CN104496895B - Method for preparing isonicotinic acid by hydrolysis - Google Patents
Method for preparing isonicotinic acid by hydrolysis Download PDFInfo
- Publication number
- CN104496895B CN104496895B CN201410797446.1A CN201410797446A CN104496895B CN 104496895 B CN104496895 B CN 104496895B CN 201410797446 A CN201410797446 A CN 201410797446A CN 104496895 B CN104496895 B CN 104496895B
- Authority
- CN
- China
- Prior art keywords
- hydrolysis
- gamma
- hole bottle
- pyridinecarboxylic acid
- purified water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
- C07D213/803—Processes of preparation
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 .gamma.-pyridinecarboxylic acid preparing technical field, especially relate to a kind of method of hydrolysis preparation .gamma.-pyridinecarboxylic acid.
Background technology
.gamma.-pyridinecarboxylic acid also known as Isonicotinic acid, are a kind of important medicine intermediates, are mainly used in synthesis antituberculotics different
Cigarette hydrazine, is also used for the derivants such as synthesizing amide, hydrazides, esters.For a long time, 4- picoline oxidizing process is mainly passed through in .gamma.-pyridinecarboxylic acid
Produce, need using the catalyst that is made up of multiple compounds, power consumption is high, and pollution is big, and product impurities are more, quality is not yet
Stable.By applying this patent, energy consumption can be greatly reduced, effectively reduce the discharge of pollutant, the quality of product can obtain simultaneously
To effective control, drastically reduce the area the impurity contained by product.
The primary raw material of traditional .gamma.-pyridinecarboxylic acid oxidation technology is 4- cyanopyridine, steam and hot-air, its basic technology stream
Journey, as shown in figure 1,4- cyanopyridine is through heating and gasifying, presses 1 with the steam of boiler room conveying and the air of hot blast stove heat:
The ratio of 10:100 is mixed, the catalyst completed in advance in oxidizing tower, at 200 DEG C, completes under 0.02～0.035mpa
Oxidation reaction, directly generates the .gamma.-pyridinecarboxylic acid solid of powder, collects successively through whirlpool pipeline under 1 to No. 4 auxiliary storage, tail gas warp
Salt acid tower reclaims, then generates .gamma.-pyridinecarboxylic acid substandard goods through filter pressing, neutralization.
This technique has an obvious defect, 1), oxidation reaction needs by catalyst catalysis, and catalyst is mainly by potassium sulfate, partially
The many kinds of substances such as ammonium vanadate, oxalic acid, sulphuric acid, silica gel form, and directly generate solid powdery finished product after the completion of reaction, do not filter
Operation, the catalyst containing in .gamma.-pyridinecarboxylic acid cannot remove, and impurity is more .gamma.-pyridinecarboxylic acid certified products content >=98.0%, and .gamma.-pyridinecarboxylic acid substandard goods contain
Amount >=97.0%, product residue on ignition≤1.0%；2), the pressed powder generating is easy to wall built-up in whirlpool pipeline, causes to manage
Road blocks, and needs workman to tap pipeline concussion with iron hammer using receptor, the rust on tube wall is mixed into finished product in company with percussion, makes product
Product are higher containing metal, affect product quality, and knock also constitutes certain noise to neighbouring village simultaneously；3), course of reaction
In have always a demand for boiler supplying steam, and workshop is also equipped with the roots blower of air stove and air inducing, and 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, air stove and blower fan, energy consumption is very big；4), tail gas
Absorb and generate big quantity of fluid, need distillation and concentration, then through filter pressing and neutralization, produce substandard goods.The power consumption of its still-process is very big, receives
Rate is but very low, but tail gas absorption liquid nor directly discharge.Therefore tail gas absorption reclaims and always is loss.
