CN115160255A - Method and system device for continuously producing 2-mercaptobenzothiazole - Google Patents
Method and system device for continuously producing 2-mercaptobenzothiazole Download PDFInfo
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- CN115160255A CN115160255A CN202211081308.4A CN202211081308A CN115160255A CN 115160255 A CN115160255 A CN 115160255A CN 202211081308 A CN202211081308 A CN 202211081308A CN 115160255 A CN115160255 A CN 115160255A
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- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 238000000034 method Methods 0.000 title claims abstract description 40
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- 239000000047 product Substances 0.000 claims abstract description 58
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 238000005406 washing Methods 0.000 claims abstract description 39
- 238000010517 secondary reaction Methods 0.000 claims abstract description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 239000011593 sulfur Substances 0.000 claims abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 21
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 18
- 239000012043 crude product Substances 0.000 claims abstract description 18
- 239000007791 liquid phase Substances 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 238000005192 partition Methods 0.000 claims description 15
- 238000004064 recycling Methods 0.000 claims description 13
- 239000012452 mother liquor Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- ISJVISYHMCSEPL-UHFFFAOYSA-N [S].S=C=S Chemical compound [S].S=C=S ISJVISYHMCSEPL-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 5
- 238000009826 distribution Methods 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000000376 reactant Substances 0.000 abstract description 8
- 229940054266 2-mercaptobenzothiazole Drugs 0.000 description 55
- 239000007789 gas Substances 0.000 description 22
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 17
- 238000002156 mixing Methods 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 11
- 238000010924 continuous production Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000013040 rubber vulcanization Methods 0.000 description 5
- 238000003541 multi-stage reaction Methods 0.000 description 4
- 208000012839 conversion disease Diseases 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- -1 etc. Chemical compound 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VILGDADBAQFRJE-UHFFFAOYSA-N n,n-bis(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SN(SC=3SC4=CC=CC=C4N=3)C(C)(C)C)=NC2=C1 VILGDADBAQFRJE-UHFFFAOYSA-N 0.000 description 1
- ILSQBBRAYMWZLQ-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-propan-2-ylpropan-2-amine Chemical compound C1=CC=C2SC(SN(C(C)C)C(C)C)=NC2=C1 ILSQBBRAYMWZLQ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000013094 purity test Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
-
- 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
- C07D277/72—2-Mercaptobenzothiazole
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for continuously producing 2-mercaptobenzothiazole and a system device thereof, wherein the method comprises the following steps: s1: sequentially carrying out primary reaction on aniline, carbon disulfide and sulfur to obtain a primary reaction product; s2: gas-liquid separation is carried out on the first-stage reaction product to obtain H 2 S gas and liquid phase products; s3: carrying out secondary reaction on the liquid-phase product to obtain a crude product of the 2-mercaptobenzothiazole; s4: purifying the 2-mercaptobenzothiazole crude product to obtain a 2-mercaptobenzothiazole product, wherein the purification comprises dissolving, cooling crystallization, filtering, washing and drying which are sequentially carried out; by adding a gas-liquid separation step between the first-stage reaction and the second-stage reaction to discharge part of H 2 The S gas product improves the reactor use efficiency of the raw materials, reduces the influence of the gas product on the residence time distribution of reactants in the reactor, has more uniform residence time distribution, further improves the reaction efficiency, and has high product yield and high product purity.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a method for continuously producing 2-mercaptobenzothiazole and a system device thereof.
Background
The accelerator 2-Mercaptobenzothiazole (MBT) is a general rubber vulcanization accelerator. The rubber vulcanization accelerator has the obvious advantages of flat vulcanization curve, easy dispersion, no pollution and the like in the aspect of promoting rubber vulcanization, and rubber products obtained by vulcanization have better tensile strength and hardness; but also precursors for accelerators MZ, DM, CBS, NS, DZ, TBSI, DIBS, etc., MBT has received much attention from the adjuvant industry.
MBT is generally produced by the Kelly process in industry. The method comprises the steps of reacting aniline, carbon disulfide and sulfur at high temperature and high pressure, and carrying out alkali dissolution, oxidation and acidification on a crude product to obtain the product MBT. The method has the disadvantages of large safety risk and low production efficiency due to the adoption of intermittent operation; the product yield is only 80-86%, a large amount of asphaltic waste and high COD wastewater are generated, and the treatment is difficult.
