CN112624946B - Method for synthesizing accelerator TMTD by continuous method - Google Patents
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Abstract
The invention relates to the technical field of rubber accelerator TMTD production, in particular to a method for continuously producing accelerator TMTD. The invention can realize continuous production from feeding to discharging, and is convenient for realizing industrialized operation. The tubular reactor has small volume and high production efficiency, and the synthesized accelerator TMTD has stable quality and no peculiar smell, and improves the yield of the further synthesized accelerator TMTD.
Description
Technical Field
The invention relates to the technical field of rubber accelerator TMTD production, in particular to a method for continuously producing accelerator TMTD.
Background
TMTD is a second excellent accelerator for thiazole-based accelerators, and may be used in combination with other accelerators, usually in combination with accelerator MBT, which is substantially similar to the vulcanization of butyl rubber. It is mainly used for making tyre, inner tube, rubber shoes, medical articles, cable, industrial rubber products, etc. and can be used as bactericide and insecticide in agriculture and also can be used as lubricant additive.
At present, an industrial synthesis accelerator TMTD generally adopts a chlorine intermittent reaction mode, and when an intermediate product accelerator S is synthesized intermittently, raw materials cannot be contacted fully in time, and are volatile, and in a production operation site, volatile odor of the raw materials is scattered in the air, so that waste of the raw materials is caused firstly; secondly, the field environment is poor, and environmental waste gas pollution is caused; thirdly, the quality batches of the synthesized accelerator S are uneven, and the stability of quality cannot be ensured; fourthly, after the reaction, a lot of incompletely reacted waste carbon exists, a carbon separation process is increased, and potential safety hazards and raw material waste exist; fifthly, batch reaction is usually kettle reaction, the number of reaction kettles is large, and the occupied area is large. When the accelerator TMTD is synthesized by a chlorine intermittent method, cancerogenic substance sodium nitrite is easy to generate in the process, and belongs to a process route to be eliminated in the chemical industry.
The tubular continuous reaction has simple equipment, high mixing speed and uniform reaction condition, is not influenced by the operation factors of personnel in the intermittent reaction process, and is favorable for improving the product yield, stabilizing the quality and ensuring the operation safety in the synthesis process. Solves some technical problems existing in batch reaction, and makes up for technical defects.
Disclosure of Invention
The invention provides a novel method and equipment for continuously synthesizing a rubber vulcanization accelerator TMTD aiming at the problems existing in the production of the traditional rubber vulcanization accelerator TMTD.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
an apparatus for continuously synthesizing a rubber vulcanization accelerator TMTD, comprising an apparatus body, characterized in that the apparatus body comprises a tubular reactor a and a tubular reactor b. The tubular reactor a is horizontally arranged, a blast pipeline is arranged above the forefront end of the inlet of the reactor, vertically penetrates into the bottom of the reactor, is horizontally paved at the bottom in the reactor, and uniformly distributes air outlet holes on a blast pipe horizontally paved at the bottom of the reactor; the inlet of the tubular reactor is sealed at the vertical foremost end, and a circular overflow port is arranged in the middle of the vertical end of the outlet; the upper end of the rear half part of the reactor is provided with a vent valve and a vent pipeline, and the vent pipeline is connected with a tail gas absorbing device; the inlet to outlet direction of the reactor is sequentially provided with a water inlet pipeline, a dimethylamine inlet pipeline, a carbon disulfide inlet pipeline and a liquid alkali inlet pipeline; the water inlet pipeline, the dimethylamine inlet pipeline, the carbon disulfide inlet pipeline and the liquid caustic soda inlet pipeline are respectively connected with the feed pump and the storage tank; in actual production, four raw materials of water, dimethylamine, carbon disulfide and liquid caustic soda can also be connected to the tubular reactor through a centrifugal pump, a flowmeter and a regulating valve. The feed pipes for the four raw materials were vertical and penetrated the inner wall of the reactor. The regulating valves for adding samples of four raw materials are automatically interlocked with the regulating valve of the air blower, and when one material stops dripping or blowing, the valves of the rest materials are immediately cut off. The four raw materials of water, dimethylamine, carbon disulfide and liquid alkali are uniformly distributed on the tubular reactor at the same distance, and an overflow port is arranged at the middle position of the outlet end of the tubular reactor, so that the residence time of the materials in the tubular reactor is kept at 3-6 seconds, the materials can react more fully and rapidly, and the pipe diameter of the tubular reactor and the position of each material feed port can be calculated and specifically designed according to the residence time and the material consumption during actual production. Before raw materials are added dropwise, an air valve is opened; when raw materials are added dropwise, a water valve is firstly opened, pure water with the temperature of about 45 