In sum, oxidation reaction major defect in .gamma.-pyridinecarboxylic acid is that impurity is higher, power consumption is excessive, has certain pollution, meanwhile,
This oxidation reaction belongs to hazardous chemical technique, its use base stock 4- picoline fall within hazardous chemical so that
This technique all has certain danger in terms of production and storage.Therefore, it is badly in need of researching and developing a kind of new preparation .gamma.-pyridinecarboxylic acid
Method, to overcome disadvantages described above.
Content of the invention
The problem to be solved in the present invention is to provide a kind of method of hydrolysis preparation .gamma.-pyridinecarboxylic acid, and the method by-product is few, product
Purity is high, and energy consumption is greatly lowered, and while effective reduction production cost, the safety of technique also increases substantially.
For solving above-mentioned technical problem, the technical solution used in the present invention is: a kind of method of hydrolysis preparation .gamma.-pyridinecarboxylic acid, bag
Include following preparation process,
1), load weighted 4- cyanopyridine, sodium hydroxide are put in four-hole bottle, then are measured accordingly with graduated cylinder by hydrolysis
The purified water of amount puts in four-hole bottle, and wherein 4- cyanopyridine, sodium hydroxide, the mass ratio of purified water are 1:0.39～0.80:2
～4；Start stirring to begin to warm up, when temperature rises to 90～115 DEG C, start timing, in hydrolysis reaction, according to raw water
Solution volume mends purified water it is ensured that volume is unchanged in four-hole bottle, and temperature control is at 90 DEG C～115 DEG C, hydrolysis 1～3
After hour, obtain 4- pyridine-carboxylic acid sodium；
The chemical equation of hydrolysis is as follows:
2), decolour
Hydrolysis cool the temperature to 70-80 DEG C after finishing, and add activated carbon to start timing and are incubated 0.5～1.5 hour, temperature
Degree controls at 70～80 DEG C, and decolouring finishes rear sucking filtration and removes activated carbon；
3), crystallize
By step 2) filtrate that obtains is reentered in the four-hole bottle of cleaning, carries out Deca, side Deca hydrochloric acid with hydrochloric acid
Side measures the ph value of solution in four-hole bottle, 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 Deca hydrochloric acid；And record the consumption of hydrochloric acid, because hydrochloric acid, as one of raw materials for production, records disappearing of hydrochloric acid
Consumption, is mainly used for calculating unit consumption and cost.
Chemical equation in crystallisation step is as follows:
4), separate
Solution in four-hole bottle is carried out sucking filtration washing after finishing by crystallization, obtains wet product；
5), dry
By step 4) wet product that obtains puts in drying baker and dries, that is, obtain .gamma.-pyridinecarboxylic acid finished product.
Preferably, step 1) in, hydrolysis are 2 hours.
Preferably, step 2) in, it is incubated 1 hour after adding activated carbon.
Preferably, by step 4) wet product that obtains puts in drying baker and carries out drying 4～6 hours at 105～110 DEG C, that is,
Obtain .gamma.-pyridinecarboxylic acid finished product.
The present invention has the advantages and positive effects that: the present invention provide hydrolysis prepare .gamma.-pyridinecarboxylic acid method, have with
Lower advantage:
1., after hydrolysis and an acid crystal reaction, product only has .gamma.-pyridinecarboxylic acid, ammonia and sodium chloride, and ammonia leads to
Cross recovery tower recovery and can make ammonia, be a kind of important agricultural fertilizer it is also possible to be used for boiler room boiler desulfuration dedusting, and
Sodium chloride can be removed by rinsing major part, the either sodium chloride in product or the sodium chloride in waste liquid, and concentration is all
Very low, product quality and environment will not be impacted.
2. hydrolyze after through filter progress so that in hydrolysis issuable impurity be removed, be greatly improved
The quality of product .gamma.-pyridinecarboxylic acid wet product content >=99.0% .gamma.-pyridinecarboxylic acid dry product content >=99.0%, residue on ignition≤0.5%.
