The main raw material of traditional γ-picolinic acid oxidizing process is 4-cyanopyridine, steam and warm air, its typical process flow as shown in Figure 1,4-cyanopyridine is through heating and gasifying, the air that the steam carried with boiler house and hotblast stove heat mixes in the ratio of 1:10:100, the catalyst completed in advance in oxidizing tower, at 200 DEG C, oxidizing reaction is completed under 0.02 ~ 0.035MPa, the pulverous γ-picolinic acid solid of direct generation, collect successively under 1 to No. 4 auxiliary storage through whirlpool pipeline, tail gas reclaims through salt acid tower, then generates γ-picolinic acid substandard goods through press filtration, neutralization.
There is obvious defect in this technique, 1), oxidizing reaction needs by catalyst catalysis, catalyst is primarily of many kinds of substance compositions such as potassium sulfate, ammonium meta-vanadate, oxalic acid, sulfuric acid, silica gel, reacted rear direct generation solid powdery finished product, do not have filter progress, the catalyst contained in γ-picolinic acid cannot be removed, impurity is more, γ-picolinic acid certified products content >=98.0%, γ-picolinic acid substandard goods content >=97.0%, product residue on ignition≤1.0%; 2) the pressed powder as easy as rolling off a log wall built-up in whirlpool pipeline, generated, cause line clogging, receptor is used to need workman to knock pipeline concussion with iron hammer, iron rust on tube wall is mixed into finished product in company with knocking, make product containing metal higher, affect quality product, knock also forms certain noise to neighbouring village simultaneously; 3), need boiler supplying steam in reaction process always, and workshop is also equipped with the roots blower of hotblast stove and air inducing, consumption coal, power consumption, water consumption are all very high, as long as in process of production, necessary 24 continuous throughout the twenty-four hour24s of steam, hotblast stove and blower fan, energy consumption is very large; 4), tail gas absorption generates large quantity of fluid, needs distillation and concentration, then through press filtration and neutralization, produces substandard goods.The power consumption of its still-process is very large, and yield is but very low, but tail gas absorption liquid can not directly discharge.Therefore tail gas absorption reclaims and always is loss.
In sum, γ-picolinic acid oxidizing reaction main drawback be impurity higher, consume energy excessive, have certain pollution, simultaneously, this oxidizing reaction belongs to hazardous chemical technique, its basic raw material 4-picoline used also belongs to hazardous chemical, makes this technique all there is certain danger in production and storage.Therefore, a kind of method preparing γ-picolinic acid newly of research and development is badly in need of, to overcome above defect.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of method that γ-picolinic acid is prepared in hydrolysis, and the method by product is few, and product purity is high, and energy consumption significantly reduces, and while effectively reducing production cost, the security of technique also increases substantially.
For solving the problems of the technologies described above, the technical solution used in the present invention is: the method for γ-picolinic acid is prepared in a kind of hydrolysis, comprises following preparation process,
1), load weighted 4-cyanopyridine, sodium hydroxide drops in four-hole bottle by hydrolysis reaction, then drops in four-hole bottle by the purified water that graduated cylinder measures respective amount, and wherein the mass ratio of 4-cyanopyridine, sodium hydroxide, purified water is 1:0.39 ~ 0.80:2 ~ 4; Start stirring and start heating, when temperature rises to 90 ~ 115 DEG C, start timing, in hydrolysis reaction, in four-hole bottle, mend purified water according to former hydrolysis volume, ensure that volume is unchanged, and temperature controls at 90 DEG C ~ 115 DEG C, hydrolysis reaction, after 1 ~ 3 hour, obtains 4-pyridine-carboxylic acid sodium;
The chemical equation of hydrolysis reaction is as follows:
2), decolour
Cool the temperature to 70-80 DEG C after hydrolysis reaction, add gac and start timing insulation 0.5 ~ 1.5 hour, temperature controls at 70 ~ 80 DEG C, and after decolouring, gac is removed by suction filtration;
3), crystallization
By step 2) filtrate that obtains is reentered in clean four-hole bottle, drips with hydrochloric acid, and limit drips the pH value that solution in four-hole bottle is measured on hydrochloric acid limit, until after its pH reaches 3.5 ~ 4.0, repetition measurement after 5 ~ 15 minutes, its pH value is still 3.5 ~ 4.0, then stop dripping hydrochloric acid; And record the consumption of hydrochloric acid, because hydrochloric acid is as one of raw materials for production, the consumption of record hydrochloric acid, is mainly used for calculating unit consumption and cost.