degrees is preferably added during production, after the water valve is opened, dimethylamine, carbon disulfide and liquid alkali valves are sequentially opened, and the opening time of the four raw materials is respectively 1 second at intervals through linkage control. The overflow outlet of the tubular reactor a is connected with the inlet of the tubular reactor b. The tubular reactor b is horizontally arranged, a blast pipeline is arranged above the forefront end of the inlet of the reactor, vertically penetrates into the bottom of the reactor, is horizontally paved at the bottom in the reactor, and uniformly distributes air outlet holes on a blast pipe horizontally paved at the bottom of the reactor; the inlet of the tubular reactor is sealed at the vertical foremost end, and a circular overflow port is arranged in the middle of the vertical end of the outlet; the upper end of the rear half part of the reactor is provided with a vent valve and a vent pipeline, and the vent pipeline is connected with a tail gas absorbing device; the inlet to the outlet of the tubular reactor b are sequentially and crosswise provided with a condensation liquid inlet pipeline and an acidic hydrogen peroxide solution inlet pipeline which are obtained from the outlet of the tubular reactor a; and the acidic hydrogen peroxide solution inlet pipeline is respectively connected with the feed pump and the storage tank. In actual production, the two raw materials of the condensed liquid and the acidic hydrogen peroxide solution can also be connected to the tubular reactor b through a centrifugal pump, a flowmeter and a regulating valve. The feed lines for both feeds were vertical and penetrated the inner wall of the reactor. The regulating valves for adding samples of two materials and the regulating valve for air blower are automatically interlocked with the regulating valves for adding samples of four materials and the regulating valve for air blower on the tubular reactor a, and when one material stops dripping or blowing, the valves for other materials are immediately cut off. The two raw materials of the condensation liquid and the acidic hydrogen peroxide solution are uniformly distributed on the tubular reactor b at equal intervals, an overflow port is arranged in the middle of the outlet end of the tubular reactor b, the residence time of the materials in the tubular reactor is kept at 3-6 seconds, the materials can react more fully and rapidly, and in actual production, the pipe diameter of the tubular reactor and the position of each material feed port can be calculated and specifically designed according to the residence time and the material consumption. Before raw materials are added dropwise, an air valve is opened; when the raw materials are dripped, the condensation liquid valve is started first, and then the acidic hydrogen peroxide solution valve is started. The outlet of the overflow port of the tubular reactor b is connected with a solid-liquid separation device, and the outlet of the solid-liquid separation device is connected with a drying system. The outside of the tubular reactor a and the tubular reactor b are wrapped with heating jackets, and the inside of the tubular reactor a and the inside of the tubular reactor b are provided with temperature sensors and pressure sensors. The reaction temperature of the tubular reactor a is kept at 30-45 ℃, the reaction temperature of the tubular reactor b is kept at 35-65 ℃, circulating water is introduced into jackets for carrying out heat preservation reaction in the embodiment, and a circulating water inlet pipeline is connected to an inlet pipeline at the lower part of the jackets of the tubular reactors through a centrifugal pump and a regulating valve. The tubular reactor is provided with a temperature sensor, when the sensed temperature deviates from the reaction required temperature through linkage control, the temperature of the circulating water is changed, the valve opening degree of the regulating valve is regulated, the circulating speed of the circulating water is regulated, the reaction temperature is controlled within the reaction required temperature range, the temperature regulating mode is a common temperature control mode in chemical production, the embodiment is not repeated, other heating modes such as electric heating, coil heating and the like can be adopted, and the temperature regulating mode is within the protection range of the invention.
Preferably, a sampling port and a feed valve are arranged between the overflow outlet of the tubular reactor a and the tubular reactor b.
Preferably, a sampling port feed valve is arranged between the overflow outlet of the tubular reactor b and the inlet of the solid-liquid separator.
Preferably, the tubular reactor a is horizontally arranged, the equipment body further comprises a controller, the input end of the controller is connected with each temperature sensor, the output end of the controller is connected with each feed valve switch, a feed pump, a heat source switch of a heating jacket and a blast valve switch of a blast blower, and the feed pumps respectively connected with the water inlet pipeline, the dimethylamine inlet pipeline, the carbon disulfide inlet pipeline and the liquid alkali inlet pipeline are in linkage control. The tubular reactor b is horizontally arranged, the equipment body further comprises a controller, the input end of the controller is connected with each temperature sensor, the output end of the controller is connected with each feed valve switch, each feed pump, the heat source switch of the heating jacket and the air valve switch of the blower, and the condensed liquid inlet pipeline and the acidic hydrogen peroxide solution inlet pipeline are respectively connected with the feed pumps in a linkage control mode.
