阅读说明：本技术 一种连续法合成促进剂tmtd的方法 (Method for synthesizing promoter TMTD by continuous method ) 是由 刘园园 张颂 姚显锋 孟凡虎 吕桂中 徐清华 于 2020-12-30 设计创作，主要内容包括：本发明涉及橡胶促进剂TMTD生产技术领域,特别涉及一种连续化生产促进剂TMTD的方法。本发明从进料到出料可实现连续化生产,便于实现工业化操作。管式反应器体积小,生产效率高,合成的促进剂TMTD质量稳定,无异味,提高了进一步合成促进剂TMTD的收率。(The invention relates to the technical field of production of rubber accelerator TMTD, 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, the synthesized promoter TMTD has stable quality and no peculiar smell, and the yield of the further synthesized promoter TMTD is improved.)

1. An apparatus for continuously synthesizing a rubber vulcanization accelerator TMTD, comprising an apparatus body, wherein the apparatus body comprises a tubular reactor a and a tubular reactor b; the tubular reactor a is horizontally installed, an air blowing pipeline is arranged above the foremost end of the inlet of the reactor, the air blowing pipeline vertically extends into the bottom of the reactor and is paved at the bottom in the reactor, and air outlet holes are uniformly distributed on the air blowing pipe paved at the bottom of the reactor; the vertical foremost end of the inlet of the tubular reactor is closed, and the middle part of the vertical end of the outlet is provided with a circular overflow port; 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 absorption device; a water inlet pipeline, a dimethylamine inlet pipeline, a carbon disulfide inlet pipeline and a liquid caustic soda inlet pipeline are sequentially arranged in the direction from the inlet to the outlet of the reactor; 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 feeding pump and the storage tank; the outlet of the overflow port is connected with the inlet of the tubular reactor b; the tubular reactor b is horizontally installed, an air blowing pipeline is arranged above the foremost end of the inlet of the reactor, the air blowing pipeline vertically extends into the bottom of the reactor and is paved at the bottom in the reactor, and air outlet holes are uniformly distributed on the air blowing pipe paved at the bottom of the reactor; the vertical foremost end of the inlet of the tubular reactor is closed, and the middle part of the vertical end of the outlet is provided with a circular overflow port; 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 absorption device; a condensation liquid inlet pipeline and an acidic hydrogen peroxide solution inlet pipeline obtained from the outlet of the tubular reactor a are sequentially and crossly arranged from the inlet to the outlet of the tubular reactor b; the acidic hydrogen peroxide solution inlet pipeline is respectively connected with the feeding pump and the storage tank; heating jackets wrap the outsides of the tubular reactor a and the tubular reactor b, and temperature sensors and pressure sensors are arranged inside the tubular reactor a and the tubular reactor b; an outlet of an overflow port of the tubular reactor b is connected with a solid-liquid separation device, and an outlet of the solid-liquid separation device is connected with a drying system.

2. The apparatus for continuous synthesis of rubber vulcanization accelerator TMTD according to claim 1, characterized in that 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 apparatus for continuous synthesis of rubber vulcanization accelerator TMTD according to claim 1, characterized in that a sampling port is provided between the overflow outlet of the tubular reactor b and the inlet of the solid-liquid separator.

4. The apparatus for continuously synthesizing a rubber vulcanization accelerator TMTD as claimed in claim 2, wherein the apparatus body further comprises a controller, the input end of the controller is connected to each temperature sensor, the output end of the controller is connected to each feed valve switch, a feed pump, a heat source switch of a heating jacket, and an air valve switch of an air blower, and the feed pumps respectively connected to the water inlet pipeline, the dimethylamine inlet pipeline, the carbon disulfide inlet pipeline, and the liquid caustic soda inlet pipeline are controlled in a linkage manner; and the feeding pumps which are respectively connected with the condensation liquid inlet pipeline and the acidic hydrogen peroxide solution inlet pipeline are in linkage control.