Chemical equation in crystallisation step is as follows:
4), be separated
After crystallization, the solution in four-hole bottle is carried out suction filtration washing, obtain wet product;
5), dry
By step 4) wet product that obtains puts into drying baker dries, and namely obtains γ-picolinic acid finished product.
Preferably, step 1) in, hydrolysis reaction is 2 hours.
Preferably, step 2) in, be incubated 1 hour after adding gac.
Preferably, by step 4) wet product that obtains puts into drying baker and carries out oven dry 4 ~ 6 hours at 105 ~ 110 DEG C, namely obtains γ-picolinic acid finished product.
The advantage that the present invention has and positively effect are: the method for γ-picolinic acid is prepared in hydrolysis provided by the invention, has the following advantages:
1. through hydrolysis reaction with after dripping acid crystal reaction, reaction product only has γ-picolinic acid, ammonia and sodium-chlor, ammonia is reclaimed can be made ammoniacal liquor by recovery tower, it is a kind of important agricultural fertilizer, also no matter may be used for boiler house boiler desulfuration dedusting, and sodium-chlor can be removed by rinsing major part, be the sodium-chlor in product or the sodium-chlor in waste liquid, concentration is all very low, can not impact quality product and environment.
2., through filter progress after being hydrolyzed, issuable impurity in hydrolysis reaction being removed, having increased substantially the quality of product, γ-picolinic acid wet product content >=99.0%, γ-picolinic acid dry product content >=99.0%, residue on ignition≤0.5%.
3. steam is only for intensification and the insulation of hydrolysis reaction, the duration of service of every day is limited, and crystallization uses circulating water cooling, does not have to expend situation that is coal-fired and electric power in oxidizing reaction in a large number, in whole technical process, energy consumption significantly reduces, and also effectively reduces production cost.
4. hydrolysis method reaction is carried out in airtight retort, and by the size control temperature of steam, production technique is simplified, and the security of whole production technique increases substantially.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that tradition prepares γ-picolinic acid;
Fig. 2 is the process flow sheet that in the present invention, γ-picolinic acid is prepared in hydrolysis;
Fig. 3 is the high performance liquid chromatography spectrogram of the product of preparation in embodiment one;
Fig. 4 is the high performance liquid chromatography spectrogram of the product of preparation in embodiment two;
Fig. 5 is the high performance liquid chromatography spectrogram of the product of preparation in embodiment three;
Fig. 6 is the high performance liquid chromatography spectrogram of the product of preparation in embodiment four;
Fig. 7 is the high performance liquid chromatography spectrogram of the product of preparation in embodiment five;
Fig. 8 is the high performance liquid chromatography spectrogram of the product of preparation in embodiment six;
Fig. 9 is the high performance liquid chromatography spectrogram of the product of preparation in embodiment seven;
Embodiment
Embodiment one
A method for γ-picolinic acid is prepared in hydrolysis, comprises following preparation process,
1), load weighted 4-cyanopyridine, sodium hydroxide drop in four-hole bottle by hydrolysis reaction, measure in the purified water input four-hole bottle of respective amount with graduated cylinder again, wherein the mass ratio of 4-cyanopyridine, sodium hydroxide, purified water is 1:0.8:4, and wherein the quality of 4-cyanopyridine is 100g; Start stirring and start heating, when temperature rises to 108 DEG C, start timing, in hydrolysis reaction, in four-hole bottle, mend purified water according to former hydrolysis volume, ensure that volume is unchanged, and temperature controls at 108 DEG C ~ 115 DEG C, hydrolysis reaction, after 2 hours, obtains 4-pyridine-carboxylic acid sodium;
2), decolour
Cool the temperature to 75 DEG C after hydrolysis reaction, add 2g gac and start timing and be incubated 1 hour, temperature controls at 70 ~ 80 DEG C, and after decolouring, gac is removed by suction filtration;
3), crystallization
By step 2) filtrate that obtains is reentered in clean four-hole bottle, drip with hydrochloric acid, limit drips the pH value that solution in four-hole bottle is measured on hydrochloric acid limit, until after its pH reaches 3.6, repetition measurement after 10 minutes, its pH is still 3.7, and the consumption of hydrochloric acid is 162mL, and wherein the massfraction of hydrochloric acid is 36.0%;
4), be separated
After crystallization, the solution in four-hole bottle is carried out suction filtration washing, obtain wet product 175g;
5), dry
By step 4) wet product that obtains puts into drying baker dries, and bake out temperature is 105 DEG C, namely obtains γ-picolinic acid finished product 115g.