The method for continuously synthesizing the rubber vulcanization accelerator TMTD comprises the steps of adjusting the reaction temperature in a tubular reactor a to 30-45 ℃, placing four raw materials of water, dimethylamine, carbon disulfide and liquid alkali in the order from an inlet end to an outlet end of the tubular reactor, starting a water feeding pump switch, sequentially starting the dimethylamine, carbon disulfide and liquid alkali feeding pump switch, and controlling the four raw materials to be started at intervals of 1TMTD through linkage; the residence time of water, dimethylamine, carbon disulfide and liquid caustic soda in the tubular reactor a is 3-6 seconds; the flow ratio of water, dimethylamine, carbon disulfide and liquid alkali is (7-8): (25-30): (10-15): (15-20); during the reaction, the synthesized condensation liquid material overflows into the tubular reactor b. Adjusting the reaction temperature in the tubular reactor b to 35-65 ℃, and opening a feed pump switch of the condensed liquid after two raw materials of the condensed liquid at the outlet of the tubular reactor b are placed in the order from the inlet end to the outlet end of the tubular reactor; then opening a switch of an acidic hydrogen peroxide solution feeding pump, wherein the opening time of the two raw materials is 1TMTD respectively by linkage control; the residence time of the condensed liquid and the acidic hydrogen peroxide solution in the tubular reactor a is 4-7 seconds; the flow ratio of the condensed liquid to the acidic hydrogen peroxide solution is (63-68): (47-50); in the reaction process, the materials enter a solid-liquid separation device through an overflow outlet, and then the solid materials enter a drying system to obtain the finished product accelerator TMTD.
Preferably, the liquid alkali is 30-35% sodium hydroxide solution by mass fraction, dimethylamine is 40-42% aqueous solution by mass fraction, carbon disulfide is not less than 98% by mass fraction, acidic hydrogen peroxide is 5-15% aqueous solution by mass fraction, and the pH of the acidic hydrogen peroxide is 1-1.5 (if sulfuric acid is used, the mass fraction of sulfuric acid is 18-30%).
Preferably, water with mass fraction lower than 2% is added into the carbon disulfide material.
The invention adopts a tubular reactor, and the reaction equation is as follows:
compared with the prior art, the invention has the advantages and positive effects that:
the invention can realize continuous production from feeding to discharging, and is convenient for realizing industrialized operation. The tubular reactor has small volume and high production efficiency, and the synthesized accelerator TMTD has stable quality and no peculiar smell, and improves the yield of the further synthesized accelerator TMTD.
Drawings
FIG. 1 is a schematic flow chart of a continuous production accelerator TMTD of the invention.
Detailed Description
In order that the above objects, features and advantages of the invention will be more clearly understood, a further description of the invention will be provided with reference to specific examples. It should be noted that, in the case of no conflict, the embodiments of the present application and the features in the embodiments may be combined with each other.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as described herein, and therefore the present invention is not limited to the specific embodiments of the disclosure that follow.
Example 1
This example provides the structure of a continuous reaction apparatus.