3. steam is served only for the liter of hydrolysis and is gently incubated, and daily use time is limited, and crystallization is dropped using recirculated water
Temperature, does not have a large amount of situations expending fire coal and electric power in oxidation reaction, in whole technological process, energy consumption is greatly lowered, also effectively
Reduce production cost.
4. Hydrolyze method reaction is carried out in airtight retort, controls temperature by the size of steam, and production technology is simple
Change, the safety of whole production technology increases substantially.
Brief description
Fig. 1 is the process chart of tradition preparation .gamma.-pyridinecarboxylic acid；
Fig. 2 is the process chart of hydrolysis preparation .gamma.-pyridinecarboxylic acid in the present invention；
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 example IV；
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；
Specific embodiment
Embodiment one
A kind of method of hydrolysis preparation .gamma.-pyridinecarboxylic acid, including following preparation process,
1), load weighted 4- cyanopyridine, sodium hydroxide are put in four-hole bottle, then are measured accordingly with graduated cylinder by hydrolysis
The purified water of amount puts in four-hole bottle, and wherein 4- cyanopyridine, sodium hydroxide, the mass ratio of purified water are 1:0.8:4, wherein 4-
The quality of cyanopyridine is 100g；Start stirring to begin to warm up, when temperature rises to 108 DEG C, start timing, in hydrolysis mistake
Cheng Zhong, mends purified water it is ensured that volume is unchanged according to raw water solution volume in four-hole bottle, and temperature control is 108 DEG C～115
DEG C, hydrolysis, after 2 hours, obtain 4- pyridine-carboxylic acid sodium；
2), decolour
Hydrolysis cool the temperature to 75 DEG C after finishing, add 2g activated carbon to start timing and be incubated 1 hour, temperature control exists
70～80 DEG C, decolouring finishes rear sucking filtration and removes activated carbon；
3), crystallize
By step 2) filtrate that obtains is reentered in the four-hole bottle of cleaning, carries out Deca, side Deca hydrochloric acid with hydrochloric acid
Side measures the ph value of solution in four-hole bottle, until after its ph reaches 3.6, repetition measurement after 10 minutes, its ph still for 3.7, the disappearing of hydrochloric acid
Consumption is 162ml, and wherein the mass fraction of hydrochloric acid is 36.0%；
4), separate
Solution in four-hole bottle is carried out sucking filtration washing after finishing by crystallization, obtains wet product 175g；
5), dry
By step 4) wet product that obtains puts in drying baker and dries, and drying temperature is 105 DEG C, that is, obtain .gamma.-pyridinecarboxylic acid finished product
115g.
The main physical and chemical index in .gamma.-pyridinecarboxylic acid prepared by above method is as follows, the content of .gamma.-pyridinecarboxylic acid: 99.8%, blazing residual
Slag: 0.04%, chloride :≤0.05%, outward appearance: white powder, solution color: qualified, clarity: qualified, differentiate: qualified, respectively
Item index is all qualified.And .gamma.-pyridinecarboxylic acid conversion ratio: 97.25%.
