CN116120168B - Preparation process for catalytic synthesis of 2, 4-D - Google Patents
Preparation process for catalytic synthesis of 2, 4-D Download PDFInfo
- Publication number
- CN116120168B CN116120168B CN202211143963.8A CN202211143963A CN116120168B CN 116120168 B CN116120168 B CN 116120168B CN 202211143963 A CN202211143963 A CN 202211143963A CN 116120168 B CN116120168 B CN 116120168B
- Authority
- CN
- China
- Prior art keywords
- sodium
- solution
- dichlorophenol
- reaction
- 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
- 238000007036 catalytic synthesis reaction Methods 0.000 title claims abstract description 9
- 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 24
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 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 17
- 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 17
- YNOHSUXKBYVVOX-UHFFFAOYSA-N 2,4-dichlorophenol;sodium Chemical compound [Na].OC1=CC=C(Cl)C=C1Cl YNOHSUXKBYVVOX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011734 sodium Substances 0.000 claims abstract description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- 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 13
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 10
- 229910052905 tridymite Inorganic materials 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
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000012043 crude product Substances 0.000 claims abstract description 4
- 238000006482 condensation reaction Methods 0.000 claims abstract description 3
- 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
- BYOIUZNBVLCMNV-UHFFFAOYSA-M sodium;2,4-dichlorophenolate Chemical compound [Na+].[O-]C1=CC=C(Cl)C=C1Cl BYOIUZNBVLCMNV-UHFFFAOYSA-M 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 238000000034 method Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004064 recycling Methods 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
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 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
- 238000004321 preservation Methods 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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- 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 a proper amount of catalyst Na 2O/SiO2, and carrying out condensation reaction on the 2, 4-dichlorophenol sodium solution and the sodium chloroacetate solution under alkaline conditions to obtain a crude product of 2, 4-dichlorophenoxyacetic acid sodium salt; 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 catalyst has the advantages of improved product conversion rate and yield, reduced side reaction, improved product conversion rate and yield, high product purity, mild conditions, recycling of process raw materials, and recycling of the catalyst, and is 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.
King et al reported in literature that Pd supported on Na/SiO 2 solid base catalyst catalyzes aldol condensation, dehydration and further hydrogenation of n-butanol with higher activity and selectivity, and the catalyst has higher conversion (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 a2, 4-dichlorophenol sodium solution;
(3) Adding the catalyst Na 2O/SiO2 into the reaction system, wherein the addition amount is 1-10% of that of the 2, 4-dichlorophenolate sodium solution, and dropwise adding sodium chloroacetate solution into the 2, 4-dichlorophenolate sodium solution for condensation reaction under the condition that the pH value is 9.5-10 to obtain a2, 4-dichlorophenoxyacetic acid sodium salt crude product (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), the catalyst Na 2O/SiO2 is added into the reaction system, the addition amount is 1-10% of 2, 4-dichlorophenol sodium solution, the condensation is carried out for 2-3 hours at the reaction temperature of 100-105 ℃ under the condition that the pH value is 9.5-10, and the heat preservation is carried out for 2-4 hours at the temperature of 100-110 ℃ 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 a 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, the yield was 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, 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 2O/SiO2 into the reaction system, wherein the addition amount is 1% of the reactant, slowly dripping the prepared sodium chloroacetate solution into the 2, 4-dichlorophenol sodium solution, 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, the yield was 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 2O/SiO2 into the reaction system, wherein the addition amount is 5% of the reactant, slowly dripping the prepared sodium chloroacetate solution into the 2, 4-dichlorophenol sodium solution, 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, 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 2O/SiO2 into the reaction system, wherein the addition amount is 5% of the reactant, slowly dripping the prepared sodium chloroacetate solution into the 2, 4-dichlorophenol sodium solution, 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 with 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 2O/SiO2 into the reaction system, wherein the addition amount is 10% of the reactant, slowly dripping the prepared sodium chloroacetate solution into the 2, 4-dichlorophenol sodium solution, 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 with 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 (7)
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 a2, 4-dichlorophenol sodium solution;
(3) Adding a catalyst which is Na 2O/SiO2 carrier catalyst into a reaction system, and dropwise adding a sodium chloroacetate solution into a 2, 4-dichlorophenolate sodium solution under the condition that the pH value is 9-10 for condensation reaction to obtain a 2, 4-dichlorophenoxyacetic acid sodium salt crude product; the addition amount of the Na 2O/SiO2 carrier catalyst is 1-10% of the 2, 4-dichlorophenol sodium solution;
(4) Further dissolving 2, 4-dichlorophenoxyacetic acid sodium salt with water, adding hydrochloric acid for acidification to obtain a2, 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: after Na 2O/SiO2 carrier catalyst is added in the step (3), condensing for 2-3 hours at 100-105 ℃, and preserving heat for 2-4 h at 100-110 ℃ after the reaction is finished.
