CN116120168A - Preparation process for catalytic synthesis of 2, 4-D - Google Patents
Preparation process for catalytic synthesis of 2, 4-D Download PDFInfo
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- CN116120168A CN116120168A CN202211143963.8A CN202211143963A CN116120168A CN 116120168 A CN116120168 A CN 116120168A CN 202211143963 A CN202211143963 A CN 202211143963A CN 116120168 A CN116120168 A CN 116120168A
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- 238000007036 catalytic synthesis reaction Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 105
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229940106681 chloroacetic acid Drugs 0.000 claims abstract description 21
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims abstract description 20
- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 claims abstract description 18
- HXKWSTRRCHTUEC-UHFFFAOYSA-N 2,4-Dichlorophenoxyaceticacid Chemical compound OC(=O)C(Cl)OC1=CC=C(Cl)C=C1 HXKWSTRRCHTUEC-UHFFFAOYSA-N 0.000 claims abstract description 18
- YNOHSUXKBYVVOX-UHFFFAOYSA-N 2,4-dichlorophenol;sodium Chemical compound [Na].OC1=CC=C(Cl)C=C1Cl YNOHSUXKBYVVOX-UHFFFAOYSA-N 0.000 claims abstract description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 14
- RFOHRSIAXQACDB-UHFFFAOYSA-M sodium;2-(2,4-dichlorophenoxy)acetate Chemical compound [Na+].[O-]C(=O)COC1=CC=C(Cl)C=C1Cl RFOHRSIAXQACDB-UHFFFAOYSA-M 0.000 claims abstract description 14
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 11
- 239000011734 sodium Substances 0.000 claims abstract description 10
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 7
- BYOIUZNBVLCMNV-UHFFFAOYSA-M sodium;2,4-dichlorophenolate Chemical compound [Na+].[O-]C1=CC=C(Cl)C=C1Cl BYOIUZNBVLCMNV-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 239000012043 crude product Substances 0.000 claims abstract description 4
- 230000020477 pH reduction Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 42
- 159000000000 sodium salts Chemical class 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- 238000000034 method Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000007614 solvation Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 16
- 238000005406 washing Methods 0.000 description 13
- 230000001276 controlling effect Effects 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 235000013399 edible fruits Nutrition 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000004009 herbicide Substances 0.000 description 3
- 239000005648 plant growth regulator Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- QIIPQYDSKRYMFG-UHFFFAOYSA-N phenyl hydrogen carbonate Chemical compound OC(=O)OC1=CC=CC=C1 QIIPQYDSKRYMFG-UHFFFAOYSA-N 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000010891 toxic waste Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
- C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation process for catalytic synthesis of 2, 4-D, which comprises the steps of taking water as a solvent, chloroacetic acid, sodium hydroxide or sodium carbonate and 2, 4-dichlorophenol as initial raw materials, obtaining sodium chloroacetate solution through neutralization reaction, and reacting 2, 4-dichlorophenol with sodium hydroxide to generate 2, 4-dichlorophenol sodium solution; adding proper amount of catalyst Na 2 O/SiO 2 Under alkaline condition, condensing 2, 4-dichlorophenolate sodium solution with sodium chloroacetate solution to obtain 2, 4-dichlorophenoxyacetic acid sodium salt crude product; and then dissolving the crude product of the 2, 4-dichlorophenoxyacetic acid sodium salt with water, adding hydrochloric acid for acidification to obtain a 2, 4-dichlorophenoxyacetic acid product. The invention adopts the catalyst to solve the solvation effect; the conversion rate and the yield of the product are improved after the catalyst is used for catalysis, the side reaction is reduced, the conversion rate and the yield of the product can be improved, the product purity is high, the condition is mild, the raw materials of the process can be recycled, and the catalyst can be recycledIs suitable for large-scale industrial production.
Description
Technical Field
The invention discloses a preparation process for catalyzing and synthesizing 2, 4-drops, belongs to the technical field of chemical production, and particularly relates to a method for catalyzing and synthesizing 2, 4-drops.