The main physical and chemical index of the γ-picolinic acid prepared by above method is as follows, the content of γ-picolinic acid: 99.8%, residue on ignition: 0.04%, muriate :≤0.05%, outward appearance: white powder, solution look: qualified, clarity: qualified, differentiates: qualified, indices is all qualified.And γ-picolinic acid transformation efficiency: 97.25%.
Embodiment two
A method for γ-picolinic acid is prepared in hydrolysis, comprises following preparation process,
1), load weighted 4-cyanopyridine, sodium hydroxide drop in four-hole bottle by hydrolysis reaction, measure in the purified water input four-hole bottle of respective amount with graduated cylinder again, wherein the mass ratio of 4-cyanopyridine, sodium hydroxide, purified water is 1:0.6:3, and wherein the quality of 4-cyanopyridine is 100g; Start stirring and start heating, when temperature rises to 100 DEG C, start timing, in hydrolysis reaction, in four-hole bottle, mend purified water according to former hydrolysis volume, ensure that volume is unchanged, and temperature controls at 100 DEG C ~ 108 DEG C, hydrolysis reaction, after 2 hours, obtains 4-pyridine-carboxylic acid sodium;
2), decolour
Cool the temperature to 80 DEG C after hydrolysis reaction, add 2g gac and start timing and be incubated 1 hour, temperature controls at 70 ~ 80 DEG C, and after decolouring, gac is removed by suction filtration;
3), crystallization
By step 2) filtrate that obtains is reentered in clean four-hole bottle, drip with hydrochloric acid, limit drips the pH value that solution in four-hole bottle is measured on hydrochloric acid limit, until after its pH reaches 3.5, repetition measurement after 10 minutes, its pH value is 3.6, then stop dripping hydrochloric acid and the consumption recording hydrochloric acid, the consumption of hydrochloric acid is 132mL, and wherein the massfraction of hydrochloric acid is 36.0%;
4), be separated
After crystallization, the solution in four-hole bottle is carried out suction filtration washing, obtain wet product 185g;
5), dry
By step 4) wet product that obtains puts into drying baker dries, and bake out temperature is 105 DEG C, namely obtains γ-picolinic acid finished product 114.9g.
The main physical and chemical index of the γ-picolinic acid prepared by above method is as follows, the content of γ-picolinic acid: 99.9%, residue on ignition: 0.05%, muriate :≤0.05%, outward appearance: white powder, solution look: qualified, clarity: qualified, differentiates: qualified, indices is all qualified.γ-picolinic acid transformation efficiency: 97.17%.
