CN103755625A - Method for cleanly preparing high-purity pyridine hydrochloride - Google Patents
Method for cleanly preparing high-purity pyridine hydrochloride Download PDFInfo
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- CN103755625A CN103755625A CN201310714902.7A CN201310714902A CN103755625A CN 103755625 A CN103755625 A CN 103755625A CN 201310714902 A CN201310714902 A CN 201310714902A CN 103755625 A CN103755625 A CN 103755625A
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- pyridine
- hydrogen chloride
- chloride gas
- pyridine hydrochloride
- hydrochloric acid
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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
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/18—Salts thereof
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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
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/127—Preparation from compounds containing pyridine rings
Abstract
The invention relates to the technical field of pyridine hydrochloride and particularly relates to a method for cleanly preparing high-purity pyridine hydrochloride. The method comprises the following steps: dissolving pyridine by using an organic solvent to obtain a mixed solution; adding 98% concentrated sulfuric acid into a container and dripping 31% hydrochloric acid into the container to generate hydrogen chloride gas, wherein the weight ratio of hydrochloric acid to concentrated sulfuric acid is 1:(2.5-3.5); introducing the hydrogen chloride gas into the mixed solution to react; filtering to obtain filtering dreg, namely pyridine hydrochloride. According to the method, the hydrogen chloride gas with low price is prepared by taking concentrated sulfuric acid and hydrochloric acid as the raw materials; after being dried by concentrated sulfuric acid, the hydrogen chloride gas is used for a production process, the chemically-pure quality of the gas stored in a steel bottle is reached and the cost is reduced by 70%; prepared pyridine hydrochloride has a white appearance, the yield is more than 98%, the purity is up to 99.5% and the water content is less than 0.2%; the quality of pyridine hydrochloride stays ahead of that of domestic products; the byproduct sulfuric acid is used for producing magnesium sulfate heptahydrate; the application is wide; the whole production process has no emission of three wastes and is clean and environment-friendly.
Description
technical field
The present invention relates to pyridine hydrochloride technical field, particularly a kind of clean method of preparing high purity pyridine hydrochloride.
background technology
Pyridine hydrochloride, has another name called pyridine hydrochloride, CAS 628-13-7, molecular formula C
5h
5nHCl, relative molecular mass: 115.56.Pyridine hydrochloride salt is white crystals body, fusing point 144-146 ℃.Dissolve each other with organic solvents such as water, ethanol, be insoluble to acetone, ether, tetracol phenixin and aromatic hydrocarbons.The very easily moisture absorption of this product, under normal temperature, the solubleness of pyridine hydrochloride in water is 560g/100g water.
High purity pyridine hydrochloride is important medicine intermediate, be mainly used in the production of macrolide antibiotics clarithromycin, clarithromycin has another name called clarithromycin, it is the derivative of erythromycin, succeeded in developing the beginning of the nineties in last century by Japanese great Zheng company, and with trade(brand)name Clarith registration, market consumption steady-state growth, and brought into play vital role in clinical.Pyridine hydrochloride also can be used for Biochemical Research, organic synthesis according to another report.
Synthesizing of pyridine hydrochloride, mainly contain following several operational paths:
1, adopt respectively the liquid liquid synthesis method of pyridine and hydrochloric acid and the gas-liquid synthesis method of pyridine and hydrogen chloride gas, liquid liquid synthesis method yield 85%, gas-liquid synthesis method 92%.Liquid liquid synthesis method need be distilled too much moisture, not only can not get anhydrous pyridine hydrochloride, and quality product is poor.
2,, take methylene dichloride as solvent, hydrogenchloride and pyridine reaction are prepared pyridine hydrochloride, product content 98%, productive rate 94%.But methylene dichloride boiling point is low, commercial recovery rate is lower, and production cost is high.
3, adopt in 20-40% pyridine anhydrous ether solution and pass into hydrogen chloride gas, quality product and yield are not quite clear.But anhydrous diethyl ether is difficult at industrial application, and boiling point is low, volatile, and the rate of recovery is low, the accident such as easily blast during recovery, this method only limits to laboratory and prepares a small amount of sample.
