CN113149878A - Water-saving high-purity monosultap synthesis process - Google Patents
Water-saving high-purity monosultap synthesis process Download PDFInfo
- Publication number
- CN113149878A CN113149878A CN202110298375.0A CN202110298375A CN113149878A CN 113149878 A CN113149878 A CN 113149878A CN 202110298375 A CN202110298375 A CN 202110298375A CN 113149878 A CN113149878 A CN 113149878A
- Authority
- CN
- China
- Prior art keywords
- reaction
- water
- monosultap
- solution
- pyridine
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/02—Thiosulfates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/02—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of hydrogen atoms by amino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a water-saving high-purity monosultap synthesis process, wherein a reaction system of amination reaction in the monosultap synthesis process is mainly improved, pyridine replaces water as the reaction system, and pyridine replaces dimethylamine as an acid-binding agent, so that the purity and the reaction yield of the prepared N, N-dimethylallylamine are improved; meanwhile, the boiling point of the pyridine is far higher than that of dimethylamine, so that the method is favorable for production and recovery, and compared with the method in which dimethylamine is used as an acid-binding agent, the method has the advantages of less volatilization, favorable production environment and high recovery rate; meanwhile, the invention can reduce the total waste water amount to 30-40% of the waste water amount of the amination reaction of the traditional dimethylamine aqueous solution system, and has extremely high environmental benefit.
Description
Technical Field
The invention relates to a synthesis process of monosultap, in particular to a synthesis process of water-saving high-purity monosultap.
Background
Monosultap, chemical name 2-dimethylamine-1-sodium thiosulfate-3-thiosulfate propane, is usually prepared by excessive alkalization to obtain bisultap, acidification with hydrochloric acid and crystallization to obtain monosultap, which generally contains one molecule of crystal water and has the following structural formula:
in the prior art, the most widely applied monosultap synthesis process comprises the following steps: 1. amination reaction of dimethylamine and chloropropene; 2. acidifying with hydrochloric acid; 3. chlorination reaction by addition with chlorine; 4. sulfonation reaction with sodium thiosulfate under alkaline conditions; 5. the hydrochloric acid is acidified and crystallized.
Wherein, the general control mode of the first step amination reaction is as follows: under a cooling environment, chloropropene was added dropwise to an excess of 40% aqueous dimethylamine solution, and then the reaction temperature was slowly raised to complete the amination reaction.
However, in actual production, the amination process has several problems:
1. the amination reaction is a nucleophilic substitution reaction, and partial side reaction is caused due to the existence of water which is a strong polar substance in a reaction system, so that the prepared N, N-dimethylallylamine (CH)3)2NCH2CH＝CH2Low purity and low yield;
2. the amination process uses dimethylamine as an acid-binding agent to absorb HCl generated by the amination process, but because the dimethylamine has a very low boiling point and is very volatile at 7 ℃, the recovery rate of the dimethylamine during alkaline washing recovery is not high, the production environment is malodorous, the dimethylamine is extremely not beneficial to human safety and environmental safety, the utilization rate of raw materials is not high, and the refrigeration energy consumption during distillation is very high;
3. due to the large amount of water introduced by the aqueous dimethylamine solution, there is a significant amount of waste water after recovery of the excess dimethylamine.
Therefore, the invention develops a novel water-saving high-purity monosultap synthesis process, which optimizes the defects of amination reaction in the prior art, realizes high utilization rate and conversion rate of raw materials and reduces waste water and waste gas.
Disclosure of Invention
The invention develops a water-saving high-purity monosultap synthesis process, which optimizes the amination reaction steps in the prior art, realizes high utilization rate and high conversion rate of raw materials and reduces waste water and waste gas.