An apparatus for continuously synthesizing a rubber vulcanization accelerator TMTD, comprising an apparatus body, characterized in that the apparatus body comprises a tubular reactor a and a tubular reactor b. The tubular reactor a is horizontally arranged, a blast pipeline is arranged above the forefront end of the inlet of the reactor, vertically penetrates into the bottom of the reactor, is horizontally paved at the bottom in the reactor, and uniformly distributes air outlet holes on a blast pipe horizontally paved at the bottom of the reactor; the inlet of the tubular reactor is sealed at the vertical foremost end, and a circular overflow port is arranged in the middle of the vertical end of the outlet; the upper end of the rear half part of the reactor is provided with a vent valve and a vent pipeline, and the vent pipeline is connected with a tail gas absorbing device; the inlet to outlet direction of the reactor is sequentially provided with a water inlet pipeline, a dimethylamine inlet pipeline, a carbon disulfide inlet pipeline and a liquid alkali inlet pipeline; the water inlet pipeline, the dimethylamine inlet pipeline, the carbon disulfide inlet pipeline and the liquid caustic soda inlet pipeline are respectively connected with the feed pump and the storage tank; in actual production, four raw materials of water, dimethylamine, carbon disulfide and liquid caustic soda can also be connected to the tubular reactor through a centrifugal pump, a flowmeter and a regulating valve. The feed pipes for the four raw materials were vertical and penetrated the inner wall of the reactor. The regulating valves for adding samples of four raw materials are automatically interlocked with the regulating valve of the air blower, and when one material stops dripping or blowing, the valves of the rest materials are immediately cut off. The four raw materials of water, dimethylamine, carbon disulfide and liquid alkali are uniformly distributed on the tubular reactor at the same distance, and an overflow port is arranged at the middle position of the outlet end of the tubular reactor, so that the residence time of the materials in the tubular reactor is kept at 3-6 seconds, the materials can react more fully and rapidly, and the pipe diameter of the tubular reactor and the position of each material feed port can be calculated and specifically designed according to the residence time and the material consumption during actual production. Before raw materials are added dropwise, an air valve is opened; when raw materials are added dropwise, a water valve is firstly opened, pure water with the temperature of about 45 degrees is preferably added during production, after the water valve is opened, dimethylamine, carbon disulfide and liquid alkali valves are sequentially opened, and the opening time of the four raw materials is respectively 1 second at intervals through linkage control. The overflow outlet of the tubular reactor a is connected with the inlet of the tubular reactor b. The tubular reactor b is horizontally arranged, a blast pipeline is arranged above the forefront end of the inlet of the reactor, vertically penetrates into the bottom of the reactor, is horizontally paved at the bottom in the reactor, and uniformly distributes air outlet holes on a blast pipe horizontally paved at the bottom of the reactor; the inlet of the tubular reactor is sealed at the vertical foremost end, and a circular overflow port is arranged in the middle of the vertical end of the outlet; the upper end of the rear half part of the reactor is provided with a vent valve and a vent pipeline, and the vent pipeline is connected with a tail gas absorbing device; the inlet to the outlet of the tubular reactor b are sequentially and crosswise provided with a condensation liquid inlet pipeline and an acidic hydrogen peroxide solution inlet pipeline which are obtained from the outlet of the tubular reactor a; and the acidic hydrogen peroxide solution inlet pipeline is respectively connected with the feed pump and the storage tank. In actual production, the two raw materials of the condensed liquid and the acidic hydrogen peroxide solution can also be connected to the tubular reactor b through a centrifugal pump, a flowmeter and a regulating valve. The feed lines for both feeds were vertical and penetrated the inner wall of the reactor. The regulating valves for adding samples of two materials and the regulating valve for air blower are automatically interlocked with the regulating valves for adding samples of four materials and the regulating valve for air blower on the tubular reactor a, and when one material stops dripping or blowing, the valves for other materials are immediately cut off. The condensation liquid and the acidic hydrogen peroxide solution are uniformly distributed (a plurality of feed inlets are respectively arranged) on the tubular reactor b at equal intervals, and an overflow port is arranged in the middle of the outlet end of the tubular reactor b, so that the residence time of the materials in the tubular reactor is kept at 3-6 seconds, the materials can react more fully and rapidly, and the pipe diameter of the tubular reactor and the positions of the feed inlets of the materials can be calculated and specifically designed according to the residence time and the material consumption during actual production. Before raw materials are added dropwise, an air valve is opened; when the raw materials are dripped, the condensation liquid valve is started first, and then the acidic hydrogen peroxide solution valve is started. The outlet of the overflow port of the tubular reactor b is connected with a solid-liquid separation device, and the outlet of the solid-liquid separation device is connected with a drying system. The outside of the tubular reactor a and the tubular reactor b are wrapped with heating jackets, and the inside of the tubular reactor a and the inside of the tubular reactor b are provided with temperature sensors and pressure sensors. The reaction temperature of the tubular reactor a is kept at 30-45 ℃, the reaction temperature of the tubular reactor b is kept at 35-65 ℃, circulating water is introduced into jackets for carrying out heat preservation reaction in the embodiment, and a circulating water inlet pipeline is connected to an inlet pipeline at the lower part of the jackets of the tubular reactors through a centrifugal pump and a regulating valve. The tubular reactor is provided with a temperature sensor, when the sensed temperature deviates from the reaction required temperature through linkage control, the temperature of the circulating water is changed, the valve opening degree of the regulating valve is regulated, the circulating speed of the circulating water is regulated, the reaction temperature is controlled within the reaction required temperature range, the temperature regulating mode is a common temperature control mode in chemical production, the embodiment is not repeated, other heating modes such as electric heating, coil heating and the like can be adopted, and the temperature regulating mode is within the protection range of the invention.