5. A method for continuously synthesizing a rubber vulcanization accelerator TMTD by using the apparatus according to any one of claims 1 to 4, characterized in that the reaction temperature in the tubular reactor a is adjusted to 30 to 45 ℃, and after the four raw materials of water, dimethylamine, carbon disulfide and liquid alkali are placed in the order from the inlet end to the outlet end of the tubular reactor, the feed pump switch of water is turned on first, then the feed pump switches of dimethylamine, carbon disulfide and liquid alkali are turned on in sequence, and the turn-on time of the four raw materials is 1 second apart by interlocking control; the retention time of water, dimethylamine, carbon disulfide and liquid alkali in the tubular reactor is 3-6 seconds; the flow ratio of water, dimethylamine, carbon disulfide and liquid alkali is (7-8): (25-30): (10-15): (15-20); in the reaction process, the synthesized condensed liquid material overflows into the tubular reactor b; adjusting the reaction temperature in the tubular reactor b to 35-65 ℃, and starting a feed pump switch of the condensation liquid after placing two raw materials of the condensation liquid at the outlet of the tubular reactor b and the acidic hydrogen peroxide solution in sequence from the inlet end to the outlet end of the tubular reactor; then opening a switch of an acidic hydrogen peroxide solution feeding pump; in the reaction process, the material enters a solid-liquid separation device through an overflow outlet, and then the solid material enters a drying system to obtain the finished product of the promoter TMTD.

6. The method for continuously synthesizing the rubber vulcanization accelerator TMTD according to claim 5, wherein the liquid alkali is a sodium hydroxide solution with a mass fraction of 30-35%, the dimethylamine is an aqueous solution with a mass fraction of 40-42%, and the carbon disulfide mass fraction is not less than 98%; the acidic hydrogen peroxide is an aqueous solution with the mass fraction of 5-15%, and the pH value of the acidic hydrogen peroxide is 1-1.5.

7. The process for the continuous synthesis of a rubber vulcanization accelerator TMTD according to claim 5, characterized in that the carbon disulfide mass is charged with less than 2% by weight of water.

Technical Field

The invention relates to the technical field of production of rubber accelerator TMTD, in particular to a method for continuously producing accelerator TMTD.

Background

TMTD is an excellent second accelerator for thiazole accelerators and can also be used in combination with other accelerators, usually MBT, in a situation substantially similar to the vulcanization of butyl rubber. The product is mainly used for manufacturing tires, inner tubes, rubber shoes, medical supplies, cables, industrial rubber products and the like, is used as a bactericide and an insecticide in agricultural use, and can also be used as a lubricating oil additive.

At present, an industrially synthesized accelerator TMTD usually adopts a chlorine intermittent reaction mode, and when an intermediate accelerator S is intermittently synthesized, raw materials cannot be timely and fully contacted and are volatile, so that volatile odor of the raw materials is dispersed in air on a production operation site, and the raw materials are wasted; secondly, the field environment is poor, and the waste gas pollution of the environment is caused; thirdly, the quality of the synthesized accelerator S is not uniform among batches, and the stability of the quality cannot be ensured; fourthly, a plurality of incompletely reacted waste carbon exist after the reaction, so that the carbon separation process is added, potential safety hazards exist, and raw materials are wasted; fifthly, the batch reaction is usually a kettle type reaction, so that a plurality of reaction kettles exist, and the occupied area is large. When the accelerant TMTD is synthesized by using a chlorine intermittent method, a carcinogenic substance sodium nitrite is easily generated in the process, and the method belongs to a process route which is about to be eliminated in the chemical industry.

The tubular continuous reaction has the advantages of simple equipment, high mixing speed, uniform reaction conditions, no influence of personnel operation factors in the intermittent reaction process, and contribution to improving the product yield, stabilizing the quality and ensuring the operation safety in the synthesis process. Solves some technical problems existing in the batch reaction and makes up for the technical defects.