Background
2, 4-drop, chemical name: 2, 4-dichlorophenoxyacetic acid belongs to phenoxy carboxylic acid herbicides and is the most widely used chemical pesticide in the world at present. The 2, 4-D, its salt and ester are high-efficiency, systemic and high-selectivity herbicide and plant growth regulator, and have strong physiological activity to plant. Is mainly used for vegetables, grains, fruit trees and other economic crops. When the concentration is low, the plant growth regulator mainly promotes growth, has the effects of preventing flower and fruit from falling, improving fruit setting rate, promoting fruit growth and increasing yield, and can be used as a plant growth regulator. At high concentration, the composition shows the characteristics of growth inhibition and herbicide, and is more obvious for preventing and killing of some broadleaf plants.
The problem of expensive three-waste treatment caused by the generation of a large amount of toxic waste when dichlorophenol reacts with chloroacetic acid also becomes a focus of attention of various technical innovations and new process research and development personnel. Therefore, there is an urgent need to find a catalyst, optimize the process of synthesizing 2, 4-D, and reduce the three-waste treatment while improving the yield.
The traditional homogeneous base catalyst has the defects of difficult separation and recovery, incapability of recycling, large amount of wastewater generated after washing and easy corrosion to equipment. Aiming at the problems, the solid base catalyst has high catalytic efficiency, is easy to separate and can be reused, and a plurality of substances with catalytic activity can be loaded on the catalyst because the catalyst is provided with a carrier.
F. King et al report in the literature that Pd is supported on Na/SiO 2 The solid base catalyst has higher activity and selectivity in catalyzing aldol condensation, dehydration and hydrogenation of n-butanol, and the catalyst has higher conversion rate (82%).
Therefore, the catalyst which has high catalytic efficiency, is easy to separate, reduces the three-waste problem and improves the purity and the yield of the product has important industrial significance.
Disclosure of Invention
The invention aims to provide a preparation process for synthesizing 2, 4-D by catalysis. In order to solve the above-mentioned problems,
the invention provides the following technical scheme: a preparation process for synthesizing 2, 4-D by catalysis comprises the following steps:
(1) Water is used as a solvent, chloroacetic acid, sodium hydroxide or sodium carbonate is used as an initial raw material, and a sodium chloroacetate solution is obtained through a neutralization reaction;
(2) 2, 4-dichlorophenol and sodium hydroxide are taken as raw materials, and the raw materials and the sodium hydroxide are mixed to react to generate a 2, 4-dichlorophenol sodium solution;
(3) Adding the catalyst into a reaction system to select Na 2 O/SiO 2 The adding amount is 1-10% of 2, 4-dichlorophenolate sodium solution, and under the condition that the pH value is 9.5-10, sodium chloroacetate solution is dropwise added into the 2, 4-dichlorophenolate sodium solution for condensation reaction to obtain a crude product of 2, 4-dichlorophenoxyacetic acid sodium salt (2, 4-sodium dropwise);
(4) Further dissolving 2, 4-dichlorophenoxyacetic acid sodium salt with water, adding hydrochloric acid for acidification to obtain 2, 4-dichlorophenoxyacetic acid product.
In the step (1), chloroacetic acid: water: the molar ratio of sodium hydroxide is 1:2.0-3.0:1.0-1.50, and neutralizing for 0.5-2 hours at the temperature of 20-35 ℃.
In the step (1), chloroacetic acid: water: the molar ratio of sodium carbonate is 1:2.0-3.0:0.50-1.0, and neutralizing for 0.5-2 hours at the temperature of 20-35 ℃.
2, 4-dichlorophenol in the step (2): the molar ratio of sodium hydroxide is 1: (0.7-1.15), and the reaction temperature is 90-100 ℃ for 1-2 hours.
The 2, 4-dichlorophenolate sodium in the step (3): the mass ratio of the sodium chloroacetate is 1 (2.50-2.70), and the catalyst is added into the reaction system to select Na 2 O/SiO 2 The addition amount is 1-10% of 2, 4-dichlorophenol sodium solution, the reaction temperature is 100-105 ℃ for condensation for 2-3 hours under the condition that the pH value is 9.5-10, and the temperature is kept at 100-110 ℃ for 2-4 hours after the reaction is finished.
