CN114713164A - Dibenzothiazole disulfide micro-reaction continuous synthesis system and synthesis method - Google Patents
Dibenzothiazole disulfide micro-reaction continuous synthesis system and synthesis method Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 75
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 34
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 34
- 238000001308 synthesis method Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 238000005516 engineering process Methods 0.000 claims abstract description 4
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 71
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 63
- 239000007788 liquid Substances 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
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- 239000000463 material Substances 0.000 claims description 3
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- 238000012986 modification Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- -1 alkali metal salt Chemical class 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
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- MACMAADVRVVHBD-VMPITWQZSA-N (e)-1-(2,4-dihydroxyphenyl)-3-(2-hydroxyphenyl)prop-2-en-1-one Chemical compound OC1=CC(O)=CC=C1C(=O)\C=C\C1=CC=CC=C1O MACMAADVRVVHBD-VMPITWQZSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229930186147 Cephalosporin Natural products 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229940124599 anti-inflammatory drug Drugs 0.000 description 1
- AHWQBWJRVSPPPB-UHFFFAOYSA-N azane;3h-1,3-benzothiazole-2-thione Chemical compound N.C1=CC=C2SC(=S)NC2=C1 AHWQBWJRVSPPPB-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
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- 229940124587 cephalosporin Drugs 0.000 description 1
- 150000001780 cephalosporins Chemical class 0.000 description 1
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- 238000003889 chemical engineering Methods 0.000 description 1
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- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- ZKTKNAXWCMIKLK-UHFFFAOYSA-M potassium;1,3-benzothiazole-2-thiolate Chemical compound [K+].C1=CC=C2SC([S-])=NC2=C1 ZKTKNAXWCMIKLK-UHFFFAOYSA-M 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/70—Sulfur atoms
- C07D277/76—Sulfur atoms attached to a second hetero atom
- C07D277/78—Sulfur atoms attached to a second hetero atom to a second sulphur atom
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The invention provides a dibenzothiazyl disulfide micro-reaction continuous synthesis system, which utilizes a micro-reaction technology to realize continuous synthesis of dibenzothiazyl disulfide under two reaction methods. In the whole micro-reaction system, the micro-mixer is used for strengthening the homogeneous mixing and the dispersion mass transfer of the gas phase and the liquid phase; the micro mixer is connected in series with a multi-layer rotating disc type reactor, so that enough reaction time is provided, higher raw material conversion rate is ensured, and the growth and curing of product particles are completed. Finally realizing the high-quality and high-efficiency production of the dibenzothiazyl disulfide.
Description
Technical Field
The invention relates to the technical field of chemical engineering, in particular to a dibenzothiazyl disulfide micro-reaction continuous synthesis system.
Background
Dibenzothiazyl disulfide, abbreviated as MBTS, is widely used as a vulcanization accelerator in rubber auxiliaries in industry. MBTS is used as a thiazole main accelerant and is used for producing rubber products for tires, rubber shoes and other non-food applications. The demand amount is about 8 ten thousand tons per year in China. High-purity MBTS is an important medical intermediate, is used for synthesizing AE-active ester, and is further used for producing cephalosporin anti-inflammatory drugs. The domestic market demand of the pharmaceutical grade MBTS is 5 ten thousand tons/year, and the method has important significance for industrial mass production.
Regarding the production process and method of dibenzothiazyl disulfide, some reports are made in domestic and foreign patents, and 2-mercaptobenzothiazole is mainly used as a raw material and is synthesized by oxidative coupling reaction by using different kinds of oxidants. The main reported oxidants include: nitrite (CN104592156), oxygen (CN108727296A), chlorine (US4482720), hydrogen peroxide (CN110590703A, CN103739570A), etc. The traditional industrial process is sodium nitrite, which consumes a large amount of acid and generates a large amount of salt and nitrogen oxides to pollute the environment. The oxidation reaction by using oxygen has long time and low efficiency, the tail oxygen treatment has potential safety hazard and catalyst residue exists in the product. The oxidation process using chlorine gas requires strict control of the pH value of the reaction system, excess chlorine gas easily generates peroxidated by-products, and generally the purity of the product obtained by the method is only 96%. Compared with the prior art, the hydrogen peroxide is safer to use as the oxidant, but because the hydrogen peroxide has high oxidation speed and large heat release, the existing industrial production generally adopts a dropwise feeding mode to feed, so that the reaction time is greatly prolonged, the production efficiency is low, the volume of a reaction tank is large, the equipment investment is high, and the stability of the product batch is poor.
