CN113173831A - Production system and process for continuous chlorination of trichlorotoluene - Google Patents

Production system and process for continuous chlorination of trichlorotoluene Download PDF

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CN113173831A
CN113173831A CN202110377325.1A CN202110377325A CN113173831A CN 113173831 A CN113173831 A CN 113173831A CN 202110377325 A CN202110377325 A CN 202110377325A CN 113173831 A CN113173831 A CN 113173831A
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chlorination
kettle
communicated
condenser
trichlorotoluene
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CN113173831B (en
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黎孔富
孙大明
方明祥
廖春院
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Yidu Jovian Industry Co ltd
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Yidu Jovian Industry Co ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00Preparation of halogenated hydrocarbons
    • C07C17/093Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C07C17/14Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the side-chain of aromatic compounds

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a production system and a process for continuous chlorination of trichlorotoluene, wherein a toluene feeding pipe is arranged above a toluene metering tank, the toluene metering tank is communicated with a chlorination absorption kettle through a first pipeline, the chlorination absorption kettle is communicated with a first chlorination kettle through a pipeline through a first pressure pump, materials in the first chlorination kettle are sequentially communicated with a second chlorination kettle, a third chlorination kettle, a fourth chlorination kettle and a fifth chlorination kettle through overflow pipes, the bottoms of the first chlorination kettle, the second chlorination kettle, the third chlorination kettle, the fourth chlorination kettle and the fifth chlorination kettle are respectively provided with a chlorine gas inlet which is communicated with a chlorine gas inlet main pipe, the tops of the first chlorination kettle, the second chlorination kettle, the third chlorination kettle, the fourth chlorination kettle and the fifth chlorination kettle are respectively provided with a gas outlet which is communicated with a chlorine gas outlet pipeline, and the chlorine gas outlet pipeline is sequentially communicated with a condenser and a freezing condenser. The invention has the advantages of continuous feeding, continuous discharging and continuous chlorination, the yield of chlorinated products is more than 98 percent, and the purity of crude products is more than 99 percent.

Description

Production system and process for continuous chlorination of trichlorotoluene
Technical Field
The invention relates to the technical field of chemical processes, in particular to a production system and a process for continuous chlorination of trichlorotoluene.
Background
Trichlorotoluene, CAS No.: 98-07-7, formula: c7H5Cl3Molecular weight: 195.474, useful as a basic raw material for dyes, pharmaceutical intermediates and ultraviolet absorbers UV-9, UV-531, and organic synthesis intermediates for the production of benzoic acid, benzoyl chloride, triphenylmethane dyes, anthraquinone dyes, quinoline dyes, etc. The traditional synthesis process comprises the steps of putting toluene into a chlorination kettle, heating to 90-120 ℃, introducing chlorine, stopping chlorination reaction until the content of dichlorotoluene is lower than 0.1%, and transferring the materials into a rectifying kettle for rectification to obtain a trichlorotoluene product. The intermittent reaction is adopted, the operation is complex, the working procedures are multiple, the energy consumption is high, and the productivity is low. There are mainly the following problems: firstly, the reaction initial stage, it is low to lead to the chlorine flow, and the material need heat up, and it is big to lead to the chlorine flow in the reaction middle stage, and the reaction exotherm is big, needs the cooling, and the operation is complicated, and improper control by temperature change leads to the secondary reaction many, and the big product quality of impurity is poor.
Disclosure of Invention
In order to solve the technical problem, the invention provides a production system and a process for continuous chlorination of trichlorotoluene.
The technical scheme adopted by the invention is as follows:
a production system for continuous chlorination of trichlorotoluene comprises a toluene feeding pipe, wherein the toluene feeding pipe is arranged above a toluene metering tank, the toluene metering tank is communicated with a chlorination absorption kettle through a first pipeline, the chlorination absorption kettle is communicated with a first chlorination kettle through a first pressure pump through a pipeline, materials in the first chlorination kettle are communicated with a second chlorination kettle, a third chlorination kettle, a fourth chlorination kettle and a fifth chlorination kettle in sequence through overflow pipes, chlorine gas inlet openings are respectively arranged at the bottoms of the first chlorination kettle, the second chlorination kettle, the third chlorination kettle, the fourth chlorination kettle and the fifth chlorination kettle and communicated with a chlorine gas inlet main pipe, gas outlet openings are respectively arranged at the tops of the first chlorination kettle, the second chlorination kettle, the third chlorination kettle, the fourth chlorination kettle and the fifth chlorination kettle and communicated with a chlorine gas outlet pipeline, the chlorine gas outlet pipeline is communicated with a condenser and a freezing condenser in sequence, a material outlet opening at the bottom of the condenser is communicated with the first chlorination kettle, the discharge port at the bottom of the freezing condenser is communicated with the chlorination absorption kettle, the exhaust port at the top of the chlorination absorption kettle is communicated with the cryogenic condenser, and a hydrogen chloride gas pipeline arranged on the cryogenic condenser is input into a hydrogen chloride absorption system for absorption to prepare hydrochloric acid.