In this embodiment, a sampling port and a feed valve are arranged between the overflow outlet of the tubular reactor a and the tubular reactor b.
In this embodiment, a sampling port is provided between the overflow outlet of the tubular reactor b and the inlet of the solid-liquid separator.
In this embodiment, tubular reactor a, tubular reactor b are all installed horizontally, tubular reactor a, tubular reactor b are inside all to be equipped with a row of blast pipe, and upper portion is equipped with the blow-down pipe and connects tail gas absorbing device, and the end is equipped with overflow export, and the equipment body all still includes the controller, and the controller input is connected radar level gauge and each temperature sensor and pressure sensor, and each feed valve switch, feed pump and heating jacket's heat source, the blast valve switch of air-blower are connected to the controller output, coordinated control between the feed pump that water inlet pipeline, dimethylamine inlet pipeline, carbon disulfide inlet pipeline, liquid alkali inlet pipeline, condensation liquid inlet pipeline, acid hydrogen peroxide solution inlet pipeline are connected respectively.
In the embodiment, the inner lining anticorrosive paint of the tubular reactor a and the tubular reactor b is horizontally arranged and installed, a row of blast pipes are arranged at the bottom inside the tubular reactor a and the tubular reactor b, the upper part is provided with a blow-down pipe connected with a tail gas absorbing device, the vertical forefront ends of the inlets of the tubular reactor a and the tubular reactor b are closed, and the tail ends of the inlets of the tubular reactor a and the tubular reactor b are provided with overflow outlets. The materials enter the tubular reactor through the feed inlet, firstly: the blast pipe is used for carrying out micro air quantity, so that various raw materials are uniformly mixed, the reaction is quick and sufficient, the burdensome of speed reduction stirring is reduced, and the equipment is simple and portable and occupies a small area; secondly, it is: the material flows into the next working procedure while reacting through the overflow port; thirdly, the method comprises the following steps: the reaction residence time of the material in the tubular reactor a is ensured to be kept between 3 and 6 seconds and the reaction residence time in the tubular reactor b is ensured to be kept between 4 and 7 seconds.
According to the advancing direction of the materials, sequentially designing water, dimethylamine, carbon disulfide, liquid alkali and acidic hydrogen peroxide storage tanks, wherein each material storage tank is connected with a peristaltic pump and a tubular reactor through a silica gel pipeline, or a stainless steel pipeline lined with anticorrosive paint is used for connecting a centrifugal pump and a flowmeter in production, and continuously entering the tubular reactor according to the designed flow rate.
The overflow outlet of the tubular reactor a is connected with the inlet of the tubular reactor b, and a sampling port is reserved at the joint of the overflow outlet and the inlet of the tubular reactor a for sampling detection; and an overflow outlet of the tubular reactor b is connected with an inlet of the solid-liquid separation device, and a sampling port is reserved at the joint of the overflow outlet and the inlet of the solid-liquid separation device for sampling and detection. The solid-liquid separation device is connected with the drying system.
Example 2
This example provides a method of continuously synthesizing the rubber vulcanization accelerator TMTD.
30ml of water, 115ml of dimethylamine aqueous solution with the mass fraction of 40%, 57ml of carbon disulfide with the mass fraction of 98% (adding a small amount of water for liquid sealing, reducing volatilization) and 81ml of sodium hydroxide aqueous solution with the mass fraction of 32% are respectively measured by using a measuring cylinder, and are put into four customized glass beakers with glass outlets and switches at the bottoms, wherein a steam pipeline is introduced into the glass beakers for placing water, the water is heated and kept at the temperature of 40-45 ℃, and meanwhile, a thermometer is inserted for measurement. The rest raw materials are fed at normal temperature. Before raw materials are added dropwise, a blower is turned on; when the raw materials are added, firstly 30ml of water is added dropwise, the rotation speed of a peristaltic pump is 7.6 revolutions per minute, then 115ml of dimethylamine is added dropwise, the rotation speed of the peristaltic pump is 25.8 revolutions per minute, then 57ml of carbon disulfide is added dropwise, the rotation speed of the peristaltic pump is 13 revolutions per minute, and finally 81ml of liquid caustic soda is added dropwise, and the rotation speed of the peristaltic pump is 18.2 revolutions per minute. The four materials are added into the tubular reactor 1 in a dripping way according to the above adding amount and peristaltic pump rotating speed and the set adding sequence at intervals of 1 second. The diameter of the tubular reactor a in this example was 2cm and the length thereof was 30cm. The positions of the feed inlets of the four substances of water, dimethylamine, carbon disulfide and liquid alkali on the tubular reactor are as follows: the inlet at the uppermost end of the tubular reactor a is 2cm, the inlet at the uppermost end of the tubular reactor a is 4 cm, the inlet at the uppermost end of the tubular reactor a is 6 cm, the inlet at the uppermost end of the tubular reactor a is 8 cm, and the tubular reactor a is horizontally arranged.