The reaction method for synthesizing MBTS by applying the continuous synthesis system is divided into two types: one type of reaction environment is an aqueous solution, in which raw material MBT is dissolved in an alkaline aqueous solution such as sodium hydroxide, carbonate, etc., to form an alkali metal salt of MBT. Then reacting the alkali metal salt of the MBT with hydrogen peroxide, and introducing carbon dioxide to adjust the pH of the reaction system to 5-10, so that the generated MBTS is separated out from the aqueous solution (CN 110590703A); the other reaction environment is an alcohol solvent, MBT is dissolved in the alcohol solvent, and then hydrogen peroxide is added for reaction, and the generated MBTS is separated out from the alcohol solution (CN 108218810A).
The application of the micro-reaction technology to the synthesis of chemicals can improve the production efficiency and the controllability of reaction conditions. For the two reaction systems, the micro mixer in the micro reaction system can strengthen the mixing of homogeneous reaction liquid and the mass transfer of gas-liquid two phases, and improve the reaction efficiency. The mixed raw material liquid enters a reactor to generate MBTS which is crystallized and separated out, and the design of the reactor has the difficulty of solving the problem of sedimentation and blockage of particles and reducing back mixing as much as possible. The rotating disc type reactor is formed by matching a tubular reactor with a rotating shaft with a plurality of discs, has the characteristic of small back mixing, and is expected to achieve an ideal effect. The micro-mixer and the rotating disc type reactor are connected in series to form a micro-reaction continuous synthesis system of dibenzothiazyl disulfide, so that the production efficiency and the consistency of the product quality can be improved, and further, a plurality of problems in the batch production mode in the current industry are solved.
Disclosure of Invention
The invention aims to provide a dibenzothiazyl disulfide micro-reaction continuous synthesis system, which utilizes a micro-reaction technology to realize continuous synthesis of dibenzothiazyl disulfide under two reaction methods. In the whole micro-reaction system, the micro-mixer is used for strengthening the homogeneous mixing and the dispersion mass transfer of the gas phase and the liquid phase; the micro mixer is connected in series with a multi-layer rotating disc type reactor through a pipeline, so that enough reaction time is provided, higher raw material conversion rate is ensured, and the growth and curing of product particles are completed. Finally realizing the high-quality and high-efficiency production of the dibenzothiazyl disulfide.
In order to achieve the technical aim, the invention provides a dibenzothiazyl disulfide micro-reaction continuous synthesis system which comprises a feed pump, a micro mixer, a multilayer rotating disc type reactor, solid-liquid separation equipment and drying equipment. The micro-reaction continuous synthesis system also comprises a gas flow controller and a gas-liquid micro-disperser.
The method for synthesizing the dibenzothiazyl disulfide by adopting the micro-reaction continuous synthesis system and taking the aqueous solution as the reaction environment comprises the following steps:
firstly, mixing an aqueous solution of 2-mercaptobenzothiazole salt and a hydrogen peroxide solution in a micro mixer to form turbid mixed solution;
secondly, mixing the mixed liquid obtained in the first step with carbon dioxide gas in a gas-liquid micro-disperser to obtain a gas-liquid two-phase flow micro-dispersing system;
thirdly, the micro dispersion system obtained in the second step is subjected to 2-mercaptobenzothiazole oxidation through a multilayer rotating disc type stirring reactor, the pH value of the reaction system is controlled by adjusting the flow of carbon dioxide, and a solution is obtained at the outlet of the reactor;
and fourthly, filtering, washing and drying the solution obtained in the third step to obtain a solid product dibenzothiazyl disulfide.