7. 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.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211143963.8A CN116120168B (en) | 2022-09-20 | 2022-09-20 | Preparation process for catalytic synthesis of 2, 4-D |
| PCT/CN2023/102424 WO2024060737A1 (en) | 2022-09-20 | 2023-06-26 | Preparation process for catalytic synthesis of 2,4-dichlorophenoxyacetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211143963.8A CN116120168B (en) | 2022-09-20 | 2022-09-20 | Preparation process for catalytic synthesis of 2, 4-D |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116120168A CN116120168A (en) | 2023-05-16 |
| CN116120168B true CN116120168B (en) | 2024-05-14 |
Family
ID=86308680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211143963.8A Active CN116120168B (en) | 2022-09-20 | 2022-09-20 | Preparation process for catalytic synthesis of 2, 4-D |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN116120168B (en) |
| WO (1) | WO2024060737A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116120168B (en) * | 2022-09-20 | 2024-05-14 | 湖北泰盛化工有限公司 | Preparation process for catalytic synthesis of 2, 4-D |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004008931A1 (en) * | 2003-02-25 | 2004-09-16 | Schott Glas | Porous glass or glass ceramic powders, used in cosmetic, biocide or health care applications, e.g. for release of cosmetic, medicinal, veterinary or pesticidal active agents, as odor absorbers or as biocides |
| CN1761651A (en) * | 2003-01-20 | 2006-04-19 | 拜尔农作物科学股份公司 | 2, 4-dihalo-6- (C)2－C3-alkyl) phenyl substituted tetramic acid derivatives |
| CN103058855A (en) * | 2011-10-20 | 2013-04-24 | 上海泰禾化工有限公司 | Method for synthesizing phenoxyacetic acid derivative |
| CN105921161A (en) * | 2016-04-27 | 2016-09-07 | 常州大学 | Catalyst used in p-dichlorobenzene hydroxylate for preparing 2,5-dichlorophenol, and preparation method thereof |
| CN108947837A (en) * | 2018-03-19 | 2018-12-07 | 山东润博生物科技有限公司 | A kind of preparation method of 2,4 dichlorophenoxyacetic acid ester |
| CN108947838A (en) * | 2018-03-19 | 2018-12-07 | 山东润博生物科技有限公司 | A kind of preparation method of 2,4 dichlorophenoxyacetic acid and its salt |
| CN113600231A (en) * | 2021-08-06 | 2021-11-05 | 西北大学 | Preparation method of catalyst for preparing 1, 3-butadiene by ethanol two-step method |
| CN115557636A (en) * | 2022-10-09 | 2023-01-03 | 湖北泰盛化工有限公司 | Treatment method of phenol-containing wastewater of 2, 4-drop condensation mother liquor |
| CN115724720A (en) * | 2022-11-23 | 2023-03-03 | 湖北泰盛化工有限公司 | 2, 4-dichlorophenol micro-channel continuous synthesis process |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101391753B (en) * | 2008-11-05 | 2012-01-25 | 中国科学院上海硅酸盐研究所 | Method for preparing mesoporous metallic oxide material |
| CN108503526A (en) * | 2017-02-28 | 2018-09-07 | 山东润博生物科技有限公司 | The preparation method of one kind 2,4- dichlorphenoxyacetic acids |
| CN108503527A (en) * | 2017-02-28 | 2018-09-07 | 山东润博生物科技有限公司 | The preparation method and its production system of one kind 2,4- dichlorphenoxyacetic acids |
| CN108503536A (en) * | 2017-02-28 | 2018-09-07 | 山东润博生物科技有限公司 | The preparation method of 2,4- dichlorphenoxyacetic acids |
| CN113336616B (en) * | 2020-02-18 | 2023-05-05 | 中国石油化工股份有限公司 | Polymerization inhibitor, preparation method thereof and method for increasing propylene yield by thermal cracking petroleum hydrocarbon |
| CN116120168B (en) * | 2022-09-20 | 2024-05-14 | 湖北泰盛化工有限公司 | Preparation process for catalytic synthesis of 2, 4-D |
-
2022
- 2022-09-20 CN CN202211143963.8A patent/CN116120168B/en active Active
-
2023
- 2023-06-26 WO PCT/CN2023/102424 patent/WO2024060737A1/en unknown
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1761651A (en) * | 2003-01-20 | 2006-04-19 | 拜尔农作物科学股份公司 | 2, 4-dihalo-6- (C)2－C3-alkyl) phenyl substituted tetramic acid derivatives |
| DE102004008931A1 (en) * | 2003-02-25 | 2004-09-16 | Schott Glas | Porous glass or glass ceramic powders, used in cosmetic, biocide or health care applications, e.g. for release of cosmetic, medicinal, veterinary or pesticidal active agents, as odor absorbers or as biocides |