Embodiment two
A kind of method of hydrolysis preparation .gamma.-pyridinecarboxylic acid, including following preparation process,
1), load weighted 4- cyanopyridine, sodium hydroxide are put in four-hole bottle, then are measured accordingly with graduated cylinder by hydrolysis
The purified water of amount puts in four-hole bottle, and wherein 4- cyanopyridine, sodium hydroxide, the mass ratio of purified water are 1:0.6:3, wherein 4-
The quality of cyanopyridine is 100g；Start stirring to begin to warm up, when temperature rises to 100 DEG C, start timing, in hydrolysis mistake
Cheng Zhong, mends purified water it is ensured that volume is unchanged according to raw water solution volume in four-hole bottle, and temperature control is 100 DEG C～108
DEG C, hydrolysis, after 2 hours, obtain 4- pyridine-carboxylic acid sodium；
2), decolour
Hydrolysis cool the temperature to 80 DEG C after finishing, add 2g activated carbon to start timing and be incubated 1 hour, temperature control exists
70～80 DEG C, decolouring finishes rear sucking filtration and removes activated carbon；
3), crystallize
By step 2) filtrate that obtains is reentered in the four-hole bottle of cleaning, carries out Deca, side Deca hydrochloric acid with hydrochloric acid
Side measures the ph value of solution in four-hole bottle, until after its ph reaches 3.5, repetition measurement after 10 minutes, its ph value is 3.6, then stop dripping
Salt adding acid simultaneously records the consumption of hydrochloric acid, and the consumption of hydrochloric acid is 132ml, and wherein the mass fraction of hydrochloric acid is 36.0%；
4), separate
Solution in four-hole bottle is carried out sucking filtration washing after finishing by crystallization, obtains wet product 185g；
5), dry
By step 4) wet product that obtains puts in drying baker and dries, and drying temperature is 105 DEG C, that is, obtain .gamma.-pyridinecarboxylic acid finished product
114.9g.
The main physical and chemical index in .gamma.-pyridinecarboxylic acid prepared by above method is as follows, the content of .gamma.-pyridinecarboxylic acid: 99.9%, blazing residual
Slag: 0.05%, chloride :≤0.05%, outward appearance: white powder, solution color: qualified, clarity: qualified, differentiate: qualified, respectively
Item index is all qualified..gamma.-pyridinecarboxylic acid conversion ratio: 97.17%.
Embodiment three
A kind of method of hydrolysis preparation .gamma.-pyridinecarboxylic acid, including following preparation process,
1), load weighted 4- cyanopyridine, sodium hydroxide are put in four-hole bottle, then are measured accordingly with graduated cylinder by hydrolysis
The purified water of amount puts in four-hole bottle, and wherein 4- cyanopyridine, sodium hydroxide, the mass ratio of purified water are 1:0.5:3, wherein 4-
The quality of cyanopyridine is 100g；Start stirring to begin to warm up, when temperature rises to 95 DEG C, start timing, in hydrolysis mistake
Cheng Zhong, mends purified water it is ensured that volume is unchanged according to raw water solution volume in four-hole bottle, and temperature control is at 90 DEG C～100 DEG C,
After hydrolysis 2 hours, obtain 4- pyridine-carboxylic acid sodium；
2), decolour
Hydrolysis cool the temperature to 80 DEG C after finishing, add 2g activated carbon to start timing and be incubated 1 hour, temperature control exists
70～80 DEG C, decolouring finishes rear sucking filtration and removes activated carbon；
3), crystallize
By step 2) filtrate that obtains is reentered in the four-hole bottle of cleaning, carries out Deca, side Deca hydrochloric acid with hydrochloric acid
Side measures the ph value of solution in four-hole bottle, until after its ph reaches 3.7, repetition measurement after 10 minutes, its ph value is 3.7, then stop dripping
Salt adding acid, the consumption of hydrochloric acid is 102ml, and wherein the mass fraction of hydrochloric acid is 36.0%；
4), separate
Solution in four-hole bottle is carried out sucking filtration washing after finishing by crystallization, obtains wet product 180g；
5), dry
By step 4) wet product that obtains puts in drying baker and dries, and drying temperature is 108 DEG C, that is, obtain .gamma.-pyridinecarboxylic acid finished product.
The main physical and chemical index in .gamma.-pyridinecarboxylic acid prepared by above method is as follows, the content of .gamma.-pyridinecarboxylic acid: 99.9%, blazing residual
Slag: 0.06%, chloride :≤0.05%, outward appearance: white powder, solution color: qualified, clarity: qualified, differentiate: qualified, respectively
Item index is all qualified..gamma.-pyridinecarboxylic acid conversion ratio: 97.45%.
