CN111909079B - Recycling treatment method of picloram solid slag - Google Patents
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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
- C07D213/72—Nitrogen atoms
- C07D213/73—Unsubstituted amino or imino radicals
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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
- C07D213/61—Halogen atoms or nitro radicals
Abstract
The invention relates to a resource treatment method of picloram solid slag, which comprises the following steps: a) carrying out decarboxylation reaction on the picloram solid residues, filtering, taking filtrate, and separating out solids; b) diazotizing and chlorinating the solid obtained in the step a), separating out the solid, filtering, taking a filter cake, and separating to obtain 2,3,4, 5-tetrachloropyridine; c) dechlorinating the 2,3,4, 5-tetrachloropyridine obtained in the step b) to obtain 2,3, 5-trichloropyridine and/or 2, 5-dichloropyridine. The resource treatment method provided by the invention can convert picloram solid residues into 2,3, 5-trichloropyridine products with good market demand prospect and higher economic value, and further high-efficiency utilization of the picloram solid residues is realized.
Description
Technical Field
The invention relates to a resource treatment method of picloram solid slag.
Background
Picloram, also called picloram, has a chemical name of 4-amino-3, 5, 6-trichloropicolinic acid, is a systemic pyridine herbicide, and has the characteristics of wide application range, low toxicity, high selectivity, small dosage, small residual quantity in plants and soil, short residual period and the like, thereby having very wide market prospect.
At present, few domestic and foreign literatures and patent reports are available on how to treat picloram production waste residues. In patents CN104649965, CN107474013 and CN111285800A, picloram waste residue is subjected to resource treatment, and is converted into 3,4,5, 6-tetrachloropicolinic acid, which is convenient for further producing picloram.
Disclosure of Invention
The picloram production waste residue mainly comprises organic matters and inorganic matters, wherein the organic matters comprise compounds with structural formulas shown in formula (I), formula (II) and formula (III) or salts thereof.
The invention provides a recycling treatment method of picloram solid slag, which is used for finally converting the picloram solid slag into 2,3, 5-trichloropyridine with higher market value, and comprises the following steps:
a) carrying out decarboxylation reaction on the picloram solid residues, filtering, taking filtrate, and separating out solids;
b) diazotizing and chlorinating the solid obtained in the step a), separating out the solid, filtering, taking a filter cake, and separating to obtain 2,3,4, 5-tetrachloropyridine;
c) dechlorinating the 2,3,4, 5-tetrachloropyridine obtained in the step b) to obtain 2,3, 5-trichloropyridine and/or 2, 5-dichloropyridine.
The picloram solid residue contains inorganic substances and organic substances, wherein the organic substances contain amino-substituted pyridine acid or salts thereof.
The organic matter comprises any one or more of compounds with structural formulas of formula (I), (II) and (III) or salts thereof
The mass ratio of the organic matters in the picloram solid slag is 30-100 wt%.
The synthesis process of picloram mostly uses 3,4,5, 6-tetrachlorocyanopyridine as raw materials, and obtains picloram crude products after ammonolysis reaction and acidification treatment. The invention analyzes the main components of the picloram solid slag, wherein the main components of the picloram solid slag comprise organic matters and inorganic matters, wherein the organic matters are relatively complex and mainly comprise any one or more of compounds with structural formulas shown in formula (I), formula (II) and formula (III) or salts thereof. According to the invention, the mass percentage of the organic matters in the solid slag is more than or equal to 30 wt% through analyzing the absolute content of the organic matters.
The organic matter component in the solid picloram dregs is mainly pyridine acid or its salt containing amino substituent, and has poor solubility in solvent and difficult complete separation of organic matter component from inorganic matter.
The step a) comprises the following steps:
a1) mixing picloram solid residues, copper oxide and hydrochloric acid in the presence of a solvent to perform decarboxylation reaction to obtain a reaction solution;
a2) filtering the reaction liquid obtained in the step a1) to obtain a first filter cake and a first filtrate;
a3) crystallizing the first filtrate obtained in the step a2) in water, and filtering and washing to obtain a second filter cake and a second filtrate;
a4) drying the second filter cake obtained in the step a3) to obtain a decarboxylated mixture.
The inventor tries to treat the picloram solid slag by a high-temperature decarboxylation mode (220-230 ℃), and the effect is poor; decarboxylation was attempted using solvent catalysis, where the catalyst was copper oxide.