Embodiment three
A method for γ-picolinic acid is prepared in hydrolysis, comprises following preparation process,
1), load weighted 4-cyanopyridine, sodium hydroxide drop in four-hole bottle by hydrolysis reaction, measure in the purified water input four-hole bottle of respective amount with graduated cylinder again, wherein the mass ratio of 4-cyanopyridine, sodium hydroxide, purified water is 1:0.5:3, and wherein the quality of 4-cyanopyridine is 100g; Start stirring and start heating, when temperature rises to 95 DEG C, start timing, in hydrolysis reaction, in four-hole bottle, mend purified water according to former hydrolysis volume, ensure that volume is unchanged, and temperature controls at 90 DEG C ~ 100 DEG C, hydrolysis reaction, after 2 hours, obtains 4-pyridine-carboxylic acid sodium;
2), decolour
Cool the temperature to 80 DEG C after hydrolysis reaction, add 2g gac and start timing and be incubated 1 hour, temperature controls at 70 ~ 80 DEG C, and after decolouring, gac is removed by suction filtration;
3), crystallization
By step 2) filtrate that obtains is reentered in clean four-hole bottle, drip with hydrochloric acid, limit drips the pH value that solution in four-hole bottle is measured on hydrochloric acid limit, until after its pH reaches 3.7, repetition measurement after 10 minutes, its pH value is 3.7, then stop dripping hydrochloric acid, the consumption of hydrochloric acid is 102mL, and wherein the massfraction of hydrochloric acid is 36.0%;
4), be separated
After crystallization, the solution in four-hole bottle is carried out suction filtration washing, obtain wet product 180g;
5), dry
By step 4) wet product that obtains puts into drying baker dries, and bake out temperature is 108 DEG C, namely obtains γ-picolinic acid finished product.
The main physical and chemical index of the γ-picolinic acid prepared by above method is as follows, the content of γ-picolinic acid: 99.9%, residue on ignition: 0.06%, muriate :≤0.05%, outward appearance: white powder, solution look: qualified, clarity: qualified, differentiates: qualified, indices is all qualified.γ-picolinic acid transformation efficiency: 97.45%.
Embodiment four
A method for γ-picolinic acid is prepared in hydrolysis, comprises following preparation process,
1), load weighted 4-cyanopyridine, sodium hydroxide drop in four-hole bottle by hydrolysis reaction, measure in the purified water input four-hole bottle of respective amount with graduated cylinder again, wherein the mass ratio of 4-cyanopyridine, sodium hydroxide, purified water is 1:0.39:2, and wherein the quality of 4-cyanopyridine is 100g; Start stirring and start heating, when temperature rises to 90 DEG C, start timing, in hydrolysis reaction, in four-hole bottle, mend purified water according to former hydrolysis volume, ensure that volume is unchanged, and temperature controls at 90 DEG C ~ 95 DEG C, hydrolysis reaction, after 2 hours, obtains 4-pyridine-carboxylic acid sodium;
2), decolour
Cool the temperature to 80 DEG C after hydrolysis reaction, add 2g gac and start timing and be incubated 1 hour, temperature controls at 70 ~ 80 DEG C, and after decolouring, gac is removed by suction filtration;
3), crystallization
By step 2) filtrate that obtains is reentered in clean four-hole bottle, drip with hydrochloric acid, limit drips the pH value that solution in four-hole bottle is measured on hydrochloric acid limit, until after its pH reaches 3.6, repetition measurement after 10 minutes, its pH value is still 3.6, then stop dripping hydrochloric acid, the consumption of hydrochloric acid is 80mL, and wherein the massfraction of hydrochloric acid is 36.0%;
4), be separated
After crystallization, the solution in four-hole bottle is carried out suction filtration washing, obtain wet product 190g;
5), dry
By step 4) wet product that obtains puts into drying baker dries, and bake out temperature is 110 DEG C, namely obtains γ-picolinic acid finished product 115.3g.
The main physical and chemical index of the γ-picolinic acid prepared by above method is as follows, the content of γ-picolinic acid: 99.8%, residue on ignition: 0.04%, muriate :≤0.05%, outward appearance: white powder, solution look: qualified, clarity: qualified, differentiates: qualified, indices is all qualified.γ-picolinic acid transformation efficiency: 97.50%.