Wherein the mass fraction of the 2-mercaptobenzothiazole salt in the aqueous solution of the 2-mercaptobenzothiazole salt is 1-30%; the mass fraction of the hydrogen peroxide is 0.01-10%, and the hydrogen peroxide is added according to the stoichiometric ratio of the hydrogen peroxide and the 2-mercaptobenzothiazole salt to synthesize the dibenzothiazyl disulfide, or the hydrogen peroxide is added within two times of the stoichiometric ratio.
The method for synthesizing the dibenzothiazyl disulfide by adopting the micro-reaction continuous synthesis system and taking the alcohol solvent as the reaction environment comprises the following steps:
firstly, mixing a 2-mercaptobenzothiazole alcohol solution and a hydrogen peroxide solution in a micro mixer to form a mixed solution;
secondly, the mixed solution obtained in the first step is subjected to 2-mercaptobenzothiazole oxidation through a multilayer rotating disc type stirring reactor, and a solution is obtained at the outlet of the reactor;
and thirdly, filtering, washing and drying the solution obtained in the second step to obtain a solid product dibenzothiazyl disulfide.
The mass fraction of the 2-mercaptobenzothiazole in the 2-mercaptobenzothiazole alcoholic solution is 1-30%; the mass fraction of the hydrogen peroxide is 0.01-30 percent; the molar ratio of the hydrogen peroxide to the 2-mercaptobenzothiazole is 0.5: 1-1: 1.
Aiming at the dibenzothiazyl disulfide micro-reaction continuous synthesis system under the two synthesis methods, the residence time of reactants in the multilayer rotating disc type reactor is 5-60 min, and the stirring speed is 50-500 rpm.
The multilayer rotating disc type reactor consists of a stirring shaft with a disc and a tubular reactor.
The invention has the advantages of
Compared with the traditional production process, the method realizes the rapid mixing of the 2-mercaptobenzothiazole salt, the 2-mercaptobenzothiazole alcohol solution and the hydrogen peroxide through the micro mixer, and inhibits side reactions caused by uneven mixing and overhigh local concentration of the hydrogen peroxide; the second micro mixer in series connection realizes the micro dispersion of gas phase and liquid phase and strengthens the mass transfer, and the pH of the reaction solution is adjusted to improve the selectivity of the main reaction and the stability of the hydrogen peroxide; the dibenzothiazyl disulfide is continuously synthesized by connecting a multi-layer rotating disc type reactor with a micro mixer in series and providing enough residence time. The invention provides a continuous synthesis system, which solves the problem of inconsistent batch production quality in the traditional stirred tank.
The invention has the advantages that:
(1) the reaction system adopts a continuous or semi-continuous production mode, so that the production efficiency is high;
(2) the volume of the reactor is obviously reduced, the potential safety hazard is reduced, and the equipment investment is reduced;
(3) the multi-layer rotating disc type reactor can provide enough reaction time and avoid solid blockage in continuous production, and high-yield and high-purity products are obtained.
Drawings
FIG. 1 a: the invention relates to a process flow chart of a micro-reaction method for synthesizing dibenzothiazyl disulfide by using an aqueous solution of 2-mercaptobenzothiazole salt; FIG. 1 b: the invention relates to a process flow chart of a micro-reaction method for synthesizing dibenzothiazyl disulfide by using an alcoholic solution of 2-mercaptobenzothiazole.
In FIG. 1 a: 1. 2-a feed pump; 3-gas flow controller; 4-micro mixer; 5-gas-liquid micro-disperser; 6-preheating pipeline; 7-temperature control device; 8-a multilayer rotating disc type stirring reactor with a heat exchange jacket; 9-solid-liquid separation equipment; 10-drying equipment; a-an aqueous solution of a 2-mercaptobenzothiazole salt; b-aqueous hydrogen peroxide solution; c-carbon dioxide; d-dibenzothiazyl disulfide; e-reaction mother liquor. In FIG. 1 b: a-an alcoholic solution of 2-mercaptobenzothiazole; the rest is the same as fig. 1 a.