Example IV
A kind of method of hydrolysis preparation .gamma.-pyridinecarboxylic acid, including following preparation process,
1), load weighted 4- cyanopyridine, sodium hydroxide are put in four-hole bottle, then are measured accordingly with graduated cylinder by hydrolysis
The purified water of amount puts in four-hole bottle, and wherein 4- cyanopyridine, sodium hydroxide, the mass ratio of purified water are 1:0.39:2, wherein
The quality of 4- cyanopyridine is 100g；Start stirring to begin to warm up, when temperature rises to 90 DEG C, start timing, in hydrolysis
During, purified water is mended it is ensured that volume is unchanged in four-hole bottle according to raw water solution volume, and temperature control is 90 DEG C～95
DEG C, hydrolysis, after 2 hours, obtain 4- pyridine-carboxylic acid sodium；
2), decolour
Hydrolysis cool the temperature to 80 DEG C after finishing, add 2g activated carbon to start timing and be incubated 1 hour, temperature control exists
70～80 DEG C, decolouring finishes rear sucking filtration and removes activated carbon；
3), crystallize
By step 2) filtrate that obtains is reentered in the four-hole bottle of cleaning, carries out Deca, side Deca hydrochloric acid with hydrochloric acid
Side measures the ph value of solution in four-hole bottle, until after its ph reaches 3.6, repetition measurement after 10 minutes, its ph value is still 3.6, then stop
Deca hydrochloric acid, the consumption of hydrochloric acid is 80ml, and wherein the mass fraction of hydrochloric acid is 36.0%；
4), separate
Solution in four-hole bottle is carried out sucking filtration washing after finishing by crystallization, obtains wet product 190g；
5), dry
By step 4) wet product that obtains puts in drying baker and dries, and drying temperature is 110 DEG C, that is, obtain .gamma.-pyridinecarboxylic acid finished product
115.3g.
The main physical and chemical index in .gamma.-pyridinecarboxylic acid prepared by above method is as follows, the content of .gamma.-pyridinecarboxylic acid: 99.8%, blazing residual
Slag: 0.04%, chloride :≤0.05%, outward appearance: white powder, solution color: qualified, clarity: qualified, differentiate: qualified, respectively
Item index is all qualified..gamma.-pyridinecarboxylic acid conversion ratio: 97.50%.
Embodiment five
A kind of hydrolysis preparation .gamma.-pyridinecarboxylic acid method it is characterised in that: include following preparation process,
1), load weighted 4- cyanopyridine, sodium hydroxide are put in four-hole bottle, then are measured accordingly with graduated cylinder by hydrolysis
The purified water of amount puts in four-hole bottle, and wherein 4- cyanopyridine, sodium hydroxide, the mass ratio of purified water are 1:0.35:2, wherein
The quality of 4- cyanopyridine is 100g；Start stirring to begin to warm up, when temperature rises to 90 DEG C, start timing, in hydrolysis
During, purified water is mended it is ensured that volume is unchanged in four-hole bottle according to raw water solution volume, and temperature control is 90 DEG C～95
DEG C, hydrolysis, after 2 hours, obtain 4- pyridine-carboxylic acid sodium；
2), decolour
Hydrolysis cool the temperature to 80 DEG C after finishing, add 2g activated carbon to start timing and be incubated 1 hour, temperature control exists
70～80 DEG C, decolouring finishes rear sucking filtration and removes activated carbon；
3), crystallize
By step 2) filtrate that obtains is reentered in the four-hole bottle of cleaning, carries out Deca, side Deca hydrochloric acid with hydrochloric acid
Side measures the ph value of solution in four-hole bottle, until after its ph reaches 3.7, repetition measurement after 10 minutes, its ph value is still 3.8, then stop
Deca hydrochloric acid, the consumption of hydrochloric acid is 72ml, and wherein the mass fraction of hydrochloric acid is 36.0%；
4), separate
Solution in four-hole bottle is carried out sucking filtration washing after finishing by crystallization, obtains wet product 160g；
5), dry
By step 4) wet product that obtains puts in drying baker and dries, and drying temperature is 110 DEG C, that is, obtain .gamma.-pyridinecarboxylic acid finished product
101.5g.