Embodiment five
A method for γ-picolinic acid is prepared in hydrolysis, it is characterized in that: comprise following preparation process,
1), load weighted 4-cyanopyridine, sodium hydroxide drop in four-hole bottle by hydrolysis reaction, measure in the purified water input four-hole bottle of respective amount with graduated cylinder again, wherein the mass ratio of 4-cyanopyridine, sodium hydroxide, purified water is 1:0.35:2, and wherein the quality of 4-cyanopyridine is 100g; Start stirring and start heating, when temperature rises to 90 DEG C, start timing, in hydrolysis reaction, in four-hole bottle, mend purified water according to former hydrolysis volume, ensure that volume is unchanged, and temperature controls at 90 DEG C ~ 95 DEG C, hydrolysis reaction, after 2 hours, obtains 4-pyridine-carboxylic acid sodium;
2), decolour
Cool the temperature to 80 DEG C after hydrolysis reaction, add 2g gac and start timing and be incubated 1 hour, temperature controls at 70 ~ 80 DEG C, and after decolouring, gac is removed by suction filtration;
3), crystallization
By step 2) filtrate that obtains is reentered in clean four-hole bottle, drip with hydrochloric acid, limit drips the pH value that solution in four-hole bottle is measured on hydrochloric acid limit, until after its pH reaches 3.7, repetition measurement after 10 minutes, its pH value is still 3.8, then stop dripping hydrochloric acid, the consumption of hydrochloric acid is 72mL, and wherein the massfraction of hydrochloric acid is 36.0%;
4), be separated
After crystallization, the solution in four-hole bottle is carried out suction filtration washing, obtain wet product 160g;
5), dry
By step 4) wet product that obtains puts into drying baker dries, and bake out temperature is 110 DEG C, namely obtains γ-picolinic acid finished product 101.5g.
The main physical and chemical index of the γ-picolinic acid prepared by above method is as follows, the content of γ-picolinic acid: 94.8%, residue on ignition: 0.03%, muriate; ≤ 0.05%, outward appearance: white powder, solution look: qualified, clarity: qualified, differentiates: defective.γ-picolinic acid transformation efficiency: 85.83%.
Embodiment six
A method for γ-picolinic acid is prepared in hydrolysis, it is characterized in that: comprise following preparation process,
1), load weighted 4-cyanopyridine, sodium hydroxide drop in four-hole bottle by hydrolysis reaction, measure in the purified water input four-hole bottle of respective amount with graduated cylinder again, wherein the mass ratio of 4-cyanopyridine, sodium hydroxide, purified water is 1:0.39:2, and wherein the quality of 4-cyanopyridine is 100g; Start stirring and start heating, when temperature rises to 100 DEG C, start timing, in hydrolysis reaction, in four-hole bottle, mend purified water according to former hydrolysis volume, ensure that volume is unchanged, and temperature controls at 100 DEG C ~ 108 DEG C, hydrolysis reaction, after 2 hours, obtains 4-pyridine-carboxylic acid sodium;
2), decolour
Cool the temperature to 80 DEG C after hydrolysis reaction, add gac and start timing and be incubated 1 hour, temperature controls at 70 ~ 80 DEG C, and after decolouring, gac is removed by suction filtration;
3), crystallization
By step 2) filtrate that obtains is reentered in clean four-hole bottle, drip with hydrochloric acid, limit drips the pH value that solution in four-hole bottle is measured on hydrochloric acid limit, until after its pH reaches 3.6, repetition measurement after 10 minutes, its pH value is 3.7, then stop dripping hydrochloric acid, the consumption of hydrochloric acid is 84mL, and wherein the massfraction of hydrochloric acid is 36.0%;
4), be separated
After crystallization, the solution in four-hole bottle is carried out suction filtration washing, obtain wet product 182g;
5), dry
By step 4) wet product that obtains puts into drying baker dries, and bake out temperature is 110 DEG C, namely obtains γ-picolinic acid finished product 114.9g.
The main physical and chemical index of the γ-picolinic acid prepared by above method is as follows, the content of γ-picolinic acid: 99.7%, residue on ignition: 0.05%, muriate :≤0.05%, outward appearance: white powder, solution look: qualified, clarity: qualified, differentiates: qualified, indices is all qualified.γ-picolinic acid transformation efficiency: 97.17%.