Detailed Description
The invention provides a micro-reaction continuous synthesis system which comprises a feeding pump, a micro mixer, a multi-layer rotating disc type reactor, solid-liquid separation equipment and drying equipment. The micro-reaction continuous synthesis system also comprises a gas flow controller and a gas-liquid micro-disperser. The feeding pump, the micro mixer or the gas-liquid micro disperser and the multilayer rotating disc type reactor are connected in series through pipes, so that the reaction liquid is continuously conveyed.
The method for synthesizing the dibenzothiazyl disulfide by adopting the micro-reaction continuous synthesis system and taking the aqueous solution as the reaction environment comprises the following steps:
firstly, mixing an aqueous solution of 2-mercaptobenzothiazole salt and a hydrogen peroxide solution in a micro mixer to form turbid mixed solution;
secondly, mixing the mixed liquid obtained in the first step with carbon dioxide gas in a gas-liquid micro-disperser to obtain a gas-liquid two-phase flow micro-dispersing system;
thirdly, the micro dispersion system obtained in the second step is subjected to 2-mercaptobenzothiazole oxidation through a multilayer rotating disc type stirring reactor, the pH value of the reaction system is controlled by adjusting the flow of carbon dioxide, and a solution is obtained at the outlet of the reactor;
and fourthly, filtering, washing and drying the solution obtained in the third step to obtain a solid product dibenzothiazyl disulfide.
The 2-mercaptobenzothiazole salt aqueous solution comprises: the 2-mercaptobenzothiazole sodium salt, the 2-mercaptobenzothiazole potassium salt and the 2-mercaptobenzothiazole ammonium salt can be obtained by mixing and dissolving 2-mercaptobenzothiazole, a sodium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium hydroxide aqueous solution and a potassium carbonate aqueous solution with an ammonia aqueous solution.
The mass fraction of the 2-mercaptobenzothiazole salt in the aqueous solution of the 2-mercaptobenzothiazole salt is 1-30%; the mass fraction of the hydrogen peroxide is 0.01-10%, and the hydrogen peroxide is added according to the stoichiometric ratio of the hydrogen peroxide and the dibenzothiazyl disulfide synthesized by the 2-mercaptobenzothiazole salt, or the hydrogen peroxide is added within twice of the stoichiometric ratio.
And in the third step, the pH value is 5-10.
The method for synthesizing the dibenzothiazyl disulfide by adopting the micro-reaction continuous synthesis system and taking the alcohol solvent as the reaction environment comprises the following steps:
firstly, mixing a 2-mercaptobenzothiazole alcohol solution and a hydrogen peroxide solution in a micro mixer to form a mixed solution;
secondly, the mixed solution obtained in the first step is subjected to 2-mercaptobenzothiazole oxidation through a multilayer rotating disc type stirring reactor, and a solution is obtained at the outlet of the reactor;
and thirdly, filtering, washing and drying the solution obtained in the second step to obtain a solid product dibenzothiazyl disulfide.
The mass fraction of the 2-mercaptobenzothiazole in the 2-mercaptobenzothiazole alcoholic solution is 1-30%; the mass fraction of the hydrogen peroxide is 0.01-30 percent; the molar ratio of the hydrogen peroxide to the 2-mercaptobenzothiazole is 0.5: 1-1: 1.
Aiming at the dibenzothiazyl disulfide micro-reaction continuous synthesis system under the two synthesis methods, the material mixing temperature of the first step and the second step is controlled to be 20-70 ℃, and the reaction temperature of the third step is controlled to be 20-70 ℃.
The residence time of reactants in the multilayer rotating disc type reactor is 5-60 min, and the stirring speed is 50-500 rpm. The micro mixer is connected with the multilayer rotating disc type reactor through a pipeline. The multi-layer rotating disc type reactor is controlled by a circulating medium in an outer jacket.
The multilayer rotating disc type reactor is composed of a stirring shaft and a tubular reactor, more than 3 discs are vertically arranged on the stirring shaft, the outer diameter of each rotating disc is 1/2-3/4 of the inner diameter of the tubular reactor, and the distance between the rotating discs is 5-20 cm. The multi-layer rotating disc type reactor is vertically arranged, and reaction liquid flows in from the bottom of the side vertical face of the reactor and flows out from the top of the side vertical face.
