CN112028737B - Method and device for preparing chloroethylene by treating bis (trichloromethyl) carbonate production tail gas through combustion method - Google Patents
Method and device for preparing chloroethylene by treating bis (trichloromethyl) carbonate production tail gas through combustion method Download PDFInfo
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- CN112028737B CN112028737B CN202010959195.8A CN202010959195A CN112028737B CN 112028737 B CN112028737 B CN 112028737B CN 202010959195 A CN202010959195 A CN 202010959195A CN 112028737 B CN112028737 B CN 112028737B
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- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
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- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/012—Preparation of hydrogen chloride from the elements
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
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- C01B7/0706—Purification ; Separation of hydrogen chloride
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Abstract
The invention discloses a method and a device for treating tail gas generated in production of bis (trichloromethyl) carbonate by a combustion method to prepare chloroethylene, wherein the treatment method comprises the following steps: (1) Introducing tail gas generated in the production of bis (trichloromethyl) carbonate, chlorine and oxygen into a mixer according to a certain proportion; (2) Introducing the uniformly mixed gas and hydrogen into a synthesis combustor according to a certain ratio, reacting chlorine and hydrogen in the mixed gas in the synthesis combustor to produce hydrogen chloride, and oxidizing organic matters into carbon dioxide and water by oxygen; (3) Introducing the mixed gas treated in the step (2) into a hydrogen chloride distribution table for distribution, and distributing part of hydrogen chloride to an absorption tower for preparing acid; a portion of the hydrogen chloride gas is distributed to a vinyl chloride production unit for the preparation of vinyl chloride. The processing method has simple flow and high safety performance; the tail gas treated by the method of the invention meets the indexes of industrial synthesis of chloroethylene and high-purity acid, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of chlorinated tail gas treatment, particularly relates to chlorinated tail gas treatment generated in the synthesis of bis (trichloromethyl) carbonate, and particularly relates to a method and a device for treating the tail gas generated in the production of bis (trichloromethyl) carbonate by a combustion method to prepare chloroethylene.
Background
The production process of bis (trichloromethyl) carbonate (BTC for short) is a chlorination process, and the production process is that dimethyl carbonate and excessive chlorine gas are subjected to substitution reaction under the action of ultraviolet rays or a catalyst. After the reaction, a large amount of tail gas is generated, and the tail gas contains chlorine and organic materials.
The existing process for treating the bis (trichloromethyl) carbonate tail gas is to directly absorb the tail gas with water to prepare hydrochloric acid (a byproduct, namely hydrogen chloride in the reaction), and the byproduct, namely the hydrochloric acid is unqualified due to the existence of excess chlorine and organic matters; in addition, the treatment process of the bis (trichloromethyl) carbonate tail gas is that the tail gas is absorbed by alkali liquor, and because the content of free chlorine in the tail gas is low and a certain amount of acid liquid drops are carried in the washed tail gas, the concentration of effective chlorine in the solution after alkali washing is extremely low, and the solution is difficult to sell. Therefore, the tail gas treatment process for producing the di (trichloromethyl) carbonate at present can generate a large amount of waste acid and high-salinity wastewater, so that serious environmental pollution is caused, and the process becomes a bottleneck restricting the development of enterprises; although hydrochloric acid and sodium hypochlorite that tail gas produced through traditional washing and alkali cleaning are the chemicals of basis, the quality is not high and the use unit is limited, and storage and transportation pressure are all very big, if the industry does not match, because of hydrochloric acid inventory pressure, can produce great potential safety hazard. Therefore, it is an urgent problem to find an environmentally friendly and safe process for treating the tail gas generated in the synthesis of bis (trichloromethyl) carbonate.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a method for preparing vinyl chloride by treating the tail gas generated in the production of bis (trichloromethyl) carbonate by a combustion method, which has the advantages of simple process, high safety and environmental protection.
The invention also aims to provide a device for preparing chloroethylene by treating the tail gas generated in the production of the bis (trichloromethyl) carbonate by a combustion method.