The decarboxylation reaction of the step a1) is carried out at 100-120 ℃;
the using amount of the copper oxide is 0.1-1 wt%, preferably 0.5 wt% of the mass of the picloram solid slag;
the solvent in the step a1) is 1, 3-dimethyl-2-imidazolidinone;
the mass ratio of the solvent to the picloram solid slag in the step a1) is 2-4: 1, and preferably 3: 1.
The main component of the solid (namely the decarboxylation product) obtained in the step a) comprises any one or more of the compounds with the structural formulas of the formula (I-1), the formula (II-1) and the formula (III-1) or salts thereof.
In the step b), reagents adopted in diazotization and chlorination reaction are concentrated hydrochloric acid and sodium nitrite aqueous solution.
In the step b), the dosage of concentrated hydrochloric acid is too small, and the reaction system is easy to be in a slurry state and is difficult to stir; the use amount is too large, so that the raw material cost is increased, and therefore, the mass ratio of the use amount of the concentrated hydrochloric acid to the solid obtained in the step a) is 7-15: 1, preferably 10: 1.
In the step b), the temperature of the reaction system is 40-70 ℃, preferably 50-60 ℃.
The organic matter component in the picloram solid slag mainly comprises a compound with a structural formula shown in a formula (I), a formula (II) and a formula (III) or a salt thereof, a corresponding decarboxylation product is generated through the step a), the decarboxylation product is subjected to diazotization and chlorination through the step b) to obtain a reaction liquid, and the reaction liquid contains a compound with a formula (IV) and other impurities. Wherein the other impurities comprise hydroxychloropyridines impurities, such as the compound of formula (V).
In the step b), the solid obtained in the step a) is subjected to diazotization and chlorination reaction in sequence, water is added to separate out the solid, the solid is filtered to obtain a filter cake, water is added to the filter cake, and 2,3,4, 5-tetrachloropyridine is obtained through distillation separation; or the like, or, alternatively,
diazotizing and chlorinating the solid obtained in the step a), cooling to separate out the solid, filtering to obtain a filter cake, mixing the filter cake with thionyl chloride to perform chlorination, distilling and separating to remove the thionyl chloride, and adding water to perform phase separation to obtain the 2,3,4, 5-tetrachloropyridine.
The mixing of the filter cake and thionyl chloride in the step b) for chlorination reaction is carried out under the participation of a small amount of N, N-dimethylformamide, wherein the amount of the N, N-dimethylformamide is 20-40 wt%, preferably 30 wt% of the mass of the filter cake; the reaction temperature of the chlorination reaction is 70-80 ℃.
And (3) after the chlorination reaction, distilling the reaction system to remove redundant thionyl chloride, adding distilled residual liquid into water for phase separation, and collecting an organic phase to obtain the compound 2,3,4, 5-tetrachloropyridine of the formula (IV).
The step c) comprises the step of reducing the 2,3,4, 5-tetrachloropyridine obtained in the step b) by using zinc powder in a mixed solvent consisting of an organic solvent and water to obtain the 2,3, 5-trichloropyridine.
The organic solvent is methanol or acetonitrile, preferably methanol.
The mass ratio of the aforementioned organic solvent to 2,3,4, 5-tetrachloropyridine is 2 to 10 to 1, preferably 4 to 6 to 1.
The mass ratio of the organic solvent to the 2,3,4, 5-tetrachloropyridine is 4 to 1.
The mass ratio of the aforementioned organic solvent to water is 0.5 to 2.5 to 1, preferably 1 to 1.5 to 1.
The mass ratio of the organic solvent to water is 1: 1.
The molar ratio of the aforementioned zinc powder to 2,3,4, 5-tetrachloropyridine is 0.5 to 4 to 1, preferably 1.2 to 1.5 to 1.
The molar ratio of the zinc powder to 2,3,4, 5-tetrachloropyridine is 1.5 to 1.
The inventors further added ammonium chloride in the reduction step and screened the amount of ammonium chloride, and found that the HPLC purity of the obtained 2,3, 5-trichloropyridine did not change significantly when the molar ratio of ammonium chloride to the starting material 2,3,4, 5-tetrachloropyridine was 0 to 5 to 1.
The reduction step also comprises screening the reaction time to screen out the reaction time with the optimal industrial application value. The reaction time is 2 hours, the result gradually becomes stable, and although the subsequent time is prolonged, the further conversion of the raw material 2,3,4, 5-tetrachloropyridine and the further generation of the target product 2,3, 5-trichloropyridine are facilitated, but the optimal selection of the industrial value is not realized from the aspect of production efficiency. Therefore, the reaction time is optimized to be 2h in comprehensive analysis.