Disclosure of Invention

The invention provides a novel method and equipment for continuously synthesizing a rubber vulcanization accelerator TMTD (tetramethylenetetrazol) aiming at the problems in the production of the traditional rubber vulcanization accelerator TMTD.

In order to achieve the 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 installed, an air blowing pipeline is arranged above the foremost end of the inlet of the reactor, the air blowing pipeline vertically extends into the bottom of the reactor and is paved at the bottom in the reactor, and air outlet holes are uniformly distributed on the air blowing pipe paved at the bottom of the reactor; the vertical foremost end of the inlet of the tubular reactor is closed, and the middle part of the vertical end of the outlet is provided with a circular overflow port; 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 absorption device; a water inlet pipeline, a dimethylamine inlet pipeline, a carbon disulfide inlet pipeline and a liquid caustic soda inlet pipeline are sequentially arranged in the direction from the inlet to the outlet of the reactor; 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 feeding pump and the storage tank; in the 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 flow meter and a regulating valve. The feed pipes for the four feedstocks are vertical and penetrate the inner wall of the reactor. The regulating valves for the sample adding of the four raw materials and the regulating valve of the air blower are automatically interlocked, and when one material stops dripping or blowing, the valves of the other materials are immediately cut off. The four raw materials of water, dimethylamine, carbon disulfide, liquid caustic soda are the same distance evenly distributed at the interval on tubular reactor, and tubular reactor exit end intermediate position sets up the overflow mouth, guarantees that the dwell time of material in tubular reactor keeps 3-6 seconds, makes the more abundant quick reaction of material, and during actual production, the pipe diameter of tubular reactor, the position of each material feed inlet can calculate and concrete design according to this dwell time and material quantity. Before the raw materials are dripped, an air valve is opened; when the raw materials are dripped, a water valve is opened firstly, pure water with the temperature of about 45 ℃ is preferably added during production, the dimethylamine, the carbon disulfide and the liquid caustic soda valve are opened sequentially after the water valve is opened, and the opening time of the four raw materials is respectively spaced by 1 second through linkage control. The outlet of the overflow port of the tubular reactor a is connected with the inlet of the tubular reactor b. The tubular reactor b is horizontally installed, an air blowing pipeline is arranged above the foremost end of the inlet of the reactor, the air blowing pipeline vertically extends into the bottom of the reactor and is paved at the bottom in the reactor, and air outlet holes are uniformly distributed on the air blowing pipe paved at the bottom of the reactor; the vertical foremost end of the inlet of the tubular reactor is closed, and the middle part of the vertical end of the outlet is provided with a circular overflow port; 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 absorption device; a condensation liquid inlet pipeline and an acidic hydrogen peroxide solution inlet pipeline obtained from the outlet of the tubular reactor a are sequentially and crossly arranged from the inlet to the outlet of the tubular reactor b; and the acidic hydrogen peroxide solution inlet pipeline is respectively connected with the feeding pump and the storage tank. In actual production, the condensation liquid and the acidic hydrogen peroxide solution can be connected to the tubular reactor b through a centrifugal pump, a flowmeter and a regulating valve. The feed pipes for both feedstocks are vertical, penetrating the inner wall of the reactor. The regulating valves for the sample adding of the two raw materials and the regulating valves for the blower and the regulating valves for the sample adding of the four raw materials on the tubular reactor a are automatically interlocked, and when one material stops dripping or blowing, the valves for the other materials are immediately cut off. The condensation liquid and the acidic hydrogen peroxide solution are uniformly distributed on the tubular reactor b at the same interval in a crossed manner, the overflow port is arranged in the middle of the outlet end of the tubular reactor b, so that the retention time of materials in the tubular reactor is kept at 3-6 seconds, the materials can be reacted more sufficiently and rapidly, and the pipe diameter of the tubular reactor and the positions of material feed inlets can be calculated and specifically designed according to the retention time and the material consumption during actual production. Before the raw materials are dripped, an air valve is opened; when the raw materials are dripped, the condensation liquid valve is opened first, and then the acid hydrogen peroxide solution valve is opened. An outlet of an overflow port of the tubular reactor b is connected with a solid-liquid separation device, and an outlet of the solid-liquid separation device is connected with a drying system. The heating jacket is wrapped outside the tubular reactor a and the tubular reactor b, and the temperature sensor and the pressure sensor are arranged inside the tubular reactor a and the tubular reactor b. 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 ℃, in the embodiment, the tubular reactor a and the tubular reactor b adopt a jacket to introduce circulating water for heat preservation reaction, and a circulating water inlet pipeline is connected to an inlet pipeline at the lower part of the jacket of the tubular reactor through a centrifugal pump and a regulating valve. The tubular reactor is provided with a temperature sensor, and when the sensed temperature deviates from the reaction required temperature, the temperature of the circulating water is changed, the opening degree of a valve of an adjusting valve is adjusted, and the circulating speed of the circulating water is adjusted, so that the reaction temperature is controlled within the reaction required temperature range.

Preferably, a sampling port and a feeding valve are arranged between the overflow outlet of the tubular reactor a and the tubular reactor b.

Preferably, a sampling port feeding 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 an air valve switch of an air blower, and the feed pumps which are respectively connected with the water inlet pipeline, the dimethylamine inlet pipeline, the carbon disulfide inlet pipeline and the liquid caustic soda 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 feeding valve switch, the feeding pump, a heat source switch of a heating jacket and an air valve switch of an air blower, and the feeding pumps which are respectively connected with the condensation liquid inlet pipeline and the acidic hydrogen peroxide solution inlet pipeline are in linkage control.

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 ℃, sequentially placing four raw materials of water, dimethylamine, carbon disulfide and liquid alkali from an inlet end to an outlet end of the tubular reactor, starting a feed pump switch of the water, then sequentially starting the feed pump switches of the dimethylamine, the carbon disulfide and the liquid alkali, and performing chain control to start the four raw materials at intervals of 1 TMTD; the retention time of water, dimethylamine, carbon disulfide and liquid alkali 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 process, the synthesized condensed liquid material overflows into the tubular reactor b. Adjusting the reaction temperature in the tubular reactor b to 35-65 ℃, and starting a feed pump switch of the condensation liquid after placing two raw materials of the condensation liquid at the outlet of the tubular reactor b and the acidic hydrogen peroxide solution in sequence from the inlet end to the outlet end of the tubular reactor; then starting a switch of an acid hydrogen peroxide solution feeding pump, and respectively starting the two raw materials at the interval of 1TMTD through linkage control; the residence time of the condensation liquid and the acidic hydrogen peroxide solution in the tubular reactor a is 4-7 seconds; the flow ratio of the condensation liquid to the acidic hydrogen peroxide solution is (63-68): (47-50); in the reaction process, the material enters a solid-liquid separation device through an overflow outlet, and then the solid material enters a drying system to obtain the finished product of the promoter TMTD.

Preferably, the liquid alkali is a sodium hydroxide solution with the mass fraction of 30-35%, the dimethylamine is an aqueous solution with the mass fraction of 40-42%, the mass fraction of the carbon disulfide is not less than 98%, the acidic hydrogen peroxide is a hydrogen peroxide solution with the mass fraction of 5-15%, the acidic hydrogen peroxide solution is an aqueous solution with the mass fraction of 5-15%, and the pH of the acidic hydrogen peroxide solution is 1-1.5 (if sulfuric acid is used, the mass fraction of sulfuric acid is 18-30%).

Preferably, the carbon disulfide material is added with water with the mass fraction of less than 2 percent.

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, the synthesized promoter TMTD has stable quality and no peculiar smell, and the yield of the further synthesized promoter TMTD is improved.

Drawings

FIG. 1 is a schematic flow diagram of a continuous process for producing promoter TMTD in accordance with the present invention.

Detailed Description

In order that the above objects, features and advantages of the present invention may be more clearly understood, the present invention will be further described with reference to specific embodiments. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.

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 in other ways than those specifically described herein, and thus the present invention is not limited to the specific embodiments of the present disclosure.

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 installed, an air blowing pipeline is arranged above the foremost end of the inlet of the reactor, the air blowing pipeline vertically extends into the bottom of the reactor and is paved at the bottom in the reactor, and air outlet holes are uniformly distributed on the air blowing pipe paved at the bottom of the reactor; the vertical foremost end of the inlet of the tubular reactor is closed, and the middle part of the vertical end of the outlet is provided with a circular overflow port; 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 absorption device; a water inlet pipeline, a dimethylamine inlet pipeline, a carbon disulfide inlet pipeline and a liquid caustic soda inlet pipeline are sequentially arranged in the direction from the inlet to the outlet of the reactor; 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 feeding pump and the storage tank; in the 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 flow meter and a regulating valve. The feed pipes for the four feedstocks are vertical and penetrate the inner wall of the reactor. The regulating valves for the sample adding of the four raw materials and the regulating valve of the air blower are automatically interlocked, and when one material stops dripping or blowing, the valves of the other materials are immediately cut off. The four raw materials of water, dimethylamine, carbon disulfide, liquid caustic soda are the same distance evenly distributed at the interval on tubular reactor, and tubular reactor exit end intermediate position sets up the overflow mouth, guarantees that the dwell time of material in tubular reactor keeps 3-6 seconds, makes the more abundant quick reaction of material, and during actual production, the pipe diameter of tubular reactor, the position of each material feed inlet can calculate and concrete design according to this dwell time and material quantity. Before the raw materials are dripped, an air valve is opened; when the raw materials are dripped, a water valve is opened firstly, pure water with the temperature of about 45 ℃ is preferably added during production, the dimethylamine, the carbon disulfide and the liquid caustic soda valve are opened sequentially after the water valve is opened, and the opening time of the four raw materials is respectively spaced by 1 second through linkage control. The outlet of the overflow port of the tubular reactor a is connected with the inlet of the tubular reactor b. The tubular reactor b is horizontally installed, an air blowing pipeline is arranged above the foremost end of the inlet of the reactor, the air blowing pipeline vertically extends into the bottom of the reactor and is paved at the bottom in the reactor, and air outlet holes are uniformly distributed on the air blowing pipe paved at the bottom of the reactor; the vertical foremost end of the inlet of the tubular reactor is closed, and the middle part of the vertical end of the outlet is provided with a circular overflow port; 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 absorption device; a condensation liquid inlet pipeline and an acidic hydrogen peroxide solution inlet pipeline obtained from the outlet of the tubular reactor a are sequentially and crossly arranged from the inlet to the outlet of the tubular reactor b; and the acidic hydrogen peroxide solution inlet pipeline is respectively connected with the feeding pump and the storage tank. In actual production, the condensation liquid and the acidic hydrogen peroxide solution can be connected to the tubular reactor b through a centrifugal pump, a flowmeter and a regulating valve. The feed pipes for both feedstocks are vertical, penetrating the inner wall of the reactor. The regulating valves for the sample adding of the two raw materials and the regulating valves for the blower and the regulating valves for the sample adding of the four raw materials on the tubular reactor a are automatically interlocked, and when one material stops dripping or blowing, the valves for the other materials are immediately cut off. The condensation liquid and the acidic hydrogen peroxide solution are uniformly distributed on the tubular reactor b at the same interval at equal intervals in a crossed manner (a plurality of feeding holes are respectively arranged), an overflow port is arranged in the middle of the outlet end of the tubular reactor b, so that the retention time of materials in the tubular reactor is kept at 3-6 seconds, the materials can be reacted more sufficiently and rapidly, and during actual production, the pipe diameter of the tubular reactor and the positions of all material feeding holes can be calculated and specifically designed according to the retention time and the material using amount. Before the raw materials are dripped, an air valve is opened; when the raw materials are dripped, the condensation liquid valve is opened first, and then the acid hydrogen peroxide solution valve is opened. An outlet of an overflow port of the tubular reactor b is connected with a solid-liquid separation device, and an outlet of the solid-liquid separation device is connected with a drying system. The heating jacket is wrapped outside the tubular reactor a and the tubular reactor b, and the temperature sensor and the pressure sensor are arranged inside the tubular reactor a and the tubular reactor b. 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 ℃, in the embodiment, the tubular reactor a and the tubular reactor b adopt a jacket to introduce circulating water for heat preservation reaction, and a circulating water inlet pipeline is connected to an inlet pipeline at the lower part of the jacket of the tubular reactor through a centrifugal pump and a regulating valve. The tubular reactor is provided with a temperature sensor, and when the sensed temperature deviates from the reaction required temperature, the temperature of the circulating water is changed, the opening degree of a valve of an adjusting valve is adjusted, and the circulating speed of the circulating water is adjusted, so that the reaction temperature is controlled within the reaction required temperature range.