Embodiment seven
A method for γ-picolinic acid is prepared in hydrolysis, it is characterized in that: comprise following preparation process,
1), load weighted 4-cyanopyridine, sodium hydroxide drop in four-hole bottle by hydrolysis reaction, measure in the purified water input four-hole bottle of respective amount with graduated cylinder again, wherein the mass ratio of 4-cyanopyridine, sodium hydroxide, purified water is 1:0.39:2, and wherein the quality of 4-cyanopyridine is 100g; Start stirring and start heating, when temperature rises to 95 DEG C, start timing, in hydrolysis reaction, in four-hole bottle, mend purified water according to former hydrolysis volume, ensure that volume is unchanged, and temperature controls at 95 DEG C ~ 100 DEG C, hydrolysis reaction, after 2 hours, obtains 4-pyridine-carboxylic acid sodium;
2), decolour
Cool the temperature to 80 DEG C after hydrolysis reaction, add 2g gac and start timing and be incubated 1 hour, temperature controls at 70 ~ 80 DEG C, and after decolouring, gac is removed by suction filtration;
3), crystallization
By step 2) filtrate that obtains is reentered in clean four-hole bottle, drip with hydrochloric acid, limit drips the pH value that solution in four-hole bottle is measured on hydrochloric acid limit, until after its pH reaches 3.7, repetition measurement after 10 minutes, its pH value is 3.8, then stop dripping hydrochloric acid, the consumption of hydrochloric acid is 83mL, and wherein the massfraction of hydrochloric acid is 36.0%;
4), be separated
After crystallization, the solution in four-hole bottle is carried out suction filtration washing, obtain wet product 170g;
5), dry
By step 4) wet product that obtains puts into drying baker dries, and bake out temperature is 110 DEG C and namely obtains γ-picolinic acid finished product 115.1g.
The main physical and chemical index of the γ-picolinic acid prepared by above method is as follows, the content of γ-picolinic acid: 99.8%, residue on ignition: 0.05%, muriate :≤0.05%, outward appearance: white powder, solution look: qualified, clarity: qualified, differentiates: qualified, indices is all qualified.γ-picolinic acid transformation efficiency: 97.34%.
Above embodiments of the invention have been described in detail, but described content being only preferred embodiment of the present invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the scope of the invention change and improve, and all should still belong within this patent covering scope.
Claims (4)
1. a method for γ-picolinic acid is prepared in hydrolysis, it is characterized in that: comprise following preparation process,
1), load weighted 4-cyanopyridine, sodium hydroxide drops in four-hole bottle by hydrolysis reaction, then drops in four-hole bottle by the purified water that graduated cylinder measures respective amount, and wherein the mass ratio of 4-cyanopyridine, sodium hydroxide, purified water is 1:0.39 ~ 0.80:2 ~ 4; Start stirring and start heating, when temperature rises to 90 ~ 115 DEG C, start timing, in hydrolysis reaction, in four-hole bottle, mend purified water according to former hydrolysis volume, ensure that volume is unchanged, and temperature controls at 90 DEG C ~ 115 DEG C, hydrolysis reaction, after 1 ~ 3 hour, obtains 4-pyridine-carboxylic acid sodium;
2), decolour
Cool the temperature to 70 ~ 80 DEG C after hydrolysis reaction, add gac and start timing insulation 0.5 ~ 1.5 hour, temperature controls at 70 ~ 80 DEG C, and after decolouring, gac is removed by suction filtration;
3), crystallization
By step 2) filtrate that obtains is reentered in clean four-hole bottle, drips with hydrochloric acid, and limit drips the pH value that solution in four-hole bottle is measured on hydrochloric acid limit, until after its pH reaches 3.5 ~ 4.0, repetition measurement after 5 ~ 15 minutes, its pH value is still 3.5 ~ 4.0, then stop dripping hydrochloric acid;
4), be separated
After crystallization, the solution in four-hole bottle is carried out suction filtration washing, obtain wet product;
5), dry
By step 4) wet product that obtains puts into drying baker dries, and namely obtains γ-picolinic acid finished product.
