CN110433636B - Chlorosulfonic acid production tail gas treatment system and method - Google Patents
Chlorosulfonic acid production tail gas treatment system and method Download PDFInfo
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- CN110433636B CN110433636B CN201910662060.2A CN201910662060A CN110433636B CN 110433636 B CN110433636 B CN 110433636B CN 201910662060 A CN201910662060 A CN 201910662060A CN 110433636 B CN110433636 B CN 110433636B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
- B01D2251/304—Alkali metal compounds of sodium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/10—Inorganic absorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
- B01D2257/2045—Hydrochloric acid
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Abstract
The invention discloses a tail gas treatment system and a tail gas treatment method for chlorosulfonic acid production.A gas inlet in the middle of a sulfuric acid absorption tower is connected with a tail gas source, concentrated sulfuric acid is filled in a tower kettle at the bottom of the sulfuric acid absorption tower, a spray structure is arranged at the top of the sulfuric acid absorption tower, and the tower kettle at the bottom of the sulfuric acid absorption tower is connected with the spray structure through a first pump; a middle gas inlet of the hydrochloric acid absorption tower is connected with a top gas outlet of the sulfuric acid absorption tower, a bottom tower kettle of the hydrochloric acid absorption tower is filled with water, the top of the hydrochloric acid absorption tower is provided with a spraying structure, and the bottom tower kettle is connected with the spraying structure through a second pump; the middle gas inlet of the alkali absorption tower is connected with the outlet at the top of the hydrochloric acid absorption tower, the bottom tower kettle of the alkali absorption tower is filled with alkali liquor, the top of the alkali absorption tower is provided with a spraying structure, and the bottom tower kettle is connected with the spraying structure through a third pump; the tail gas inlet and the tail gas outlet of the tail gas buffer tank are both arranged at the top of the tail gas buffer tank, the tail gas inlet is connected with the top outlet of the alkali absorption tower, and the tail gas outlet is connected with the chimney through a fourth pump.
Description
Technical Field
The invention belongs to the technical field of tail gas treatment in chlorosulfonic acid production, and particularly relates to a tail gas treatment system and a tail gas treatment method in chlorosulfonic acid production.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The chlorosulfonic acid is produced by burning chlorine and hydrogen from chlor-alkali system in HCl synthesizing furnace to produce HCl, which is dried to eliminate water and SO from sulfuric acid plant3Mixing the gas and the gas returned from the auxiliary absorption tower by a mixer, directly entering a synthesis tower, controlling the reaction temperature at 80-150 ℃, synthesizing chlorosulfonic acid at high temperature, and sending the non-condensable gas to a tail gas treatment system for treatment. The non-condensable gas contains a small amount of SO2、SO3HCl and a large amount of air. The existing method for treating non-condensable gas generally comprises the steps of introducing tail gas into an acid washing tower, and circularly absorbing SO in mixed gas by using 98 percent sulfuric acid in the acid washing tower3Gas is pumped when the sulfuric acid in the tower reaches a certain liquid levelAnd (3) the gas (hydrogen chloride gas) which is not absorbed in the acid washing tower enters a tail gas absorption tower finally, and the tail gas is circularly sprayed and absorbed in the tail gas absorption tower by using water. And a tail gas fan is arranged at a gas outlet of the tail gas absorption tower, and residual gas is pumped to a chimney by the fan for emptying. The inventor finds that the tail gas treatment method cannot effectively remove SO in the tail gas2The problem that the environment is not up to standard exists in tail gas of gas and emission, and the influence on the surrounding environment is easily caused. And moreover, a large amount of water drops are carried in the emptying tail gas after the circulating water spraying, and the emptying tail gas still contains acidic gas, so that acid liquor is easily formed when the emptying tail gas is discharged through a chimney, the inner wall of the chimney is corroded, and the service life of the chimney is influenced.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a system and a method for treating tail gas generated in chlorosulfonic acid production. Can effectively remove various acid gases in the tail gas, can remove a large amount of water drops carried in the tail gas after being sprayed, and reduces the corrosion to a chimney.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a tail gas treatment system for chlorosulfonic acid production comprises a sulfuric acid absorption tower, a hydrochloric acid absorption tower, an alkali absorption tower, a tail gas buffer tank and a chimney, wherein,