Preferably, a crude product discharge pipeline is arranged at the upper part of the pentachlorinated kettle.
Preferably, there are three condensers in series.
Preferably, a feeding valve is arranged on the toluene feeding pipe and is interlocked with the liquid level of the toluene storage tank.
Preferably, the toluene metering tank is arranged above the chlorination absorption kettle.
The production process for carrying out continuous chlorination on trichlorotoluene by adopting the production system is characterized in that in the process, the chlorination absorption kettle is heated to 70-80 ℃ through steam, the temperature of materials in the chlorination absorption kettle is controlled, so that residual chlorine can be reacted completely, and the reaction temperature of the materials in the chlorination kettle can be ensured.
Preferably, the temperature of the first chlorination kettle is controlled to be 90-95 ℃, and the chlorine flow of the first chlorination kettle is not more than 110m3And h, controlling the chlorine overflowing amount.
Preferably, the temperature of the second chlorination kettle material is controlled to be 95-100 ℃, the temperature of the third chlorination kettle material is controlled to be 110-3/h,170-190m3/h,230-250m3The chlorination reaction degree is enabled to reach 95 percent.
Preferably, the temperature of the fifth chlorination kettle is controlled at 115 ℃ and 120 ℃, and the chlorine flow is controlled at 70-90m3And h, ensuring that the materials in the kettle react completely, and controlling the dichloro content to be below 0.05 percent.
Preferably, the gas phase condensed by the condenser is condensed again by a freezing condenser, the condenser is cooled by cooling water, the condensed material and residual chlorine gas enter the chlorination absorption kettle through a pipeline for reaction, all hydrogen chloride gas and the material are condensed again by the freezing condenser, the freezing condenser is cooled by freezing water, and the deep cooling condenser is condensed by deep cooling brine. The gas-phase liquid-phase mixed material cooled by the freezing condenser enters the absorption kettle for secondary reaction, the gas-phase material generated in the reaction process of the absorption kettle is condensed by a cryogenic condenser by cryogenic brine at the temperature of-20 ℃, the organic matter components are completely condensed to be liquid-phase and flow back to the absorption kettle, the hydrogen chloride gas which is not condensed is absorbed by water through a hydrogen chloride gas pipeline to prepare hydrochloric acid, and the organic matter content in the hydrogen chloride is controlled at the lowest amount.
Preferably, the first chlorination kettle, the second chlorination kettle, the third chlorination kettle, the fourth chlorination kettle and the fifth chlorination kettle are sequentially kept at a position difference of 95-105mm from high to low, so that the materials are ensured to overflow smoothly.
The invention has the beneficial effects that:
1. the invention has the advantages of continuous feeding, continuous discharging and continuous chlorination, wherein the feeding is controlled according to the liquid level of discharged materials, the yield of chlorinated products is more than 98 percent, and the purity of crude products is more than 99 percent. The invention adopts continuous feeding, continuous discharging and continuous chlorination, the feeding is automatically supplemented according to the liquid level of the discharged material, the temperature of each chlorination reaction kettle can be effectively controlled by continuous feeding and chlorination, and the reaction is stable. After the reaction is finished, the reaction product is directly transferred to a rectifying still for rectification, so that the manual material transferring operation is omitted, and the labor is saved.
2. 5 set chlorination cauldron react in succession, communicate the gaseous phase and carry out the condensation together and retrieve the material, reduced condenser quantity to adopt multistage condensation, make the material retrieve more completely, reduced the equipment input.
3. Every chlorine of going on alone of chlorination reaction kettle leads to chlorine, and every chlorination reaction kettle sets up and leads to chlorine flow according to the technological parameter control of setting for alone to lead to the chlorine valve, and according to reaction stage difference, each cauldron leads to chlorine simultaneously and improves whole reaction rate, improves production efficiency, and the reaction is more stable controllable, and control chlorine leads to chlorine flow, makes the reaction more stable, and the control of being convenient for, and the chlorine reaction is more complete. The impurities generated by the reaction are few, and the product quality is high.
4. The chlorine flow of each chlorination kettle for continuous chlorination of trichlorotoluene can be stably controlled, the flow is not required to be adjusted, the reaction is stable, the operation is simple and convenient, and the safety is higher.
Drawings
FIG. 1: the invention has a schematic structure;
in the figure: toluene inlet pipe 1, toluene metering tank 2, chlorination absorption kettle 3, first pipeline 4, first force pump 5, first chlorination kettle 6, overflow pipe 7, second chlorination kettle 8, third chlorination kettle 9, fourth chlorination kettle 10, fifth chlorination kettle 11, chlorine gas inlet manifold 12, chlorine gas discharge pipeline 13, condenser 14, freezing condenser 15, deep cooling condenser 16, hydrogen chloride gas pipeline 17, crude product discharge pipeline 18.
Detailed Description
Example 1
As shown in figure 1, a production system for continuous chlorination of trichlorotoluene comprises a toluene feeding pipe 1, wherein the toluene feeding pipe 1 is arranged above a toluene metering tank 2, the toluene metering tank 2 is communicated with a chlorination reactor 3 by a first pipeline 4, the chlorination reactor 3 is communicated with a first chlorination reactor 6 by a first pressure pump 5 through a pipeline, materials in the first chlorination reactor 6 are sequentially communicated with a second chlorination reactor 8, a third chlorination reactor 9, a fourth chlorination reactor 10 and a fifth chlorination reactor 11 through an overflow pipe 7, the bottoms of the first chlorination reactor 6, the second chlorination reactor 8, the third chlorination reactor 9, the fourth chlorination reactor 10 and the fifth chlorination reactor 11 are respectively provided with a chlorine gas inlet and a chlorine gas inlet header pipe 12, the tops of the first chlorination reactor 6, the second chlorination reactor 8, the third chlorination reactor 9, the fourth chlorination reactor 10 and the fifth chlorination reactor 11 are respectively provided with a gas outlet and are respectively communicated with a chlorine gas outlet pipe 13, the chlorine gas discharge pipeline 13 is sequentially communicated with the condenser 14 and the freezing condenser 15, a material discharge port at the bottom of the condenser 14 is communicated with the first chlorination kettle 6, a discharge port at the bottom of the freezing condenser 15 is communicated with the chlorination absorption kettle 3, a gas exhaust port at the top of the chlorination absorption kettle 3 is communicated with the cryogenic condenser 16, and a hydrogen chloride gas pipeline 17 arranged on the cryogenic condenser 16 is input into a hydrogen chloride absorption system for absorption to prepare hydrochloric acid.
Preferably, a crude product discharge pipeline 18 is arranged at the upper part of the pentachlorinated kettle 11.
Preferably, three condensers 14 are provided in series.
Preferably, a feeding valve is arranged on the toluene feeding pipe 1 and is interlocked with the liquid level of the toluene storage tank. The automatic feeding is carried out according to the liquid level, guarantees material liquid level and toluene quiescent time in toluene metering tank 2 in the toluene, can deposit the storage tank bottom completely with moisture and the impurity in the toluene, regularly divides. And a feeding valve is arranged on the toluene feeding pipe 1 and is interlocked with a toluene storage tank discharging valve and the liquid level of the toluene metering tank 2. The feeding is automatically carried out according to the liquid level. The toluene storage tank is equipped with the water diversion device, and the toluene that gets into in the storage tank stews more than 2h, guarantees that moisture and impurity in the toluene can deposit the storage tank bottom completely, regularly divides out, makes the toluene moisture content of getting into toluene metering tank 2 no longer than 800 ppm.
Preferably, the toluene metering tank 2 is arranged above the chlorination absorption kettle 3.
Preferably, the toluene metering tank 2 is arranged above the chlorination absorption kettle 3. The material is automatically fed by potential difference, the material is automatically fed in a liquid level linkage mode of a feeding valve of the first pipeline 4 and the chlorination absorption kettle 3, the material is fed from the middle lower part, the material is discharged from the upper part, and the retention time of the material is ensured.
The production process for carrying out continuous chlorination on trichlorotoluene by adopting the production system comprises the following steps:
1. hydrogen chloride gas generated in the chlorination process, residual chlorine gas and carried-out materials enter a condenser 14 through a gas phase pipe, the materials are cooled and enter a first chlorination kettle 6 through a recovery pipe, uncondensed materials, unreacted chlorine gas and hydrogen chloride gas enter a freezing condenser 15 for cooling again and enter a chlorination absorption kettle 3 through a pipeline, the materials are recovered and reacted again, the unreacted chlorine gas is completely reacted in the chlorination absorption kettle 3, the gas phase materials in the chlorination absorption kettle 3 are cooled and refluxed again through a cryogenic condenser 16, and the hydrogen chloride gas enters a hydrochloric acid absorption system through a hydrogen chloride gas pipeline 17. The temperature of the first chlorination reactor 6 is controlled between 90 ℃ and 95 ℃, and the chlorine flow of the first chlorination reactor 6 is not more than 110m3And h, controlling the chlorine overflowing amount.
2. Chlorine gas enters each chlorination kettle through a chlorine gas inlet main pipe 12 and a regulating valve.
Preferably, the toluene storage tank is higher than the chlorination absorption kettle 3 through the installation position of the toluene feeding pipe 1, the toluene automatically enters in a mode of liquid level linkage of the first pipeline 4 feeding valve and the chlorination absorption kettle 3, and the toluene flows into the chlorination absorption kettle 3 through the position difference.
Preferably, the discharge port of the toluene metering tank 2 is arranged on the side surface of the storage tank, so that the moisture in the toluene is precipitated to the bottom of the storage tank, and the moisture is periodically distributed.
Preferably, the toluene inlet of the chlorination absorption kettle 3 is arranged at the lower part of the chlorination absorption kettle 3, the toluene feeding amount is controlled by interlocking the liquid level of the chlorination absorption kettle 3 with the regulating valve, and the temperature of the chlorination absorption kettle 3 is controlled, so that the entering chlorine can completely react with the toluene.
Preferably, the feeding of the first chlorination reactor 6 enters through a pipeline 14, the first pressure pump 5 is used for switching in, the feeding control valve and the liquid level of the first chlorination reactor 6 are used for interlocking control adjustment, the material enters from the lower part of the first chlorination reactor 6, and the upper part overflows to the next chlorination reactor.
Preferably, the first chlorination kettle 6, the second chlorination kettle 8, the third chlorination kettle 9, the fourth chlorination kettle 10 and the fifth chlorination kettle 11 are communicated with each other through an overflow pipe 7, and all adopt upper-outlet feeding and lower-inlet feeding, and the materials after chlorination are directly discharged into the next working procedure through a crude product discharge pipeline 18.
Preferably, the chlorine feeding holes of the first chlorination kettle 6, the second chlorination kettle 8, the third chlorination kettle 9, the fourth chlorination kettle 10 and the fifth chlorination kettle 11 are all arranged at the lower part, so that the chlorine is in long-time contact with the materials more fully, and the reaction speed is improved.
Preferably, the gas phase materials of the first chlorination kettle 6, the second chlorination kettle 8, the third chlorination kettle 9, the fourth chlorination kettle 10 and the fifth chlorination kettle 11 are communicated through a chlorine gas inlet main pipe 12, circulating water cooling is carried out by adopting a three-stage condenser 14, then freezing water cooling is carried out by adopting a freezing condenser 15, deep cooling water is carried out on tail gas by adopting a deep cooling condenser 16 again, and the organic materials are completely condensed and recovered.
Preferably, the material temperature of the second chlorination kettle 8 is controlled to be 95-100 ℃, the material temperature of the third chlorination kettle 9 is controlled to be 110 ℃ C., the material temperature of the fourth chlorination kettle 10 is controlled to be 115 ℃ C., the chlorine introduction flow rates of the second chlorination kettle 8, the third chlorination kettle 9 and the fourth chlorination kettle 10 are respectively 150m3/h、180m3/h、240m3/h。
Preferably, the gas phase condensed by the condenser 14 is condensed again by the freezing condenser 15, the condenser 14 is cooled by cooling water, the gas phase and liquid phase mixed material cooled by the freezing condenser 15 enters the absorption kettle 3 for reaction again, all hydrogen chloride gas and materials are condensed again by the freezing condenser 15, the freezing condenser 15 is cooled by freezing water, the gas phase materials generated in the reaction process of the absorption kettle 3 are condensed by a deep cooling condenser 16 by deep cooling saline water with the temperature of-20 ℃, organic matter components are completely condensed to be liquid phase and flow back to the absorption kettle 3, and the hydrogen chloride gas which is not condensed is absorbed by water by a hydrogen chloride gas pipeline 17 to prepare hydrochloric acid. The content of organic matters in the hydrogen chloride is controlled to be the minimum, and the hydrogen chloride gas is absorbed by water through a hydrogen chloride gas pipeline 17 to prepare the hydrochloric acid.
Preferably, the first chlorination kettle 6, the second chlorination kettle 8, the third chlorination kettle 9, the fourth chlorination kettle 10 and the fifth chlorination kettle 11 are sequentially arranged from high to low, and the position difference of 100mm is kept, so that smooth overflow of materials is ensured.

Claims (10)

1. A production system for trichlorotoluene continuous chlorination comprises a toluene feeding pipe (1), and is characterized in that: the toluene feeding pipe (1) is arranged above the toluene metering tank (2), the toluene metering tank (2) is communicated with the chlorination absorption kettle (3) by a first pipeline (4), the chlorination absorption kettle (3) is communicated with the first chlorination kettle (6) by a first pressure pump (5) through a pipeline, materials in the first chlorination kettle (6) are sequentially communicated with the second chlorination kettle (8), the third chlorination kettle (9), the fourth chlorination kettle (10) and the fifth chlorination kettle (11) through an overflow pipe (7), the first chlorination kettle (6), the second chlorination kettle (8), the third chlorination kettle (9), the fourth chlorination kettle (10) and the fifth chlorination kettle (11) are respectively provided with a chlorine gas inlet which is communicated with a chlorine gas inlet main pipe (12), the tops of the first chlorination kettle (6), the second chlorination kettle (8), the third chlorination kettle (9), the fourth chlorination kettle (10) and the fifth chlorination kettle (11) are respectively communicated with a chlorine gas outlet pipeline (13), the chlorine gas discharge pipeline (13) is sequentially communicated with the condenser (14) and the freezing condenser (15), a material discharge port at the bottom of the condenser (14) is communicated with the first chlorination kettle (6), a discharge port at the bottom of the freezing condenser (15) is communicated with the chlorination absorption kettle (3), an exhaust port at the top of the chlorination absorption kettle (3) is communicated with the cryogenic condenser (16), and a hydrogen chloride gas pipeline (17) arranged on the cryogenic condenser (16) is input into a hydrogen chloride absorption system for absorption to prepare hydrochloric acid.
2. The system for continuously chlorinating trichlorotoluene according to claim 1, wherein: a crude product discharge pipeline (18) is arranged at the upper part of the pentachlorinated kettle (11).
3. The system for continuously chlorinating trichlorotoluene according to claim 1, wherein: the number of the condensers (14) is three.
4. The system for continuously chlorinating trichlorotoluene according to claim 1, wherein: and a feeding valve is arranged on the toluene feeding pipe (1) and is interlocked with the liquid level of the toluene storage tank.
5. The system for continuously chlorinating trichlorotoluene according to claim 1, wherein: and the toluene metering tank (2) is arranged above the chlorination absorption kettle (3).
6. The production process for carrying out continuous chlorination of trichlorotoluene by using the production system of any one of claims 1 to 5 is characterized in that: in the process, the chlorination absorption kettle (3) is heated to 70-80 ℃ through steam, the temperature of the materials in the chlorination absorption kettle (3) is controlled, so that residual chlorine can be reacted completely, and the reaction temperature of the materials in the chlorination kettle can be ensured.
7. The continuous chlorination production process of trichlorotoluene according to claim 6, wherein: the temperature of the first chlorination kettle (6) is controlled to be 90-95 ℃, and the chlorine flow of the first chlorination kettle (6) is not more than 110m3Controlling the chlorine gas overflowing amount; the material temperature of the second chlorination kettle (8) is controlled between 95 ℃ and 100 ℃, and the third chlorination is carried outThe material temperature of the kettle (9) is controlled to be 110-3/h,170-190m3/h,230-250m3The chlorination reaction degree is enabled to reach 95 percent.
8. The continuous chlorination production process of trichlorotoluene according to claim 6, wherein: the material temperature of the pentachlorinated kettle (11) is controlled at 115 ℃ and 120 ℃, and the chlorine flow is controlled at 70-90m3And h, ensuring that the materials in the kettle react completely, and controlling the dichloro content to be below 0.05 percent.
9. The continuous chlorination production process of trichlorotoluene according to claim 6, wherein: the condenser (14) is cooled by cooling water, the freezing condenser (15) is cooled by freezing water, and the cryogenic condenser (16) is condensed by cryogenic brine.
10. The continuous chlorination production process of trichlorotoluene according to claim 6, wherein: the first chlorination kettle (6), the second chlorination kettle (8), the third chlorination kettle (9), the fourth chlorination kettle (10) and the fourth chlorination kettle (11) are sequentially arranged from high to low, and the position difference is kept between 95 and 105 mm.
CN202110377325.1A 2021-04-08 2021-04-08 Production system and process for continuous chlorination of trichlorotoluene Active CN113173831B (en)

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