During < < chemical industry, print the gas-liquid synthesis technique of mentioning in the synthesis technique > > of article < < pyridine hydrochloride of > > 1999 (13) volume the 2nd interim Zhu's Xiao Ling as follows: at 1000mL, stirring is housed, in the four-hole boiling flask of dropping funnel and escape pipe, add hydrochloric acid 300mL, sodium-chlor 310g, start stirring, slowly drip sulfuric acid, generate hydrogen chloride gas, after vitriol oil scrubbing bottle and a surge flask, obtain dry hydrogen chloride gas.The four-hole boiling flask that stirring, thermometer, reflux exchanger and inlet pipe are housed is placed in to cold water bath, in flask, add 300g pyridine and 300mL methylene dichloride, start agitator, by inlet pipe, pass into dry hydrogen chloride gas (the air inlet mouth of pipe should just under liquid), keep still temperature to be less than 30 ℃, now adularescent PDHC generates.When the hydrogen chloride gas occurring has all led to, stop stirring, the PDHC in flask and methylene dichloride are filtered rapidly, filtrate is methylene dichloride, and for lower secondary response, filter cake is PDHC.When producing hydrogen chloride gas, in hydrochloric acid, also added sodium-chlor, produce after hydrogen chloride gas, can generate sodium sulfate, aftertreatment is caused to trouble.And liquid liquid synthesis method yield only has 85%, and gas-liquid synthesis method yield only has 92%, and yield is lower.
But at present commercially available prod quality is very different, and price is higher, in production process, waste liquid aftertreatment cost is high and difficulty is large.
summary of the invention
Poor in order to solve above pyridine hydrochloride quality product, cost is higher, large, the unmanageable problem of waste liquid of energy consumption in preparation process, the invention provides a kind of preparation process with low cost, superior in quality, reaction conditions is easy to control, the easy-to-handle clean method of preparing high purity pyridine hydrochloride of waste liquid.Pyridine hydrochloride quality index is as follows:
Index name index
Appearance white crystalline powder
Fusing point, ℃ 144-146
Content, %≤99.0
Water content, %≤0.2
The present invention is achieved by the following measures:
A clean method of preparing high purity pyridine hydrochloride, comprises the following steps:
(1) pyridine is obtained to mixing solutions with organic solvent dissolution;
(2) in glassed steel reaction vessels, add 98% the vitriol oil, slowly drip wherein 31% hydrochloric acid under stirring, produce hydrogen chloride gas, wherein, the weight ratio of hydrochloric acid and the vitriol oil is 1:2.5-3.5;
(3) hydrogen chloride gas that step (2) produces is after the vitriol oil is dry, through surge tank, pass in the mixing solutions in step (1), at the temperature of 20-60 ℃, react, by controlling the feed rate of hydrochloric acid, make still internal pressure at 0.01-0.05MPa, in hydrogenchloride and mixed solvent, the mol ratio of pyridine is 1:1.0-1.2, filter, filter cake is wet product pyridine hydrochloride, and filtrate is returned to production system and reused;
(4) step (3) obtains filter cake is through vacuum-drying, controls vacuum tightness at-0.090-0.095MPa, temperature 50-80 ℃, gas reclaims solvent through condensation, return in production system, after distillation dewaters, recycle, the crystallization of gained pressed powder is high purity pyridine hydrochloride.
(5), in whole production process, for avoiding moisture in air to enter system, adopted nitrogen protection, before and after comprising and passing into before hydrogen chloride gas, filter, dry, in the processes such as packing.
Described method, the organic solvent that step (1) is used is: methylene dichloride, trichloromethane, 1,2-ethylene dichloride, toluene, dimethylbenzene, sherwood oil etc., wherein preferred toluene;
Described method, the volume ratio of step (1) pyridine and organic solvent is 1:5-7, preferably 1:6;
Described method, in step (2), the weight ratio of hydrochloric acid and the vitriol oil is 1:2.5-3.5, preferably 1:3;
Described method, in the middle liquid that has produced hydrogen chloride gas of step (2), add metal oxide to carry out neutralizing treatment, metal oxide is: calcium oxide, magnesium oxide, ferric oxide, aluminum oxide etc., wherein preferred light-burned technical grade magnesium oxide, prepares technical grade magnesium sulfate heptahydrate.
Described method, in step (3), in hydrogenchloride and mixing solutions, the mol ratio of pyridine is 1:1.0-1.2, preferably 1:1.05-1.1.
Described method, in step (3), reactor pressure is at 0.01-0.05MPa, preferably 0.02-0.04MPa;
Described method, in step (3), temperature of reaction is at 20-60 ℃, preferably 30-40 ℃;
Described method, the filtrate after filtering in step (3) adds the mixing solutions obtaining after pyridine to carry out the operation of step (1) (2) (3), is cycled to repeat use;
Described method, vacuum-drying control temperature 50-80 ℃ in step (4), preferably controls 50-60 ℃.