The sodium salt of 2, 4-dichlorophenoxyacetic acid in the step (4): the mass ratio of water is 1: (1.5-3.5), dropwise adding hydrochloric acid into the 2, 4-dichlorophenoxyacetic acid sodium salt solution, acidifying to a pH value of 0.5-1.5, wherein the acidifying reaction temperature is 90-115 ℃ for 0.5-2 hours, and after the reaction is finished, the pH value is 0.5-1.5.
In the technical scheme, the chemical reaction process is as follows:
the main reaction:
side reaction:
in the invention, the reaction conversion rate is 78.9-98.9% based on 2, 4-dichlorophenol, and compared with the prior art, the invention has the outstanding advantages that:
1. the method adopts the chlorination process and condensation, uses water as a solvent, has low cost, is nontoxic and odorless, but has low yield due to hydrolysis of chloroacetic acid in the reaction. Therefore, the solid base catalyst adopted by the invention has the advantages of high stability, high reaction activity, no environmental pollution, no equipment corrosion and the like, and has important enlightening significance for recycling the catalyst and developing green chemical industry.
2. The reaction adopts water as a solvent, and has the advantages of homogeneous phase reaction, short reaction time and convenient control. The use of organic solvents is reduced, the cost is reduced, and the organic solvents have low boiling points, high volatility and toxic and odorous properties.
Detailed Description
For further explanation of the present invention, the following examples are provided to further illustrate the gist of the present invention, but are not intended to limit the present invention:
example 1
1mol of chloroacetic acid, (2.50-2.65) mol of water are mixed and stirred until chloroacetic acid is completely dissolved. Slowly adding (1.10-1.20) mol of 32% sodium hydroxide aqueous solution into the reactor, controlling the temperature at 20-35 ℃, reacting for 0.5-2h, and controlling the pH value at the neutralization end point to be 6-6.5, thus obtaining sodium chloroacetate solution.
1mol of 2, 4-dichlorophenol and (0.7-1.15 mol) 32% sodium hydroxide aqueous solution are mixed and stirred, the temperature is raised to 80-95 ℃, the pH is regulated to 9.5-10 by dropwise adding sodium hydroxide aqueous solution, and the temperature is maintained at 90-100 ℃ for 1-2 hours, so as to obtain the 2, 4-dichlorophenol sodium solution.
Slowly dripping the prepared sodium chloroacetate solution into the 2, 4-dichlorophenol sodium solution, simultaneously adding 32% sodium hydroxide solution (2.50-2.70) in a mass ratio, refluxing, condensing and stirring for 2-3h at 100-105 ℃, and preserving heat for 2-4h at 100-110 ℃ after the reaction is finished. After filtration, washing with water for 2 times and drying, 207.05g of 2, 4-dichlorophenoxyacetic acid sodium salt solid was obtained in a yield of 85.2%.
According to the sodium salt of 2, 4-dichlorophenoxyacetic acid: the mass ratio of water is 1:1.5 adding water, stirring until the mixture is dissolved, adding 30% hydrochloric acid (1.0-1.05 mol), preserving heat at 90-115 ℃ for 0.5-2h, maintaining pH=about 0.5-1.5 after the reaction is finished, filtering, washing with water for 3 times, and drying to obtain 2, 4-dichlorophenoxyacetic acid solid.
Example 2
1mol of chloroacetic acid, (2.50-2.65) mol of water are mixed and stirred until chloroacetic acid is completely dissolved. Slowly adding (0.50-0.65) mol sodium carbonate solid into the reactor, controlling the temperature at 20-35 ℃, reacting for 0.5-2h, and controlling the pH value at the neutralization end point to be 6-6.5, thus obtaining sodium chloroacetate solution.
1mol of 2, 4-dichlorophenol and (0.7-1.15 mol) 32% sodium hydroxide aqueous solution are mixed and stirred, the temperature is raised to 80-95 ℃, the pH is regulated to 9.5-10 by dropwise adding sodium hydroxide aqueous solution, and the temperature is maintained at 90-100 ℃ for 1-2 hours, so as to obtain the 2, 4-dichlorophenol sodium solution.