The following embodiments are described in detail to solve the technical problems by applying technical means to the present invention, and the implementation process of achieving the technical effects can be fully understood and implemented.
As shown in FIG. 1a, a container A containing an aqueous solution of 2-mercaptobenzothiazole salt is connected with a micro mixer 4 through a feed pump 1 and a preheating pipeline 6, a container B containing an aqueous solution of hydrogen peroxide is connected with the micro mixer 4 through a feed pump 2 and a preheating pipeline 6, the micro mixer 4 is connected with a gas-liquid micro diffuser 5 through a pipeline, a device C containing carbon dioxide is connected with the gas-liquid micro diffuser 5 through a pipeline, the gas-liquid micro diffuser 5 is connected with a multilayer rotating disc type stirring reactor 8 with a heat exchange jacket through a pipeline, the reactor 8 is connected with a solid-liquid separation device 9 through a pipeline, the solid-liquid separation device 9 is connected with a drying device 10 through a pipeline, and the preheating pipeline 6, the micro mixer 4 and the gas-liquid micro diffuser 5 are controlled in temperature through a temperature control device 7.
As shown in FIG. 1B, a container A containing an aqueous solution of 2-mercaptobenzothiazole salt is connected with a micromixer 4 through a feed pump 1 and a preheating pipeline 6, a container B containing an aqueous solution of hydrogen peroxide is connected with the micromixer 4 through a feed pump 2 and a preheating pipeline 6, the micromixer 4 is connected with a multilayer rotating disc type stirring reactor 8 with a heat exchange jacket through a pipeline, the reactor 8 is connected with a solid-liquid separation device 9 through a pipeline, the solid-liquid separation device 9 is connected with a drying device 10 through a pipeline, and the preheating pipeline 6 and the micromixer 4 control the temperature through a temperature control device 7.
According to the process route shown in fig. 1a and fig. 1b, a metering pump is adopted to convey reaction raw materials, a solid-liquid mixture is obtained at the outlet of a multilayer rotating disc type reactor, the product dibenzothiazyl disulfide MBTS is obtained after filtration, washing and drying, the purity of the product is analyzed by liquid chromatography, the content of residual raw material 2-mercaptobenzothiazole salt (or 2-mercaptobenzothiazole) is analyzed by liquid chromatography of filtered reaction mother liquor, and the conversion rate is calculated.
The specific experimental results are as follows:
TABLE 1
All of the above mentioned intellectual property rights are not intended to be restrictive to other forms of implementing the new and/or new products. Those skilled in the art will take advantage of this important information, and the foregoing will be modified to achieve similar performance. However, all modifications or alterations are based on the new products of the invention and belong to the reserved rights.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any person skilled in the art may modify or modify the technical details disclosed above into equivalent embodiments with equivalent variations. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (9)
1. A micro-reaction continuous synthesis system for dibenzothiazyl disulfide utilizes a micro-reaction technology to realize continuous synthesis of dibenzothiazyl disulfide under two reaction methods of taking an aqueous solution as a reaction environment and taking an alcohol solvent as a reaction environment. The micro-reaction continuous synthesis system comprises a feeding pump, a gas flow controller, a micro mixer, a gas-liquid micro disperser, a multilayer rotating disc type reactor, solid-liquid separation equipment and drying equipment. Aiming at a reaction method taking alcohol solvent as a reaction environment, the micro-reaction continuous synthesis system comprises a feeding pump, a micro mixer, a multi-layer rotating disc type reactor, solid-liquid separation equipment and drying equipment. In the dibenzothiazyl disulfide continuous synthesis system under the above two reaction methods, a micro mixer or a gas-liquid micro disperser and a multilayer rotating disc type reactor are connected in series through a pipe, so that the reaction liquid is continuously conveyed.