2. the method for γ-picolinic acid is prepared in hydrolysis according to claim 1, it is characterized in that: step 1) in, hydrolysis reaction is 2 hours.
3. the method for γ-picolinic acid is prepared in hydrolysis according to claim 1, it is characterized in that: step 2) in, be incubated 1 hour after adding gac.
4. the method for γ-picolinic acid is prepared in hydrolysis according to claim 1, it is characterized in that: step 5) in, by step 4) wet product that obtains puts into drying baker dries at 105 ~ 110 DEG C, namely obtains γ-picolinic acid finished product.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1214679A (en) * | 1996-02-09 | 1999-04-21 | 莱利工业公司 | Continuous processes for hydrolysis of cyanopyridines under substantially adiabatic conditions |
| JP2006206516A (en) * | 2005-01-28 | 2006-08-10 | Koei Chem Co Ltd | Method for producing 4,4'-dicarboxy-2,2'-bipyridine |
| CN101265230A (en) * | 2008-04-18 | 2008-09-17 | 浙江大学 | No-catalyst hydrolysis method for preparing nicotinic acid from nicotinonitrile in near-critical water medium |
| US20090143439A1 (en) * | 2007-11-30 | 2009-06-04 | Wolfgang Haap | New pyridines as fbpase inhibitors for treatment of diabetes |
| CN101463004A (en) * | 2009-01-15 | 2009-06-24 | 浙江大学 | Method for preparing isonicotinic acid by non-catalytic hydrolyzing isonicotinonitrile in near-critical water medium |
| CN101475527A (en) * | 2009-01-22 | 2009-07-08 | 浙江大学 | Method for preparing isonicotinic acid and pyrazinamide by non-catalytic hydrolyzing isonicotinonitrile in near-critical water medium |
| CN101597258A (en) * | 2009-04-29 | 2009-12-09 | 南通醋酸化工股份有限公司 | The technology of 3-cyanopyridine synthesizing niacinamide and co-producing niacin by hydrolyzing |
-
2014
- 2014-12-18 CN CN201410797446.1A patent/CN104496895B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1214679A (en) * | 1996-02-09 | 1999-04-21 | 莱利工业公司 | Continuous processes for hydrolysis of cyanopyridines under substantially adiabatic conditions |
| JP2006206516A (en) * | 2005-01-28 | 2006-08-10 | Koei Chem Co Ltd | Method for producing 4,4'-dicarboxy-2,2'-bipyridine |
| US20090143439A1 (en) * | 2007-11-30 | 2009-06-04 | Wolfgang Haap | New pyridines as fbpase inhibitors for treatment of diabetes |
| CN101265230A (en) * | 2008-04-18 | 2008-09-17 | 浙江大学 | No-catalyst hydrolysis method for preparing nicotinic acid from nicotinonitrile in near-critical water medium |
| CN101463004A (en) * | 2009-01-15 | 2009-06-24 | 浙江大学 | Method for preparing isonicotinic acid by non-catalytic hydrolyzing isonicotinonitrile in near-critical water medium |
| CN101475527A (en) * | 2009-01-22 | 2009-07-08 | 浙江大学 | Method for preparing isonicotinic acid and pyrazinamide by non-catalytic hydrolyzing isonicotinonitrile in near-critical water medium |
| CN101597258A (en) * | 2009-04-29 | 2009-12-09 | 南通醋酸化工股份有限公司 | The technology of 3-cyanopyridine synthesizing niacinamide and co-producing niacin by hydrolyzing |
Non-Patent Citations (3)
| Title |
|---|
| SHYAMAPADA NANDI,等: "Tuning porosity via control of interpenetration in a zinc isonicotinate metal organic framework", 《J.CHEM.SCI.》 * |
| 刘小华,等: "吡啶甲酸的制备研究进展", 《化学研究与应用》 * |
| 吴枫,等: "电解合成4吡啶甲酸", 《广东化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114773262A (en) * | 2022-05-19 | 2022-07-22 | 兄弟科技股份有限公司 | Synthesis method of 2-cyano-4-pyridine carboxylic acid methyl ester |
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