Compared with article in background technology < < chemical industry periodical > >, technical scheme of the present invention is when preparing hydrogen chloride gas, in hydrochloric acid, no longer add sodium-chlor, by controlling the ratio of sulfuric acid and hydrochloric acid, realize the abundant effusion of hydrogen chloride gas, thereby omitted this key element of sodium-chlor, this single stepping, make the acid solution that has produced hydrogen chloride gas can directly add magnesium oxide to generate magnesium sulfate heptahydrate, thereby simplified the step of acid solution aftertreatment, whole technique is produced without waste liquid, reach the object of cleaner production.So, from this point of view, the invention belongs to the invention of key element elliptical, dispensing after this key element of sodium-chlor, still can complete whole technique, and the purity of the pyridine hydrochloride obtaining and yield all increased before omitting.
Beneficial effect of the present invention:
1. take the vitriol oil and hydrochloric acid as raw material, prepared cheap hydrogen chloride gas, after the vitriol oil is dry, in process, has reached steel cylinder and filled chemical pure quality, cost 70%;
2. the pyridine hydrochloride appearance white xln making, yield is greater than 98%, and purity is up to 99.0-99.5%, and moisture is less than 0.2%, home products quality leadership;
3. by product dilute sulphuric acid is for the production of magnesium sulfate heptahydrate, of many uses, whole production process three-waste free discharge, clean environment firendly.
Embodiment
For a better understanding of the present invention, below in conjunction with specific embodiment, further illustrate.
embodiment 1:
A clean method of preparing pyridine hydrochloride, comprises the following steps:
(1) pyridine is dissolved to obtain to mixing solutions with toluene, wherein the volume ratio of pyridine and toluene is 1:5;
(2) in glassed steel reaction vessels, add wherein 98% the vitriol oil, drip 31% hydrochloric acid generation hydrogen chloride gas, wherein, the weight ratio of hydrochloric acid and the vitriol oil is 1:2.5;
(3) hydrogen chloride gas that step (2) produces is after the vitriol oil is dry, after surge tank, pass in the mixing solutions in step (1), in hydrogenchloride and mixing solutions, the mol ratio of pyridine is 1:1.05, at the temperature of 30-35 ℃, react, still internal pressure 0.01-0.02MPa, filter, filtrate continues to add pyridine to react after reclaiming, carry out recirculation utilization, filter cake is through vacuum-drying, temperature 50-55 ℃, vacuum tightness-0.090-0.092MPa, recovery solvent returns in production system and recycles, the crystallization of gained pressed powder is pyridine hydrochloride, after testing: purity 99.1%, water content 0.18%, yield 97.8% as calculated,
(4) by adding magnesium oxide in middle step (2) liquid that has produced hydrogen chloride gas, prepare magnesium sulfate heptahydrate.
embodiment 2:
A clean method of preparing pyridine hydrochloride, comprises the following steps:
(1) pyridine is dissolved to obtain to mixing solutions with toluene, wherein the volume ratio of pyridine and toluene is 1:7;
(2) in glassed steel reaction vessels, add wherein 98% the vitriol oil, drip 31% hydrochloric acid generation hydrogen chloride gas, wherein, the weight ratio of hydrochloric acid and the vitriol oil is 1:3.5;
(3) hydrogen chloride gas that step (2) produces is after the vitriol oil is dry, after surge tank, pass in the mixing solutions in step (1), in hydrogenchloride and mixing solutions, the mol ratio of pyridine is 1:1.1, at the temperature of 35-45 ℃, react, still internal pressure 0.01-0.02MPa, filter, filtrate continues to add pyridine to react after reclaiming, carry out recirculation utilization, filter cake is through vacuum-drying, temperature 50-55 ℃, vacuum tightness-0.090-0.092MPa, recovery solvent returns in production system and recycles, the crystallization of gained pressed powder is pyridine hydrochloride, after testing: purity 99.2%, water content 0.13%, yield 98.2% as calculated, (4) by adding magnesium oxide in middle step (2) liquid that has produced hydrogen chloride gas, prepare magnesium sulfate heptahydrate.