A water-saving high-purity monosultap synthesis process comprises the following specific steps:
(I) amination reaction
(1) Starting an amination reaction kettle to cool brine, and cooling the kettle to below 0 ℃;
(2) starting a reflux condenser on the amination reaction kettle, and adding a concentrated dimethylaminopyridine solution;
(3) stirring, uniformly dropwise adding chloropropene and pyridine, and keeping the molar ratio of dimethylamine to chloropropene to pyridine at 1:1:1 after dropwise addition;
(4) after the reaction is finished, adding water with the total molar weight of 1/4-1/3 of pyridine, stirring for 10-20 min, and then standing for layering;
(5) standing and layering for 30-40 min, and separating a lower wastewater layer, wherein the upper layer is N, N-dimethylallylamine;
(6) repeating the step (4) and the step (5) for 3-5 times, and washing out pyridine hydrochloride to prepare N, N-dimethylallylamine;
(II) acidification with hydrochloric acid
Adding concentrated hydrochloric acid into the N, N-dimethylallylamine prepared in the step (first) for acidification, controlling the pH to be 2-3 at the end point of acidification, then distilling to remove water, and adding dichloroethane to obtain an N, N-dimethylallylamine hydrochloride solution after the water removal is finished;
(III) Chlorination
Heating the N, N-dimethylallylamine hydrochloride solution prepared in the step (II) in a chlorination reaction kettle for azeotropic dehydration to further remove water in the N, N-dimethylallylamine hydrochloride solution, introducing chlorine after azeotropic dehydration is finished, heating to remove dichloroethane after chlorination reaction is finished, and adding toluene to prepare a chlorinated solution;
(IV) sulfonation
Diluting the chlorinated solution prepared in the step (three) with methanol, then dropwise adding alkali liquor, quickly mixing with a sodium bicarbonate solution, carrying out sulfonation reaction under the condition of heating, evaporating the methanol after the reaction is finished, and then removing waste salt to prepare a sulfonated solution;
(V) hydrochloric acid acidification crystallization
And (3) dropwise adding concentrated hydrochloric acid into the sulfonated liquid prepared in the fourth step, controlling the pH value of the dropwise adding solution to be 4-5, cooling and crystallizing, filtering crystals, and drying to obtain the monosultap.
Further, the amination reaction process stage in the first step (first step) may preferably be:
(I) amination reaction
(1) Starting an amination reaction kettle to cool brine, and cooling the kettle to-2 ℃;
(2) starting a reflux condenser on the amination reaction kettle, and adding a concentrated dimethylaminopyridine solution;
(3) stirring, uniformly dropwise adding chloropropene and pyridine, and keeping the molar ratio of dimethylamine to chloropropene to pyridine at 1:1:1 after dropwise addition;
(4) after the reaction is finished, adding water with the total molar weight of the pyridine being 1/4, stirring for 15min, and then standing for layering;
(5) standing for layering for 30min, and separating a lower wastewater layer, wherein the upper layer is N, N-dimethylallylamine;
(6) repeating the step (4) and the step (5) for 4 times, and washing out pyridine hydrochloride to obtain the N, N-dimethylallylamine.
Further, the concentrated dimethylamine-pyridine solution in the amination process of the first step is prepared by mixing dimethylamine and pyridine in a molar ratio of 2-3: 1.
Further, the reaction temperature when chloropropene is dripped in the amination process section in the first step (a) is controlled as follows: controlling the temperature at the initial stage to be 5-10 ℃, controlling the temperature at the middle stage to be 10-15 ℃ and controlling the temperature at the later stage to be 20-30 ℃; after the chloropropene is dripped, the temperature is controlled to be 35-40 ℃, and the reaction is carried out for 1-2 h under the condition of heat preservation.
Furthermore, the concentrated hydrochloric acid used in the hydrochloric acid acidification process section of the second step and the hydrochloric acid acidification crystallization process section of the fifth step is 30-37 percent of concentrated hydrochloric acid.
Further, the temperature of azeotropic dehydration in the chlorination reaction process section of the third step is controlled to be 80-90 ℃; after the water removal is finished, chlorine is introduced to carry out chlorination reaction, and the temperature is controlled to be 60-70 ℃; when the chlorine flux approaches 71kg/kmol N, N-dimethyl allylamine hydrochloride, the chlorination reaction is completed if bromine water is not faded by observation with adding bromine water.
Further, the specific process for preparing the chlorination liquid in the chlorination reaction process section in the third step is as follows: heating to remove the solvent and chlorine after the chlorination reaction is completed, removing most of dichloroethane, adding water, standing for layering to remove the lower dichloroethane, heating the upper feed liquid to 85-95 ℃ for azeotropic desolvation, removing most of water after the desolvation is finished, and adding toluene to obtain the chlorinated solution.
Further, the specific process of the sulfonation reaction process section in the fourth step is as follows:
dissolving sodium bicarbonate and heating to 60-70 ℃, diluting chloride solution with methanol, dropwise adding alkali liquor in the chloride solution cooling environment, controlling the pH of the chloride solution to be 6.5-7.0, quickly mixing the chloride solution into the sodium bicarbonate solution, heating to 60-70 ℃ for reaction, heating to remove methanol after complete reaction, cooling, and centrifuging to remove waste salt to obtain the sulfonated solution.
Further, the concrete process of the hydrochloric acid acidification crystallization process section in the fifth step is as follows:
and (3) after cooling the sulfonation liquid, dropwise adding concentrated hydrochloric acid until the pH value is 4-5, cooling to-5-0 ℃ for crystallization, centrifugally discharging after crystallization is completed, and drying crystals to obtain the monosultap.