Slowly dripping the prepared sodium chloroacetate solution into the 2, 4-dichlorophenol sodium solution, simultaneously adding 32% sodium hydroxide solution (2.50-2.70) in a mass ratio, refluxing, condensing and stirring for 2-3h at 100-105 ℃, and preserving heat for 2-4h at 100-110 ℃ after the reaction is finished. After filtration, washing with water for 2 times and drying, 191.74g of 2, 4-dichlorophenoxyacetic acid sodium salt solid was obtained, and the yield was 78.9%.
According to the sodium salt of 2, 4-dichlorophenoxyacetic acid: the mass ratio of water is 1:2.0 adding water, stirring until dissolving, adding 30% hydrochloric acid (1.0-1.05 mol), maintaining at 90-115 deg.C for 0.5-2 hr, maintaining pH=0.5-1.5 after reaction, filtering, washing with water for 3 times, and drying to obtain 2, 4-dichlorophenoxyacetic acid solid.
Example 3
1mol of chloroacetic acid, (2.50-2.65) mol of water are mixed and stirred until chloroacetic acid is completely dissolved. Slowly adding (1.10-1.20) mol of 32% sodium hydroxide aqueous solution into the reactor, controlling the temperature at 20-35 ℃, reacting for 0.5-2h, and controlling the pH value at the neutralization end point to be 6-6.5, thus obtaining sodium chloroacetate solution.
1mol of 2, 4-dichlorophenol and (0.7-1.15 mol) 32% sodium hydroxide aqueous solution are mixed and stirred, the temperature is raised to 80-95 ℃, the pH is regulated to 9.5-10 by dropwise adding sodium hydroxide aqueous solution, and the temperature is maintained at 90-100 ℃ for 1-2 hours, so as to obtain the 2, 4-dichlorophenol sodium solution.
Adding a catalyst Na into a reaction system 2 O/SiO 2 Slowly dropwise adding the prepared sodium chloroacetate solution into the 2, 4-dichlorophenol sodium solution with the addition amount of 1% of the reactants, simultaneously adding 32% sodium hydroxide solution with the mass ratio of (2.50-2.70), refluxing, condensing and stirring at 100-105 ℃ for 2-3h, and preserving heat at 100-110 ℃ for 2-4h after the reaction is finished. After filtration, washing with water for 2 times and drying, 219.93g of 2, 4-dichlorophenoxyacetic acid sodium salt solid was obtained in a yield of 90.5%.
According to the sodium salt of 2, 4-dichlorophenoxyacetic acid: the mass ratio of water is 1:1.5 adding water, stirring until the mixture is dissolved, adding 30% hydrochloric acid (1.0-1.05 mol), preserving heat at 90-115 ℃ for 0.5-2h, maintaining pH=about 0.5-1.5 after the reaction is finished, filtering, washing with water for 3 times, and drying to obtain 2, 4-dichlorophenoxyacetic acid solid.
Example 4
1mol of chloroacetic acid, (2.50-2.65) mol of water are mixed and stirred until chloroacetic acid is completely dissolved. Slowly adding (1.10-1.20) mol of 32% sodium hydroxide aqueous solution into the reactor, controlling the temperature at 20-35 ℃, reacting for 0.5-2h, and controlling the pH value at the neutralization end point to be 6-6.5, thus obtaining sodium chloroacetate solution.
1mol of 2, 4-dichlorophenol and (0.7-1.15 mol) 32% sodium hydroxide aqueous solution are mixed and stirred, the temperature is raised to 80-95 ℃, the pH is regulated to 9.5-10 by dropwise adding sodium hydroxide aqueous solution, and the temperature is maintained at 90-100 ℃ for 1-2 hours, so as to obtain the 2, 4-dichlorophenol sodium solution.