The main physical and chemical index in .gamma.-pyridinecarboxylic acid prepared by above method is as follows, the content of .gamma.-pyridinecarboxylic acid: 94.8%, blazing residual
Slag: 0.03%, chloride；≤ 0.05%, outward appearance: white powder, solution color: qualified, clarity: qualified, differentiate: unqualified.
.gamma.-pyridinecarboxylic acid conversion ratio: 85.83%.
Embodiment six
A kind of hydrolysis preparation .gamma.-pyridinecarboxylic acid method it is characterised in that: include following preparation process,
1), load weighted 4- cyanopyridine, sodium hydroxide are put in four-hole bottle, then are measured accordingly with graduated cylinder by hydrolysis
The purified water of amount puts in four-hole bottle, and wherein 4- cyanopyridine, sodium hydroxide, the mass ratio of purified water are 1:0.39:2, wherein
The quality of 4- cyanopyridine is 100g；Start stirring to begin to warm up, when temperature rises to 100 DEG C, start timing, in hydrolysis
During, purified water is mended it is ensured that volume is unchanged in four-hole bottle according to raw water solution volume, and temperature control is 100 DEG C～108
DEG C, hydrolysis, after 2 hours, obtain 4- pyridine-carboxylic acid sodium；
2), decolour
Hydrolysis cool the temperature to 80 DEG C after finishing, add activated carbon to start timing and be incubated 1 hour, temperature control is 70
～80 DEG C, decolouring finishes rear sucking filtration and removes activated carbon；
3), crystallize
By step 2) filtrate that obtains is reentered in the four-hole bottle of cleaning, carries out Deca, side Deca hydrochloric acid with hydrochloric acid
Side measures the ph value of solution in four-hole bottle, until after its ph reaches 3.6, repetition measurement after 10 minutes, its ph value is 3.7, then stop dripping
Salt adding acid, the consumption of hydrochloric acid is 84ml, and wherein the mass fraction of hydrochloric acid is 36.0%；
4), separate
Solution in four-hole bottle is carried out sucking filtration washing after finishing by crystallization, obtains wet product 182g；
5), dry
By step 4) wet product that obtains puts in drying baker and dries, and drying temperature is 110 DEG C, that is, obtain .gamma.-pyridinecarboxylic acid finished product
114.9g.
The main physical and chemical index in .gamma.-pyridinecarboxylic acid prepared by above method is as follows, the content of .gamma.-pyridinecarboxylic acid: 99.7%, blazing residual
Slag: 0.05%, chloride :≤0.05%, outward appearance: white powder, solution color: qualified, clarity: qualified, differentiate: qualified, respectively
Item index is all qualified..gamma.-pyridinecarboxylic acid conversion ratio: 97.17%.
Embodiment seven
A kind of hydrolysis preparation .gamma.-pyridinecarboxylic acid method it is characterised in that: include following preparation process,
1), load weighted 4- cyanopyridine, sodium hydroxide are put in four-hole bottle, then are measured accordingly with graduated cylinder by hydrolysis
The purified water of amount puts in four-hole bottle, and wherein 4- cyanopyridine, sodium hydroxide, the mass ratio of purified water are 1:0.39:2, wherein
The quality of 4- cyanopyridine is 100g；Start stirring to begin to warm up, when temperature rises to 95 DEG C, start timing, in hydrolysis
During, purified water is mended it is ensured that volume is unchanged in four-hole bottle according to raw water solution volume, and temperature control is 95 DEG C～100
DEG C, hydrolysis, after 2 hours, obtain 4- pyridine-carboxylic acid sodium；
2), decolour
Hydrolysis cool the temperature to 80 DEG C after finishing, add 2g activated carbon to start timing and be incubated 1 hour, temperature control exists
70～80 DEG C, decolouring finishes rear sucking filtration and removes activated carbon；
3), crystallize
By step 2) filtrate that obtains is reentered in the four-hole bottle of cleaning, carries out Deca, side Deca hydrochloric acid with hydrochloric acid
Side measures the ph value of solution in four-hole bottle, until after its ph reaches 3.7, repetition measurement after 10 minutes, its ph value is 3.8, then stop dripping
Salt adding acid, the consumption of hydrochloric acid is 83ml, and wherein the mass fraction of hydrochloric acid is 36.0%；
4), separate
Solution in four-hole bottle is carried out sucking filtration washing after finishing by crystallization, obtains wet product 170g；
5), dry
By step 4) wet product that obtains puts in drying baker and dries, and drying temperature obtains .gamma.-pyridinecarboxylic acid finished product for 110 DEG C
115.1g.