The invention has the advantages that: 1. the invention improves the reaction system of amination reaction in the monosultap synthesis process, takes pyridine substituted water as the reaction system, and takes pyridine substituted dimethylamine as an acid-binding agent; due to the large pi bond of the pyridine, active hydrogen is not contained in the pyridine, the selectivity of amination reaction is not influenced, and the purity of the prepared N, N-dimethyl allylamine is improved; meanwhile, N of the pyridine is alkaline, so that HCl generated in the amination reaction can be absorbed, the reaction completion of the amination reaction is promoted, and the reaction yield is improved; the technical scheme of dripping pyridine can absorb reaction heat release and improve the stability of temperature control;
2. because the boiling point of pyridine is 115.2 ℃, the volatility of the pyridine in the production environment is far lower than that of dimethylamine, the production and the recovery are facilitated, and the recovery rate after alkalization is higher than 98 percent; excessive dimethylamine is used as an acid-binding agent, is extremely easy to volatilize, causes the production environment to be malodorous, and is extremely not beneficial to the human safety and the environmental safety; the refrigeration energy consumption is very high during distillation recovery, and the recovery rate is only about 85 percent, so that the utilization rate of raw materials is reduced;
3. in the amination reaction of the pyridine system, the waste water is introduced by cleaning pyridine hydrochloride, and the total waste water amount can be reduced to 30-40% of that of the amination reaction of the traditional dimethylamine aqueous solution system by a small amount of multiple processes, so that the method has extremely high environmental benefit.
Detailed Description
Example 1
A water-saving high-purity monosultap synthesis process comprises the following specific steps:
(I) amination reaction
(1) Starting an amination reaction kettle to cool brine, and cooling the kettle to 0 ℃;
(2) starting a reflux condenser on the amination reaction kettle, and adding a concentrated dimethylaminopyridine solution;
(3) stirring, uniformly dropwise adding chloropropene and pyridine, and keeping the molar ratio of dimethylamine to chloropropene to pyridine at 1:1:1 after dropwise addition;
(4) after the reaction is finished, adding water with the total molar weight of the pyridine being 1/3, stirring for 10min, and then standing for layering;
(5) standing for layering for 30min, and separating a lower wastewater layer, wherein the upper layer is N, N-dimethylallylamine;
(6) repeating the step (4) and the step (5) for 5 times, and washing out pyridine hydrochloride to prepare N, N-dimethylallylamine;
(II) acidification with hydrochloric acid
Adding concentrated hydrochloric acid into the N, N-dimethylallylamine prepared in the step (first) for acidification, controlling the pH to be 2 at the end point of acidification, then distilling to remove water, and adding dichloroethane to obtain an N, N-dimethylallylamine hydrochloride solution after the water removal is finished;
(III) Chlorination
Heating the N, N-dimethylallylamine hydrochloride solution prepared in the step (II) in a chlorination reaction kettle for azeotropic dehydration to further remove water in the N, N-dimethylallylamine hydrochloride solution, introducing chlorine after azeotropic dehydration is finished, heating to remove dichloroethane after chlorination reaction is finished, and adding toluene to prepare a chlorinated solution;
(IV) sulfonation
Diluting the chlorinated solution prepared in the step (three) with methanol, then dropwise adding alkali liquor, quickly mixing with a sodium bicarbonate solution, carrying out sulfonation reaction under the condition of heating, evaporating the methanol after the reaction is finished, and then removing waste salt to prepare a sulfonated solution;
(V) hydrochloric acid acidification crystallization
And (4) dropwise adding concentrated hydrochloric acid into the sulfonated liquid prepared in the fourth step, controlling the pH at the end point of dropwise adding to 4, cooling for crystallization, filtering crystals and drying to prepare the monosultap.
In the amination process of the first step, the concentrated dimethylamine-pyridine solution has a molar ratio of dimethylamine to pyridine of 2: 1.
The reaction temperature when chloropropene is dripped in the amination process section in the first step is controlled as follows: controlling the temperature at 5 ℃ in the initial stage, 10 ℃ in the middle stage and 20 ℃ in the later stage; after the chloropropene is dripped, the temperature is controlled to be 35 ℃, and the reaction is carried out for 1.5h under the condition of heat preservation.
The temperature of azeotropic dehydration in the chlorination reaction process section of the third step is controlled at 80 ℃; after the water removal is finished, chlorine is introduced to carry out chlorination reaction, and the temperature is controlled at 60 ℃.
The third step of chlorination reaction process section is used for preparing the chlorination liquid, and the specific process comprises the following steps:
heating to remove the solvent and chlorine after the chlorination reaction is completed, removing most of dichloroethane, adding water, standing for layering to remove the lower dichloroethane, heating the upper feed liquid to 85 ℃ for azeotropic desolvation, removing most of water after the desolvation is finished, and adding toluene to obtain the chlorinated solution.
