CN112221314A - Process system for treating aldehyde-containing waste acid by using manganese dioxide and treatment method thereof - Google Patents

Process system for treating aldehyde-containing waste acid by using manganese dioxide and treatment method thereof Download PDF

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Publication number
CN112221314A
CN112221314A CN202011171238.2A CN202011171238A CN112221314A CN 112221314 A CN112221314 A CN 112221314A CN 202011171238 A CN202011171238 A CN 202011171238A CN 112221314 A CN112221314 A CN 112221314A
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liquid
absorption tower
spray absorption
manganese dioxide
inlet
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焦朋朋
尹国逊
段玉慧
王子辰
王庆阳
王子佳
刘子田
刘晓强
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Zaozhuang University
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Zaozhuang University
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/10—Particle separators, e.g. dust precipitators, using filter plates, sheets or pads having plane surfaces
    • B01D46/12—Particle separators, e.g. dust precipitators, using filter plates, sheets or pads having plane surfaces in multiple arrangements
    • 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
    • B01D53/1406—Multiple stage absorption
    • 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
    • B01D53/1425—Regeneration of liquid absorbents
    • 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
    • B01D53/1456—Removing acid components
    • 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
    • B01D53/1487—Removing organic compounds

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Gas Separation By Absorption (AREA)
  • Treating Waste Gases (AREA)

Abstract

The invention relates to a process system for treating aldehyde-containing waste acid by using manganese dioxide and a treatment method thereof. During treatment, the mixed gas is cooled through a heat exchange process, then is sprayed and absorbed, is absorbed by manganese dioxide, is aerated after solid-liquid separation, is sprayed and absorbed for the second time, and is discharged after the waste gas generated in the process is treated, so that the obtained liquid is collected in a classified manner. According to the invention, the waste acid containing aldehyde is treated by using manganese dioxide, and a hydrochloric acid solution with a certain concentration and a manganese chloride solution approaching or reaching saturation are finally obtained, so that the utilization value and the economic benefit of the waste acid containing aldehyde can be improved.