The main physical and chemical index in .gamma.-pyridinecarboxylic acid prepared by above method is as follows, the content of .gamma.-pyridinecarboxylic acid: 99.8%, blazing residual
Slag: 0.05%, chloride :≤0.05%, outward appearance: white powder, solution color: qualified, clarity: qualified, differentiate: qualified, respectively
Item index is all qualified..gamma.-pyridinecarboxylic acid conversion ratio: 97.34%.
Above embodiments of the invention are described in detail, but described content have been only presently preferred embodiments of the present invention,
It is not to be regarded as the practical range for limiting the present invention.All impartial changes made according to the scope of the invention and improvement etc., all should
Still belong within this patent covering scope.
Claims (4)
1. a kind of hydrolysis preparation .gamma.-pyridinecarboxylic acid method it is characterised in that: include following preparation process,
1), load weighted 4- cyanopyridine, sodium hydroxide are put in four-hole bottle, then measure respective amount with graduated cylinder by hydrolysis
Purified water puts in four-hole bottle, and wherein 4- cyanopyridine, sodium hydroxide, the mass ratio of purified water are 1:0.39～0.80:2～4；
Start stirring to begin to warm up, when temperature rises to 90～115 DEG C, start timing, in hydrolysis reaction, disintegrated according to raw water
Amass and mend purified water in four-hole bottle it is ensured that volume is unchanged, and temperature control is at 90 DEG C～115 DEG C, hydrolysis 1～3 hour
Afterwards, obtain 4- pyridine-carboxylic acid sodium；
2), decolour
Hydrolysis cool the temperature to 70～80 DEG C after finishing, add activated carbon to start timing and be incubated 0.5～1.5 hour, temperature
Control at 70～80 DEG C, decolouring finishes rear sucking filtration and removes activated carbon；
3), crystallize
By step 2) filtrate that obtains is reentered in the four-hole bottle of cleaning, carries out Deca with hydrochloric acid, survey in Deca hydrochloric acid
The ph value of solution in amount four-hole bottle, until after its ph reaches 3.5～4.0, repetition measurement after 5～15 minutes, its ph value still for 3.5～
4.0, then stop Deca hydrochloric acid；
4), separate
Solution in four-hole bottle is carried out sucking filtration washing after finishing by crystallization, obtains wet product；
5), dry
By step 4) wet product that obtains puts in drying baker and dries, that is, obtain .gamma.-pyridinecarboxylic acid finished product.
2. according to claim 1 hydrolysis preparation .gamma.-pyridinecarboxylic acid method it is characterised in that: step 1) in, hydrolysis be 2
Individual hour.
3. according to claim 1 hydrolysis preparation .gamma.-pyridinecarboxylic acid method it is characterised in that: step 2) in, add activated carbon
It is incubated 1 hour afterwards.