embodiment 3:
A clean method of preparing pyridine hydrochloride, comprises the following steps:
(1) pyridine is dissolved to obtain to mixing solutions with toluene, wherein the volume ratio of pyridine and toluene is 1:6;
(2) in glassed steel reaction vessels, add wherein 98% the vitriol oil, drip 31% hydrochloric acid generation hydrogen chloride gas, wherein, the weight ratio of hydrochloric acid and the vitriol oil is 1:3;
(3) hydrogen chloride gas that step (2) produces is after the vitriol oil is dry, after surge tank, pass in the mixing solutions in step (1), in hydrogenchloride and mixing solutions, the mol ratio of pyridine is 1:1.1, at the temperature of 35-40 ℃, react, still internal pressure 0.01-0.02MPa, filter, filtrate continues to add pyridine to react after reclaiming, carry out recirculation utilization, filter cake is through vacuum-drying, temperature 50-55 ℃, vacuum tightness-0.090-0.092MPa, recovery solvent returns in production system and recycles, the crystallization of gained pressed powder is pyridine hydrochloride, after testing: purity 99.6%, water content 0.11%, yield 98.1% as calculated,
(4) in the middle liquid that has produced hydrogen chloride gas of step (2), add magnesium oxide, prepare magnesium sulfate heptahydrate, make acid solution aftertreatment simple.
embodiment 4:
A clean method of preparing pyridine hydrochloride, comprises the following steps:
(1) pyridine is dissolved to obtain to mixing solutions with toluene, wherein the volume ratio of pyridine and toluene is 1:6;
(2) in glassed steel reaction vessels, add wherein 98% the vitriol oil, drip 31% hydrochloric acid generation hydrogen chloride gas, wherein, the weight ratio of hydrochloric acid and the vitriol oil is 1:3;
(3) hydrogen chloride gas that step (2) produces is after the vitriol oil is dry, after surge tank, pass in the mixing solutions in step (1), in hydrogenchloride and mixing solutions, the mol ratio of pyridine is 1:0.95, at the temperature of 35-45 ℃, react, still internal pressure 0.01-0.02MPa, filter, filtrate continues to add pyridine to react after reclaiming, carry out recirculation utilization, filter cake is through vacuum-drying, temperature 50-55 ℃, vacuum tightness-0.090-0.092MPa, recovery solvent returns in production system and recycles, the crystallization of gained pressed powder is pyridine hydrochloride, after testing: purity 98%, water content 0.19%, yield 92% as calculated, product colour is rubescent.
(4) in the middle liquid that has produced hydrogen chloride gas of step (2), add magnesium oxide, prepare magnesium sulfate heptahydrate, make acid solution aftertreatment simple.
embodiment 5:
A clean method of preparing pyridine hydrochloride, comprises the following steps:
(1) pyridine is dissolved to obtain to mixing solutions with toluene, wherein the volume ratio of pyridine and toluene is 1:6;
(2) in glassed steel reaction vessels, add wherein 98% the vitriol oil, drip 31% hydrochloric acid generation hydrogen chloride gas, wherein, the weight ratio of hydrochloric acid and the vitriol oil is 1:3;
(3) hydrogen chloride gas that step (2) produces is after the vitriol oil is dry, after surge tank, pass in the mixing solutions in step (1), in hydrogenchloride and mixing solutions, the mol ratio of pyridine is 1:1.2, at the temperature of 35-45 ℃, react, still internal pressure 0.01-0.02MPa, filter, filtrate continues to add pyridine to react after reclaiming, carry out recirculation utilization, filter cake is through vacuum-drying, temperature 50-55 ℃, vacuum tightness-0.090-0.092MPa, recovery solvent returns in production system and recycles, the crystallization of gained pressed powder is pyridine hydrochloride, after testing: purity 99.5%, water content 0.17%, yield 97.5% as calculated,
(4) in the middle liquid that has produced hydrogen chloride gas of step (2), add magnesium oxide, prepare magnesium sulfate heptahydrate, make acid solution aftertreatment simple.
embodiment 6:
A clean method of preparing pyridine hydrochloride, comprises the following steps:
(1) pyridine is dissolved to obtain to mixing solutions with toluene, wherein the volume ratio of pyridine and toluene is 1:6;
(2) in glassed steel reaction vessels, add wherein 98% the vitriol oil, drip 31% hydrochloric acid generation hydrogen chloride gas, wherein, the weight ratio of hydrochloric acid and the vitriol oil is 1:2;
(3) hydrogen chloride gas that step (2) produces is after the vitriol oil is dry, after surge tank, pass in the mixing solutions in step (1), in hydrogenchloride and mixing solutions, the mol ratio of pyridine is 1:1.3, at the temperature of 35-45 ℃, react, still internal pressure 0.01-0.02MPa, filter, filtrate continues to add pyridine to react after reclaiming, carry out recirculation utilization, filter cake is through vacuum-drying, temperature 50-55 ℃, vacuum tightness-0.090-0.092MPa, recovery solvent returns in production system and recycles, the crystallization of gained pressed powder is pyridine hydrochloride, after testing: purity 98.5%, water content 0.20%, yield 95.3% as calculated,
(4) in the middle liquid that has produced hydrogen chloride gas of step (2), add magnesium oxide, prepare magnesium sulfate heptahydrate, make acid solution aftertreatment simple.