173.34g of an acidic hydrogen peroxide solution with a mass fraction of 9% (the mass fraction of sulfuric acid is 25.9%) is weighed by using a measuring cylinder and placed in a glass beaker with a glass outlet and a switch at the bottom. When the overflow outlet of the tubular reactor a overflows materials into the tubular reactor b, a blast valve is opened, and meanwhile, the acidic hydrogen peroxide solution is dripped, and the rotating speed of a peristaltic pump is 16.3 revolutions per minute. The reaction temperature in the tubular reactor b was adjusted to 35-65℃and the diameter of the tubular reactor b was 2cm and the length was 50cm in this example. The two substances of the condensed liquid and the acidic hydrogen peroxide solution are distributed at the position of a feed inlet on the tubular reactor in a crossing way, and the position of the feed inlet of the condensed liquid on the tubular reactor is as follows: 2cm of the uppermost inlet of the tubular reactor b and 6 cm of the uppermost inlet of the tubular reactor b; the position of the feeding port of the acidic hydrogen peroxide solution on the tubular reactor b is: the inlet at the uppermost end of the tubular reactor b is 4 cm and the inlet at the uppermost end of the tubular reactor b is 8 cm. The tubular reactor b is placed horizontally.
The same amount of material was used to synthesize 1 batch in 90 minutes for batch reaction. In the first stage, the material of the condensation liquid synthesized in the tubular reactor a is dark yellow in color, has a non-uniform specific gravity of between 1.070 and 1.076g/ml and has a pungent taste. In the second stage, TMTD synthesized in the tubular reactor b has a low initial melting point, about 140.0 ℃ and an average purity of 96.0%. By adopting the embodiment, 1 batch of material can be synthesized within 30 minutes. The material appearance of the condensation liquid synthesized in the first stage is colorless or light yellow, the process is repeated for 3 times in parallel, the obtained product has uniform specific gravity and is stable at 1.070g/ml, and the material has almost no peculiar smell. The TMTD synthesized in the second stage has high initial melting point of 142.9 ℃ and average purity of 98.9%.
Example 3
The feed reaction was carried out by increasing the feed rate of the raw materials based on the conditions in example 2.
When the temperature of the reaction system is 25-45 ℃, 57ml of water, the peristaltic pump rotating speed is 28.8 revolutions per minute, 218.5ml of dimethylamine, the peristaltic pump rotating speed is 98.0 revolutions per minute, 108.3ml of carbon disulfide, the peristaltic pump rotating speed is 49.4 revolutions per minute, 153.9ml of liquid alkali and the peristaltic pump rotating speed is 69.2 revolutions per minute are sequentially opened, and the four materials are dripped into the tubular reactor a according to the adding amount and the peristaltic pump rotating speed.
The liquid flowing out of the tubular reactor 1 is condensation liquid, the appearance is light yellow liquid, no peculiar smell exists, the specific gravity is 1.070g/ml, no waste carbon exists, and the purity is 99.9%.
The liquid condensate obtained overflows into the tubular reactor b through the overflow outlet of the tubular reactor a. The mass fraction of the condensate was 19.5%.329.44g of acidic hydrogen peroxide solution with mass fraction of 9% is put into a glass beaker with a glass outlet and a switch at the bottom, when the overflow outlet of the tubular reactor a overflows and materials enter the tubular reactor b, a blast valve is started, meanwhile, the acidic hydrogen peroxide solution is dripped, the reaction temperature in the tubular reactor b is regulated to 35-65 ℃, and the rotation speed of a peristaltic pump is 66.7 r/min. The diameter of the tubular reactor b in this example was 2cm and the length was 50cm. The two substances of the condensed liquid and the acidic hydrogen peroxide solution are distributed at the position of a feed inlet on the tubular reactor in a crossing way, and the position of the feed inlet of the condensed liquid on the tubular reactor is as follows: 2cm of the uppermost inlet of the tubular reactor b and 6 cm of the uppermost inlet of the tubular reactor b; the position of the feeding port of the acidic hydrogen peroxide solution on the tubular reactor b is: the inlet at the uppermost end of the tubular reactor b is 4 cm and the inlet at the uppermost end of the tubular reactor b is 8 cm. The tubular reactor b is placed horizontally.