The reduction step also comprises a post-treatment step of obtaining a first filter cake and a first filtrate through heat preservation and filtration. Wherein the heat preservation filtering refers to heat preservation heat filtering (40-80 ℃), the obtained first filter cake is zinc powder and zinc chloride, and the obtained first filtrate needs further post-treatment to obtain the target 2,3, 5-trichloropyridine.
And cooling and crystallizing the first filtrate in the heat preservation filtration, filtering and washing with hydrochloric acid to obtain a second filter cake and a second filtrate. Wherein, the temperature of the cooling crystallization step is preferably 0-5 ℃, and the obtained crystal is filtered and washed by a small amount of hydrochloric acid to obtain a second filter cake, namely the high-purity target product 2,3, 5-trichloropyridine. The second filtrate can be recycled and used as a mixed solvent in the reduction step, so that the production cost is further reduced, and the industrial application value is maximized.
The invention provides a resource treatment method of picloram solid slag, which comprises the following steps: a) carrying out decarboxylation reaction on the picloram solid residues, filtering, taking filtrate, and separating out solids; b) diazotizing and chlorinating the solid obtained in the step a), separating out the solid, filtering, taking a filter cake, and separating to obtain 2,3,4, 5-tetrachloropyridine; c) dechlorinating the 2,3,4, 5-tetrachloropyridine obtained in the step b) to obtain 2,3, 5-trichloropyridine and/or 2, 5-dichloropyridine. The invention adopts the steps of decarboxylation, diazotization, chlorination and dechlorination to treat the picloram solid slag, so as to convert the picloram solid slag into a2, 3, 5-trichloropyridine product with good market demand prospect and higher economic value, thereby realizing the further high-efficiency utilization of the picloram solid slag.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Detailed Description
The invention aims at recycling picloram waste residues, and the picloram waste residue raw material comprises two parts of organic matters and inorganic matters. Wherein the organic component comprises compounds of formula (I), formula (II) and formula (III) or salts thereof.
Example 1
30kg of 1, 3-dimethyl-2-imidazolidinone is added into a 50L reaction kettle, 10kg of picloram waste residue (wherein 554g of the compound I, 610g of the compound II and 4210g of the compound III) is added, 50g of copper oxide is added into a four-mouth bottle, and mechanical stirring and heating are started. When the temperature of the mixed system is raised to 100 ℃, stirring is kept, 5kg of concentrated hydrochloric acid with 37 wt% is dripped, the temperature is controlled at 100 ℃ and 110 ℃, and a large amount of carbon dioxide gas is generated in the dripping process. After the hydrochloric acid is added, the mixed system is kept at 105-110 ℃, and the stirring reaction is continued for 2 h. After the reaction, a sample is taken for HPLC detection (monitoring whether the conversion of the raw material is complete), and the reaction is finished.
The reaction system is filtered (50-60 ℃) in a heat preservation way, and a filter cake is leached by 500g of 1, 3-dimethyl-2-imidazolidinone, and the filter cake is white crystal-shaped and weighs 5 kg.
Collecting the filtrate, adding the filtrate into 90kg of water for crystallization, separating out a large amount of white solid, stirring for 1h, filtering, leaching the filter cake with water, and drying the filter cake at 50-60 ℃ for 8h to obtain 5.3kg of white solid, namely a decarboxylation product (containing the compounds of the structural formulas I-1, II-1 and III-1), wherein the relative content of the compound of the structural formula III-1 in the decarboxylation product is 96% through HPLC detection. The obtained filtrate is subjected to reduced pressure distillation to remove water, the obtained water is used for the crystallization process of the second batch, and the obtained solvent is directly subjected to the reaction of the second batch (meanwhile, copper oxide is not required to be added during the reaction of the second batch).
Example 2
3kg of decarboxylation product obtained in example 1 was added into a reaction kettle, 30kg of 37 wt% concentrated hydrochloric acid was added, the temperature was raised and stirred, the system temperature was kept at 50-60 ℃, and 5.28kg of aqueous solution of sodium nitrite (containing 1.58kg of sodium nitrite) was added dropwise. The dropping process is accompanied with gas generation, and the temperature of the system is controlled to be 55-65 ℃ in the dropping process. After the dropwise addition is finished, the temperature of the system is kept between 55 and 65 ℃, the stirring reaction is continued for 2 hours, and the reaction is finished.
And (3) cooling the reaction system to 20-25 ℃, filtering, leaching a filter cake with a small amount of water, drying the filter cake in a vacuum environment at 70 ℃ for 8 hours to obtain 2.9kg of a dried product, wherein the relative content of 2,3,4, 5-tetrachloropyridine in the dried product is 60% and the relative content of 2-hydroxy-3, 4, 5-trichloropyridine in the dried product is 40% through HPLC detection.