Description

Process system for treating aldehyde-containing waste acid by using manganese dioxide and treatment method thereof
Technical Field
The invention relates to the technical field of treatment of industrial aldehyde-containing waste acid, in particular to a process system for treating aldehyde-containing waste acid by using manganese dioxide and a treatment method thereof.
Background
Nowadays, the economy of China is rapidly developing, and the demand of the organic phosphorus scale inhibitor is also increasing. During the production process of the organic phosphorus scale inhibitor, a large amount of waste gas containing formaldehyde and hydrogen chloride is generated, the waste gas is absorbed by water to become waste acid containing aldehyde, and the use and treatment of the waste acid are influenced by the presence of formaldehyde in the solution. The waste acid containing aldehyde becomes a 'hot sweet potato', and the enterprises producing the organic phosphorus scale inhibitor feel very difficult to treat the waste acid.
Disclosure of Invention
The invention aims to solve the defects of the prior art, and provides a process system for treating aldehyde-containing waste acid by using manganese dioxide and a treatment method thereof in order to improve the economic value and the utilization value of the aldehyde-containing waste acid.
In order to achieve the purpose, the invention adopts the following technical scheme:
the process system for treating the aldehyde-containing waste acid by using the manganese dioxide comprises a heat exchange unit, a first-stage spraying absorption unit, a feed liquid mixing reaction unit, a solid-liquid separation unit, an aeration unit, a second-stage spraying absorption unit and an acid liquid storage unit which are sequentially connected, wherein the first-stage spraying absorption unit and the second-stage spraying absorption unit are both connected with a tail gas treatment unit, and the aeration unit is connected with an air purification unit and a salt liquid storage unit.
The heat exchange unit comprises a heat exchanger, a cooling medium inlet, a cooling medium outlet, a gas inlet and a gas outlet are arranged on the heat exchanger, and the gas inlet of the heat exchanger is connected with a mixed gas inlet pipe of hydrogen chloride and formaldehyde;
the primary spray absorption unit comprises a primary spray absorption tower, the lower end of the side wall of the primary spray absorption tower is provided with a gas inlet, the bottom of the side wall of the primary spray absorption tower is provided with a liquid outlet, the top of the side wall of the primary spray absorption tower is provided with a liquid inlet, the upper end of the side wall of the primary spray absorption tower is provided with an exhaust port, the gas inlet of the primary spray absorption tower is connected with the gas outlet of the heat exchanger, and the liquid inlet of the primary;
the feed liquid mixing reaction unit comprises a feed liquid mixing reaction kettle, the top of the side wall of the feed liquid mixing reaction kettle is provided with a manganese dioxide feed inlet, the inlet of the feed liquid mixing reaction kettle is connected with the liquid outlet of the primary spray absorption tower through a first acid-resistant pump, the feed liquid mixing reaction kettle is connected with the exhaust port of the primary spray absorption tower through a pipeline, and the pipeline is provided with a pressure reducing valve;
the solid-liquid separation unit comprises a solid-liquid separator, the solid-liquid separator is provided with a mixture inlet, a solid outlet and a liquid outlet, the mixture inlet of the solid-liquid separator is connected with the outlet of the feed liquid mixing reaction kettle through a second acid-resistant pump, and the solid outlet of the solid-liquid separator is connected with the feed liquid mixing reaction kettle through a solid medicament return pump;
the aeration unit comprises an aeration tank, an inlet of the aeration tank is connected with a liquid outlet of the solid-liquid separator through a third acid-resistant pump, and an aeration head is arranged in the aeration tank;
the air purification unit comprises an air purifier, and the air purifier is connected with an aeration head in the aeration tank through an aeration pump;
the salt solution storage unit comprises a salt solution storage tank, and an outlet at the bottom of the aeration tank is connected with the salt solution storage tank;
the second-stage spraying absorption unit comprises a second-stage spraying absorption tower, a gas inlet is formed in the lower end of the side wall of the second-stage spraying absorption tower, a liquid outlet is formed in the bottom of the side wall of the second-stage spraying absorption tower, a liquid inlet is formed in the top of the second-stage spraying absorption tower, an exhaust port is formed in the upper end of the side wall of the second-stage spraying absorption tower, the gas inlet of the second-stage spraying absorption tower is connected with the gas outlet in the top of the aeration tank through;
the acid liquid storage unit comprises a hydrochloric acid storage tank, and the hydrochloric acid storage tank is connected with a liquid outlet of the secondary spray absorption tower through a fifth acid-resistant pump;
the tail gas treatment unit comprises a first tail gas processor and a second tail gas processor, the first tail gas processor is connected with a pipeline where a pressure reducing valve between the first-stage spray absorption tower and the feed liquid mixing reaction kettle is located, and the second tail gas processor is connected with an exhaust port of the second-stage spray absorption tower.
And a liquid foam filtering plate layer is arranged at the upper part in the aeration tank.
And a circulating liquid port is arranged below the liquid foam filtering plate layer on the aeration tank and is connected with a top liquid inlet of the first-stage spray absorption tower through a sixth acid-resistant pump.
The feed liquid is stirred and is mixed and be equipped with agitating unit in the reation kettle, agitating unit even has agitator motor.
The heat exchanger is internally provided with a snakelike heat exchange tube which is connected with a cooling medium inlet and a cooling medium outlet.
The treatment method of the process system for treating the aldehyde-containing waste acid by using the manganese dioxide comprises the following specific steps:
s1, enabling the mixed gas of hydrogen chloride and formaldehyde to enter a heat exchanger through a hydrogen chloride and formaldehyde mixed gas inlet pipe, and realizing the reduction of the temperature of the mixed gas by exchanging heat with a cooling medium flowing in the heat exchanger;
s2, allowing the cooled mixed gas to enter a primary spray absorption tower, continuously spraying an absorption liquid downwards from a liquid inlet at the top of the primary spray absorption tower, and absorbing the mixed gas of hydrogen chloride and formaldehyde to form aldehyde-containing waste acid liquid L1The tail gas is discharged after being treated by the first tail gas treater;
s3 aldehyde-containing waste acid feed liquid L1Pumping into a material liquid mixing reaction kettle, and adding manganese dioxide and manganese dioxide into the material liquid mixing reaction kettle, wherein the adding amount of the manganese dioxide and the aldehyde-containing waste acid material liquid L1Of formaldehydeThe mass ratio is 1.5-5.0, and the waste acid feed liquid L containing aldehyde1The retention time in the material liquid mixing reaction kettle is 10min-300min, the formaldehyde can be completely consumed, and finally the material liquid L for removing the formaldehyde is obtained2；
S4 feed liquid L for removing formaldehyde2Pumping into a solid-liquid separator to realize solid-liquid separation to obtain a solution L3The unreacted manganese dioxide and the unreacted manganese dioxide are returned to the material liquid mixing reaction kettle through a solid medicament return pump to be reused;
s5 solution L3The aeration tank is aerated by clean air, the upper part of the aeration tank is provided with a liquid foam filtering laminate, the separation of gas and liquid foam can be realized, and the solution L3The retention time in the aeration tank is 10min-300min, the aeration volume flow is 0.1-200L/min, and the solution L from which the hydrogen chloride is removed4Pumping to a first-stage spray absorption tower for cyclic utilization, and obtaining solution L4Recycling the solution L when the saturation of manganese chloride is approached or reached4Pumping the salt solution into a salt solution storage tank for storage;
s6, enabling the gas flowing out of the aeration tank to enter a secondary spraying absorption tower, controlling the concentration of hydrochloric acid by controlling the using amount of spraying clear water, storing the finally obtained hydrochloric acid solution into a hydrochloric acid storage tank, and treating the tail gas generated by the secondary spraying absorption tower by a second tail gas processor to achieve the standard and discharge.
In step S2, during operation in the first-stage spray absorption tower, aldehyde-containing waste acid feed liquid L is controlled1The concentration of the hydrogen chloride is between 1mol/L and 5 mol/L.
In step S3, the manganese dioxide feed inlet is timely replenished with the required manganese dioxide according to the consumption of the manganese dioxide.
The invention has the beneficial effects that: according to the invention, the waste acid containing aldehyde is treated by using manganese dioxide, and a hydrochloric acid solution with a certain concentration and a manganese chloride solution approaching or reaching saturation are finally obtained, so that the utilization value and the economic benefit of the waste acid containing aldehyde can be improved.
Drawings
FIG. 1 is a schematic view of a processing system of the present invention;
in the figure: a 1-hydrogen chloride and formaldehyde mixed gas inlet pipe; 2-a heat exchanger; 3-first stage spray absorption tower; 4-a first acid-resistant pump; 5-mixing the feed liquid in a reaction kettle; 6-a second acid-resistant pump; 7-a solid-liquid separator; 8-a third acid-resistant pump; 9-an aeration tank; 10-a fourth acid-resistant pump; 11-a secondary spray absorption tower; 12-a fifth acid resistant pump; 13-a hydrochloric acid storage tank; 14-a water inlet pump of the secondary spray absorption tower; 15-an air purifier; 16-an aeration pump; 17-a salt solution storage tank; 18-a pressure relief valve; 19-a first tail gas processor; 20-a first-stage spray absorption tower water inlet pump; 21-solid dose return pump; 22-a second tail gas processor; 23-manganese dioxide feed inlet; 24-a sixth acid-resistant pump;
the following detailed description will be made in conjunction with embodiments of the present invention with reference to the accompanying drawings.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings:
as shown in fig. 1, a process system for treating aldehyde-containing waste acid by using manganese dioxide comprises a heat exchange unit, a primary spray absorption unit, a feed liquid mixing reaction unit, a solid-liquid separation unit, an aeration unit, a secondary spray absorption unit and an acid liquid storage unit which are connected in sequence, wherein the primary spray absorption unit and the secondary spray absorption unit are both connected with a tail gas treatment unit, and the aeration unit is connected with an air purification unit and a salt liquid storage unit.
The heat exchange unit comprises a heat exchanger 2, a cooling medium inlet, a cooling medium outlet, a gas inlet and a gas outlet are arranged on the heat exchanger 2, and the gas inlet of the heat exchanger 2 is connected with a mixed gas inlet pipe 1 of hydrogen chloride and formaldehyde;
the primary spray absorption unit comprises a primary spray absorption tower 3, the lower end of the side wall of the primary spray absorption tower 3 is provided with a gas inlet, the bottom of the side wall of the primary spray absorption tower 3 is provided with a liquid outlet, the top of the side wall of the primary spray absorption tower 3 is provided with a liquid inlet, the upper end of the side wall of the primary spray absorption tower is provided with an exhaust port, the gas inlet of the primary spray absorption tower 3 is connected with the gas outlet of the heat exchanger 2, and the liquid inlet of the primary;
the feed liquid mixing reaction unit comprises a feed liquid mixing reaction kettle 5, the top of the side wall of the feed liquid mixing reaction kettle 5 is provided with a manganese dioxide feed inlet 23, the inlet of the feed liquid mixing reaction kettle 5 is connected with the liquid outlet of the primary spray absorption tower 3 through a first acid-resistant pump 4, the feed liquid mixing reaction kettle 5 is connected with the exhaust port of the primary spray absorption tower 3 through a pipeline, and the pipeline is provided with a pressure reducing valve 18;