| CN103058855A (en) * | 2011-10-20 | 2013-04-24 | 上海泰禾化工有限公司 | Method for synthesizing phenoxyacetic acid derivative |
| CN105921161A (en) * | 2016-04-27 | 2016-09-07 | 常州大学 | Catalyst used in p-dichlorobenzene hydroxylate for preparing 2,5-dichlorophenol, and preparation method thereof |
| CN108947837A (en) * | 2018-03-19 | 2018-12-07 | 山东润博生物科技有限公司 | A kind of preparation method of 2,4 dichlorophenoxyacetic acid ester |
| CN108947838A (en) * | 2018-03-19 | 2018-12-07 | 山东润博生物科技有限公司 | A kind of preparation method of 2,4 dichlorophenoxyacetic acid and its salt |
| CN113600231A (en) * | 2021-08-06 | 2021-11-05 | 西北大学 | Preparation method of catalyst for preparing 1, 3-butadiene by ethanol two-step method |
| CN115557636A (en) * | 2022-10-09 | 2023-01-03 | 湖北泰盛化工有限公司 | Treatment method of phenol-containing wastewater of 2, 4-drop condensation mother liquor |
| CN115724720A (en) * | 2022-11-23 | 2023-03-03 | 湖北泰盛化工有限公司 | 2, 4-dichlorophenol micro-channel continuous synthesis process |
Non-Patent Citations (2)
| Title |
|---|
| 2—甲4—氯苯氧乙酸生产工艺述评;曹广宏;《化学工程与装备》;19921231(第04期);第14-18页 * |
| 磁性催化剂Na2O·SiO2/Fe3O4的制备及其催化酯交换反应;郭萍梅等;《中国油料作物学》;20110228;第33卷(第01期);第71-76、86页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2024060737A1 (en) | 2024-03-28 |
| CN116120168A (en) | 2023-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110028399B (en) | Preparation method of 2-methyl-4-chlorophenoxyacetic acid | |
| CN102125035B (en) | Preparation process of herbicide dicamba | |
| CN116120168B (en) | Preparation process for catalytic synthesis of 2, 4-D | |
| CN101489970B (en) | Method for producing succinic acid | |
| CN105921161B (en) | A kind of catalyst and preparation method thereof preparing 2,5- chlorophenesic acids for paracide hydroxylating | |
| CN111187148B (en) | Method for simultaneously preparing o-hydroxy phenetole and 1, 3-benzodioxole-2-one | |
| CN108467343A (en) | The preparation method of 2,4- dichlorphenoxyacetic acids | |
| CN117623872A (en) | Synthesis method of 2-methyl-4-chloro | |
| CN111635375B (en) | Method for synthesizing thiothiazole | |
| CN108947838A (en) | A kind of preparation method of 2,4 dichlorophenoxyacetic acid and its salt | |
| CN103752339A (en) | Aluminum-doped mesoporous molecular sieve loaded phosphotungstic heteropoly acid catalyst, preparation thereof and application thereof to benzoic acid synthesis | |
| CN109776301A (en) | The synthetic method of one kind 2,4- dichlorphenoxyacetic acid compound | |
| CN113173844B (en) | Preparation method of 2-methyl-4-chlorophenoxyacetic acid | |
| CN106748747B (en) | Preparation method of palladium trifluoroacetate | |
| CN113045424B (en) | Synthesis method of 2- (5-fluoro-2-nitrophenoxy) acetate compound | |
| CN111187146B (en) | Process for producing 2-methyl-3-buten-2-ol | |
| CN102146022B (en) | Method for preparing 3-chlorine-5-bromophenol | |
| CN108191814A (en) | A kind of method that phosphotungstic acid titanium ammonium compound salt catalyzes and synthesizes cyclohexanone ethylene ketal | |
| CN109772345B (en) | Preparation of nickel catalyst for synthesizing ester by aldehyde oxidation esterification and application of nickel catalyst and ionic liquid co-catalysis system | |
| CN107311858B (en) | Synthesis process of naphthoxyacetic acid | |
| CN106317042B (en) | A kind of synthetic method of the fluoro- 6- amino -4- of 7- (2- propargyls) -1,4- benzoxazines -3 (4H) -one derivative | |
| CN111153794A (en) | Method for synthesizing ethyl palmitate by using dodecyl trimethyl ammonium chloride-based eutectic solvent catalyst | |
| CN111825711B (en) | Vanadium pyridine catalyst for preparing 2, 5-dichlorophenol by catalytic oxidation and synthesis method and application thereof | |
| CN117902971A (en) | Preparation method for synthesizing 2, 4-dichlorophenoxyacetic acid by composite molecular sieve ZSM-5 catalysis and applying water reducing process | |
| CN108187744A (en) | A kind of method that aluminium phosphotungstic acid ammonium compound salt catalyzes and synthesizes furfural glycol acetal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |