CN217808769U

CN217808769U - Device for preparing chlorine by low-temperature plasma hydrogen chloride oxidation

Info

Publication number: CN217808769U
Application number: CN202221242470.5U
Authority: CN
Inventors: 宋晓玲; 周军; 熊新阳; 黄峥嵘; 慕龙; 王守国; 孙健; 李自兵; 冯俊; 刘军; 徐勇; 张萍
Original assignee: Xinjiang Zhizhen Chemical Engineering Research Center Co ltd; Qilu University of Technology; Xinjiang Tianye Group Co Ltd
Current assignee: Xinjiang Zhizhen Chemical Engineering Research Center Co ltd; Qilu University of Technology; Xinjiang Tianye Group Co Ltd
Priority date: 2022-05-23
Filing date: 2022-05-23
Publication date: 2022-11-15
Anticipated expiration: 2032-05-23

Abstract

The utility model belongs to the technical field of the chemical synthesis, especially, relate to a device of low temperature plasma hydrogen chloride oxidation preparation chlorine, include: cylindric outer tube, cylindric inner tube, inner electrode, outer electrode, gaseous preheater tube, plasma power, a tube-shape cavity is constituteed as the reactor to inner tube and the outer tube of cover outside the inner tube, sets up N intake pipe and 1 outlet duct on the outer tube, and reaction gas is dissociated through initiation and the high energy electron bombardment of low temperature plasma, utilizes the strong oxidation nature of active oxygen group to realize the oxidation reaction of hydrogen chloride, the utility model discloses equipment is simple, and sealed some is few, and the energy consumption is low, and operation elasticity is big, and the conversion rate of hydrogen chloride is high, and is environment-friendly.

Description

Device for preparing chlorine by low-temperature plasma hydrogen chloride oxidation

Technical Field

The utility model belongs to the technical field of the chemical synthesis, especially, relate to a device of low temperature plasma hydrogen chloride oxidation preparation chlorine.

Background

Chlorine is used as an important raw material for producing a plurality of chlorine-containing chemicals and is mainly used for organic synthesis, such as production of polyvinyl chloride, chlorinated polyethylene, synthetic rubber, synthetic fiber, fuel, pesticide, bleaching agent, disinfectant, solvent and the like, and other chlorides. In modern industry, chlorine is mainly obtained by electrolyzing saline solution, and caustic soda is a byproduct, so that the so-called chlor-alkali industry is formed.

In the gas-solid phase chlorination reaction process of numerous chlorine-related products such as chlorinated polyvinyl chloride, chlorinated polyethylene, chlorinated paraffin and the like, equipment is seriously corroded due to water content, and the chlorination effect is influenced; hydrogen chloride is a byproduct in the chlorination reaction process, and is allowed to exist in a certain concentration, but the gas-solid phase chlorination reaction is influenced by the concentration which is too high. The equimolar chlorine gas is consumed in the chlorination reaction process to generate equimolar hydrogen chloride, and after the hydrogen chloride content is accumulated to be higher and higher, the hydrogen chloride needs to be removed when the concentration of the hydrogen chloride reaches a certain value, so that the content of the hydrogen chloride is ensured to be in a certain range, and the concentration of the chlorine gas in the feed gas is increased. Although the prior art can convert the hydrogen chloride into the chlorine, the mixed gas can contain catalyst particles, byproduct water and even oxygen in the conversion process, or the hydrogen chloride is abandoned to be directly recycled after being converted into the chlorine for a series of reasons of mismatching of a process device for treating the mixed gas and a gas-solid phase chlorination reaction device, high operation difficulty, high investment cost, high energy consumption and the like. The method causes low utilization rate of chlorine, the continuous treatment of the discharged chlorine and hydrogen chloride also causes production cost increase, the burden of enterprises is increased, and the environmental protection problem that individual enterprises sacrifice the environment to obtain the benefits of the enterprises often occurs. Therefore, the byproduct hydrogen chloride is directly converted into chlorine gas and then recycled, the closed cycle of chlorine element and zero emission of the reaction process are realized, on one hand, the problems of large surplus of hydrogen chloride and high energy consumption of chlorine gas production are solved, the continuously increasing demand of chlorine gas in industry is met to a certain extent, and huge economic benefits are brought; on the other hand, chlor-alkali equilibrium will also be promoted; meanwhile, the problem of pollution caused by chlorine and hydrogen chloride can be solved, and great contribution is made to environmental protection. Moreover, the successful development of the process for preparing chlorine from hydrogen chloride can also have a decisive influence on a plurality of important chemical processes, and promote the emergence of a plurality of new processes and industries with high added values.

There are many methods for producing chlorine from hydrogen chloride, such as electrolysis, direct oxidation, and catalytic oxidation. The electrolysis method is to convert the byproduct hydrogen chloride into chlorine and hydrogen by electrolysis, and can be divided into a dry method and a wet method, and belongs to a traditional method. The direct oxidation method is a method for preparing Cl2 by directly oxidizing HCl by using inorganic oxidants such as NO2, SO3, naHSO4, mixed acid HNO3/H2SO4 and the like, and the reaction is carried out in a liquid phase, and typical methods include a Weldson method, a KCl-chlorine process and the like; the outstanding defects of the methods are that the equipment is complicated, corrosive substances are generated in the reaction process, the hydrogen chloride is not completely converted, the product is difficult to separate, the waste liquid is difficult to treat, and the energy consumption is high, so that the methods cannot be widely applied. The catalytic oxidation method is a method for oxidizing HCl to generate C12 by taking air or oxygen as an oxidant in the presence of a catalyst, the reaction process is a reversible exothermic process, the method has the advantages of low energy consumption, simplicity in operation and the like, the method is the method which is most easy to realize industrialization at present, and representative catalytic oxidation methods mainly comprise a Deacon process, an MT-chlorine process, a Shell-chlorine process and the like. In comparison with the prior art, the relatively feasible method for preparing chlorine from hydrogen chloride in the prior art is a catalytic oxidation method, but the catalytic oxidation method also has various defects and shortcomings.

CN 100343208C, jed limited, discloses a process for producing unsaturated halocarbons and an apparatus suitable for the process, in which a feed line and a device for generating radicals are separated from each other, and radicals generated from a cracking promoter are introduced into the feed line before a feed pipe enters a reactor, the cracking promoter contains an inert gas and reaction system component gases, the inert gas is difficult to chemically react under normal conditions, but is possible under plasma conditions, impurities are introduced into reaction products, and in addition, the time for existence of the radicals is in the order of milliseconds, and the separation of the reaction gas and the cracking promoter affects the conversion rate, resulting in a low conversion rate of the raw material gas.

Patent CN 104591090B of shanghai dynasty made by sekelon new materials science and technology limited discloses a method for preparing chlorine by catalytic oxidation of hydrogen chloride, which is one or more reactors connected in parallel or in series, by supplying a hydrogen chloride gas-containing stream and an oxygen-containing gas stream for oxidizing the hydrogen chloride gas-containing stream to the one or more reactors. The strong acid is formed due to the generation of water in the reaction process, which affects the service life of the catalyst and equipment and has high production cost.

Patent 200710023245.6 of Nanjing university of industry discloses a process system for producing chlorine by hydrogen chloride catalytic oxidation, which introduces a reaction device with a fluidized bed and an adiabatic fixed bed in series. The reaction device comprises a fluidized bed reactor, a heater, an adiabatic fixed bed reactor and other units, mixed gas flow of hydrogen chloride and oxygen firstly enters the fluidized bed reactor for oxidation reaction, the conversion rate of 30% -70% is realized, and after the mixed gas flow passes through the heat exchanger, the mixed gas flow enters the adiabatic fixed bed reactor, and finally the conversion rate of more than 90% of hydrogen chloride is realized. The device has simple process flow, but the conversion rate is not high enough due to the serious back mixing phenomenon.

Disclosure of Invention

For overcoming current hydrogen chloride oxidation system chlorine device investment big, the conversion rate is low, and the energy consumption is high, and the back mixes seriously etc. not enough, the utility model provides a device of low temperature plasma hydrogen chloride oxidation preparation chlorine when hydrogen chloride and oxygen process plasma discharge region, realizes the swift conversion of hydrogen chloride.

The utility model discloses the technical scheme who takes does: a device for preparing chlorine by low-temperature plasma hydrogen chloride oxidation comprises a cylindrical outer tube, a cylindrical inner tube, an inner electrode, an outer electrode, a gas preheating tube and a plasma power supply which are sequentially connected, wherein the inner electrode is arranged on the inner surface of the inner tube, and the outer electrode is arranged on the outer surface of the outer tube; the inner electrode and the outer electrode are connected with a plasma power supply together, the inner tube and the outer tube sleeved outside the inner tube form a cylindrical cavity with two closed ends as a reactor, and the outer tube is provided with N air inlet tubes and 1 air outlet tube.

The outer pipe and the inner pipe of the reactor are integrated by welding, riveting or one-step forming, and the reactor is reliable in use, air-tight and simple in manufacture.

According to the device for preparing chlorine by low-temperature plasma hydrogen chloride oxidation, the outer surface of the outer tube and the inner surface of the inner tube are both provided with the conductive layers to form electrodes, the electrodes are divided into the inner electrode and the outer electrode, the inner tube and the inner electrode are tightly connected in a layered mode, the inner electrode is cylindrical, the outer tube and the outer electrode are tightly connected in a layered mode, and the outer electrode is cylindrical.

According to the device for preparing chlorine by using low-temperature plasma hydrogen chloride, the conductive layers on the surfaces of the outer pipe and the inner pipe are manufactured in a spraying or coating mode, so that the conductivity is excellent. The external electrode and the internal electrode are connected by spraying or coating.

According to the device for preparing chlorine by using low-temperature plasma hydrogen chloride, the conductive layers on the surfaces of the outer pipe and the inner pipe are made of conductive materials or metal wire nets or the combination of the conductive materials and the metal wire nets.

According to the device for preparing chlorine by low-temperature plasma hydrogen chloride oxidation, the preheating pipe is further arranged inside the inner pipe, and a cavity is formed between the preheating pipe and the inner pipe.

According to the device for preparing chlorine by using low-temperature plasma hydrogen chloride, the two ends of the preheating pipe are respectively provided with the vent holes for introducing gas or liquid fluid.

Advantageous effects

The utility model has the advantages that: the device for preparing chlorine by oxidizing hydrogen chloride with low-temperature plasma has the advantages of simple parts, few sealing points and improved reliability and stability of equipment.

Drawings

FIG. 1 is a schematic diagram of a low temperature plasma hydrogen chloride oxidation apparatus for producing chlorine;

figure 2 is a schematic view of embodiment 2 of the present invention;

figure 3 is a schematic view of embodiment 3 of the present invention;

FIG. 4 is a schematic view of the structure of the preheating tube 13;

figure 5 is a schematic diagram of embodiment 4 of the present invention.

Reference numbers: the plasma gas source comprises an inner pipe 1, an outer pipe 2, a first gas inlet pipe 3, an outer electrode 4, an inner electrode 5, a second gas inlet pipe 6, an Nth gas inlet pipe 7, a plasma power supply 8, a gas outlet pipe 9, a positioning ring 10, a limiting ring 11, a lock nut 12, a preheating pipe 13 and a vent hole 14.

Detailed Description

The present invention will be further explained with reference to the accompanying drawings:

example 1, referring to fig. 1, a device for preparing chlorine by low temperature plasma hydrogen chloride oxidation includes an inner tube 1, an outer tube 2, a first gas inlet tube 3, an outer electrode 4, an inner electrode 5, a second gas inlet tube 6, an nth gas inlet tube 7, a plasma power supply 8, a gas outlet tube 9, a positioning ring 10, a limiting ring 11, a locking nut 12, a preheating tube 13, and a vent 14, wherein the inner tube 1 and the outer tube 2 are cylindrical, the inner tube 1 and the outer tube 2 sleeved outside the inner tube form a cylindrical cavity reactor, and a dielectric barrier plasma reactor of an integrated structure can be formed by sintering, welding, bonding, or one-step molding, HCL and O2 gases are proportionally introduced into an annular gap gas passage formed by the inner tube 1 and the outer tube 2 through the first gas inlet tube 3, the inner tube 1 and the outer tube 2 are made of quartz, ceramic, or an organic polymer material, the inner surface of the inner tube 1 is provided with a conductive layer, the inner electrode 5 is provided with a conductive layer, the outer surface of the outer tube 2 is provided with a conductive layer, the outer electrode 2 is provided with a conductive layer, the outer surface of the outer electrode 4, the inner electrode 5 and the outer electrode 4 are made of a conductive material, one or a combination of a metal wire mesh, the inner electrode 5 and the outer electrode 4 are embedded or a combination thereof, and a high voltage source are axially connected with the outer electrode 5, the outer tube 4, the inner electrode 4, the outer tube 2, the high voltage discharge tube 2 is axially connected with the outer electrode 4, the outer electrode 5, and the high voltage discharge tube 2, the high voltage discharge tube 4 is connected with the outer electrode 4, the discharge tube 2, and the high voltage discharge tube 2.

Embodiment 2, referring to fig. 2, the difference between this embodiment and embodiment 1 is that the inner tube 1 and the outer tube 2 are separate structures, and the position relationship between the two is controlled by the positioning ring 10 to ensure concentricity.

Embodiment 3, refer to fig. 3 and 4, this embodiment is different from embodiment 1 in that a preheating pipe 13 is arranged in an inner pipe 1, a cavity is formed between the preheating pipe 13 and the inner pipe 1, a limiting ring 11 and a lock nut 12 are arranged at both ends of the preheating pipe 13 to be combined with the inner pipe 1 into a whole, vent holes 14 are arranged at both ends of the preheating pipe 13, reaction gas enters from the vent hole 14 at the right end of the preheating pipe 13 to form a closed annular space with the limiting ring 11 and the inner electrode 5, and the reaction taking heat away from the inner electrode 5 is stably performed for a long time.

Embodiment 4, referring to fig. 5, the difference between this embodiment and embodiment 3 is that the inner tube 1 and the outer tube 2 are separate structures, and the position relationship between the two is controlled by the positioning ring 10 to ensure concentricity.

Claims

1. A device for preparing chlorine by low-temperature plasma hydrogen chloride oxidation comprises a cylindrical outer tube, a cylindrical inner tube, an inner electrode, an outer electrode, a gas preheating tube and a plasma power supply which are sequentially connected, wherein the inner electrode is arranged on the inner surface of the inner tube, and the outer electrode is arranged on the outer surface of the outer tube; the inner electrode and the outer electrode are connected with a plasma power supply together, and the plasma power supply is characterized in that: the inner pipe and the outer pipe sleeved outside the inner pipe form a cylindrical cavity with two closed ends, and the outer pipe is further provided with N air inlet pipes and 1 air outlet pipe.

2. A low temperature plasma hydrochloric acid oxidation apparatus for producing chlorine as claimed in claim 1, wherein the outer tube and the inner tube of the reactor are formed by welding, riveting or one-step forming.

3. The apparatus for preparing chlorine through oxidation of hydrogen chloride at a low temperature according to any one of claims 1 and 2, wherein the inner tube is closely connected to the inner electrode in a layered manner, and the inner electrode has a cylindrical shape.

4. The apparatus according to claim 3, wherein the outer tube is closely connected to the outer electrode in a layered manner, and the outer electrode is cylindrical.

5. The apparatus according to claim 3, wherein the external electrode and the internal electrode are connected by spraying or coating.

6. The apparatus of claim 3, wherein the outer electrode and the inner electrode are made of conductive material, wire mesh, or a combination thereof.

7. The apparatus of claim 1, wherein a preheating tube is further disposed inside the inner tube, and a cavity is formed between the preheating tube and the inner tube.

8. The apparatus for preparing chlorine by low-temperature plasma hydrogen chloride oxidation according to any one of claims 1 and 6, wherein the preheating pipe is provided with vent holes at both ends thereof.