embodiment 7:
Compared with embodiment 3, in step (3), the temperature of reaction of hydrogenchloride and pyridine is 35-40 ℃, still internal pressure 0.03-0.04MPa during reaction, and all the other conditions are identical with embodiment 3, after testing: purity 99.2%, water content 0.10%, as calculated yield 95.6%.
embodiment 8:
Compared with embodiment 3, in step (3), the temperature of reaction of hydrogenchloride and pyridine is 60 ℃, still internal pressure 0.01-0.02MPa during reaction, and all the other conditions are identical with embodiment 3, after testing: purity 98.6.%, water content 0.13%, as calculated yield 95.8%.
embodiment 9:
Compared with embodiment 3, in step (3), the temperature of reaction of hydrogenchloride and pyridine is 35-40 ℃, still internal pressure 0.04-0.05MPa during reaction, and all the other conditions are identical with embodiment 3, after testing: purity 98.3%, water content 0.15%, as calculated yield 95.7%.
Claims (6)
1. a clean method of preparing pyridine hydrochloride, is characterized in that comprising the following steps:
(1) pyridine is obtained to mixing solutions with organic solvent dissolution, the volume ratio of pyridine and organic solvent is 1:5-7;
(2) in container, add 98% the vitriol oil, drip wherein 31% hydrochloric acid, produce hydrogen chloride gas, wherein, the weight ratio of hydrochloric acid and the vitriol oil is 1:2.5-3.5;
(3) hydrogen chloride gas that step (2) produces eases up and rushes after device through super-dry, pass in the mixing solutions in step (1), in hydrogenchloride and mixing solutions, the mol ratio of pyridine is 1:1.0-1.2, at not higher than the temperature of 60 ℃, react, still internal pressure 0.01-0.02MPa, filters, filter cake is through vacuum-drying, temperature 50-55 ℃, vacuum tightness-0.090-0.092MPa, the crystallization of gained pressed powder is pyridine hydrochloride;
(4) by adding magnesium oxide in middle step (2) liquid that has produced hydrogen chloride gas, prepare magnesium sulfate heptahydrate.
2. method according to claim 1, is characterized in that the weight ratio of the middle hydrochloric acid of step (2) and the vitriol oil is 1:3.
3. method according to claim 1, is characterized in that the mol ratio of pyridine in the middle hydrogenchloride of step (3) and mixing solutions is 1:1.05-1.1.
4. method according to claim 1, is characterized in that described organic solvent is toluene.
5. method according to claim 1, is characterized in that in step (3), the filtrate after filtration adds the mixing solutions obtaining after pyridine to carry out the operation of step (2) (3).
6. method according to claim 1, is characterized in that in vacuum-drying, reclaiming in step (3) solvent and returns in production system and recycle.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105800828A (en) * | 2016-04-27 | 2016-07-27 | 滨海明鸿精细化工有限公司 | Method for recycling sodium pyrithione in waste water |
| CN107056683A (en) * | 2017-06-26 | 2017-08-18 | 蒋潇 | A kind of synthetic method of pyridine hydrochloride |
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| JP2009137936A (en) * | 2007-11-13 | 2009-06-25 | Hokko Chem Ind Co Ltd | Method for producing amine-alkyl(diaryl)borane complex |
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| JP2009137936A (en) * | 2007-11-13 | 2009-06-25 | Hokko Chem Ind Co Ltd | Method for producing amine-alkyl(diaryl)borane complex |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105800828A (en) * | 2016-04-27 | 2016-07-27 | 滨海明鸿精细化工有限公司 | Method for recycling sodium pyrithione in waste water |
| CN105800828B (en) * | 2016-04-27 | 2019-07-23 | 滨海明鸿精细化工有限公司 | The recovery method of sodium pyrithione in a kind of waste water |
| CN107056683A (en) * | 2017-06-26 | 2017-08-18 | 蒋潇 | A kind of synthetic method of pyridine hydrochloride |
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