The continuous reactor is adopted for MBT synthesis reaction, so that the problems of high safety risk, low production efficiency and the like caused by intermittent operation can be solved, for example, CN107629024A discloses a rubber vulcanization accelerator M continuous synthesis device and a production process thereof, wherein the device comprises at least two high-pressure synthesis kettles, a discharging kettle and a gas-liquid separation tank; the high-pressure synthesis kettle, the discharge kettle and the gas-liquid separation tank are sequentially connected in series through the discharge pipe; the upper ends of the high-pressure synthesis kettle and the discharge kettle are connected through a pressure balance pipe; the high-pressure synthesis kettle is respectively connected with an aniline preheater, a sulfur solution preheater, an aniline metering pump and a sulfur solution metering pump through pipelines, and the method realizes the continuous synthesis of the rubber vulcanization accelerator M, realizes continuous operation and has high degree of mechanization and automation.
On the basis, CN109810074A discloses a reaction device for continuously synthesizing 2-mercaptobenzothiazole, which comprises a raw material preheater, a micro mixer, a multi-stage reaction kettle and a stripping tower which are connected in series, and the processes of preheating, mixing, reacting and phase separation of raw materials are sequentially completed; the raw materials comprise aniline, carbon disulfide and sulfur, the aniline, the carbon disulfide and the sulfur are respectively heated in a preheating device to respective initial temperatures, then adiabatic mixing is carried out in a micro mixer, the raw material mixture sequentially enters from the bottom of a series-connected multistage reaction kettle and leaves from the top of the multistage reaction kettle, and 2-mercaptobenzothiazole is generated through multistage reaction; the top of the last-stage reaction kettle is communicated with a stripping tower, the stripping tower is used for separating materials after reaction into tail gas and a 2-mercaptobenzothiazole crude product, continuous production can be realized by using the device, the production efficiency is high, and the product stability is good.
Compared with the batch kettle type reaction, the continuous reaction is carried out by adopting the multistage series stirred kettles, and the method is of great importance for obtaining higher reaction conversion rate and product yield and ensuring the uniformity of the residence time distribution of reactants in the reactor. MBT is synthesized by a Kelly method, and a large amount of hydrogen sulfide gas is generated in the reaction process. On one hand, the gas volume is large, and the utilization efficiency of the reactor is reduced; on the other hand, the gas rises fast in the stirring kettle, so that reactants are back-mixed in the axial direction, and the reaction conversion rate and the product yield are reduced. Although the problem of uneven residence time distribution caused by a large amount of bubbles can be alleviated to a certain extent by adopting the multistage serial stirred tanks for continuous reaction, the yield of MBT products produced by the continuous reaction of the multistage serial stirred tanks is still lower than that of batch tank type reaction.
Therefore, it is necessary to provide a new apparatus and method for producing 2-mercaptobenzothiazole, which ensures the uniformity of the residence time distribution of the reactants in the reactor, and provides the reaction conversion rate and the product yield.
Disclosure of Invention
The invention aims to provide a method for continuously producing 2-mercaptobenzothiazole and a system device thereof 2 The S gas product improves the reactor use efficiency of the raw materials, reduces the influence of the gas product on the residence time distribution of reactants in the reactor, has more uniform residence time distribution, further improves the reaction efficiency, and has high product yield and high product purity.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the objects of the present invention is to provide a method for continuously producing 2-mercaptobenzothiazole, which comprises the following steps:
s1: aniline, carbon disulfide and sulfur are subjected to primary reaction to obtain a primary reaction product;
s2: carrying out gas-liquid separation on the primary reaction product obtained in the step S1 to obtain H 2 S gas and liquid phase products;
s3: performing a secondary reaction on the liquid-phase product obtained in the step S2 to obtain a crude product of 2-mercaptobenzothiazole;
s4: and (4) purifying the crude product of the 2-mercaptobenzothiazole obtained in the step (S3) to obtain a 2-mercaptobenzothiazole product.
The invention adds a step of gas-liquid separation between the first-stage reaction and the second-stage reaction to discharge part of H 2 S gas product, the influence of the gas product on the residence time distribution of reactants in the reactor is reduced, the residence time distribution is more uniform, the reaction efficiency is higher, the residence time distribution is uniform, the generation of byproducts can be reduced, and the product purity is improved.
It is to be noted that, in the actual production process, when the first-order reaction product is subjected to gas-liquid separation in step S2, H is 2 The S gas may entrain a part of carbon disulfide, aniline and primary reaction products, and the H gas is separated 2 And (3) condensing and recovering the materials carried in the S gas, and mixing the materials with the liquid-phase product to perform a secondary reaction.
As a preferred technical scheme of the invention, before the first-stage reaction in the step S1, carbon disulfide and sulfur are mixed into a carbon disulfide-sulfur solution, and then the carbon disulfide-sulfur solution is mixed with aniline to carry out the first-stage reaction.
According to a preferred technical scheme of the invention, the molar ratio of the aniline, the carbon disulfide and the sulfur is 1.2.
In a preferred embodiment of the present invention, the temperature of the first-stage reaction in step S1 is 240 to 270 ℃, for example, 240 ℃,243 ℃,248 ℃,250 ℃,252 ℃,255 ℃,258 ℃,260 ℃,262 ℃,265 ℃,267 ℃,270 ℃ and the like, and the pressure is 8.5 to 13.0MPa, for example, 8.5MPa,8.8MPa,9.0MPa,9.2MPa,9.5MPa,9.7MPa,10.0MPa,10.3MPa,10.5MPa,10.8MPa, 111MPa, 11.3MPa,11.7MPa,12MPa,12.2MPa,12.5MPa,12.8MPa,13.0MPa and the like, and the retention time is 1 to 4 hours, for example, 1.2h,1.5h, 1.4h, 2h,2.2h, 2.7h, 2.3h, 3.3h,3.5h,3.8h and the like, and the values are not limited to the above-mentioned values.
Further, the H obtained in the step S2 2 And (4) carrying out alkali absorption or Claus furnace incineration on the S gas.
As a preferable embodiment of the present invention, the temperature of the second-order reaction in step S3 is 200 to 240 ℃ and may be, for example, 200 ℃,203 ℃,205 ℃,208 ℃,210 ℃,212 ℃,215 ℃,218 ℃,220 ℃,223 ℃,225 ℃,227 ℃,230 ℃,232 ℃,235 ℃,238 ℃,240 ℃ or the like, and the pressure is 8.0 to 12.5MPa, and may be, for example, 8.0MPa,8.2MPa,8.5MPa,8.8MPa,9.0MPa,9.2MPa,9.5MPa,9.7MPa,10.0MPa,10.3MPa, 10.8MPa, 10.1111MPa, 11.3MPa,11.7MPa, 2MPa,12.2MPa,12.5MPa or the like, and the residence time is 1 to 3h, and may be, for example, 1h,1.2h,1.4h,1.6h,1.8h,2h, 2.4h, 2.8h, 2.6h, 2.3h or the like, and the residence time is not limited to the above-mentioned values, and the other values are not limited to values.
In a preferred embodiment of the present invention, in the tubular reactor for carrying out the two-stage reaction described in the step S3, the flow rate of the liquid in the tube is 0.01 to 0.03m/S, and may be, for example, 0.01m/S,0.012m/S,0.014m/S,0.016m/S,0.018m/S,0.02m/S,0.022m/S,0.024m/S,0.026m/S,0.028m/S,0.03m/S, etc., but these values are not limited thereto and other values not specified in the above numerical range are also applicable.
As a preferred technical scheme of the invention, the purification in the step S4 comprises dissolving, cooling crystallization, filtering, washing and drying which are sequentially carried out.
Further, the solvent used for dissolving is carbon disulfide, and on one hand, MBT and resin are utilized to dissolve in CS 2 The purification can be realized by different medium solubility, and the mother liquor can be recycled.
Further, the temperature of the temperature-decreasing crystallization is 90 to 120 ℃, and may be, for example, 90 ℃,95 ℃,100 ℃,105 ℃,110 ℃,115 ℃,120 ℃ or the like, but is not limited to the recited values, and other values not recited in the above numerical range are also applicable.
Further, the mother liquor obtained by filtering is concentrated to obtain concentrated liquor and condensate, the concentrated liquor is recycled to the step S1 to be used as carbon disulfide for primary reaction, and the condensate is used as a detergent in the washing process.
It is worth noting that when the whole system is capable of stable operation, the mother liquor obtained by filtration is the main source of carbon disulfide in the first-order reaction process.
Further, the detergent used for washing is carbon disulfide.
Further, washing liquor generated after washing is recycled and used as a solvent in the dissolving process.
Further, 5-15% of the concentrate needs to be drained from the system to prevent the accumulation of impurities and ensure the quality of the MBT product.
Further, recycling the filtered mother liquor to the step S1 as carbon disulfide for primary reaction; and washing liquor obtained by washing is recycled and used as a solvent in the dissolving process.
As a preferred technical scheme of the invention, the method comprises the following steps:
s1: mixing carbon disulfide and sulfur into a carbon disulfide-sulfur solution, then mixing the solution with aniline, carrying out primary reaction in a kettle type stirring reactor at the temperature of 240-270 ℃ and under the pressure of 8.5-13.0MPa, and controlling the retention time of the primary reaction to be 1-4h to obtain a primary reaction product;
wherein the mol ratio of the aniline to the carbon disulfide to the sulfur is 1 (1.2-1.8) to 1.2-3;
s2: carrying out gas-liquid separation on the first-stage reaction product obtained in the step S1 to obtain H 2 S gas and liquid phase products;
s3: carrying out a secondary reaction on the liquid-phase product obtained in the step S2 in a tubular reactor at the temperature of 200-240 ℃ and under the pressure of 8.0-12.5MPa, and controlling the flow rate of liquid in the tube of the secondary reaction to be 0.01-0.03m/S to obtain a crude product of 2-mercaptobenzothiazole;
s4: dissolving the 2-mercaptobenzothiazole crude product obtained in the step S3 by using carbon disulfide, then, cooling and crystallizing at 90-120 ℃, filtering, washing by using the carbon disulfide, and drying to obtain a 2-mercaptobenzothiazole product;
concentrating the filtered mother liquor to obtain concentrated solution and condensate, recycling the concentrated solution to the step S1 for primary reaction as carbon disulfide, and washing the condensate in a washing process; and recycling the washing liquid generated after washing for dissolving.
The second purpose of the invention is to provide a system device of the method for continuously producing 2-mercaptobenzothiazole, which comprises a reaction system and a purification system which are connected in sequence; the reaction system comprises a first-stage reaction device, a gas-liquid separation device and a second-stage reaction device which are connected in sequence; the first-stage reaction device comprises at least one kettle type stirring reactor; the gas-liquid separation device comprises at least one gas-liquid separator; the secondary reaction device comprises at least one tubular reactor.
The invention arranges a gas-liquid separation device between the first-stage reaction device and the second-stage reaction device to discharge part H 2 S gas product, improves the reactor use efficiency of the raw materials, reduces the influence of the gas product on the residence time distribution of the reactants in the reactor, has more uniform residence time distribution, and further has reaction efficiencySo that the improvement is achieved; the first-stage reaction device comprises at least one kettle type stirring reactor; the secondary reaction device comprises at least one tubular reactor, so that the volume of the reactor can be reduced while the retention time is ensured, and the mass and heat transfer efficiency is improved.
As a preferred technical scheme of the invention, the kettle type stirring reactor comprises a shell, an annular partition plate and a stirrer.
Further, the annular partition is disposed on an inner wall of the housing.
Further, a space exists between two adjacent annular partition plates.
Further, the number of the annular partition plates is 2 to 6, and may be, for example, 2, 3, 4, 5, or 6.
Further, the annular partition plate and the shell are connected through an insert or welding.
In a preferred embodiment of the present invention, the inner diameter of the annular partition is 5 to 20% of the inner diameter of the casing, and may be, for example, 5%,6%,7%,8%,9%,10%,11%,12%,13%,14%,15%,16%,17%,18%,19%,20%, or the like, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
Further, the outer diameter of the annular partition is 90 to 95% of the inner diameter of the housing, and may be, for example, 90%,90.5%,91%,91.5%,92%,92.5%,93%,93.5%,94%,94.5%,95%, etc., but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
Further, the spacing between adjacent annular baffles is 60-120% of the inner diameter of the housing, and may be, for example, 60%,65%,70%,75%,80%,85%,90%,95%,100%,105%,110%,115%,120%, etc., but is not limited to the recited values, and other values not recited within the above range are also applicable.
Further, the stirrer comprises a paddle stirrer and/or an open turbine stirrer.
Further, the purification system comprises a dissolving device, a cooling crystallization device, a filtering device, a washing device and a drying device which are connected in sequence.
Further, the cooling crystallization device is connected with the dissolving device through a pipeline.
Furthermore, the dissolving device is connected with the washing device through a pipeline.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the system device for continuously producing the 2-mercaptobenzothiazole, the gas-liquid separation device is arranged between the primary reaction device and the secondary reaction device to discharge part of gas products, so that the influence of the gas products on the residence time distribution of reactants in the reactor is reduced, and the reaction efficiency is improved;
(2) The method for continuously producing the 2-mercaptobenzothiazole provided by the invention uses carbon disulfide as a solvent to carry out MBT refining, and the crystallization mother liquor is recycled as a reaction raw material, so that the recycling of intermediate products is realized, the product yield can reach more than 94%, and the product purity can reach 99%.
Drawings
FIG. 1 is a flow chart for the continuous production of 2-mercaptobenzothiazole.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
It is to be noted that, in the present invention, a method for continuously producing 2-mercaptobenzothiazole is shown in FIG. 1, and the method includes the steps of:
s1: mixing carbon disulfide and sulfur into a carbon disulfide-sulfur solution, mixing the carbon disulfide-sulfur solution with aniline, and carrying out primary reaction in a kettle type stirring reactor to obtain a primary reaction product;
s2: will be described in step S1Gas-liquid separation is carried out on the first-stage reaction product to obtain H 2 S gas and liquid phase products;
s3: carrying out a secondary reaction on the liquid-phase product obtained in the step S2 in a tubular reactor to obtain a crude product of 2-mercaptobenzothiazole;
s4: dissolving the 2-mercaptobenzothiazole crude product obtained in the step S3 by using carbon disulfide, then cooling and crystallizing, filtering, washing by using carbon disulfide, and finally drying to obtain a 2-mercaptobenzothiazole product;
concentrating the filtered mother liquor to obtain concentrated solution and condensate, recycling the concentrated solution to the step S1 for primary reaction as carbon disulfide, and washing the condensate in a washing process; and recycling the washing liquid generated after washing for dissolving.
It is to be noted that, in all the examples of the present invention, the system apparatus for continuously producing 2-mercaptobenzothiazole comprises a reaction system and a purification system which are connected in series; the reaction system comprises a first-stage reaction device, a gas-liquid separation device and a second-stage reaction device which are connected in sequence; the first-stage reaction device is a kettle type stirring reactor; the gas-liquid separation device is a gas-liquid separator; the second-stage reaction device is a tubular reactor; the kettle type stirring reactor comprises a shell, an annular partition plate and a stirrer; the annular partition plate is arranged on the inner wall of the shell; the stirrer is a paddle stirrer; the purification system comprises a dissolving device, a cooling crystallization device, a filtering device, a washing device and a drying device which are connected in sequence.
Example 1
This example provides a process for the continuous production of 2-mercaptobenzothiazole, comprising the steps of:
s1: mixing carbon disulfide and sulfur into a carbon disulfide-sulfur solution, mixing the solution with aniline, carrying out primary reaction in a kettle type stirring reactor at the temperature of 240 ℃ and under the pressure of 13.0MPa, and controlling the retention time of the primary reaction to be 4h to obtain a primary reaction product;
wherein the molar ratio of aniline, carbon disulfide and sulfur is 1.5;
s2: carrying out gas-liquid separation on the first-stage reaction product obtained in the step S1 to obtain H 2 S gas and liquid phase products;
s3: carrying out a secondary reaction on the liquid-phase product obtained in the step S2 in a tubular reactor at the temperature of 220 ℃ and under the pressure of 12.5MPa, and controlling the flow rate of liquid in the tube of the secondary reaction to be 0.03m/S to obtain a crude product of 2-mercaptobenzothiazole, wherein the retention time of the secondary reaction is 1h;
s4: dissolving the 2-mercaptobenzothiazole crude product obtained in the step S3 by using carbon disulfide, then cooling and crystallizing at 90 ℃, filtering, washing by using carbon disulfide, and drying to obtain a 2-mercaptobenzothiazole product; concentrating the filtered mother liquor to obtain concentrated solution and condensate, recycling the concentrated solution to the step S1 for primary reaction as carbon disulfide, and washing the condensate in a washing process; and recycling the washing liquid generated after washing for dissolving.