The concrete process of the sulfonation reaction process section in the fourth step comprises the following steps:
dissolving sodium bicarbonate and heating to 60 ℃, diluting chloride solution with methanol, dropwise adding alkali liquor in the chloride solution cooling environment, controlling the pH of the chloride solution to be 6.5, quickly mixing the chloride solution into the sodium bicarbonate solution, heating to 60 ℃ for reaction, heating after complete reaction to remove methanol, cooling, and centrifuging to remove waste salt to obtain the sulfonated liquid.
The concrete process of the hydrochloric acid acidification crystallization process section in the step (fifth) is as follows:
after cooling the sulfonated liquid, dropwise adding concentrated hydrochloric acid until the pH value is 4, cooling to 0 ℃ for crystallization, after the crystallization is finished, centrifugally discharging, and drying the crystal to obtain the monosultap.
Example 2
A water-saving high-purity monosultap synthesis process comprises the following specific steps:
(I) amination reaction
(1) Starting an amination reaction kettle to cool brine, and cooling the kettle to-2 ℃;
(2) starting a reflux condenser on the amination reaction kettle, and adding a concentrated dimethylaminopyridine solution;
(3) stirring, uniformly dropwise adding chloropropene and pyridine, and keeping the molar ratio of dimethylamine to chloropropene to pyridine at 1:1:1 after dropwise addition;
(4) after the reaction is finished, adding water with the total molar weight of the pyridine being 1/4, stirring for 15min, and then standing for layering;
(5) standing for layering for 30min, and separating a lower wastewater layer, wherein the upper layer is N, N-dimethylallylamine;
(6) repeating the step (4) and the step (5) for 4 times, and washing out pyridine hydrochloride to prepare N, N-dimethylallylamine;
(II) acidification with hydrochloric acid
Adding concentrated hydrochloric acid into the N, N-dimethylallylamine prepared in the step (first) for acidification, controlling the pH to be 2 at the end point of acidification, then distilling to remove water, and adding dichloroethane to obtain an N, N-dimethylallylamine hydrochloride solution after the water removal is finished;
(III) Chlorination
Heating the N, N-dimethylallylamine hydrochloride solution prepared in the step (II) in a chlorination reaction kettle for azeotropic dehydration to further remove water in the N, N-dimethylallylamine hydrochloride solution, introducing chlorine after azeotropic dehydration is finished, heating to remove dichloroethane after chlorination reaction is finished, and adding toluene to prepare a chlorinated solution;
(IV) sulfonation
Diluting the chlorinated solution prepared in the step (three) with methanol, then dropwise adding alkali liquor, quickly mixing with a sodium bicarbonate solution, carrying out sulfonation reaction under the condition of heating, evaporating the methanol after the reaction is finished, and then removing waste salt to prepare a sulfonated solution;
(V) hydrochloric acid acidification crystallization
And (4) dropwise adding concentrated hydrochloric acid into the sulfonated liquid prepared in the fourth step, controlling the pH at the end point of dropwise adding to 4, cooling for crystallization, filtering crystals and drying to prepare the monosultap.
In the amination process of the first step, the concentrated dimethylamine-pyridine solution has a molar ratio of dimethylamine to pyridine of 3: 1.
The reaction temperature when chloropropene is dripped in the amination process section in the first step is controlled as follows: controlling the temperature at 5 ℃ in the initial stage, 10 ℃ in the middle stage and 30 ℃ in the later stage; and after the chloropropene is dropwise added, controlling the temperature to be 35 ℃, and carrying out heat preservation reaction for 2 hours.
The temperature of azeotropic dehydration in the chlorination reaction process section of the third step is controlled at 85 ℃; after the water removal is finished, chlorine is introduced to carry out chlorination reaction, and the temperature is controlled to be 65 ℃.
The third step of chlorination reaction process section is used for preparing the chlorination liquid, and the specific process comprises the following steps:
heating to remove the solvent and chlorine after the chlorination reaction is completed, removing most of dichloroethane, adding water, standing for layering to remove the lower dichloroethane, heating the upper feed liquid to 90 ℃ for azeotropic desolvation, vacuum dehydrating after the desolvation is completed, removing most of water, and adding toluene to prepare the chlorinated solution.
The concrete process of the sulfonation reaction process section in the fourth step comprises the following steps:
dissolving sodium bicarbonate and heating to 65 ℃, diluting chloride solution with methanol, dropwise adding alkali liquor in the chloride solution cooling environment, controlling the pH of the chloride solution to be 6.7, quickly mixing the chloride solution into the sodium bicarbonate solution, heating to 65 ℃ for reaction, heating after complete reaction to remove methanol, cooling, and centrifuging to remove waste salt to obtain the sulfonated liquid.