The material appearance of the condensation liquid synthesized in the first stage is colorless or light yellow, the specific gravity is 1.070g/ml, and no peculiar smell exists. After the second stage synthesis is finished, filtering and drying are carried out to obtain 206.72g of white finished TMTD, the yield is 98.6%, the initial melting point is 142.5 ℃, and the purity is 98.9%.
Example 4
This embodiment randomly samples the operation in the following condition interval. A method for continuously producing an accelerator TMTD, comprising the steps of:
(1) At normal temperature, 520g of 30% hydrogen peroxide by mass fraction is taken and put into 520-2600g of water, 459g of 98% sulfuric acid by mass fraction is taken and put into water, and 15% acid hydrogen peroxide solution is prepared for standby;
(2) The four materials of water, liquid alkali, dimethylamine and carbon disulfide are respectively connected with a peristaltic pump;
(3) 3000-6000ml of water, 7.6 revolutions per minute of peristaltic pump, 1150-2310ml of dimethylamine, 25.8 revolutions per minute of peristaltic pump, 570-1120ml of carbon disulfide, 13 revolutions per minute of peristaltic pump, 810-1790ml of liquid alkali and 18.2 revolutions per minute of peristaltic pump are added into the tubular reactor a according to the adding amount and the peristaltic pump rotational speed, and the outlet liquid in the tubular reactor a is the accelerator S.
(4) The accelerator S flowing out of the tubular reactor a enters the tubular reaction 2 through a plurality of points, simultaneously, 1499-3579g of acid hydrogen peroxide solution enters the tubular reactor b from different distribution points at the speed of 56.7 r/min by a peristaltic pump, the reaction temperature is 35-65 ℃, the outlet of the tubular reactor b is connected with a suction filtration device, and the white finished product TMTD is obtained through suction filtration, water washing and drying. The TMTD finished product has high initial melting point, stability at 142.2-142.6 deg.C and purity of 98.8-99.2%.
Example 5
This example differs from example 2 in that the raw materials for the entire reaction were expanded in equal proportions and continuously operated for 24 hours. After 30min, sampling is carried out from two sampling ports on the equipment at random, the sampling frequency is not less than 10 times, and the stability of the product is detected. The results are shown in Table 1.
TABLE 1 sampling test results of condensate at different times after the start of the reaction
TABLE 2 TMTD sampling test results at different times after the reaction was started
From the detection data, the quality of the continuous reaction product of the embodiment is very stable, the specific gravity of the condensed liquid is stabilized at 1.070g/ml, and the condensed liquid is light yellow to colorless in appearance and has no peculiar smell. The TMTD finished product has high initial melting point, is stable at 142.2-142.6 ℃, and has high purity of 98.8-99.2%.
The present invention is not limited to the above-mentioned embodiments, and any equivalent embodiments which can be changed or modified by the technical content disclosed above can be applied to other fields, but any simple modification, equivalent changes and modification made to the above-mentioned embodiments according to the technical substance of the present invention without departing from the technical content of the present invention still belong to the protection scope of the technical solution of the present invention.
Claims (6)
1. A method for continuously synthesizing a rubber vulcanization accelerator TMTD, which comprises an equipment body, and is characterized in that the equipment body comprises a tubular reactor a and a tubular reactor b; the tubular reactor a is horizontally arranged, a blast pipeline A is arranged above the forefront end of the inlet of the tubular reactor a, vertically penetrates into the bottom of the tubular reactor a, is flatly paved at the inner bottom of the tubular reactor a, and uniformly distributes air outlet holes on the blast pipeline A flatly paved at the bottom of the tubular reactor a; the vertical foremost end of the inlet of the tubular reactor a is closed, and a circular overflow port A is arranged in the middle of the vertical end of the outlet; the upper end of the rear half part of the tubular reactor a is provided with a vent valve A and a vent pipeline A, and the vent pipeline A is connected with a tail gas absorbing device; the inlet to outlet direction of the tubular reactor a is provided with a water inlet pipeline, a dimethylamine inlet pipeline, a carbon disulfide inlet pipeline and a liquid alkali inlet pipeline which are sequentially and uniformly distributed at equal intervals; the water inlet pipeline, the dimethylamine inlet pipeline, the carbon disulfide inlet pipeline and the liquid caustic soda inlet pipeline are respectively connected with the feed pump and the storage tank; the outlet of the overflow port A is connected with the inlet of the tubular reactor b; the tubular reactor B is horizontally arranged, a blast pipeline B is arranged above the forefront end of the inlet of the tubular reactor B, the blast pipeline B vertically penetrates into the bottom of the tubular reactor B and is flatly paved at the inner bottom of the tubular reactor B, and air outlet holes are uniformly distributed on the blast pipeline B flatly paved at the bottom of the tubular reactor B; the inlet of the tubular reactor B is sealed at the vertical foremost end, and a circular overflow port B is arranged in the middle of the vertical end of the outlet; the upper end of the rear half part of the tubular reactor B is provided with a vent valve B and a vent pipeline B, and the vent pipeline B is connected with a tail gas absorbing device; the inlet to the outlet of the tubular reactor b are sequentially and crosswise provided with a condensation liquid inlet pipeline and an acidic hydrogen peroxide solution inlet pipeline which are obtained from the outlet of the tubular reactor a; the acidic hydrogen peroxide solution inlet pipeline is respectively connected with the feed pump and the storage tank; the outside of the tubular reactor a and the outside of the tubular reactor b are respectively wrapped with a heating jacket, and the inside of the tubular reactor a and the inside of the tubular reactor b are respectively provided with a temperature sensor and a pressure sensor; the outlet of the overflow port of the tubular reactor b is connected with a solid-liquid separation device, and the outlet of the solid-liquid separation device is connected with a drying system;
adjusting the reaction temperature in the tubular reactor a to 30-45 ℃, placing four raw materials of water, dimethylamine, carbon disulfide and liquid caustic soda in the order from the inlet end to the outlet end of the tubular reactor, and opening an air valve before dripping the raw materials; when raw materials are added dropwise, firstly starting a water feed pump switch, and then sequentially starting dimethylamine, carbon disulfide and liquid alkali feed pump switches, wherein the four raw materials are started at intervals of 1 second respectively through linkage control; the residence time of water, dimethylamine, carbon disulfide and liquid caustic soda in the tubular reactor a is 3-6 seconds; the flow ratio of water, dimethylamine, carbon disulfide and liquid alkali is (7-8): (25-30): (10-15): (15-20); during the reaction, the synthesized condensed liquid material overflows into a tubular reactor b; adjusting the reaction temperature in the tubular reactor b to 35-65 ℃, placing two raw materials of the condensation liquid and the acidic hydrogen peroxide solution at the outlet of the tubular reactor a in the order from the inlet end to the outlet end of the tubular reactor, and opening an air valve before dripping the raw materials; when the raw materials are dripped, a feed pump switch of the condensed liquid is started; then opening a switch of an acidic hydrogen peroxide solution feeding pump; the starting time of the two raw materials is respectively 1 second at intervals through linkage control; the residence time of the condensed liquid and the acidic hydrogen peroxide solution in the tubular reactor b is 4-7 seconds; the flow ratio of the condensed liquid to the acidic hydrogen peroxide solution is (63-68): (47-50); in the reaction process, the materials enter a solid-liquid separation device through an overflow outlet, and then the solid materials enter a drying system to obtain the finished product accelerator TMTD.
2. The method of continuous synthetic rubber vulcanization accelerator TMTD according to claim 1, where a sampling port and a feed valve are provided between the overflow outlet of the tubular reactor a and the tubular reactor b.
3. The method for continuously synthesizing a rubber vulcanization accelerator TMTD according to claim 1, wherein a sampling port is provided between the overflow outlet of the tubular reactor b and the inlet of the solid-liquid separator.
4. The method for continuously synthesizing the rubber vulcanization accelerator TMTD according to claim 2, wherein the equipment body further comprises a controller, the input end of the controller is connected with each temperature sensor, the output end of the controller is connected with each feed valve switch, a feed pump, a heat source switch of a heating jacket and a blast valve switch of a blast blower, and the linkage control is carried out among the feed pumps respectively connected with a water inlet pipeline, a dimethylamine inlet pipeline, a carbon disulfide inlet pipeline and a liquid alkali inlet pipeline; and the condensed liquid inlet pipeline and the acidic hydrogen peroxide solution inlet pipeline are respectively connected with the feeding pumps in linkage control.
5. The method for continuously synthesizing a rubber vulcanization accelerator TMTD according to claim 1, wherein the liquid alkali is 30-35% sodium hydroxide solution by mass, the dimethylamine is 40-42% aqueous solution by mass, and the carbon disulfide mass is not less than 98%; the acidic hydrogen peroxide is an aqueous solution with the mass fraction of 5-15%, and the PH of the acidic hydrogen peroxide is 1-1.5.
6. The method of claim 1, wherein less than 2% water by mass is added to the carbon disulfide formulation.
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