In this embodiment, a sampling port and a feeding valve are arranged between the overflow outlet of the tubular reactor a and the tubular reactor b.

In this embodiment, a sampling port is disposed between the overflow outlet of the tubular reactor b and the inlet of the solid-liquid separator.

In this embodiment, tubular reactor a, the equal horizontal installation of tubular reactor b, tubular reactor a, tubular reactor b is inside all to be equipped with one row of blast pipe, upper portion is equipped with blow-down pipe connection tail gas absorbing device, the end is equipped with the overflow export, the equipment body all still includes the controller, radar level gauge is connected to the controller input and each temperature sensor and pressure sensor are taken into account, each feed valve switch is connected to the controller output, the heat source that feed pump and heating jacket, the blast gate switch of air-blower, water inlet pipeline, dimethylamine inlet pipeline, carbon disulfide inlet pipeline, liquid caustic soda inlet pipeline, condensation liquid inlet pipeline, coordinated control between the feed pump that acid hydrogen peroxide solution inlet pipeline connects respectively.

Tubular reactor an, tubular reactor b inside lining anticorrosive coating in this embodiment, the installation is placed to the level simultaneously, and tubular reactor an, the inside bottom of tubular reactor b all are equipped with one row of blast pipe, and upper portion is equipped with the blow-down pipe and connects tail gas absorbing device, and tubular reactor an, tubular reactor b entry are vertical all to be sealed foremost, and the end all is equipped with the overflow outlet. The material enters the tubular reactor through the feed inlet, and firstly: the blast pipe is used for carrying out micro air quantity, so that various raw materials are uniformly mixed, the reaction is rapid and sufficient, the encumbrance of speed reduction stirring is reduced, the equipment is simple and portable, and the occupied area is small; secondly, the following steps: the materials flow into the next working procedure while reacting through the overflow port; thirdly, the method comprises the following steps: ensures that the reaction residence time of the materials in the tubular reactor a is kept between 3 and 6 seconds, and the reaction residence time in the tubular reactor b is kept between 4 and 7 seconds.

According to the material advancing direction, water, dimethylamine, carbon disulfide, liquid caustic soda and acidic hydrogen peroxide storage tanks are designed in sequence, and 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 connected with a centrifugal pump and a flowmeter in production, and continuously enters 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 b 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 solid-liquid separation device for sampling detection. The solid-liquid separation device is connected with the drying system.