The concrete process of the hydrochloric acid acidification crystallization process section in the step (fifth) is as follows:
after cooling the sulfonated liquid, dropwise adding concentrated hydrochloric acid until the pH value is 4, cooling to 0 ℃ for crystallization, after the crystallization is finished, centrifugally discharging, and drying the crystal to obtain the monosultap.
Example 3
A water-saving high-purity monosultap synthesis process comprises the following specific steps:
(I) amination reaction
(1) Starting an amination reaction kettle to cool brine, and cooling the kettle to-2 ℃;
(2) starting a reflux condenser on the amination reaction kettle, and adding a concentrated dimethylaminopyridine solution;
(3) stirring, uniformly dropwise adding chloropropene and pyridine, and keeping the molar ratio of dimethylamine to chloropropene to pyridine at 1:1:1 after dropwise addition;
(4) after the reaction is finished, adding water with the total molar weight of the pyridine being 1/4, stirring for 20min, and then standing for layering;
(5) standing for layering for 40min, and separating a lower wastewater layer, wherein the upper layer is N, N-dimethylallylamine;
(6) repeating the step (4) and the step (5) for 3 times, and washing out pyridine hydrochloride to prepare N, N-dimethylallylamine;
(II) acidification with hydrochloric acid
Adding concentrated hydrochloric acid into the N, N-dimethylallylamine prepared in the step (first) for acidification, controlling the pH to 3 at the end point of acidification, then distilling to remove water, and adding dichloroethane to obtain an N, N-dimethylallylamine hydrochloride solution after the water removal is finished;
(III) Chlorination
Heating the N, N-dimethylallylamine hydrochloride solution prepared in the step (II) in a chlorination reaction kettle for azeotropic dehydration to further remove water in the N, N-dimethylallylamine hydrochloride solution, introducing chlorine after azeotropic dehydration is finished, heating to remove dichloroethane after chlorination reaction is finished, and adding toluene to prepare a chlorinated solution;
(IV) sulfonation
Diluting the chlorinated solution prepared in the step (three) with methanol, then dropwise adding alkali liquor, quickly mixing with a sodium bicarbonate solution, carrying out sulfonation reaction under the condition of heating, evaporating the methanol after the reaction is finished, and then removing waste salt to prepare a sulfonated solution;
(V) hydrochloric acid acidification crystallization
And (4) dropwise adding concentrated hydrochloric acid into the sulfonated liquid prepared in the fourth step, controlling the pH of the dropwise adding end point to be 5, cooling and crystallizing, filtering crystals and drying to prepare the monosultap.
In the amination process of the first step, the concentrated dimethylamine-pyridine solution has a molar ratio of dimethylamine to pyridine of 3: 1.
The reaction temperature when chloropropene is dripped in the amination process section in the first step is controlled as follows: controlling the temperature at 10 ℃ in the initial stage, controlling the temperature at 15 ℃ in the middle stage and controlling the temperature at 30 ℃ in the later stage; and after the chloropropene is dropwise added, controlling the temperature at 40 ℃, and carrying out heat preservation reaction for 1 h.
The temperature of azeotropic dehydration in the chlorination reaction process section of the third step is controlled at 90 ℃; after the water removal is finished, chlorine is introduced to carry out chlorination reaction, and the temperature is controlled at 70 ℃.
The third step of chlorination reaction process section is used for preparing the chlorination liquid, and the specific process comprises the following steps:
heating to remove the solvent and chlorine after the chlorination reaction is completed, removing most of dichloroethane, adding water, standing for layering to remove the lower dichloroethane, heating the upper feed liquid to 95 ℃ for azeotropic desolvation, removing most of water after the desolvation is finished, and adding toluene to obtain the chlorinated solution.
The concrete process of the sulfonation reaction process section in the fourth step comprises the following steps:
dissolving sodium bicarbonate and heating to 70 ℃, diluting chloride solution with methanol, dropwise adding alkali liquor in the chloride solution cooling environment, controlling the pH of the chloride solution to be 7.0, quickly mixing the chloride solution into the sodium bicarbonate solution, heating to 70 ℃ for reaction, heating after complete reaction to remove methanol, cooling, and centrifuging to remove waste salt to obtain the sulfonated liquid.
The concrete process of the hydrochloric acid acidification crystallization process section in the step (fifth) is as follows:
after cooling the sulfonated solution, dropwise adding concentrated hydrochloric acid until the pH value is 5, cooling to-5 ℃ for crystallization, after the crystallization is finished, centrifugally discharging, and drying the crystal to obtain the monosultap.
Comparative example 1
A monosultap synthesis process, which uses a system of 40% dimethylamine aqueous solution to carry out amination reaction, and the rest processes are the same as the process in the example 2.
Detection and analysis:
1. the purities of the N, N-dimethylallylamine prepared in the amination process section in the first step of the examples and the comparative example are detected by gas chromatography, and the conversion rate of the N, N-dimethylallylamine is calculated by chloropropene;
2. the wastewater ratio of the first amination process stage of each example and comparative example was calculated as follows:
the wastewater ratio (%). total wastewater/N, total N-dimethylallylamine is 100%
As can be seen from the above table, the invention improves the reaction system of the amination reaction in the monosultap synthesis process, and improves the purity and reaction yield of the prepared N, N-dimethylallylamine, and through gas chromatography detection, the impurities in the prepared N, N-dimethylallylamine are mainly residual pyridine, while the impurities in the N, N-dimethylallylamine prepared in the comparative example 1 include dimethylamine, side reaction products, and the like; meanwhile, the invention can reduce the waste water amount of the amination process section to 30-40% of that of the traditional dimethylamine aqueous solution system; meanwhile, dimethylamine is avoided being used as an acid-binding agent, the production environment is purified, the utilization rate of dimethylamine is improved, and the method has excellent economic value and environmental benefit.
And finally: the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. A water-saving high-purity monosultap synthesis process is characterized by comprising the following steps: the synthesis process comprises the following steps:
(I) amination reaction
(1) Starting an amination reaction kettle to cool brine, and cooling the kettle to below 0 ℃;
(2) starting a reflux condenser on the amination reaction kettle, and adding a concentrated dimethylaminopyridine solution;
(3) stirring, uniformly dropwise adding chloropropene and pyridine, and keeping the molar ratio of dimethylamine to chloropropene to pyridine at 1:1:1 after dropwise addition;
(4) after the reaction is finished, adding water with the total molar weight of 1/4-1/3 of pyridine, stirring for 10-20 min, and then standing for layering;
(5) standing and layering for 30-40 min, and separating a lower wastewater layer, wherein the upper layer is N, N-dimethylallylamine;
(6) repeating the step (4) and the step (5) for 3-5 times, and washing out pyridine hydrochloride to prepare N, N-dimethylallylamine;
(II) acidification with hydrochloric acid
Adding concentrated hydrochloric acid into the N, N-dimethylallylamine prepared in the step (first) for acidification, controlling the pH to be 2-3 at the end point of acidification, then distilling to remove water, and adding dichloroethane to obtain an N, N-dimethylallylamine hydrochloride solution after the water removal is finished;
(III) Chlorination
Heating the N, N-dimethylallylamine hydrochloride solution prepared in the step (II) in a chlorination reaction kettle for azeotropic dehydration to further remove water in the N, N-dimethylallylamine hydrochloride solution, introducing chlorine after azeotropic dehydration is finished, heating to remove dichloroethane after chlorination reaction is finished, and adding toluene to prepare a chlorinated solution;
(IV) sulfonation
Diluting the chlorinated solution prepared in the step (three) with methanol, then dropwise adding alkali liquor, quickly mixing with a sodium bicarbonate solution, carrying out sulfonation reaction under the condition of heating, evaporating the methanol after the reaction is finished, and then removing waste salt to prepare a sulfonated solution;
(V) hydrochloric acid acidification crystallization
And (3) dropwise adding concentrated hydrochloric acid into the sulfonated liquid prepared in the fourth step, controlling the pH value of the dropwise adding solution to be 4-5, cooling and crystallizing, filtering crystals, and drying to obtain the monosultap.
2. A process for synthesizing a water-saving high-purity monosultap as claimed in claim 1, which comprises the following steps: the amination process section in the first step comprises the following steps:
(I) amination reaction
(1) Starting an amination reaction kettle to cool brine, and cooling the kettle to-2 ℃;
(2) starting a reflux condenser on the amination reaction kettle, and adding a concentrated dimethylaminopyridine solution;
(3) stirring, uniformly dropwise adding chloropropene and pyridine, and keeping the molar ratio of dimethylamine to chloropropene to pyridine at 1:1:1 after dropwise addition;
(4) after the reaction is finished, adding water with the total molar weight of the pyridine being 1/4, stirring for 15min, and then standing for layering;
(5) standing for layering for 30min, and separating a lower wastewater layer, wherein the upper layer is N, N-dimethylallylamine;
(6) repeating the step (4) and the step (5) for 4 times, and washing out pyridine hydrochloride to obtain the N, N-dimethylallylamine.
3. A process for synthesizing a water-saving high-purity monosultap as claimed in claim 1 or 2, which comprises the following steps: in the amination process of the first step, the concentrated dimethylamine pyridine solution is prepared by mixing dimethylamine and pyridine in a molar ratio of 2-3: 1.
4. A process for synthesizing a water-saving high-purity monosultap as claimed in claim 1 or 2, which comprises the following steps: the reaction temperature when chloropropene is dripped in the amination process section in the first step is controlled as follows: controlling the temperature at the initial stage to be 5-10 ℃, controlling the temperature at the middle stage to be 10-15 ℃ and controlling the temperature at the later stage to be 20-30 ℃; after the chloropropene is dripped, the temperature is controlled to be 35-40 ℃, and the reaction is carried out for 1-2 h under the condition of heat preservation.
5. A process for synthesizing a water-saving high-purity monosultap as claimed in claim 1 or 2, which comprises the following steps: the hydrochloric acid acidification process section of the second step and the hydrochloric acid acidification crystallization process section of the fifth step use 30 to 37 percent of concentrated hydrochloric acid.
6. A process for synthesizing a water-saving high-purity monosultap as claimed in claim 1 or 2, which comprises the following steps: the temperature of azeotropic dehydration in the chlorination reaction process section of the third step is controlled between 80 ℃ and 90 ℃; after the water removal is finished, chlorine is introduced to carry out chlorination reaction, and the temperature is controlled to be 60-70 ℃; the end point of the chlorination reaction is that when the chlorine flux is close to 71kg/kmolN, N-dimethylallylamine hydrochloride, bromine water is added for observation, and the chlorination reaction is complete if the bromine water does not fade.
7. A process for synthesizing a water-saving high-purity monosultap as claimed in claim 1 or 2, which comprises the following steps: the third step of chlorination reaction process section is used for preparing the chlorination liquid, and the specific process comprises the following steps:
heating to remove the solvent and chlorine after the chlorination reaction is completed, removing most of dichloroethane, adding water, standing for layering to remove the lower dichloroethane, heating the upper feed liquid to 85-95 ℃ for azeotropic desolvation, removing most of water after the desolvation is finished, and adding toluene to obtain the chlorinated solution.
8. A process for synthesizing a water-saving high-purity monosultap as claimed in claim 1 or 2, which comprises the following steps: the concrete process of the sulfonation reaction process section in the fourth step comprises the following steps:
dissolving sodium bicarbonate and heating to 60-70 ℃, diluting chloride solution with methanol, dropwise adding alkali liquor in the chloride solution cooling environment, controlling the pH of the chloride solution to be 6.5-7.0, quickly mixing the chloride solution into the sodium bicarbonate solution, heating to 60-70 ℃ for reaction, heating to remove methanol after complete reaction, cooling, and centrifuging to remove waste salt to obtain the sulfonated solution.
9. A process for synthesizing a water-saving high-purity monosultap as claimed in claim 1 or 2, which comprises the following steps: the concrete process of the hydrochloric acid acidification crystallization process section in the step (fifth) is as follows:
and (3) after cooling the sulfonation liquid, dropwise adding concentrated hydrochloric acid until the pH value is 4-5, cooling to-5-0 ℃ for crystallization, centrifugally discharging after crystallization is completed, and drying crystals to obtain the monosultap.
10. A monosultap prepared using the water-saving high-purity monosultap synthesis process of claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110298375.0A CN113149878A (en) | 2021-03-19 | 2021-03-19 | Water-saving high-purity monosultap synthesis process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110298375.0A CN113149878A (en) | 2021-03-19 | 2021-03-19 | Water-saving high-purity monosultap synthesis process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113149878A true CN113149878A (en) | 2021-07-23 |
Family
ID=76887936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110298375.0A Pending CN113149878A (en) | 2021-03-19 | 2021-03-19 | Water-saving high-purity monosultap synthesis process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113149878A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113200907A (en) * | 2021-03-19 | 2021-08-03 | 江西欧氏化工有限公司 | Novel treatment method of amination wastewater in monosultap synthesis process |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102989A (en) * | 1985-04-01 | 1987-01-10 | 贵州省化工研究所 | New process for synthesizing of dimethylallyl amine |
| CN1094396A (en) * | 1993-04-11 | 1994-11-02 | 中国人民解放军第九七六三工厂 | N, N-dimethyl amido-1, the production technique of 3-dithio sodium sulfate base propane and analogue thereof |
| CN1273240A (en) * | 1999-05-07 | 2000-11-15 | 湖南南天实业股份有限公司 | Sulfonating reaction process in production of bisultap |
| CN1278531A (en) * | 1999-06-18 | 2001-01-03 | 贵州群星科学技术经济合作公司 | Preparation of refined organic thiosulfate |
| CN107739326A (en) * | 2017-10-13 | 2018-02-27 | 重庆农药化工（集团）有限公司 | Monosultap wet powder and its production method and application |
-
2021
- 2021-03-19 CN CN202110298375.0A patent/CN113149878A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102989A (en) * | 1985-04-01 | 1987-01-10 | 贵州省化工研究所 | New process for synthesizing of dimethylallyl amine |
| CN1094396A (en) * | 1993-04-11 | 1994-11-02 | 中国人民解放军第九七六三工厂 | N, N-dimethyl amido-1, the production technique of 3-dithio sodium sulfate base propane and analogue thereof |
| CN1273240A (en) * | 1999-05-07 | 2000-11-15 | 湖南南天实业股份有限公司 | Sulfonating reaction process in production of bisultap |
| CN1278531A (en) * | 1999-06-18 | 2001-01-03 | 贵州群星科学技术经济合作公司 | Preparation of refined organic thiosulfate |
| CN107739326A (en) * | 2017-10-13 | 2018-02-27 | 重庆农药化工（集团）有限公司 | Monosultap wet powder and its production method and application |
Non-Patent Citations (5)
| Title |
|---|
| 吴美宁: "以二甲胺为缚酸剂合成N, N-二甲基烯丙胺的工艺研究", 浙江化工, no. 04, pages 24 - 26 * |
| 李平辉;童孟良;梁美东;: "杀虫双胺化工艺条件探讨", 化工时刊, no. 02, pages 49 - 51 * |
| 王国杰, 吴汝安, 杨晓明: "杀虫双胺化新工艺改进", 精细化工中间体, no. 03, pages 20 - 23 * |
| 裔连祥: "虫双（单）合成反应的研究及其生产工艺技术改进", 《客道巴巴HTTPS://WWW.DOC88.COM/P-1995425471783.HTML》, pages 1 - 30 * |
| 赵卫东;杨学慧;邢华;: "提高杀虫双合成中胺化收率的工艺改进", 现代农药, no. 01, pages 18 - 20 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113200907A (en) * | 2021-03-19 | 2021-08-03 | 江西欧氏化工有限公司 | Novel treatment method of amination wastewater in monosultap synthesis process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106045879B (en) | Method for preparing cyanoacetic acid | |
| CN107986944B (en) | Method for synthesizing difluoroethanol by taking 2, 2-difluoro-1-chloroethane as raw material | |
| CN113149878A (en) | Water-saving high-purity monosultap synthesis process | |
| WO2016202252A1 (en) | Method for synthesizing d-para-hydroxyphenylglycine methyl ester | |
| CN111170898B (en) | Preparation method of potassium perfluorobutane sulfonate | |
| CN110642790B (en) | Preparation method of rosuvastatin calcium and intermediate thereof | |
| CN108947870B (en) | Preparation method of bromosartanbiphenyl | |
| CN109232274B (en) | A kind of bromination new process of 2,4- dinitroaniline | |
| CN104355990B (en) | Method for recycling and mechanically using L- (+) -tartaric acid in D-ethyl ester production | |
| CN113200907A (en) | Novel treatment method of amination wastewater in monosultap synthesis process | |
| TWI828930B (en) | Production of malic acid | |
| CN114477235A (en) | Crystallization method of sodium chloride | |
| CN111217720B (en) | Synthetic method of 3- (N, N-dimethoxycarbonylmethyl) amino-4-methoxyacetanilide | |
| CN109280011B (en) | Synthesis method of OLED intermediate 2-bromopyrene | |
| CN107311990B (en) | Preparation method of olmesartan medoxomil | |
| JP2002030044A (en) | Method for producing tetraalkylammonium halide | |
| CN117777034A (en) | Synthesis method of difluoromethyl triazolinone intermediate with reduced fluoride ion content | |
| CN112679360A (en) | Preparation method of oxadiazon intermediate 1, 5-dichloro-2-isopropoxy-4-nitrobenzene | |
| CN110950809B (en) | Synthetic post-treatment method of aryl triazolinone compound | |
| CN113024484B (en) | Method for purifying and preparing high-purity promoter CZ and application thereof | |
| CN111320593B (en) | Refining method of high-purity Carilazine | |
| CN114634492A (en) | Preparation method of lanoconazole | |
| CN116332789A (en) | Preparation method of 4-amino-2-fluorobenzamide | |
| JP2641022B2 (en) | Purification method of 4,4'-dihydroxydiphenyl sulfone | |
| CN117327021A (en) | Method for removing sticky impurities in hexahydropyridazine synthesis |
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 |