2. The method for continuously synthesizing dibenzothiazyl disulfide by using the micro-reaction continuous synthesis system in the aqueous solution as the reaction environment according to claim 1, comprising:
firstly, mixing an aqueous solution of 2-mercaptobenzothiazole salt and a hydrogen peroxide solution in a micro mixer to form turbid mixed solution;
secondly, mixing the mixed liquid obtained in the first step with carbon dioxide gas in a gas-liquid micro-disperser to obtain a gas-liquid two-phase flow micro-dispersing system;
thirdly, the micro dispersion system obtained in the second step is subjected to 2-mercaptobenzothiazole oxidation through a multilayer rotating disc type stirring reactor, carbon dioxide is continuously introduced to adjust the pH value of the reaction system, and a solution is obtained at the outlet of the reactor;
and fourthly, carrying out post-treatment on the solution obtained in the third step to obtain a solid product dibenzothiazyl disulfide.
3. The method for continuous synthesis by micro-reaction according to claim 2, wherein: the mass fraction of the 2-mercaptobenzothiazole salt in the aqueous solution of the 2-mercaptobenzothiazole salt is 1-30%; the mass fraction of the hydrogen peroxide is 0.01-10%, and the hydrogen peroxide is added according to the stoichiometric ratio of the hydrogen peroxide and the dibenzothiazyl disulfide synthesized by the 2-mercaptobenzothiazole salt, or the hydrogen peroxide is added within two times of the stoichiometric ratio; the mixing temperature of the materials in the first step and the second step is controlled to be 20-70 ℃, and the reaction temperature in the third step is controlled to be 20-70 ℃.
4. The method for continuously synthesizing dibenzothiazyl disulfide by using the continuous micro-reaction synthesis system using an alcohol solvent as a reaction environment according to claim 1, comprising:
firstly, mixing a 2-mercaptobenzothiazole alcohol solution and a hydrogen peroxide solution in a micro mixer to form turbid mixed solution;
secondly, the micro dispersion system obtained in the first step is subjected to 2-mercaptobenzothiazole oxidation through a multilayer rotating disc type stirring reactor, and a solution is obtained at the outlet of the reactor;
and thirdly, carrying out post-treatment on the solution obtained in the second step to obtain a solid product dibenzothiazyl disulfide.
5. The method for continuous synthesis by micro-reaction according to claim 4, wherein: the mass fraction of the 2-mercaptobenzothiazole in the 2-mercaptobenzothiazole alcoholic solution is 1-30%; the mass fraction of the hydrogen peroxide is 0.01-30 percent; the molar ratio of the hydrogen peroxide to the 2-mercaptobenzothiazole is 0.5: 1-1: 1; the material mixing temperature in the first step is controlled to be 20-70 ℃, and the reaction temperature in the second step is controlled to be 20-70 ℃.
6. The micro-reaction continuous synthesis system according to claim 1, wherein: the micro mixer is selected from one of a micro-sieve-hole dispersing mixer, a micro-channel mixer, a stainless steel tee joint and a polyether-ether-ketone tee joint.
7. The micro-reaction continuous synthesis system according to claim 1, wherein: the gas-liquid micro-disperser is selected from membrane micro-disperser, micro-sieve-hole micro-disperser, microchannel micro-disperser, stainless steel tee and polyether-ether-ketone tee.
8. The micro-reaction continuous synthesis system according to claim 1, wherein: the residence time of reactants in the multilayer rotating disc type reactor is 5-60 min, and the stirring speed is 50-500 rpm.
9. The micro-reaction continuous synthesis system of claim 1, wherein: the multilayer rotating disc type reactor consists of a stirring shaft and a tubular reactor, more than 3 discs are vertically arranged on the stirring shaft, the outer diameter of each rotating disc is 1/2-3/4 of the inner diameter of the tubular reactor, and the distance between the rotating discs is 5-20 cm; the multilayer rotating disc type reactor is vertically arranged, and reaction liquid flows in from the bottom of the side vertical face of the reactor and flows out from the top end of the side vertical face; the multi-layer rotating disc type reactor is controlled by a circulating medium in an outer jacket.
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