Example 2

This example provides a process for the continuous synthesis of 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 seal and reducing volatilization) and 81ml of sodium hydroxide aqueous solution with the mass fraction of 32% are respectively measured by using a measuring cylinder, put into four customized glass beakers with glass outlets and switches at the bottoms, wherein a steam pipeline is introduced into the glass beakers in which the water is placed, the water is heated and kept at the temperature of between 40 and 45 ℃, and meanwhile, thermometers are inserted for measurement. The rest raw materials are fed at normal temperature. Before the raw materials are dripped, an air blower is turned on; when the raw materials are dripped, 30ml of water is firstly dripped, the rotating speed of a peristaltic pump is 7.6 r/min, then 115ml of dimethylamine is dripped, the rotating speed of the peristaltic pump is 25.8 r/min, then 57ml of carbon disulfide is dripped, the rotating speed of the peristaltic pump is 13 r/min, and finally 81ml of liquid caustic soda is dripped, wherein the rotating speed of the peristaltic pump is 18.2 r/min. And (3) dropwise adding the four materials into the tubular reactor 1 at an interval of 1 second according to the adding amount and the rotating speed of the peristaltic pump and the set feeding sequence. The tubular reactor a in this example had a diameter of 2cm and a length of 30 cm. The feed inlet positions of the four substances of water, dimethylamine, carbon disulfide and liquid caustic soda on the tubular reactor are as follows in sequence: 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 a 9% by weight aqueous acidic hydrogen peroxide solution (25.9% by weight of sulfuric acid) were weighed out using a measuring cylinder and placed in a glass beaker with a glass outlet and a switch at the bottom. And when the material overflows into the tubular reactor b from the overflow outlet of the tubular reactor a, opening the blast valve, and simultaneously dropwise adding the acidic hydrogen peroxide solution at the rotation speed of 16.3 revolutions per minute by the peristaltic pump. The reaction temperature in the tubular reactor b was adjusted to 35 to 65 ℃ and the tubular reactor b in this example had a diameter of 2cm and a length of 50 cm. The condensation liquid and the acidic hydrogen peroxide solution are distributed at the feed inlet position on the tubular reactor in a cross way, and the feed inlet position of the condensation liquid on the tubular reactor is as follows: the inlet at the uppermost end of the tubular reactor b is 2cm, and the inlet at the uppermost end of the tubular reactor b is 6 cm; the feed inlet positions of the acidic aqueous hydrogen peroxide solution on the tubular reactor b are as follows: 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.

1 batch was synthesized using the same amount of material as a batch reaction requiring 90 minutes. In the first stage, the resultant condensate in the tubular reactor a had a dark yellow color, a non-uniform specific gravity of 1.070-1.076g/ml, and a sharp taste. In the second stage, the initial melting point of TMTD synthesized in the tubular reactor b is low, about 140.0 ℃, and the average purity is 96.0%. 1 batch of material was synthesized in 30 minutes using this example. The material appearance of the condensation liquid synthesized in the first stage is colorless or light yellow, the condensation liquid is repeated for 3 times in parallel, the obtained product has uniform average 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, 142.9 ℃ and average purity of 98.9%.

Example 3

The feeding reaction was carried out by increasing the feeding rate of the raw material based on the conditions in example 2.

When the temperature of the reaction system is 25-45 ℃, 57ml of water, 28.8 revolutions per minute of a peristaltic pump, 218.5ml of dimethylamine, 98.0 revolutions per minute of the peristaltic pump, 108.3ml of carbon disulfide, 49.4 revolutions per minute of the peristaltic pump, 153.9ml of liquid caustic soda and 69.2 revolutions per minute of the peristaltic pump are sequentially opened, and the four materials are dripped into the tubular reactor a according to the adding amount and the rotational speed of the peristaltic pump.