a gas inlet in the middle of the sulfuric acid absorption tower is connected with a tail gas source, concentrated sulfuric acid is contained in a tower kettle at the bottom of the sulfuric acid absorption tower, a spraying structure is arranged at the top of the sulfuric acid absorption tower, and the tower kettle at the bottom of the sulfuric acid absorption tower is connected with the spraying structure through a first pump;
a middle gas inlet of the hydrochloric acid absorption tower is connected with a top gas outlet of the sulfuric acid absorption tower, a bottom tower kettle of the hydrochloric acid absorption tower is filled with water, the top of the hydrochloric acid absorption tower is provided with a spraying structure, and the bottom tower kettle is connected with the spraying structure through a second pump;
the middle gas inlet of the alkali absorption tower is connected with the outlet at the top of the hydrochloric acid absorption tower, the bottom tower kettle of the alkali absorption tower is filled with alkali liquor, the top of the alkali absorption tower is provided with a spraying structure, and the bottom tower kettle is connected with the spraying structure through a third pump;
the tail gas inlet and the tail gas outlet of the tail gas buffer tank are both arranged at the top of the tail gas buffer tank, the tail gas inlet is connected with the top outlet of the alkali absorption tower, and the tail gas outlet is connected with the chimney through a fourth pump.
In a sulfuric acid absorption tower, circularly spraying the tail gas by adopting concentrated sulfuric acid to fully absorb sulfur trioxide in the tail gas; circularly spraying the tail gas by adopting water in a hydrochloric acid absorption tower so as to fully absorb HCl gas in the tail gas; in the alkali absorption tower, alkali liquor is adopted to circularly spray the tail gas so as to fully absorb acid gases such as sulfur dioxide in the tail gas.
Even spray through alkali lye, inevitably remain acid material such as sulfur dioxide in the tail gas still, and carry a large amount of water droplets in the tail gas after water spraying and alkali lye spray, in order to avoid appearing the acidizing fluid at the chimney inner wall, cause the corruption to the chimney, increase the tail gas buffer tank between chimney and alkali absorption tower, the tail gas velocity of flow reduces in the tail gas buffer tank in the twinkling of an eye, and the flow direction changes, the water droplet of carrying can be with gas separation under its gravity and inertial action, and collect in the tail gas buffer tank, in order to reduce moisture content in the tail gas.
Meanwhile, the discharge amount of tail gas in the living process of chlorosulfonic acid is unstable, so that the load of the pump is easy to change continuously when the tail gas is conveyed to a chimney for discharge, the stable operation of the pump is influenced, and the service life of the pump is adversely affected. When the tail gas buffer tank is arranged between the chimney and the alkali absorption tower, the tail gas flow can be buffered and homogenized to ensure that the load of the pump tends to be uniform, and the tail gas buffer tank is favorable for prolonging the service life of the pump.
In some embodiments, the number of hydrochloric acid absorption columns is 1-3, and different hydrochloric acid absorption columns are connected in series.
A plurality of hydrochloric acid absorption towers are connected in series to ensure that HCl gas in tail gas is fully absorbed.
In some embodiments, the number of alkaline absorption towers is 1-3, and different alkaline absorption towers are connected in series.
A plurality of alkali absorption towers are connected in series to improve the removal rate of sulfur dioxide in tail gas as much as possible.
In some embodiments, the tail gas buffer tank is of a horizontal structure and is divided into an upper layer and a lower layer by a separation structure, a leakage groove structure is arranged on the separation structure, the bottom of the leakage groove structure is open, and a diameter reducing structure is formed from top to bottom;
the tail gas buffer tank also comprises at least one baffle, the top of the baffle is fixed at the top of the tail gas buffer tank, the bottom of the baffle extends to the bottom of the leakage groove structure, and the set distance is reserved between the bottom of the baffle and the bottom of the leakage groove structure.
After tail gas which is sprayed to remove acid gas enters the tail gas buffer tank through the tail gas inlet, the flow velocity of the tail gas is remarkably reduced due to sudden change of the circulation diameter, water drops carried in the tail gas are under the action of inertia and self gravity to realize separation of partial water drops and the tail gas, and the reduced water drops are collected on the separation structure and flow to the lower part of the separation structure through the bottom opening of the leakage groove structure. The separation structure separates the tail gas from the collected water to prevent re-evaporation of the water.
The tail gas through preliminary gas-liquid separation flows through from the space between the bottom of hourglass groove structure and the baffle, because the cross-sectional area in this space is showing and is reducing, lead to the velocity of flow of tail gas to show and improve, in addition, because the hourglass groove structure is the indent structure, when tail gas flows through here, take place the drastic change of flow direction and velocity of flow, and the inertia of water droplet is showing and is greater than gaseous inertia, so, the water droplet changes inconsistently with gaseous flow direction, the water droplet collides the lateral wall of hourglass groove structure more easily, realize the re-separation of gas-liquid, the water droplet of being collected flows downwards from the lateral wall of hourglass groove structure, bottom export through the hourglass groove structure flows in the below of baffle structure.
Furthermore, the number of the leakage groove structures is 1-10, further 2-6, further 3-6, and the number of the baffle plates is equal to that of the leakage groove structures.
Furthermore, the included angle between the side wall of the leakage groove structure and the baffle is 20-45 degrees.
After the gas is primarily separated, most of water drops with large particle sizes carried in the gas are removed, and the water drops separated by the leakage groove structure have small particle sizes, small mass and small inertia difference with the gas. Therefore, when the flow direction is changed, the change in the flow direction of the liquid droplets is less different from the change in the flow direction of the gas. If the included angle between the side wall of the leakage groove structure and the baffle is small, the liquid drop catching is facilitated, and when the included angle is too large, most of the liquid drops are difficult to catch, so that the liquid drop removing efficiency is influenced.
Furthermore, the leakage groove structure is perpendicular to the axial direction of the tail gas buffer tank and covers the diameter of the section of the tail gas buffer tank.
A method for treating tail gas generated in chlorosulfonic acid production comprises the following steps:
the production tail gas from the chlorosulfonic acid synthesis process enters a sulfuric acid absorption tower, and sulfur trioxide in the production tail gas is removed under the circulating spraying of concentrated sulfuric acid;
the production tail gas flowing out of the sulfuric acid absorption tower enters a hydrochloric acid absorption tower, and HCl in the production tail gas is removed under the circulating spraying of water;
the production tail gas flowing out of the hydrochloric acid absorption tower enters an alkali absorption tower, and sulfur dioxide in the production tail gas is removed under the circulating spraying of alkali liquor;
and the production tail gas flowing out of the hydrochloric acid absorption tower is buffered by a tail gas buffer tank, subjected to gas-liquid separation and then pumped to a chimney for emission.
In some embodiments, the concentrated sulfuric acid has a concentration of 98-98.7% by mass.
In some embodiments, the concentration of the lye is 8-15% by mass.
The invention has the beneficial effects that:
SO contained in tail gas2、SO3、HCl、Cl2The components are treated, and hydrochloric acid, sodium hypochlorite and sodium sulfite are by-produced.
The tail gas can reach the national emission index after being sprayed and absorbed, and the environmental protection effect is obvious.
Due to the arrangement of the tail gas buffer tank, water drops carried in the tail gas can be obviously removed, and the corrosion to the inner wall of the chimney is reduced.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a process flow diagram of an environment-friendly treatment system for tail gas from chlorosulfonic acid production according to an embodiment of the present invention;
fig. 2 is a schematic view of the internal structure of the exhaust buffer tank according to the embodiment of the present invention.
The system comprises a sulfuric acid absorption tower, a first hydrochloric acid absorption tower, a second hydrochloric acid absorption tower, a first alkali absorption tower, a second alkali absorption tower, a tail gas buffer tank, a tail gas fan, a chimney, a tail gas inlet, a tail gas baffle, a tail gas outlet, a tail gas guide plate and a leakage groove structure, wherein the sulfuric acid absorption tower is 1, the first hydrochloric acid absorption tower is 2, the second hydrochloric acid absorption tower is 3, the first alkali absorption tower is 4, the second alkali absorption tower is 5, the tail gas buffer tank is 6, the tail gas fan is 7, the tail gas fan is 8, the chimney, the tail gas inlet is 9, the tail gas inlet is 10, the baffle is 11, the tail gas outlet is 12, the guide plate is 13, and the leakage groove structure is formed.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Example (b):
as shown in figure 1, the environment-friendly treatment process and device for tail gas generated in chlorosulfonic acid production mainly comprise a sulfuric acid absorption system, a hydrochloric acid absorption system, an alkali absorption system and a tail gas buffer system. The sulfuric acid absorption system comprises a tail gas inlet pipeline, a tail gas outlet pipeline, a sulfuric acid absorption tower 1 and a sulfuric acid absorption tower circulating pump. The tail gas inlet pipeline of the sulfuric acid absorption system is connected with the outlet pipeline of the synthesis tower, the chlorosulfonic acid tail gas enters the sulfuric acid absorption tower 1 along a gas phase pipeline, 98-98.7% concentrated sulfuric acid is adopted in the sulfuric acid absorption tower 1 for washing, and the sulfuric acid absorption tower is filled with the concentrated sulfuric acidCountercurrent contact in the material layer, SO in chlorosulfonic acid tail gas3Is absorbed.
The hydrochloric acid absorption system consists of a first hydrochloric acid absorption tower 2, a second hydrochloric acid absorption tower 3, a first hydrochloric acid absorption tower circulating pump, a second hydrochloric acid absorption tower circulating pump, a water adding pipeline and a tail gas inlet and outlet pipeline, wherein the equipment and the pipeline are made of glass fiber reinforced plastic, and the connection positions are pasted by glass fiber reinforced plastic resin and felt.
Absorbing the residual gas in a hydrochloric acid absorption tower, wherein the residual gas contains HCl and Cl2The gas of (2) gets into first hydrochloric acid absorption tower 2 through glass steel tail gas pipeline, adopts water circulation once in first hydrochloric acid absorption tower 2, and chlorosulfonic acid tail gas contacts with water countercurrent flow once in first hydrochloric acid absorption tower packing layer, and HCl in the tail gas is absorbed and is generated hydrochloric acid, and tail gas reentries second hydrochloric acid absorption tower 3 through first hydrochloric acid absorption tower 2, and HCl in the remaining tail gas is further absorbed in second hydrochloric acid absorption tower 3.
The alkali recovery system consists of a first alkali absorption tower 4, a second alkali absorption tower 4, a first alkali absorption tower circulating pump and a second alkali absorption tower circulating pump. The first alkali absorption tower 4 and the second alkali absorption tower 5 adopt a carbon steel fluorine lining form, the equipment is a carbon steel shell, and a lining F40 is arranged.
The residual gas enters an alkali absorption tower, and a filling layer of the first alkali absorption tower contains SO2And Cl2The tail gas is in countercurrent contact with 8 percent of caustic soda circulating liquid to generate sodium sulfite substances, and SO in the tail gas2Absorbed by caustic soda solution and residual Cl is contained2The tail gas enters a second alkali absorption tower 5, and a filling layer of the second alkali absorption tower contains Cl2The tail gas is in countercurrent contact with 8 percent of caustic soda circulating liquid to generate sodium hypochlorite substances.
The tail gas buffer system is composed of a tail gas buffer tank 6, a tail gas fan 7 and a chimney 8. As shown in fig. 2, the exhaust buffer tank 6 is a horizontal structure, and is divided into an upper layer and a lower layer by a separation structure, the separation structure is provided with a leakage groove structure 13, the bottom of the leakage groove structure 13 is open, and a diameter reducing structure is formed from top to bottom;
the tail gas buffer tank 6 further comprises at least one baffle plate 10, the top of the baffle plate 10 is fixed to the top of the tail gas buffer tank 6, the bottom of the baffle plate 10 extends to the bottom of the leakage groove structure 13, and a set distance is reserved between the bottom of the leakage groove structure 13 and the bottom of the leakage groove structure.
The number of the leakage groove structures 13 is 1-10, and can be 2, 3, 4, 5, 6, 7, 8 and the like, the included angle between the side wall of the leakage groove structure 13 and the baffle plate 10 is 30 degrees, and the leakage groove structure 13 is perpendicular to the axial direction of the tail gas buffer tank 6 and covers the section diameter of the tail gas buffer tank 6.
And finally, the gas after the fifth-stage tail gas treatment enters a tail gas buffer tank, and the tail gas reaching the standard after treatment is conveyed to a chimney through a tail gas fan for emptying. The HCl emission content of the exhaust tail gas is less than or equal to 60mg/Nm3To exhaust SO in the tail gas2The discharge content is less than or equal to 30mg/Nm3。
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (8)
1. A chlorosulfonic acid production tail gas treatment system which characterized in that: comprises a sulfuric acid absorption tower, a hydrochloric acid absorption tower, an alkali absorption tower, a tail gas buffer tank and a chimney, wherein,
a gas inlet in the middle of the sulfuric acid absorption tower is connected with a tail gas source, concentrated sulfuric acid is contained in a tower kettle at the bottom of the sulfuric acid absorption tower, a spraying structure is arranged at the top of the sulfuric acid absorption tower, and the tower kettle at the bottom of the sulfuric acid absorption tower is connected with the spraying structure through a first pump;
a middle gas inlet of the hydrochloric acid absorption tower is connected with a top gas outlet of the sulfuric acid absorption tower, a bottom tower kettle of the hydrochloric acid absorption tower is filled with water, the top of the hydrochloric acid absorption tower is provided with a spraying structure, and the bottom tower kettle is connected with the spraying structure through a second pump;
a middle gas inlet of the alkali absorption tower is connected with a top outlet of the hydrochloric acid absorption tower, a bottom tower kettle of the alkali absorption tower is filled with alkali liquor, the top of the alkali absorption tower is provided with a spraying structure, and the bottom tower kettle is connected with the spraying structure through a third pump;
a tail gas inlet and a tail gas outlet of the tail gas buffer tank are both arranged at the top of the tail gas buffer tank, the tail gas inlet is connected with a top outlet of the alkali absorption tower, and the tail gas outlet is connected with a chimney through a fourth pump;
the tail gas buffer tank is of a horizontal structure and is divided into an upper layer and a lower layer by a separation structure, a leakage groove structure is arranged on the separation structure, the bottom of the leakage groove structure is open, and a reducing structure is formed from top to bottom; the tail gas buffer tank also comprises at least one baffle, the top of the baffle is fixed at the top of the tail gas buffer tank, the bottom of the baffle extends to the bottom of the leakage groove structure, and the set distance is reserved between the bottom of the baffle and the bottom of the leakage groove structure.
2. The chlorosulfonic acid production tail gas treatment system of claim 1, wherein: the number of the hydrochloric acid absorption towers is 1-3, and different hydrochloric acid absorption towers are connected in series.
3. The chlorosulfonic acid production tail gas treatment system of claim 1, wherein: the number of the alkali absorption towers is 1-3, and different alkali absorption towers are connected in series.
4. The chlorosulfonic acid production tail gas treatment system of claim 1, wherein: the number of the leak groove structures is 1-10, and the number of the baffle plates is equal to that of the leak groove structures.
5. The chlorosulfonic acid production tail gas treatment system of claim 4, wherein: the number of the leak groove structures is 2-6.
6. The chlorosulfonic acid production tail gas treatment system of claim 5, wherein: the number of the leak groove structures is 3-6.
7. The chlorosulfonic acid production tail gas treatment system of claim 1, wherein: the included angle between the side wall of the leakage groove structure and the baffle is 20-45 degrees.
8. The chlorosulfonic acid production tail gas treatment system of claim 1, wherein: the leakage groove structure is perpendicular to the axial direction of the tail gas buffer tank and covers the section diameter of the tail gas buffer tank.
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Address after: 252000 Luxi Industrial Park, high tech Industrial Development Zone, Liaocheng City, Shandong Province Patentee after: Liaocheng Luxi methyl chloride Chemical Co.,Ltd. Address before: 252211 Shandong city of Liaocheng province Dong'e County Gu Guan Tun Zhen Luxi Chemical Industrial Park Patentee before: SHANDONG LIAOCHENG LUXI SIXTH CHEMICAL FERTILIZER Co.,Ltd. |