In order to achieve the two purposes, the invention adopts the following technical scheme:
a method for treating tail gas generated in production of bis (trichloromethyl) carbonate by a combustion method for preparing vinyl chloride comprises the following steps:
(1) Introducing tail gas generated in the production of bis (trichloromethyl) carbonate, chlorine and oxygen into a mixer according to a certain proportion, and uniformly mixing;
(2) Introducing the uniformly mixed gas in the step (1) and hydrogen into a synthesis combustor according to a certain ratio, reacting chlorine and hydrogen in the mixed gas in the synthesis combustor to produce hydrogen chloride, and oxidizing organic matters into carbon dioxide and water by oxygen;
(3) Introducing the mixed gas treated in the step (2) into a hydrogen chloride distribution table for distribution, and distributing part of hydrogen chloride to an absorption tower for preparing acid; a portion of the hydrogen chloride gas is distributed to a vinyl chloride production unit for the preparation of vinyl chloride.
Further, the tail gas generated by the bis (trichloromethyl) carbonate in the step (1) is chlorination tail gas, and the main components of the chlorination tail gas are hydrogen chloride, chlorine, dimethyl carbonate gas and chlorine compounds of dimethyl carbonate.
Further, the volume percentage of each gas in the chlorination tail gas is respectively as follows: 96.5-97.8% of hydrogen chloride, 0.3-1.5% of chlorine, 0.2-0.7% of dimethyl carbonate gas and 0.8-2.0% of chloride of dimethyl carbonate.
Further, the chloride of dimethyl carbonate is C 3 H 6-n O 3 CL n Wherein n is an integer of 1 to 6.
Further, the volume ratio of the tail gas generated in the production of the bis (trichloromethyl) carbonate in the step (1) to the chlorine gas and the oxygen gas is 1:1.5-2.5:0.1.
furthermore, the volume ratio of the hydrogen to the uniformly mixed gas in the step (2) is (1.2-2.5): 1.
Further, in the step (3), the hydrogen chloride gas used for preparing vinyl chloride is prepared according to the following standard: 99.5-99.9 percent of hydrogen chloride by volume percentage and 0-0.3 percent of oxygen by volume percentage.
The device for treating the tail gas generated in the production of the bis (trichloromethyl) carbonate by the combustion method for preparing the chloroethylene comprises a mixer, wherein the mixer is connected with a burner of a synthesis furnace through a pipeline, the burner of the synthesis furnace is connected with a hydrogen chloride distribution table through a pipeline, and the hydrogen chloride distribution table is respectively connected with a hydrogen chloride absorption tower and a chloroethylene production device through pipelines; and an XV ignition valve, an FV regulating valve, an HV stop valve and an FC orifice flowmeter are arranged on a pipeline connected with the mixer and the burner of the synthetic furnace.
Compared with the prior art, the invention has the beneficial effects that: and (1) the process is simple, and the safety performance is high. Automatically adjusting the amount of chlorination tail gas according to the amount of chlorine entering the mixer; and setting the flow value of the oxygen according to the average value of the flow of the chlorination tail gas stage. The hydrogen flow rate is set according to the gas flow rate and the chlorine purity of the gas discharged from the mixer. Under the control of a Distributed Control System (DCS), the automatic control and purification treatment of the flow of each gas are realized through the automatic control setting. (2) After the tail gas generated by producing the bis (trichloromethyl) carbonate is treated by the device, all indexes of the tail gas meet the requirements of the acetylene method chloroethylene production process (the volume fraction of hydrogen chloride is more than or equal to 93 percent, chlorine gas is not detected by using a starch potassium iodide reagent, and the volume fraction of oxygen is less than or equal to 0.3 percent); in addition, after the treated chlorination tail gas is absorbed by pure water, the high-purity acid can be produced and meets the index of high-purity acid. The purification treatment of the process realizes the high-value recycling of the chlorinated tail gas, and is environment-friendly and safe.
Drawings
FIG. 1 is a flow device for processing tail gas in the production of bis (trichloromethyl) carbonate by a combustion method for preparing vinyl chloride.
Wherein: 1-a mixer; 2-a synthetic furnace burner; 3-hydrogen chloride distribution table.
Detailed Description
The present application is described in further detail below with reference to examples, and it should be noted that the following detailed description is provided for further explanation of the present application and should not be construed as limiting the scope of the present application, and that certain insubstantial modifications and adaptations of the present application may be made by those skilled in the art based on the above-mentioned disclosure.
Example 1
A method for treating tail gas generated in production of bis (trichloromethyl) carbonate by a combustion method for preparing vinyl chloride comprises the following steps:
(1) The tail gas generated in the production of the bis (trichloromethyl) carbonate is called chlorination tail gas, and the main components are as follows: 96.7 percent of hydrogen chloride by volume, 0.9 percent of chlorine by volume, 0.6 percent of dimethyl carbonate gas by volume and a chlorinated substance of dimethyl carbonate (the chlorinated substance of the dimethyl carbonate is C) 3 H 6-n O 3 CL n Where n is an integer from 1 to 6) is 1.8% by volume. Introducing the chlorination tail gas, chlorine and oxygen into a mixer 1 according to a volume ratio of 1.5; the chlorination tail gas, chlorine and oxygen respectively enter the mixer 1 through 3 pipelines, and each pipeline is provided with an automatic gas flow control valve; automatically adjusting the amount of tail gas generated by producing the bis (trichloromethyl) carbonate through a flow control valve according to the amount of chlorine entering a mixer, and then setting the flow value of oxygen according to the average value of the flow of the tail gas generated by producing the bis (trichloromethyl) carbonate; the flow control valve is automatically controlled and monitored by a Distributed Control System (DCS);
(2) Introducing the uniformly mixed gas in the step (1) and hydrogen into a synthesis furnace burner 2 according to the volume ratio of 1.2, reacting chlorine and hydrogen in the mixed gas in the synthesis burner 2 to produce hydrogen chloride, and oxidizing organic matters into carbon dioxide and water by oxygen; automatically setting a hydrogen flow value according to the gas flow value out of the mixer and the chlorine purity, wherein an XV ignition valve, an FV regulating valve, an HV cut-off valve and an FC orifice flowmeter are arranged on a pipeline for introducing hydrogen; the flow of hydrogen into the synthesis combustor 2 is regulated and controlled by an FV regulating valve and an FC flowmeter;
(3) Introducing the mixed gas treated in the step (2) into a hydrogen chloride distribution table 3 for distribution, and distributing part of hydrogen chloride to an absorption tower for preparing acid; distributing a part of hydrogen chloride gas to a chloroethylene production device for preparing chloroethylene; the production process standard of synthesizing chloroethylene by the acetylene method is as follows: the volume percentage of the hydrogen chloride is more than or equal to 93 percent; chlorine gas, detected by starch potassium iodide reagent and not detected; the volume percentage of oxygen is less than or equal to 0.3 percent), and the content of each gas in the hydrogen chloride gas for preparing the chloroethylene in the invention is as follows: 99.6 percent of hydrogen chloride by volume, chlorine: the starch potassium iodide reagent is not detected, and the oxygen volume percentage content is 0.2%.
The device for treating the tail gas generated in the production of the bis (trichloromethyl) carbonate by the combustion method for preparing the chloroethylene comprises a mixer 1, wherein the mixer 1 is connected with a synthesis furnace burner 2 through a pipeline, the synthesis furnace burner 2 is connected with a hydrogen chloride distribution table 3 through a pipeline, and the hydrogen chloride distribution table 3 is respectively connected with a hydrogen chloride absorption tower and a chloroethylene production device through pipelines; and an XV ignition valve, an FV regulating valve, an HV stop valve and an FC orifice flowmeter are arranged on a pipeline connected with the mixer and the burner of the synthetic furnace.
Example 2
A method for treating tail gas generated in production of bis (trichloromethyl) carbonate by a combustion method for preparing vinyl chloride comprises the following steps:
(1) The tail gas generated in the production of the bis (trichloromethyl) carbonate is called chlorination tail gas, and the main components are as follows: 97.2 percent of hydrogen chloride by volume, 0.6 percent of chlorine by volume, 0.4 percent of dimethyl carbonate gas by volume and a chlorinated substance of dimethyl carbonate (the chlorinated substance of the dimethyl carbonate is C) 3 H 6-n O 3 CL n Where n is an integer from 1 to 6) is 1.2% by volume. Introducing the chlorination tail gas, chlorine and oxygen into a mixer 1 according to a volume ratio of 1.9; the chlorination tail gas, chlorine and oxygen respectively enter the mixer 1 through 3 pipelines, and each pipeline is provided with an automatic gas flow control valve; according to the amount of chlorine entering the mixerAutomatically adjusting the amount of tail gas generated by producing the bis (trichloromethyl) carbonate through a flow control valve, and then setting the flow value of oxygen according to the average value of the flow of the tail gas generated by producing the bis (trichloromethyl) carbonate; the flow control valve is automatically controlled and monitored by a Distributed Control System (DCS);
(2) Introducing the uniformly mixed gas in the step (1) and hydrogen into a synthesis furnace burner 2 according to the volume ratio of 1.8, reacting chlorine and hydrogen in the mixed gas in the synthesis burner 2 to produce hydrogen chloride, and oxidizing organic matters into carbon dioxide and water by oxygen; automatically setting a hydrogen flow value according to the gas flow value out of the mixer and the chlorine purity, wherein an XV ignition valve, an FV regulating valve, an HV cut-off valve and an FC orifice flowmeter are arranged on a pipeline for introducing hydrogen; regulating the flow of hydrogen into the synthesis combustor 2 through an FV regulating valve and an FC flowmeter;
(3) Introducing the mixed gas treated in the step (2) into a hydrogen chloride distribution table 3 for distribution, and distributing part of hydrogen chloride to an absorption tower for preparing acid; distributing a part of hydrogen chloride gas to a chloroethylene production device for preparing chloroethylene; the production process standard of vinyl chloride synthesized by the acetylene method is as follows: the volume percentage of the hydrogen chloride is more than or equal to 93 percent; chlorine gas, detected by starch potassium iodide reagent and not detected; the volume percentage of oxygen is less than or equal to 0.3 percent), and the content of each gas in the hydrogen chloride gas for preparing the chloroethylene in the invention is as follows: 99.8% of hydrogen chloride by volume, chlorine: the starch potassium iodide reagent is not detected, and the oxygen volume percentage content is 0.1%.
The apparatus for processing the tail gas from the production of bis (trichloromethyl) carbonate by the combustion method in this example 2 for preparing vinyl chloride is the same as that in example 1.
Example 3
A method for treating tail gas generated in production of bis (trichloromethyl) carbonate by a combustion method for preparing vinyl chloride comprises the following steps:
(1) The tail gas generated in the production of the bis (trichloromethyl) carbonate is called chlorination tail gas, and the main components are as follows: 97.5 percent of hydrogen chloride by volume, 0.4 percent of chlorine by volume, 0.3 percent of dimethyl carbonate gas by volume and chloride of dimethyl carbonate(the chloride of dimethyl carbonate is C 3 H 6-n O 3 CL n Where n is an integer from 1 to 6) is 0.8% by volume. Introducing the chlorination tail gas, chlorine and oxygen into a mixer 1 according to a volume ratio of 1.4; the chlorination tail gas, chlorine and oxygen respectively enter the mixer 1 through 3 pipelines, and each pipeline is provided with an automatic gas flow control valve; automatically adjusting the amount of tail gas generated by producing the bis (trichloromethyl) carbonate through a flow control valve according to the amount of chlorine entering a mixer, and then setting the flow value of oxygen according to the average value of the flow of the tail gas generated by producing the bis (trichloromethyl) carbonate; the flow control valve is automatically controlled and monitored by a Distributed Control System (DCS);
(2) Introducing the uniformly mixed gas and hydrogen in the step (1) into a synthesis furnace burner 2 according to the volume ratio of 1.5, reacting chlorine and hydrogen in the mixed gas in the synthesis burner 2 to produce hydrogen chloride, and oxidizing organic matters into carbon dioxide and water by oxygen; automatically setting a hydrogen flow value according to the gas flow value out of the mixer and the chlorine purity, wherein an XV ignition valve, an FV regulating valve, an HV cut-off valve and an FC orifice flowmeter are arranged on a pipeline for introducing hydrogen; regulating the flow of hydrogen into the synthesis combustor 2 through an FV regulating valve and an FC flowmeter;
(3) Introducing the mixed gas treated in the step (2) into a hydrogen chloride distribution table 3 for distribution, and distributing part of hydrogen chloride to an absorption tower for preparing acid; distributing a part of hydrogen chloride gas to a chloroethylene production device for preparing chloroethylene; the production process standard of synthesizing chloroethylene by the acetylene method is as follows: the volume percentage of the hydrogen chloride is more than or equal to 93 percent; chlorine gas, detected by starch potassium iodide reagent and not detected; the volume percentage of oxygen is less than or equal to 0.3 percent), and the content of each gas in the hydrogen chloride gas for preparing the chloroethylene in the invention is as follows: 99.9% of hydrogen chloride by volume, chlorine: the starch potassium iodide reagent is not detected, and the oxygen volume percentage content is 0.05 percent.
The apparatus for processing the tail gas from the production of bis (trichloromethyl) carbonate by the combustion method in this example 3 for preparing vinyl chloride is the same as that in example 1.
The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.
Claims (4)
1. A method for treating tail gas generated in production of bis (trichloromethyl) carbonate by a combustion method for preparing vinyl chloride is characterized by comprising the following steps:
(1) Introducing tail gas generated by producing bis (trichloromethyl) carbonate, chlorine and oxygen into a mixer according to a certain proportion, wherein the volume ratio of the tail gas generated by producing bis (trichloromethyl) carbonate to the chlorine to the oxygen is 1: (1.5-2.5): 0.1;
(2) Introducing the uniformly mixed gas and hydrogen into a synthesis combustor according to a certain ratio, reacting chlorine and hydrogen in the mixed gas in the synthesis combustor to produce hydrogen chloride, and oxidizing organic matters into carbon dioxide and water by oxygen, wherein the volume ratio of the hydrogen to the uniformly mixed gas is (1.2-2.5): 1;
(3) Introducing the mixed gas treated in the step (2) into a hydrogen chloride distribution table for distribution, and distributing part of hydrogen chloride to an absorption tower for preparing acid; distributing a part of hydrogen chloride gas to a chloroethylene production device for preparing chloroethylene;
the tail gas generated by the bis (trichloromethyl) carbonate in the step (1) is chlorination tail gas, and the main components of the chlorination tail gas are hydrogen chloride, chlorine, dimethyl carbonate gas and chlorinated products of dimethyl carbonate; the volume percentage of each gas in the chlorination tail gas is respectively as follows: 96.5-97.8% of hydrogen chloride, 0.3-1.5% of chlorine, 0.2-0.7% of dimethyl carbonate gas and 0.8-2.0% of chloride of dimethyl carbonate.
2. The method for processing the tail gas generated in the production of the bis (trichloromethyl) carbonate by the combustion method for preparing the vinyl chloride according to claim 1, wherein the chloride of the dimethyl carbonate is C 3 H 6-n O 3 Cl n Wherein n is an integer of 1 to 6.
3. The method for processing bis (trichloromethyl) carbonate production tail gas for preparing vinyl chloride by using the combustion method as claimed in claim 1, wherein in the step (3), the standard of the refined hydrogen chloride gas for preparing vinyl chloride is as follows: 99.5-99.9 percent of hydrogen chloride by volume percentage and 0-0.3 percent of oxygen by volume percentage.
4. The method for preparing vinyl chloride by processing the tail gas generated in the production of bis (trichloromethyl) carbonate through the combustion method according to claim 1, wherein the preparation device adopted by the method for preparing vinyl chloride comprises a mixer, the mixer is connected with a synthesis furnace burner through a pipeline, the synthesis furnace burner is connected with a hydrogen chloride distribution table through a pipeline, and the hydrogen chloride distribution table is respectively connected with a hydrogen chloride absorption tower and a vinyl chloride production device through pipelines; and an XV ignition valve, an FV regulating valve, an HV stop valve and an FC orifice flowmeter are arranged on a pipeline connected with the mixer and the burner of the synthetic furnace.
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