The liquid flowing out of the tubular reactor 1 is condensation liquid, the appearance of the condensation liquid 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 obtained liquid condensate overflows to the tubular reactor b through an overflow outlet of the tubular reactor a. The mass fraction of the condensation liquid is 19.5%. 329.44g of acid hydrogen peroxide solution with the mass fraction of 9 percent is put into a glass beaker with a glass outlet and a switch at the bottom, when materials overflow into the tubular reactor b from the overflow outlet of the tubular reactor a, a blast valve is opened, and simultaneously the acid hydrogen peroxide solution is dripped, the reaction temperature in the tubular reactor b is adjusted to 35-65 ℃, and the rotating speed of a peristaltic pump is 66.7 r/min. The tubular reactor b of this example had a diameter of 2cm and a length of 50 cm. The condensation liquid and the acidic hydrogen peroxide solution are distributed at the feed inlet position on the tubular reactor in a cross way, and the feed inlet position of the condensation liquid on the tubular reactor is as follows: the inlet at the uppermost end of the tubular reactor b is 2cm, and the inlet at the uppermost end of the tubular reactor b is 6 cm; the feed inlet positions of the acidic aqueous hydrogen peroxide solution on the tubular reactor b are as follows: 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 condensed liquid synthesized in the first stage has colorless or light yellow material appearance, specific gravity of 1.070g/ml and no peculiar smell. After the second stage of synthesis, 206.72g of white finished TMTD product is obtained by filtering and drying, 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 within the following condition intervals. A process for the continuous production of promoter TMTD comprising the steps of:

(1) at normal temperature, 520g of hydrogen peroxide with the mass fraction of 30% is put into 520-2600g of water, 459g of sulfuric acid with the mass fraction of 98% is put into the water, and is stirred to prepare 15% acidic hydrogen peroxide solution for later use;

(2) the four materials of water, liquid alkali, dimethylamine and carbon disulfide are respectively connected with a peristaltic pump;

(3) when the temperature of the reaction system is 25-45 ℃, 3000-6000ml of water, 7.6 revolutions per minute of a peristaltic pump, 1150-2310ml of dimethylamine, 25.8 revolutions per minute of the peristaltic pump, and 1120ml of 570-1120ml of carbon disulfide are adopted as the peristaltic pump, 13 revolutions per minute of the peristaltic pump, 810-1790ml of liquid alkali are adopted as the peristaltic pump, 18.2 revolutions per minute of the peristaltic pump are adopted as the four materials, the four materials are simultaneously dripped into the tubular reactor a according to the adding amount and the rotational speed of the peristaltic pump, and the outlet liquid in the tubular reactor a is the accelerant S.

(4) And (2) allowing the accelerant S flowing out of the tubular reactor a to enter a tubular reactor 2 through a plurality of points, allowing 1499-3579g of acidic hydrogen peroxide solution to enter a tubular reactor b from different distribution points at the speed of 56.7 revolutions per minute by using a peristaltic pump, allowing the acidic hydrogen peroxide solution and the acidic hydrogen peroxide solution to enter the tubular reactor b at the reaction temperature of 35-65 ℃, connecting an outlet of the tubular reactor b with a suction filtration device, and performing suction filtration, washing and drying to obtain a white finished product TMTD. The obtained finished product TMTD has high initial melting point, is stable at 142.2-142.6 ℃, and has high purity of 98.8-99.2%.

Example 5

This example is different from example 2 in that the raw materials for the whole reaction are expanded in equal proportion and the operation is continued for 24 hours. After 30min, sampling is carried out from two sampling ports on the equipment in the invention irregularly, 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 condensation liquid sampling test results at different times after the start of the reaction

TABLE 2 TMTD sampling test results at different times after the start of the reaction

From the detection data, the quality of the continuous reaction product in the embodiment is very stable, the specific gravity of the condensation liquid is stable at 1.070g/ml, the appearance is light yellow to colorless, and no peculiar smell exists. The finished product TMTD has high initial melting point, is stable at 142.2-142.6 ℃, and has high purity of 98.8-99.2%.

The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention in other forms, and any person skilled in the art may apply the above modifications or changes to the equivalent embodiments with equivalent changes, without departing from the technical spirit of the present invention, and any simple modification, equivalent change and change made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the technical spirit of the present invention.