4. according to claim 1 hydrolysis preparation .gamma.-pyridinecarboxylic acid method it is characterised in that: step 5) in, by step 4)
To wet product put in drying baker and dried at 105～110 DEG C, that is, obtain .gamma.-pyridinecarboxylic acid finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410797446.1A CN104496895B (en) | 2014-12-18 | 2014-12-18 | Method for preparing isonicotinic acid by hydrolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410797446.1A CN104496895B (en) | 2014-12-18 | 2014-12-18 | Method for preparing isonicotinic acid by hydrolysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104496895A CN104496895A (en) | 2015-04-08 |
| CN104496895B true CN104496895B (en) | 2017-02-01 |
Family
ID=52938369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410797446.1A Active CN104496895B (en) | 2014-12-18 | 2014-12-18 | Method for preparing isonicotinic acid by hydrolysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104496895B (en) |
Families Citing this family (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 |
Citations (6)
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4796776B2 (en) * | 2005-01-28 | 2011-10-19 | 広栄化学工業株式会社 | Method for producing 4,4'-dicarboxy-2,2'-bipyridine |
-
2014
- 2014-12-18 CN CN201410797446.1A patent/CN104496895B/en active Active
Patent Citations (6)
| 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 |
| 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 |
|---|
| Tuning porosity via control of interpenetration in a zinc isonicotinate metal organic framework;SHYAMAPADA NANDI,等;《J.Chem.Sci.》;20140930;第126卷(第5期);第1393-1398页 * |
| 吡啶甲酸的制备研究进展;刘小华,等;《化学研究与应用》;20030430;第15卷(第02期);第161-164页 * |
| 电解合成4吡啶甲酸;吴枫,等;《广东化工》;19911231(第04期);第21-24页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104496895A (en) | 2015-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Todkar et al. | Extraction of silica from rice husk | |
| CN110272299A (en) | Coal ash for manufacturing for siliceous fertilizer method | |
| CN104495899A (en) | Method for synergic resource utilization of acetylene sludge and coal ash | |
| CN104451883B (en) | A kind of preparation method of eakleite whisker | |
| CN104016325B (en) | A kind of production method of tricalcium phosphate | |
| CN105732986B (en) | A kind of technique preparing Methyl Hydrogen Polysiloxane Fluid | |
| CN110115877A (en) | A kind of magnesia filtering material and preparation method thereof | |
| CN106082715B (en) | Method for preparing light calcined magnesium oxide by using magnesite | |
| CN105800653A (en) | Method for extracting aluminum oxide from fly ash on basis of soda-lime sintering process | |
| CN104496895B (en) | Method for preparing isonicotinic acid by hydrolysis | |
| CN108424206A (en) | Flyash acid system residue of aluminum-extracted prepares the method containing silicon composite fertilizer and the utilization method containing silicon composite fertilizer and flyash | |
| CN105565272A (en) | Method for preparing high-purity hydrogen chloride gas | |
| CN101439867A (en) | Method for extracting potassium carbonate from cabo and refining carbon | |
| CN105858688A (en) | Method for quickly converting NOx tail gas into potassium nitrate | |
| CN105254575A (en) | Synthetic method for sulfadiazine | |
| CN100575512C (en) | A kind of microwave heating, solid state reduction and gaseous dephosphorization method of manganese ore powder | |
| CN106865565A (en) | A kind of flyash synthesizes the method for X-type zeolite | |
| CN108017089B (en) | A method of recycling ammonium molybdate from useless molybdenum catalyst | |
| CN107140660B (en) | A kind of preparation method of potassium carbonate | |
| CN102659143A (en) | Method for producing sodium metabisulfite or sodium sulphite by using gypsum as raw material | |
| CN104609444B (en) | Straightization method produces potassium sulfate and the method for several high level byproduct of by-product | |
| CN104557685A (en) | Method for producing nicotinic acid by using nicotinamide mother solution | |
| CN104671295A (en) | Method for preparing polyaluminum ferric chloride water purifier | |
| Chao et al. | A novel process for one-step preparing potassium-containing fertilizer using red mud or CFA synergistic extraction of alumina | |
| US2809880A (en) | Production of magnesium oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |