CN113582883B - Method for continuously synthesizing p-toluenesulfonyl chloride - Google Patents
Method for continuously synthesizing p-toluenesulfonyl chloride Download PDFInfo
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- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/08—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with halogenosulfonic acids
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Abstract
The invention discloses a method for continuously synthesizing paratoluensulfonyl chloride, wherein toluene, sulfur trioxide, chlorosulfonic acid, organic alkali and a solvent are mixed in a first static mixer and then pumped into a first microreactor for reaction; the first reaction mixture discharged from the outlet of the first microreactor flows into a second static mixer, and is mixed with sulfur trioxide, chlorosulfonic acid, low-carbon chain fatty acid and a solvent which are respectively pumped into the second static mixer, and the obtained mixed material is pumped into a second microreactor for reaction; and cooling, crystallizing and separating the secondary reaction mixture discharged from the second microreactor to obtain the p-toluenesulfonyl chloride as a product. The invention greatly improves the production efficiency, effectively solves the problem that a large amount of sulfone substances and polysulfonates are easy to generate due to the sulfonation of sulfur trioxide by adding the sulfone inhibitor, and avoids the generation of hydrogen chloride gas.
Description
Technical Field
The invention relates to the technical field of fine chemical intermediates, in particular to a green process for preparing paratoluensulfonyl chloride by using sulfur trioxide, chlorosulfonic acid, toluene, a catalyst and an inhibitor in a microchannel reactor.
Background
The synthesis route of p-toluenesulfonyl chloride is mainly to prepare the p-toluenesulfonyl chloride by using toluene and chlorosulfonic acid as raw materials and ammonium chloride, N-dimethylacetamide and triethylamine as catalysts through sulfonation and acylchlorination reactions. Such as German patent Ger P1172258, ger P1112978, US patent US3.686.300, japanese JP 56-46860. The methods not only need higher reaction temperature (generally 60-90 ℃), have low production efficiency, but also generate a large amount of dilute sulfuric acid waste liquid and a large amount of hydrogen chloride gas, seriously corrode equipment, pollute the environment, can not accurately control the reaction process, and the yield needs to be improved. 5363 the yield of US3.686.300 is up to 83%. However, at present, domestic manufacturers mostly adopt the method to produce the paratoluensulfonyl chloride by adopting the process route, because the process has the characteristics of few operation steps, short reaction period and the like. However, due to the limitation of the production process, the large amount of acidic raw materials used in the process, the large amount of hydrogen chloride gas and the large amount of dilute sulfuric acid generated in the reaction process severely corrode equipment, the treatment difficulty and the cost are quite high, the environment is seriously polluted, and the product yield is low.
CN107344922A discloses a method for preparing paratoluensulfonyl chloride, which comprises the steps of firstly adding magnesium paratoluenesulfonate into an aprotic polar organic solvent, and then reacting with a chlorination reagent under an inert atmosphere to prepare the paratoluensulfonyl chloride. CN201310476616.1 discloses a synthesis process of p-toluenesulfonyl chloride, wherein chlorosulfonic acid and a mixed sulfonation auxiliary agent are added into a glass reactor; dropwise adding toluene for three times, and keeping the temperature for 2 hours after dropwise adding; then cooling, vacuum filtering, solvent extracting, crystallizing and drying the reaction liquid to obtain the p-toluenesulfonyl chloride. CN102408364A discloses a preparation method of p-toluenesulfonyl chloride, which comprises reacting ammonium p-toluenesulfonate with bis (trichloromethyl) carbonate (commonly known as triphosgene) in an inert organic solvent under the condition of taking organic base as a catalyst to synthesize the p-toluenesulfonyl chloride. CN201520995039 reports a production system of paratoluensulfonyl chloride, which comprises a sulfonation reaction kettle, a decomposition reaction kettle and a product post-treatment system which are connected in sequence, and the mode of connecting the reaction kettles in series does not solve the problems of control, continuity, yield and waste acid in the production process, and even can not realize automation.
The process or production system disclosed in the above-mentioned document can only be perfected on the basis of conventional processes without substantial technical progress. CN101195593 discloses a process for producing alkyl benzene sulfonyl chloride by sulfonating with sulfur trioxide and alkylbenzene as diluent to obtain alkyl benzene sulfonic acid, and then sulfochlorination with chlorosulfonic acid. The production process actually divides one-step chemical reaction into two steps, particularly separates sulfones substances and polysulfonates generated in the sulfonation process of sulfur trioxide, the intermediate process is complicated, the recovery and separation process of the diluent is long, the yield is low, and the problems of difficult realization of accurate control and pollution are not effectively solved due to the structural characteristics of the tubular reactor.
As is known from the reaction mechanism of sulfonation and chlorosulfonation, the sulfonation and chlorosulfonation processes of toluene are closely related. Toluene is first sulfonated by sulfonating agent (sulfonating agent can be sulfur trioxide, high-concentration sulfuric acid or fuming sulfuric acid, chlorosulfonic acid) to produce p-toluenesulfonic acid, and then sulfochlorinated by chlorosulfonic acid to produce p-toluenesulfonyl chloride. The p-toluenesulfonic acid can also react with phosgene, thionyl chloride, phosphorus oxychloride, phosphorus pentachloride and the like to prepare p-toluenesulfonyl chloride. The disadvantages of these methods are: (I) Phosgene in the phosgene method is a highly toxic gas, so that the use is unsafe and the cost of the raw material of thionyl chloride is high; (2) The thionyl chloride process produces sulfur dioxide by-products that pollute the environment; (3) The phosphorous acid or phosphoric acid which is a byproduct generated by a phosphorus oxychloride method or a phosphorus pentachloride method is difficult to remove, and the quality of the product is influenced. In fact, these acid chlorination reactions are only used in the preparation of the particular case.
The microchannel reactor is a new type of miniaturized continuous flow pipeline reactor, a three-dimensional structural element that can be used for carrying out chemical reactions, manufactured in a solid matrix by means of special microfabrication techniques. The microchannels in the reactor are fabricated by precision machining techniques, typically with feature sizes between 10 and 1000 microns, with channel diversity. Fluids flow in these channels and the desired chemical reactions take place in these channels. The microchannel reactor has a very large specific surface area/volume ratio in the aspect of the design of a microstructure, so that a great mass and heat transfer capacity is generated, and the fundamental advantages brought by the very high heat exchange efficiency and mixing efficiency are that the reaction temperature and the proportion of reaction materials can be accurately controlled, and instantaneous mixing is realized, which are key factors for improving the yield, selectivity and safety and improving the product quality.
In recent years, a great deal of research is carried out at home and abroad, and the microchannel reactor technology is rapidly developed, so that the microchannel reactor technology is more and more applied to process research and development and industrial production. The microchannel reactor has incomparable characteristics in organic synthesis with the traditional reactor, the reaction temperature, the reaction time, the material proportion and the mass transfer rate can be accurately controlled, the structure is safe, and the operability is good (the microreactor technology)Application in organic Synthesis "chemical reagents", volume 29, sixth 2007, 6 months, p 339). Particularly in the field of fine chemical industry, the potential application prospect of the method has been widely accepted by academia and business circles (application of microreactor technology in fine chemical industry, volume 32, 2006, first stage). Chen Yan et al studied the sulfonation of toluene with sulfur trioxide in a microchannel reactor to prepare p-toluenesulfonic acid, and studied the influence of various reaction conditions on the reaction results (toluene liquid phase SO in microreactor) 3 Study on sulfonation process "chemical reaction engineering and Process", volume 29, third stage 2013, page 253).
Disclosure of Invention
The technical problem to be solved by the invention is to provide a process for preparing paratoluensulfonyl chloride by performing continuous chlorosulfonation of toluene by using sulfur trioxide and chlorosulfonic acid in a microchannel reactor (hereinafter referred to as a microreactor).
In order to solve the technical problems, the invention provides a method for continuously synthesizing paratoluensulfonyl chloride, which takes methylbenzene as a reaction raw material:
1) Toluene, sulfur trioxide, chlorosulfonic acid, organic alkali and a solvent are mixed in a first static mixer and then pumped into a first microreactor for reaction (sulfonation reaction) under the action of a constant flow pump I;
the reaction temperature in the first micro-reactor is 10-60 ℃, and the reaction time is 10-35 minutes;
2) The first reaction mixture discharged from the outlet of the first microreactor flows into a second static mixer, is mixed with sulfur trioxide, chlorosulfonic acid, low-carbon chain fatty acid and a solvent which are respectively pumped into the second static mixer in the second static mixer, and the obtained mixed material is pumped into the second microreactor to react (sulfonation and chlorosulfonation reactions) under the action of a constant flow pump II;
the reaction temperature of the second micro-reactor is 20-60 ℃, and the reaction time is 10-40 minutes;
toluene: (sulfur trioxide entering the first microreactor + sulfur trioxide entering the second microreactor): (chlorosulfonic acid entering the first microreactor + chlorosulfonic acid entering the second microreactor): organic bases: low-carbon fatty acid =1, 0.8-1.5: 0.8 to 1.5:0.018 to 0.022, and the molar ratio is between 0.18 and 0.22;
sulfur trioxide entering the first microreactor: the molar ratio of sulfur trioxide entering the second microreactor is = (1.5 +/-0.1) to 1;
chlorosulfonic acid entering the first microreactor: chlorosulfonic acid entering the second microreactor is in a molar ratio of (1 +/-0.1) of 1;
3) And cooling, crystallizing and separating the secondary reaction mixture discharged from the second microreactor to obtain the p-toluenesulfonyl chloride as a product.
In the invention, a mixture of sulfur trioxide (liquid) and chlorosulfonic acid is used as a chlorosulfonation reagent, low-carbon chain fatty acid is used as a sulfone inhibitor, and organic alkali is used as a sulfonation reaction positioning catalyst, and the positioning catalyst aims to reduce the generation of o-toluenesulfonyl chloride as a byproduct as much as possible. The reaction of the first microreactor and the reaction of the second microreactor are carried out simultaneously in practice.
As an improvement of the process for the continuous synthesis of p-toluenesulfonyl chloride of the present invention:
the organic alkali is any one of the following: piperazine, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, melamine, pyridine, dodecylanilinomethylammonium chloride; preferably pyridine;
the low-carbon chain fatty acid is any one of the following: acetic acid, propionic acid, isopropanoic acid, chloroacetic acid, trifluoroacetic acid; acetic acid and trifluoroacetic acid are preferred.
As a further improvement of the process for the continuous synthesis of p-toluenesulfonyl chloride of the present invention:
the sum of the solvent entering the first micro-reactor and the solvent entering the second micro-reactor is defined as the total solvent, and 200-300 ml of the total solvent is used for every 1mol of toluene;
the solvent is any one of the following solvents: dichloromethane, trichloromethane, 1,2-dichloroethane.
As a further improvement of the process for the continuous synthesis of p-toluenesulfonyl chloride of the present invention:
the temperature in the first static mixer is less than or equal to minus 5 ℃ (generally minus 10 ℃ to minus 5 ℃);
the temperature in the second static mixer is less than or equal to 25 ℃ (generally 10 ℃ -25 ℃).
As a further improvement of the process for the continuous synthesis of p-toluenesulfonyl chloride of the present invention:
preferably, the method comprises the following steps:
the reaction temperature in the first micro-reactor is 20-40 ℃, and the reaction time is 20-33 minutes;
the reaction temperature in the second micro-reactor is 40-60 ℃, and the reaction time is 23-39 minutes;
toluene: (sulfur trioxide entering the first microreactor + sulfur trioxide entering the second microreactor): (chlorosulfonic acid entering the first microreactor + chlorosulfonic acid entering the second microreactor): organic bases: low-chain fatty acid =1:1 to 1.2:0.9 to 1.0:0.018 to 0.022, and the molar ratio is between 0.18 and 0.22;
as further preferred:
the reaction temperature in the first microreactor is 25 ℃, and the reaction time is 20 minutes;
the reaction temperature in the second microreactor is 40 ℃, and the reaction time is 23 minutes;
toluene: (sulfur trioxide entering the first microreactor + sulfur trioxide entering the second microreactor): (chlorosulfonic acid entering the first microreactor + chlorosulfonic acid entering the second microreactor): organic bases: low-chain fatty acids =1:1.01:1.0:0.02:0.2.
as a further improvement of the process for the continuous synthesis of p-toluenesulfonyl chloride of the present invention:
the secondary reaction mixture discharged by the second microreactor is cooled to 0-5 ℃ in a material cooling pipeline, then enters a constant-temperature static collector, water (the water temperature is less than or equal to 5 ℃) is added into the constant-temperature static collector, so that the crude tosyl chloride is separated out in a crystallization state, and finally, the crude tosyl chloride is filtered and separated in a tubular filter; the filter cake is crude p-toluenesulfonyl chloride.
The filtrate is solvent, dilute sulfuric acid and a small amount of residual solute (such as o-toluenesulfonyl chloride as a byproduct, low-carbon chain fatty acid as a sulfone inhibitor, organic base as a chlorosulfonation reaction positioning catalyst and the like).
As a further improvement of the process for the continuous synthesis of p-toluenesulfonyl chloride of the present invention:
the device for synthesizing the paratoluensulfonyl chloride comprises a first microreactor and a second microreactor which are connected in series, and the pipe diameters of the first microreactor and the second microreactor are both 100-1000 microns.
The liquid holdup (volume of the contained liquid) of the first microreactor is about 5-20 ml, and the channel length is about 5000-20000 mm;
the liquid holdup of the second microreactor is about 10-40 ml, and the channel length is about 10000-30000 mm.
The method has the advantages of continuous production, realization of accurate control of reaction temperature, reaction time and reaction material proportion, great improvement of production efficiency, effective solution of the problem that a large amount of sulfone and polysulfonate are easily generated by sulfonation of sulfur trioxide due to the addition of the sulfone inhibitor, and avoidance of generation of hydrogen chloride gas.
The invention adopts a micro-reactor to carry out reaction and has the following characteristics: the material flow in the channel is turbulent flow, the mass transfer efficiency is high, the specific surface area is large, the heat transfer capacity is strong, the reaction conditions such as reaction temperature, reaction time, material proportion and the like can be accurately controlled, the process is continuous and automatic, and the multiple amplification can be realized without amplification effect. The microreactor adopted by the invention has a structural design of efficient mass transfer and heat transfer, can ensure that chlorosulfonation reaction materials are fully mixed in a very short time and a very small space to reach a set temperature, and react under the optimal condition, so that side reactions (inhibiting the generation of 'sulfone substances' and 'polysulfonate substances') are inhibited to the maximum extent, and the microreactor can not cause the aggravation of local overheating side reactions and has no possibility of flammability and explosiveness. Under the reaction condition set by the invention, due to the addition of sulfur trioxide, hydrogen chloride gas generated by trace decomposition or reaction of trace hydrogen trioxide and toluene is absorbed by sulfur trioxide and becomes chlorosulfonic acid again, so that the use of chlorosulfonic acid can be close to the theoretical amount, the product yield is high, the quality is good, the output of waste acid can be greatly reduced, and the automatic production is easy to realize. These characteristics are not comparable to those of conventional tube reactors and tank reactors.
Description of the drawings: the hydrogen chloride gas is generated when chlorosulfonic acid is used for sulfonating toluene, and sulfur trioxide exists while the hydrogen chloride gas is generated, so that the hydrogen chloride gas can be absorbed by the sulfur trioxide. The prior art has no process for simultaneously using sulfur trioxide and chlorosulfonic acid, and the process usually uses sulfur trioxide for sulfonation firstly and then uses chlorosulfonic acid for acyl chlorination after sulfonation.
In the invention process, the following technical points are fully considered:
1. sulfur trioxide and chlorosulfonic acid enter the microchannel reactor at the same time; the advantages are that: because the reactivity of sulfur trioxide is higher than chlorosulfonic acid, chlorosulfonic acid can be regarded as sulfur trioxide's diluent, reduce sulfur trioxide's reactivity, and the inhibitor (lower fatty acid) of sulfone class material is added in addition, can effectively prevent the production of sulfone class material and polysulfonate, and simultaneously, sulfur trioxide can effectively absorb the hydrogen chloride gas that produces because of chlorosulfonic acid micro-decomposition or micro-reaction, makes it become chlorosulfonic acid again, just can accomplish in the process not produce hydrogen chloride gas:
SO 3 +HCl→HSO 3 Cl
2. the first micro-reactor is used for carrying out a chemical reaction which mainly comprises a sulfonation reaction, and in the sulfonation reaction in which sulfur trioxide participates, the generation of sulfone substances is the most main side reaction, and the problem of inhibiting the generation of sulfone substances is the core problem. Therefore, when the catalyst enters the first microreactor, the molar quantity of sulfur trioxide is far less than that of toluene, and the sulfur trioxide is not enough to generate sulfone substances, so that the production of the sulfone substances and polysulfonate substances is effectively inhibited;
at the outlet of the first microreactor, the reacted mixture enters a second static mixer, is mixed with sulfur trioxide, chlorosulfonic acid and a sulfone inhibitor and then enters a second microreactor, the sulfur trioxide continues to sulfonate toluene in the second microreactor to generate p-toluenesulfonic acid, and at the moment, the sulfone inhibitor plays a role; at the same time, p-toluenesulfonic acid reacts with chlorosulfonic acid to form p-toluenesulfonyl chloride (this reaction does not produce hydrogen chloride gas).
3. The invention is to continuously feed materials;
sulphur trioxide sulfonation under specific reaction conditions, such as: under the most suitable conditions of mass transfer, heat transfer, reaction temperature and catalyst, the amount of sulfur trioxide can be close to the theoretical amount, namely, the ratio of toluene: sulfur trioxide =1:1 (molar ratio), and the invention creates the most suitable reaction conditions in the microreactor.
As can be seen from the preferred examples, the molar ratio of toluene to sulfur trioxide is: 1:1.01 and the 0.01 mole excess is actually used to absorb hydrogen chloride gas.
The invention solves the technical problem which puzzles the industry for years; compared with the prior art, the invention has the following technical advantages:
1. the continuous production of the tosyl chloride is realized by taking a mixture of sulfur trioxide and chlorosulfonic acid as a chlorosulfonating agent and adopting a continuous feeding mode in the presence of a catalyst, the accurate control of reaction temperature, reaction time and reaction material ratio can be realized, the product yield is obviously improved (up to 95.38 percent in terms of methylbenzene), the product quality is stable, and the content of impurities is obviously reduced. The process has the characteristics of continuous and automatic production.
2. The proper nitrogenous organic compound is selected as the catalyst (preferably pyridine and tetraethylammonium chloride), the positioning catalysis effect is good, the catalyst can completely replace the existing ammonium chloride or ammonium sulfate, and the usage amount is only 0.5-1% of the existing catalyst ammonium chloride or ammonium sulfate. The low-carbon chain fatty acid substances are selected as inhibitors of the sulfone substances, so that the generation of the sulfone substances is effectively inhibited in the reaction process; the subsequent separation and purification process can be greatly simplified.
3. The addition of sulfur trioxide absorbs trace hydrogen chloride gas generated by trace decomposition of chlorosulfonic acid, no hydrogen chloride is generated in the whole production process, and the technical process and equipment for absorbing the hydrogen chloride gas are omitted; greatly simplifying the subsequent separation and purification process and equipment.
4. Greatly reduces the consumption of raw materials, shortens the production process flow, reduces a large amount of production equipment, and further reduces the production cost.
5. Reduces the environmental pollution and improves the operation environment.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a process flow diagram of a microchannel reactor for continuously preparing paratoluensulfonyl chloride.
FIG. 2 is a schematic view of a channel plate installation of the microchannel reactor of FIG. 1;
FIG. 3 is a schematic view of side A of the microchannel reactor channel plate of FIG. 2;
FIG. 4 is a schematic view of the side B of the microchannel reactor channel plate of FIG. 2;
FIG. 5 is a schematic drawing of the outlet of the second microreactor of FIG. 1 to a temperature reduction conduit (material cooling conduit) connected to a thermostated static collector;
FIG. 6 is a schematic view of the candle filter of FIG. 1;
fig. 7 is a schematic view of the static mixer of fig. 1.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
an example of the apparatus, an apparatus for synthesizing p-toluenesulfonyl chloride, is shown in fig. 1 to 7, and comprises a first static mixer, a first microreactor, a second static mixer, a second microreactor, a constant-temperature static collector, and a tubular filter;
the outlet of the first static mixer is provided with a constant flow pump I, and the outlet of the second static mixer is provided with a constant flow pump II; the outlet of the first micro-reactor is provided with a first one-way valve, and the outlet of the second micro-reactor is provided with a second one-way valve; the first check valve is used for ensuring that the material can only flow from the first microreactor to the second static mixer and can not flow reversely;
toluene, sulfur trioxide, chlorosulfonic acid and a solvent containing a catalyst (chlorosulfonation reaction positioning catalyst), wherein reservoirs of the 4 are respectively connected with a feed inlet of the first static mixer through respective metering pumps;
the reservoirs of the 3 sulfur trioxide, the chlorosulfonic acid and the solvent containing the inhibitor are respectively connected with the feed inlet of the second static mixer through respective metering pumps;
the outlet of the first static mixer, the first constant flow pump, the first microreactor, the first check valve and the inlet of the second static mixer are sequentially connected, and the outlet of the second static mixer, the second constant flow pump, the second microreactor, the second check valve, the material cooling pipeline and the inlet of the constant-temperature static collector are sequentially connected;
the inlet of the constant-temperature static collector is positioned at the top of the constant-temperature static collector (namely, an upper inlet), the top of the constant-temperature static collector is also provided with a water feeding hole for adding dilution water, and the bottom of the constant-temperature static collector is provided with an outlet (namely, a lower outlet);
the outlet of the constant-temperature static collector, the feed delivery pump and the tubular filter are connected in sequence;
the constant temperature static collector is about 10 to 15 times of the volume of the second micro-reactor channel.
The first microreactor and the second microreactor are conventional microreactors, and specifically comprise the following components: FIGS. 3 and 4 show two faces A, B of microchannel plates made of silicon carbide material in a microreactor. In use, the microchannel plate is positioned with face A facing face A of the other microchannel plate and face B facing face B of the other microchannel plate. The material flows throughbase:Sub>A micro-channel formed on the surface A-A to carry out chemical reaction; the temperature control liquid flows in the channel formed by the B-B surface, so that the temperature of the material in the channel of the A-A surface is controlled. The temperature control liquid used in the invention is: diethylene glycol dimethyl ether.
The total length ofbase:Sub>A reaction channel (namely,base:Sub>A microchannel formed on the surface A-A) of the first microreactor is 10000-30000 mm, and the pipe diameter is 100-1000 microns; the total length of the reaction channel of the second micro-reactor (i.e. the micro-channel formed by the A-A surface) is 20000-40000 mm, and the pipe diameter is 100-1000 microns.
The material of the material cooling pipeline is 316L stainless steel, and the length and the pipe diameter can be set according to the cooling requirement, for example, the length is about 50cm, and the pipe diameter is about 1 mm.
During actual work:
1) Toluene, sulfur trioxide, chlorosulfonic acid and a solvent containing a catalyst (sulfonation reaction positioning catalyst) are mixed in a first static mixer and then injected into a first microreactor by a first constant flow pump to carry out sulfonation reaction;
2) The reaction product (i.e. the first reaction mixture) obtained by the first microreactor flows into a second static mixer, and is mixed with sulfur trioxide, chlorosulfonic acid and an inhibitor-containing solvent which are pumped into the second static mixer by means of respective metering pumps; injecting the obtained mixed material into a second microreactor by using a constant flow pump II to continue sulfonation and chlorosulfonation reactions;
3) And the reaction product obtained by the second micro-reactor flows into a material cooling pipeline for cooling, and the cooled reaction product (with the temperature of about 0-5 ℃) enters a post-treatment process (comprising cooling, crystallization and separation), and the method comprises the following specific steps:
the cooled reaction product enters a constant-temperature static collector, and water (the water temperature is less than or equal to 5 ℃) is added into the constant-temperature static collector from a feed inlet of the constant-temperature static collector; the crude tosyl chloride is separated out in a crystallization state, and a solid-liquid mixture discharged from the constant temperature static collector enters a tubular filter for filtration and separation; the filter cake is a crude product of p-toluenesulfonyl chloride, and the filtrate is a solvent, dilute sulfuric acid and a small amount of residual solute (such as o-toluenesulfonyl chloride as a byproduct, low-carbon chain fatty acid as a sulfone inhibitor, organic base as a chlorosulfonation reaction positioning catalyst and the like).
The crude tosyl chloride can be purified by conventional solvent methods, which are conventional techniques and therefore not described in detail in the present invention.
Description of the drawings: in a second micro-reactor, chlorosulfonic acid and p-toluenesulfonic acid are subjected to sulfonyl chlorination reaction to generate sulfuric acid. After entering the thermostatic trap, the sulfuric acid, when added with water, remained as dilute sulfuric acid in the reaction mixture.
The following examples: the above example of the apparatus is used. And: the chlorosulfonic acid is industrial chlorosulfonic acid with the purity of 98 percent; the amount is calculated as 100%.
Example 1, a method for continuous synthesis of p-toluenesulfonyl chloride using a microreactor:
the feed rate to the first static mixer is shown in Table 1, and the feed rate in Table 1 refers to the amount of raw material entering the first static mixer. The batch meter entering the second static mixer, as described in table 2; the feed amounts in table 2 refer to the amount of feed entering the second static mixer.
Pyridine is selected as a sulfonation reaction positioning catalyst (catalyst for short), acetic acid (acetic acid) is selected as a sulfone inhibitor (inhibitor for short), and dichloromethane is selected as an organic solvent.
TABLE 1 batch meter into the first static mixer
| Name (R) | Molecular weight | Number of moles | Feed amount (g) |
| Toluene | 92.14 | 1 | 92.14 |
| Sulfur trioxide | 80.06 | 0.6 | 48.00 |
| Chlorosulfonic acid (100%) | 116.52 | 0.5 | 58.26 |
| Pyridine compound | 79.10 | 0.02 | 1.58 |
| Methylene dichloride | 135.4ml (about 180.10 g) |
TABLE 2 batch meter entering the second static mixer
| Name (R) | Molecular weight | Number of moles | Feed amount (gram) |
| Toluene | 92.14 | 0 | 0 |
| Sulfur trioxide | 80.06 | 0.41 | 32.8 |
| Chlorosulfonic acid (100%) | 116.52 | 0.50 | 58.26 |
| Acetic acid | 46.05 | 0.2 | 9.21 |
| Methylene dichloride | 99.6ml(132.50g) |
The method comprises the following specific steps:
1) 0.02mol of pyridine is dissolved in 135.4ml of dichloromethane to be used as a solvent containing the catalyst;
according to the weight ratio of toluene: sulfur trioxide: chlorosulfonic acid: pyridine =1:0.6, 0.02, feeding toluene, sulfur trioxide, chlorosulfonic acid, and a catalyst-containing solvent into a first static mixer by respective metering pumps to mix, wherein the temperature in the first static mixer is not higher than-5 ℃ (generally-10 ℃ to-5 ℃);
injecting the mixed material flowing out of the outlet of the first static mixer into a first microreactor by a constant flow pump at 1.0 ml/min for toluene sulfonation reaction, wherein the retention volume of the first microreactor is about 20ml, and the residence time (reaction time) of the mixed material in the first microreactor is about 20 minutes; controlling the reaction temperature in the first microreactor to be 25 ℃; an outlet of the first microreactor discharges a primary reaction mixture; the first reaction mixture consists essentially of toluene, chlorosulfonic acid, p-toluenesulfonic acid, and a solvent, at which time sulfur trioxide has been substantially consumed;
2) The first reaction mixture discharged by the first microreactor enters a second static mixer after passing through a one-way valve I; when the first reaction mixture appeared in the second static mixer, the injection of the reaction starting materials listed in table 2 into the second static mixer was started.
Dissolving 0.2mol of acetic acid in 99.6ml of dichloromethane to serve as a solvent containing an inhibitor;
according to sulfur trioxide: chlorosulfonic acid: acetic acid =0.41, 0.5, and sulfur trioxide, chlorosulfonic acid, and the inhibitor-containing solvent are fed into a second static mixer by respective metering pumps to mix with the first reaction mixture flowing out of the first microreactor; controlling the temperature in the second static mixer to be not higher than 25 ℃ (generally 10 ℃ to 25 ℃);
the reaction raw materials in table 1 and table 2 were fed for the same time; namely, control of toluene: (sulfur trioxide entering the first microreactor + sulfur trioxide entering the second microreactor): (chlorosulfonic acid entering the first microreactor + chlorosulfonic acid entering the second microreactor): pyridine as a catalyst: acetic acid as inhibitor =1: (0.6+0.41): (0.5+0.5): 0.02:0.2=1:1.01:1:0.02:0.2.
injecting the mixed material flowing out of the outlet of the second static mixer into a second microreactor by a constant flow pump II at a rate of 1.50 ml/min to continue sulfonation and chlorosulfonation reactions, wherein the retention volume of the second microreactor is about 35ml; thus, the residence time (reaction time) of the mixed mass in the second microreactor is about 23 minutes; controlling the reaction temperature in the second microreactor to be 40 ℃;
an outlet of the second microreactor discharges the secondary reaction mixture; the secondary reaction mixture mainly comprises a solvent, p-toluenesulfonic acid as a main product, sulfuric acid, o-toluenesulfonyl chloride as a byproduct, residual low-carbon chain fatty acid (used as a sulfone inhibitor) and organic base (used as a sulfonation reaction positioning catalyst).
4) And after the secondary reaction mixture discharged from the outlet of the second microreactor passes through a material cooling pipeline, the temperature is reduced to 0-5 ℃, and then the secondary reaction mixture enters a constant-temperature static collector. And (3) injecting water into the constant-temperature static collector, wherein the time for injecting the water into the constant-temperature static collector is equal to the time for the secondary reaction mixture to enter the constant-temperature static collector. The added water for dilution is about 400ml (the water temperature is less than or equal to 5 ℃).
The diluted reaction mixture is detected to have the total content of 99 g of sulfuric acid, so that the invention realizes that the production amount of waste acid is reduced to be close to the theoretical amount (the theoretical amount is 98.12 g).
Pumping the diluted reaction mixture into a tubular filter by a delivery pump positioned at the bottom of a constant-temperature static collector for filtering, wherein a filter cake is a crude product of the tosyl chloride, and analyzing by capillary gas chromatography: purity of p-toluenesulfonyl chloride 98.86%, yield: 95.38 percent.
The filtrate is solvent, dilute sulphuric acid and a small amount of residual solute (such as o-toluenesulfonyl chloride, low-carbon chain fatty acid used as sulfone inhibitor, organic base used as sulfonation reaction positioning catalyst and the like).
Examples 2 to 5
The catalyst in example 1 was replaced with pyridine respectively: piperazine, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride; the molar amount remains constant, still 0.02mol, the remainder being equivalent to example 1.
Example 6, the use of the catalyst in example 1 was eliminated, and the rest was the same as example 1.
The results obtained are shown in table 3 below:
TABLE 3
| Examples | Catalyst and process for preparing same | Molar ratio of | Input amount (g) | Yield% | Purity% |
| 2 | Piperazine derivatives | 0.02 | 1.72 | 95.20 | 98.33 |
| 3 | Tetramethylammonium chloride | 0.02 | 2.19 | 94.69 | 98.45 |
| 4 | Tetraethyl ammonium chloride | 0.02 | 3.31 | 94.55 | 98.45 |
| 5 | Tetrabutyl ammonium chloride | 0.02 | 5.56 | 94.03 | 98.36 |
| 6 | Blank space | 85.15 | 92.66 |
Examples 7 to 10
The inhibitor in example 1 is replaced by trifluoroacetic acid, propionic acid, isopropyl acid and chloroacetic acid respectively, the molar amount is kept unchanged and is still 0.2mol, and the rest is equal to example 1.
Example 11, the use of the inhibitor in example 1 was eliminated, and the rest was identical to example 1.
The results obtained are shown in table 4 below:
TABLE 4
| Examples | Inhibitors | Molar ratio of | Input amount (g) | Yield% | Purity% |
| 7 | Trifluoroacetic acid | 0.2 | 22.8 | 95.28 | 98.36 |
| 8 | Propionic acid | 0.2 | 14.8 | 94.36 | 98.06 |
| 9 | Isopropionic acid | 0.2 | 14.8 | 93.69 | 98.00 |
| 10 | Chloroacetic acid | 0.2 | 18.9 | 93.66 | 98.00 |
| 11 | Blank space | 88.00 | 91.36 |
Examples 12 to 15
The molar ratio of toluene to sulfur trioxide in example 1 was changed from 1.01 to the following table 5, respectively, with the amount of toluene remaining unchanged, and the amounts of sulfur trioxide entering the first static mixer and sulfur trioxide entering the second static mixer were specifically set forth in table 5 below; the rest is equivalent to example 1.
The results obtained are shown in Table 5 below:
TABLE 5
Examples 16 to 19
The molar ratio of toluene to chlorosulfonic acid in example 1 was changed from 1:1 to the following table 6, respectively, with the amount of toluene being kept constant, and the amounts of chlorosulfonic acid entering the first static mixer and chlorosulfonic acid entering the second static mixer being specifically set forth in table 6 below; the rest is equivalent to embodiment 1.
The results obtained are shown in Table 6 below:
TABLE 6
Note: examples 16 and 17 have the defects that the generation of hydrogen chloride gas forms gaps in the channels of the microreactor, the normal turbulent flow state is influenced, and the yield and the purity are obviously reduced.
Chlorosulfonic acid and toluene produce hydrogen chloride gas during sulfonation. In the invention, the designed reaction condition of the first microreactor is the optimal condition of sulfonation reaction of sulfur trioxide and toluene, the sulfonation reaction is preferentially carried out, and the reaction amount of chlorosulfonic acid is extremely low under the condition; however, when the concentration ratio of chlorosulfonic acid is greatly increased, the sulfonation reaction of chlorosulfonic acid and toluene is also aggravated, the generated hydrogen chloride gas is greatly increased, sulfur trioxide in the system cannot absorb excessive hydrogen chloride, and the hydrogen chloride gas can cause a gap in the microreactor to influence the reaction result.
Examples 20 to 23
The reaction temperature in the first microreactor, the temperature in the second static mixer, and the reaction temperature in the second microreactor were varied and the rest were identical to those of example 1.
The results obtained are shown in Table 7 below:
TABLE 7
Examples 24 to 25
The residence time of the material in the microreactors was varied by varying the feed rates of the first and second microreactors, and the rest was identical to example 1.
The results obtained are shown in Table 8 below:
TABLE 8
Example 26, the solvent in example 1 was changed from dichloromethane to chloroform or 1,2-dichloroethane, and the volume and amount were kept the same, the result was substantially the same as example 1.
Comparative example 1, referring to the manner of using "sulfur trioxide, chlorosulfonic acid" in sequence in the prior art:
1.01mol of sulfur trioxide is completely added into a first microreactor to react, namely, the amount of the sulfur trioxide added into a second microreactor is 0; and 1mol of chlorosulfonic acid is completely fed into a second microreactor for reaction, namely, the amount of chlorosulfonic acid fed into a first microreactor is 0; the residence time of the reaction mass in the first and second microreactors was substantially equivalent to that of example 1. The rest is equivalent to example 1.
The results obtained were: yield of product p-toluenesulfonyl chloride: 75.21% and 81.00% pure. And the defects of very disordered reaction products and great separation difficulty exist.
Comparative example 2: 1.00mol of toluene, 1.01mol of sulfur trioxide, 1mol of chlorosulfonic acid, 235ml of methylene chloride, 1.58g (0.02 mol) of pyridine and 9.2g (0.2 mol) of acetic acid are all fed to a first static mixer, the mixture obtained enters a first microreactor via a constant flow pump at a flow rate of 1 ml/min, the reaction mixture enters a second microreactor directly without passing through a second static mixer, so that the reaction time in the first microreactor is about 20 minutes and the reaction time in the second microreactor is about 35 minutes. The rest is equivalent to embodiment 1.
The results obtained were: yield of product p-toluenesulfonyl chloride: 65.21%, purity: 71.00 percent. And the defects of very disordered reaction products and great separation difficulty exist.
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (6)
1. The method for continuously synthesizing the paratoluensulfonyl chloride takes methylbenzene as a reaction raw material and is characterized in that:
the device for synthesizing the paratoluensulfonyl chloride comprises a first microreactor and a second microreactor which are connected in series, wherein the pipe diameters of the first microreactor and the second microreactor are both 100-1000 micrometers;
the method comprises the following steps:
1) Toluene, sulfur trioxide, chlorosulfonic acid, organic alkali and a solvent are mixed in a first static mixer and then pumped into a first microreactor for reaction under the action of a constant flow pump I;
the reaction temperature in the first micro-reactor is 10-60 ℃, and the reaction time is 10-35 minutes;
2) The first reaction mixture discharged from the outlet of the first microreactor flows into a second static mixer, is mixed with sulfur trioxide, chlorosulfonic acid, low-carbon chain fatty acid and a solvent which are respectively pumped into the second static mixer in the second static mixer, and the obtained mixed material is pumped into a second microreactor for reaction under the action of a constant flow pump II;
the reaction temperature of the second micro-reactor is 20-60 ℃, and the reaction time is 10-40 minutes;
toluene: the sum of the amounts of sulfur trioxide entering the first microreactor and sulfur trioxide entering the second microreactor: the sum of the dosage of chlorosulfonic acid entering the first microreactor and the dosage of chlorosulfonic acid entering the second microreactor is as follows: organic bases: low-carbon fatty acid =1, 0.8-1.5: 0.8 to 1.5:0.018 to 0.022, and the molar ratio is between 0.18 and 0.22;
sulfur trioxide entering the first microreactor: sulfur trioxide entering the second microreactor at a molar ratio of =1.5 ± 0.1;
chlorosulfonic acid entering the first microreactor: chlorosulfonic acid =1:1 ± 0.1 molar ratio entering the second microreactor;
in the above step 1) and step 2): the organic alkali is any one of the following: piperazine, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, melamine, pyridine, dodecylanilinomethylammonium chloride;
the low-carbon chain fatty acid is any one of the following: acetic acid, propionic acid, isopropyl acid, chloroacetic acid, trifluoroacetic acid
3) And cooling, crystallizing and separating the secondary reaction mixture discharged from the second microreactor to obtain the p-toluenesulfonyl chloride as a product.
2. The process for the continuous synthesis of paratoluensulfonyl chloride according to claim 1, characterized in that:
the sum of the solvent entering the first micro-reactor and the solvent entering the second micro-reactor is defined as the total solvent, and 200-300 ml of the total solvent is used for every 1mol of toluene;
the solvent is any one of the following solvents: dichloromethane, trichloromethane, 1,2-dichloroethane.
3. The process for the continuous synthesis of p-toluenesulfonyl chloride according to claim 2, characterized in that:
the temperature in the first static mixer is less than or equal to-5 ℃;
the temperature in the second static mixer is less than or equal to 25 ℃.
4. The process for continuously synthesizing paratoluensulfonyl chloride according to any one of claims 1 to 3, characterized in that:
the reaction temperature in the first micro-reactor is 20-40 ℃, and the reaction time is 20-33 minutes;
the reaction temperature in the second micro-reactor is 40-60 ℃, and the reaction time is 23-39 minutes;
toluene: the sum of the amounts of sulfur trioxide entering the first microreactor and sulfur trioxide entering the second microreactor: the sum of the dosage of chlorosulfonic acid entering the first microreactor and the dosage of chlorosulfonic acid entering the second microreactor is as follows: organic bases: low-chain fatty acid =1: 1-1.2: 0.9 to 1.0:0.018 to 0.022, and a molar ratio of between 0.18 and 0.22.
5. The process for the continuous synthesis of paratoluensulfonyl chloride according to claim 4, characterized in that:
the reaction temperature in the first microreactor is 25 ℃, and the reaction time is 20 minutes;
the reaction temperature in the second microreactor is 40 ℃, and the reaction time is 23 minutes;
toluene: the sum of the amounts of sulfur trioxide entering the first microreactor and sulfur trioxide entering the second microreactor: the sum of the dosage of chlorosulfonic acid entering the first microreactor and the dosage of chlorosulfonic acid entering the second microreactor is as follows: organic bases: low-chain fatty acid =1:1.01:1.0:0.02:0.2.
6. the process for continuously synthesizing paratoluensulfonyl chloride according to any one of claims 1 to 3, characterized in that:
the secondary reaction mixture discharged by the second microreactor is cooled to 0-5 ℃ in a material cooling pipeline, then enters a constant-temperature static collector, water is added into the constant-temperature static collector, so that the crude p-toluenesulfonyl chloride is separated out in a crystalline state, and finally, the crude p-toluenesulfonyl chloride is filtered and separated in a tubular filter; the filter cake is crude p-toluenesulfonyl chloride.
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