Example 3
Adding 1kg of the dried product obtained in the example 2 into a reaction kettle, adding 20kg of thionyl chloride, adding 0.3kg of N, N-dimethylformamide, starting to heat and stir, reacting at 70-80 ℃, and finishing chlorination reaction when the content of 2-hydroxy-3, 4, 5-trichloropyridine is less than 1% by HPLC (high performance liquid chromatography).
Heating and distilling to obtain thionyl chloride, adding 5kg of ice water into residual liquid in the reaction kettle for cooling, standing and phase splitting, collecting a lower organic phase to obtain 1kg of 2,3,4, 5-tetrachloropyridine product, and detecting by HPLC, wherein the purity is 99%.
Example 4
2kg of the 2,3,4, 5-tetrachloropyridine product obtained in example 3 was put into a reaction vessel, 8kg of methanol, 0.906kg of zinc powder, 1.5kg of ammonium chloride and 8kg of water were added, the temperature rise and stirring were started, the reaction system was allowed to react at 70 to 80 ℃, and dechlorination was terminated when the content of 2,3,4, 5-tetrachloropyridine was less than 1% by HPLC.
And (3) carrying out heat preservation and heat filtration on the reaction liquid, wherein the filter cake mainly comprises zinc powder and zinc chloride. Collecting filtrate, cooling to 0-5 deg.C for crystallization, filtering again to obtain filter cake of mixture of 2,3, 5-trichloropyridine and 2, 5-dichloropyridine, washing with small amount of hydrochloric acid to obtain 1.4kg of 2,3, 5-trichloropyridine, and detecting by HPLC to obtain product with purity of more than 98%.
Example 5
3kg of the decarboxylation product obtained in example 1 was added to a reaction kettle, 30kg of 37 wt% concentrated hydrochloric acid was added, the temperature was raised and stirred, the system temperature was kept at 50-60 ℃, and 5.28kg of an aqueous solution of sodium nitrite (containing 1.58kg of sodium nitrite) was added dropwise. The dropping process is accompanied with gas generation, and the temperature of the system is controlled to be 55-65 ℃ in the dropping process. After the dropwise addition is finished, the temperature of the system is kept between 55 and 65 ℃, the stirring reaction is continued for 2 hours, and the reaction is finished.
Adding 30kg of water into the reaction system to generate a large amount of white solid, filtering, leaching a filter cake with a small amount of water, and concentrating the filtrate for recycling.
Taking a filter cake, adding 15kg of water, and then distilling, wherein the distillate is a mixture of 2,3,4, 5-tetrachloropyridine and water, and the distillation residual liquid is a mixture of 2-hydroxy-3, 4, 5-trichloropyridine and water. The mixture of 2,3,4, 5-tetrachloropyridine and water is cooled to 5 ℃ to precipitate 2,3,4, 5-tetrachloropyridine solid, and the 2,3,4, 5-tetrachloropyridine is separated to obtain 1.4kg of 2,3,4, 5-tetrachloropyridine, and the purity is 99% by HPLC detection.
Example 6
2,3,4, 5-tetrachloropyridine (50g, 0.231mol) obtained in example 3 was put into a 1000ml four-necked flask, and a solvent (solvent composition: 200g of methanol and 200g of water) was added and mixed with stirring. Then, zinc powder (22.6g, 0.346mol) and ammonium chloride (37.1g, 0.693mol) are added, the temperature is increased to 72 ℃, the reaction is continuously stirred for 2 hours under the temperature, and a sample is taken for HPLC detection, and the detection result is as follows: 82.25% of 2,3, 5-trichloropyridine, 13.42% of 2, 5-dichloropyridine and 4.33% of 2,3,4, 5-tetrachloropyridine.
After the reaction is finished, carrying out heat preservation and heat filtration on the reaction liquid to obtain a filter cake and a filtrate. The filter cake is zinc powder and zinc chloride. The filtrate was worked up, the filtrate was cooled to 0-5 ℃ and crystallized for 2h to give a solid which was a mixture of 2.3.5-trichloropyridine and 2.5-dichloropyridine, which was filtered and washed with a small amount of hydrochloric acid to give a filter cake of 37.9g of 2,3, 5-trichloropyridine with an HPLC purity of 98% in a molar yield of 90% based on 2,3,4, 5-tetrachloropyridine.