Adding a catalyst Na into a reaction system 2 O/SiO 2 Slowly dropwise adding the prepared sodium chloroacetate solution into the 2, 4-dichlorophenol sodium solution with the addition amount of 5% of reactants, simultaneously adding 32% sodium hydroxide solution with the mass ratio of (2.50-2.70), refluxing, condensing and stirring at 100-105 ℃ for 2-3h, and preserving heat at 100-110 ℃ for 2-4h after the reaction is finished. After filtration, washing with water for 2 times and drying, 240.34g of 2, 4-dichlorophenoxyacetic acid sodium salt solid was obtained, and the yield was 98.9%.
According to the sodium salt of 2, 4-dichlorophenoxyacetic acid: the mass ratio of water is 1:1.5 adding water, stirring until the mixture is dissolved, adding 30% hydrochloric acid (1.0-1.05 mol), preserving heat at 90-115 ℃ for 0.5-2h, maintaining pH=about 0.5-1.5 after the reaction is finished, filtering, washing with water for 3 times, and drying to obtain 2, 4-dichlorophenoxyacetic acid solid.
Example 5
1mol of chloroacetic acid, (2.50-2.65) mol of water are mixed and stirred until chloroacetic acid is completely dissolved. Slowly adding (0.50-0.65) mol sodium carbonate solid into the reactor, controlling the temperature at 20-35 ℃, reacting for 0.5-2h, and controlling the pH value at the neutralization end point to be 6-6.5, thus obtaining sodium chloroacetate solution.
1mol of 2, 4-dichlorophenol and (0.7-1.15 mol) 32% sodium hydroxide aqueous solution are mixed and stirred, the temperature is raised to 80-95 ℃, the pH is regulated to 9.5-10 by dropwise adding sodium hydroxide aqueous solution, and the temperature is maintained at 90-100 ℃ for 1-2 hours, so as to obtain the 2, 4-dichlorophenol sodium solution.
Adding a catalyst Na into a reaction system 2 O/SiO 2 Slowly dropwise adding the prepared sodium chloroacetate solution into the 2, 4-dichlorophenol sodium solution with the addition amount of 5% of reactants, simultaneously adding 32% sodium hydroxide solution with the mass ratio of (2.50-2.70), refluxing, condensing and stirring at 100-105 ℃ for 2-3h, and preserving heat at 100-110 ℃ for 2-4h after the reaction is finished. After filtration, washing with water for 2 times and drying, 229.65g of 2, 4-dichlorophenoxyacetic acid sodium salt solid was obtained in a yield of 94.5%.
According to the sodium salt of 2, 4-dichlorophenoxyacetic acid: the mass ratio of water is 1:1.5 adding water, stirring until the mixture is dissolved, adding 30% hydrochloric acid (1.0-1.05 mol), preserving heat at 90-115 ℃ for 0.5-2h, maintaining pH=about 0.5-1.5 after the reaction is finished, filtering, washing with water for 3 times, and drying to obtain 2, 4-dichlorophenoxyacetic acid solid.
Example 6
1mol of chloroacetic acid, (2.50-2.65) mol of water are mixed and stirred until chloroacetic acid is completely dissolved. Slowly adding (1.10-1.20) mol of 32% sodium hydroxide aqueous solution into the reactor, controlling the temperature at 20-35 ℃, reacting for 0.5-2h, and controlling the pH value at the neutralization end point to be 6-6.5, thus obtaining sodium chloroacetate solution.
1mol of 2, 4-dichlorophenol and (0.7-1.15 mol) 32% sodium hydroxide aqueous solution are mixed and stirred, the temperature is raised to 80-95 ℃, the pH is regulated to 9.5-10 by dropwise adding sodium hydroxide aqueous solution, and the temperature is maintained at 90-100 ℃ for 1-2 hours, so as to obtain the 2, 4-dichlorophenol sodium solution.
Adding a catalyst Na into a reaction system 2 O/SiO 2 Slowly dropwise adding the prepared sodium chloroacetate solution into the 2, 4-dichlorophenol sodium solution with the addition amount of 10% of the reactants, simultaneously adding 32% sodium hydroxide solution with the mass ratio of (2.50-2.70), refluxing, condensing and stirring at 100-105 ℃ for 2-3h, and preserving heat at 100-110 ℃ for 2-4h after the reaction is finished. After filtration, washing with water for 2 times and drying, 236.21g of 2, 4-dichlorophenoxyacetic acid sodium salt solid was obtained in a yield of 97.2%.