Example 2
This example provides a process for the continuous production of 2-mercaptobenzothiazole, comprising the steps of:
s1: mixing carbon disulfide and sulfur into a carbon disulfide-sulfur solution, mixing the solution with aniline, carrying out primary reaction in a kettle type stirring reactor at the temperature of 270 ℃ and under the pressure of 8.5MPa, and controlling the retention time of the primary reaction to be 1h to obtain a primary reaction product;
wherein the molar ratio of aniline, carbon disulfide and sulfur is 1.2;
s2: carrying out gas-liquid separation on the primary reaction product obtained in the step S1 to obtain H 2 S gas and liquid phase products;
s3: carrying out a secondary reaction on the liquid-phase product obtained in the step S2 in a tubular reactor at the temperature of 240 ℃ and under the pressure of 8.0MPa, and controlling the flow velocity of liquid in a tube of the secondary reaction to be 0.01m/S to obtain a crude product of 2-mercaptobenzothiazole, wherein the retention time of the secondary reaction is 3h;
s4: dissolving the 2-mercaptobenzothiazole crude product obtained in the step S3 by using carbon disulfide, then, cooling and crystallizing at 100 ℃, filtering, washing by using carbon disulfide, and drying to obtain a 2-mercaptobenzothiazole product; concentrating the filtered mother liquor to obtain concentrated solution and condensate, recycling the concentrated solution to the step S1 for primary reaction as carbon disulfide, and washing the condensate in a washing process; and recycling the washing liquid generated after washing for dissolving.
Example 3
This example provides a process for the continuous production of 2-mercaptobenzothiazole, comprising the steps of:
s1: mixing carbon disulfide and sulfur into a carbon disulfide-sulfur solution, mixing the solution with aniline, carrying out primary reaction in a kettle type stirring reactor at the temperature of 270 ℃ and the pressure of 10.0MPa, and controlling the retention time of the primary reaction to be 2 hours to obtain a primary reaction product;
wherein, the molar ratio of aniline, carbon disulfide and sulfur is 1.8;
s2: carrying out gas-liquid separation on the primary reaction product obtained in the step S1 to obtain H 2 S gas and liquid phase products;
s3: carrying out a secondary reaction on the liquid-phase product obtained in the step S2 in a tubular reactor at the temperature of 200 ℃ and under the pressure of 10.0MPa, and controlling the flow rate of liquid in the tube of the secondary reaction to be 0.02m/S to obtain a crude product of 2-mercaptobenzothiazole, wherein the retention time of the secondary reaction is 1.5h;
s4: dissolving the 2-mercaptobenzothiazole crude product obtained in the step S3 by using carbon disulfide, then cooling and crystallizing at 120 ℃, filtering, washing by using carbon disulfide, and drying to obtain a 2-mercaptobenzothiazole product; concentrating the filtered mother liquor to obtain concentrated solution and condensate, recycling the concentrated solution to the step S1 for primary reaction as carbon disulfide, and washing the condensate in a washing process; and recycling the washing liquid generated after washing for dissolving.
Example 4
This example provides a process for the continuous production of 2-mercaptobenzothiazole as described with reference to example 1, except that: the residence time of the first-stage reaction in the step S1 is replaced by 0.5h from 4h, and other conditions are completely the same as those in the example 1.
Example 5
This example provides a process for the continuous production of 2-mercaptobenzothiazole as described with reference to example 1, except that: the residence time of the first-stage reaction in the step S1 is changed from 4h to 5h, and other conditions are completely the same as in the example 1.
Example 6
This example provides a process for the continuous production of 2-mercaptobenzothiazole as described with reference to example 1, except that: the flow rate of the liquid in the secondary reaction tube in the step S3 is 0.06m/S, that is, the residence time is 0.5h, and other conditions are completely the same as those in example 1.
Example 7
This example provides a process for the continuous production of 2-mercaptobenzothiazole as described with reference to example 1, except that: the flow rate of the liquid in the secondary reaction tube in the step S3 was 0.0075m/S, that is, the residence time was 4 hours, and the other conditions were exactly the same as in example 1.
The 2-mercaptobenzothiazole obtained in the above example was tested for yield and purity by the following method:
yield: calculated on aniline basis, i.e. yield = moles cumulative product/moles cumulative aniline added
100%；
Purity: detecting according to GB/T11407-2013 vulcanization accelerator 2-Mercapto Benzothiazole (MBT);
the results of the 2-mercaptobenzothiazole yield and purity test in the above example are shown in Table 1.