Examples 7 to 10
The amount of zinc powder used was selected in the same manner as in example 6, and the results are shown in Table 1 below, which is most preferable when the amount of zinc powder is 1.5 times equivalent to 2,3,4, 5-tetrachloropyridine.
TABLE 1
Example 11
The reaction temperature was screened according to the method of example 6, and the results are shown in Table 2 below.
TABLE 2
Example 12
The solvent species were selected according to the method of example 6, and the results are shown in Table 3 below.
TABLE 3
Examples 13 to 14
The solvent composition was screened according to the method of example 6, and the results are shown in table 4 below. The layering phenomenon can occur when the dosage of organic solvents is too small; when the amount of the organic solvent is increased, that is, the mass ratio of the 2,3,4, 5-tetrachloropyridine to the methanol is 1:6, although the HPLC content of the 2,3, 5-trichloropyridine is relatively high by 1.49%, actually, in the step of cooling crystallization, the precipitation rate of the 2,3, 5-trichloropyridine product is reduced, and the yield is reduced.
TABLE 4
Examples 15 to 17
The reaction time was screened according to the method of example 6, and the results are shown in Table 5 below.
TABLE 5
Claims (8)
1. A resource treatment method of picloram solid slag is characterized by comprising the following steps:
a) carrying out decarboxylation reaction on the picloram solid residues, filtering, taking filtrate, and separating out solids; the picloram solid slag contains organic matters which comprise compounds with structural formulas of a formula (I), a formula (II) and a formula (III) or salts thereof
b) Diazotizing and chlorinating the solid obtained in the step a), separating out the solid, filtering, taking a filter cake, and separating to obtain 2,3,4, 5-tetrachloropyridine;
c) dechlorinating the 2,3,4, 5-tetrachloropyridine obtained in the step b) to obtain 2,3, 5-trichloropyridine;
wherein the step a) comprises the following steps:
a1) mixing picloram solid residues, copper oxide and hydrochloric acid in the presence of a solvent to perform decarboxylation reaction to obtain a reaction solution;
a2) filtering the reaction liquid obtained in the step a1) to obtain a first filter cake and a first filtrate;
a3) separating out solids from the first filtrate obtained in the step a2) in water, and filtering and washing to obtain a second filter cake and a second filtrate;
a4) drying the second filter cake obtained in the step a3) to obtain a decarboxylation product.
2. The method as claimed in claim 1, wherein the organic matter accounts for 30-100 wt% of the picloram solid slag.
3. The method as claimed in claim 1, wherein the decarboxylation in step a1) is carried out at 100-120 ℃;
the using amount of the copper oxide is 0.1-1 wt% of the mass of the picloram solid slag;
the solvent is 1, 3-dimethyl-2-imidazolidinone;
the mass ratio of the solvent to the picloram solid residues is 2-4: 1.
4. The method as claimed in claim 1, wherein the decarboxylation in step a1) is carried out at 100-120 ℃;
the using amount of the copper oxide is 0.5 wt% of the mass of the picloram solid slag;
the solvent is 1, 3-dimethyl-2-imidazolidinone;
the mass ratio of the solvent to the picloram solid slag is 3: 1.
5. The method as claimed in claim 1, wherein in step b), reagents used in diazotization and chlorination are concentrated hydrochloric acid and sodium nitrite aqueous solution.
6. The method for recycling picloram solid slag according to claim 1 or 5, wherein in the step b), the solid obtained in the step a) is sequentially subjected to diazotization and chlorination, water is added to separate out the solid, a filter cake is obtained by filtration, water is added to the filter cake, and 2,3,4, 5-tetrachloropyridine is obtained by distillation separation; or the like, or, alternatively,
diazotizing and chlorinating the solid obtained in the step a), cooling to separate out the solid, filtering to obtain a filter cake, mixing the filter cake with thionyl chloride to perform chlorination, distilling and separating to remove the thionyl chloride, and adding water to perform phase separation to obtain the 2,3,4, 5-tetrachloropyridine.
7. The method as claimed in claim 1, wherein the step c) comprises a step of reducing the 2,3,4, 5-tetrachloropyridine obtained in the step b) with zinc powder in a mixed solvent of an organic solvent and water to obtain 2,3, 5-trichloropyridine.
8. The method as claimed in claim 7, wherein the organic solvent is methanol, and the molar ratio of the zinc powder to 2,3,4, 5-tetrachloropyridine is 1.5: 1.
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| CN111285800A (en) * | 2020-02-07 | 2020-06-16 | 山东潍坊润丰化工股份有限公司 | Method for treating picloram waste residue |
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