According to the sodium salt of 2, 4-dichlorophenoxyacetic acid: the mass ratio of water is 1:1.5 adding water, stirring until the mixture is dissolved, adding 30% hydrochloric acid (1.0-1.05 mol), preserving heat at 90-115 ℃ for 0.5-2h, maintaining pH=about 0.5-1.5 after the reaction is finished, filtering, washing with water for 3 times, and drying to obtain 2, 4-dichlorophenoxyacetic acid solid.
The above description is merely illustrative of the preferred embodiments of the present invention, but not limiting the scope of the present invention, and various modifications or variations can be made by those skilled in the art without the need for inventive effort on the basis of the technical solutions of the present invention.
Claims (8)
1. The preparation process for synthesizing 2, 4-D by catalysis is characterized by comprising the following steps:
(1) Water is used as a solvent, chloroacetic acid and sodium hydroxide are used as initial raw materials, and a sodium chloroacetate solution is obtained through a neutralization reaction;
(2) 2, 4-dichlorophenol and sodium hydroxide are taken as raw materials, and the raw materials and the sodium hydroxide are mixed to react to generate a 2, 4-dichlorophenol sodium solution;
(3) Adding a catalyst in a reaction system, wherein the catalyst is Na 2 O/SiO 2 Under the condition that the pH value is 9-10, the carrier catalyst is added with sodium chloroacetate solution dropwise into 2, 4-dichlorophenol sodium solution for condensation reaction to obtain a crude product of 2, 4-dichlorophenoxyacetic acid sodium salt;
(4) Further dissolving 2, 4-dichlorophenoxyacetic acid sodium salt with water, adding hydrochloric acid for acidification to obtain a 2, 4-dichlorophenoxyacetic acid product, which is abbreviated as: 2, 4-drop.
2. The process for preparing 2, 4-D by catalytic synthesis according to claim 1, wherein: in the step (1), chloroacetic acid: water: the molar ratio of sodium hydroxide is 1:2.0-3.0:1.0-1.50, and neutralizing reaction for 0.5-2 hours at the temperature of 20-35 ℃.
3. The process for preparing 2, 4-D by catalytic synthesis according to claim 1, wherein: and (2) replacing sodium hydroxide in the step (1) with sodium carbonate, and then chloroacetic acid: water: the molar ratio of sodium carbonate is 1:2.0-3.0:0.50-1.0.
4. The process for preparing 2, 4-D by catalytic synthesis according to claim 1, wherein: 2, 4-dichlorophenol in the step (2): the molar ratio of sodium hydroxide is 1:0.7-1.15, and the reaction temperature is 90-100 ℃ for 1-2 hours.
5. The process for preparing 2, 4-D by catalytic synthesis according to claim 1, wherein: the 2, 4-dichlorophenolate sodium in the step (3): the mass ratio of the sodium chloroacetate is 1:2.50-2.70.
6. The process for preparing 2, 4-D by catalytic synthesis according to claim 1, wherein: na in the step (3) 2 O/SiO 2 The addition amount of the carrier catalyst is 1-10% of the 2, 4-dichlorophenol sodium solution.
7. The process for preparing 2, 4-D by catalytic synthesis according to claim 1, wherein: na is added in the step (3) 2 O/SiO 2 Condensing for 2-3 hours at 100-105 ℃ after the catalyst is supported, and preserving heat for 2-4h at 100-110 ℃ after the reaction is finished.
8. The process for preparing 2, 4-D by catalytic synthesis according to claim 1, wherein: the sodium salt of 2, 4-dichlorophenoxyacetic acid in the step (4): the mass ratio of water is 1: (1.0-4.0), dropwise adding hydrochloric acid into the 2, 4-dichlorophenoxyacetic acid sodium salt solution, acidifying to a pH value of 0.5-1.5, wherein the acidifying reaction temperature is 90-115 ℃ for 0.5-2 hours, and the pH value is 0.5-1.5 after the reaction is finished.
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