TABLE 1
The following points can be derived from table 1:
(1) As can be seen from the examples 1-3, the product yield of the method for continuously producing 2-mercaptobenzothiazole can reach more than 94 percent, and the product purity reaches more than 99 percent;
(2) Comparing example 1 with example 4 and example 5, it can be seen that the residence time of the first-order reaction in step S1 in example 4 is 0.5h, which is lower than the preferred 1-4h of the present invention, resulting in insufficient first-order reaction and reduced product yield; since the residence time of the first-stage reaction in the step S1 in the embodiment 5 is 5 hours, which exceeds the preferable 1-4 hours of the invention, the product purity is low and the yield is reduced;
(3) Comparing example 1 with example 6 and example 7, it can be seen that the flow rate of the liquid in the tube of the secondary reaction in step S3 of example 6 is 0.06m/S, which exceeds the preferable 0.01-0.03m/S of the present invention, resulting in a retention time of 0.5h, which in turn results in insufficient secondary reaction and reduced product yield; since the flow rate of the liquid in the tube of the secondary reaction described in step S3 of example 7 is 0.0075m/S, which is lower than the preferred 0.01-0.03m/S of the present invention, the retention time is 4h, which in turn leads to low product purity and reduced yield.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A method for continuously producing 2-mercaptobenzothiazole, characterized in that the method comprises the following steps:
s1: aniline, carbon disulfide and sulfur are subjected to primary reaction to obtain a primary reaction product;
s2: carrying out gas-liquid separation on the first-stage reaction product obtained in the step S1 to obtain H 2 S gas and liquid phase products;
s3: performing a secondary reaction on the liquid-phase product obtained in the step S2 to obtain a crude product of 2-mercaptobenzothiazole;
s4: and (4) purifying the crude product of the 2-mercaptobenzothiazole obtained in the step (S3) to obtain a 2-mercaptobenzothiazole product.
2. The method of claim 1, wherein the carbon disulfide and sulfur are mixed into a carbon disulfide-sulfur solution before the primary reaction in step S1, and then mixed with aniline for the primary reaction.
3. The method as claimed in claim 1 or 2, wherein the molar ratio of aniline, carbon disulfide and sulfur in the primary reaction of step S1 is 1 (1.2-1.8) to (1.2-3).
4. The method according to claim 1, wherein the temperature of the first-stage reaction in step S1 is 240-270 ℃, the pressure is 8.5-13.0MPa, and the residence time is 1-4h.
5. The method of claim 1, wherein the temperature of the secondary reaction in step S3 is 200-240 ℃ and the pressure is 8.0-12.5MPa.
6. The method according to claim 1, wherein the flow rate of the liquid in the tube reactor for performing the secondary reaction of step S3 is 0.01 to 0.03m/S.
7. The method according to claim 1, wherein the purification of step S4 comprises dissolving, cooling crystallization, filtering, washing and drying in sequence; concentrating the filtered mother liquor, and recycling the concentrated mother liquor to the step S1 to be used as carbon disulfide for primary reaction; and washing liquor obtained by washing is recycled and used as a solvent in the dissolving process.
8. A system-apparatus for a process for continuously producing 2-mercaptobenzothiazole according to any one of claims 1 to 7, wherein the system-apparatus comprises a reaction system and a purification system connected in series; the reaction system comprises a first-stage reaction device, a gas-liquid separation device and a second-stage reaction device which are connected in sequence; the first-stage reaction device comprises at least one kettle type stirring reactor; the gas-liquid separation device comprises at least one gas-liquid separator; the secondary reaction device comprises at least one tubular reactor.
9. The system set-up of claim 8, wherein the stirred-tank reactor comprises a housing, an annular partition, and an agitator; the annular partition plate is arranged on the inner wall of the shell; a space exists between two adjacent annular partition plates; the number of the annular partition plates is 2-6.
10. The system-device of claim 9, wherein the inner diameter of the annular partition is 5-20% of the inner diameter of the housing; the outer diameter of the annular partition plate is 90-95% of the inner diameter of the shell; the spacing between adjacent annular baffles is 60-120% of the inner diameter of the shell.
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