the solid-liquid separation unit comprises a solid-liquid separator 7, the solid-liquid separator 7 is provided with a mixture inlet, a solid outlet and a liquid outlet, the mixture inlet of the solid-liquid separator 7 is connected with the outlet of the feed liquid mixing reaction kettle 5 through a second acid-resistant pump 6, and the solid outlet of the solid-liquid separator 7 is connected with the feed liquid mixing reaction kettle 5 through a solid medicament return pump 21;
the aeration unit comprises an aeration tank 9, the inlet of the aeration tank 9 is connected with the liquid outlet of the solid-liquid separator 7 through a third acid-proof pump 8, and an aeration head is arranged in the aeration tank 9;
the air purification unit comprises an air purifier 15, and the air purifier 15 is connected with an aeration head in the aeration tank 9 through an aeration pump 16;
the salt solution storage unit comprises a salt solution storage tank 17, and an outlet at the bottom of the aeration tank 9 is connected with the salt solution storage tank 17;
the secondary spray absorption unit comprises a secondary spray absorption tower 11, a gas inlet is formed in the lower end of the side wall of the secondary spray absorption tower 11, a liquid outlet is formed in the bottom of the side wall of the secondary spray absorption tower, a liquid inlet is formed in the top of the side wall of the secondary spray absorption tower 11, an exhaust port is formed in the upper end of the side wall of the secondary spray absorption tower, the gas inlet of the secondary spray absorption tower 11 is connected with the gas outlet in the top of the aeration tank 9 through a fourth acid-resistant pump 10, and the liquid inlet;
the acid liquid storage unit comprises a hydrochloric acid storage tank 13, and the hydrochloric acid storage tank 13 is connected with a liquid outlet of the secondary spray absorption tower 11 through a fifth acid-resistant pump 12;
the tail gas treatment unit comprises a first tail gas processor 19 and a second tail gas processor 22, the first tail gas processor 19 is connected with a pipeline where a pressure reducing valve 18 between the first-stage spray absorption tower 3 and the feed liquid mixing reaction kettle 5 is located, and the second tail gas processor 22 is connected with an exhaust port of the second-stage spray absorption tower 11.
And a liquid foam filtering plate layer is arranged at the upper part in the aeration tank 9.
And a circulating liquid port is arranged below the liquid foam filtering plate layer on the aeration tank 9 and is connected with a top liquid inlet of the first-stage spray absorption tower 3 through a sixth acid-resistant pump 24.
A stirring device is arranged in the feed liquid mixing reaction kettle 5, and the stirring device is connected with a stirring motor.
And a snake-shaped heat exchange tube is arranged in the heat exchanger 2 and is connected with a cooling medium inlet and a cooling medium outlet.
The treatment method of the process system for treating the aldehyde-containing waste acid by using the manganese dioxide comprises the following specific steps:
s1, enabling the mixed gas of hydrogen chloride and formaldehyde to enter a heat exchanger 2 through a hydrogen chloride and formaldehyde mixed gas inlet pipe 1, and achieving self temperature reduction through heat exchange with a cooling medium flowing inside the heat exchanger 2;
s2, allowing the cooled mixed gas to enter a primary spray absorption tower 3, continuously spraying an absorption liquid downwards from a liquid inlet at the top of the primary spray absorption tower 3, and absorbing the mixed gas of hydrogen chloride and formaldehyde to form aldehyde-containing waste acid feed liquid L1The tail gas is discharged after being treated by the first tail gas treater 19;
s3 aldehyde-containing waste acid feed liquid L1Pumping into a feed liquid mixing reaction kettle 5, adding manganese dioxide into the feed liquid mixing reaction kettle 5, adding the manganese dioxide and the aldehyde-containing waste acid feed liquid L1The mass ratio of the formaldehyde in the waste acid liquid is 1.5-5.0, and the waste acid liquid containing the formaldehyde L1The retention time in the feed liquid mixing reaction kettle 5 is 10min-300min, the formaldehyde can be completely consumed, and finally the feed liquid L for removing the formaldehyde is obtained2；
S4 feed liquid L for removing formaldehyde2Pumping into a solid-liquid separator 7 to realize solid-liquid separation to obtain a solution L3The unreacted manganese dioxide and the unreacted manganese dioxide are returned to the material liquid mixing reaction kettle 5 through the solid medicament return pump 21 for reuse;
s5 solution L3Aerating in the aeration tank 9 with clean air, wherein the upper part of the aeration tank 9Is provided with a liquid foam filtering laminate which can realize the separation of gas and liquid foam, and a solution L3The retention time in the aeration tank 9 is 10min-300min, the aeration volume flow is 0.1-200L/min, and the solution L from which the hydrogen chloride is removed4Pumping to a first-stage spray absorption tower 3 for cyclic utilization, and recycling the solution L4Recycling the solution L when the saturation of manganese chloride is approached or reached4Pumping to a salt solution storage tank 17 for storage;
s6, the gas flowing out of the aeration tank 9 enters a secondary spray absorption tower 11, the concentration of hydrochloric acid is controlled by controlling the amount of spray clear water, the finally obtained hydrochloric acid solution is stored in a hydrochloric acid storage tank 13, and the tail gas generated by the secondary spray absorption tower 11 is treated by a second tail gas processor 22 and then is discharged after reaching the standard.
In step S2, during operation in the first-stage spray absorption tower 3, the aldehyde-containing waste acid feed liquid L is controlled1The concentration of the hydrogen chloride is between 1mol/L and 5 mol/L.
In step S3, the manganese dioxide supply port 23 is replenished with the required manganese dioxide in time in accordance with the consumption of the manganese dioxide.
The specific embodiment is as follows:
containing a mixed gas of hydrogen chloride and formaldehyde, wherein the concentration of formaldehyde is 0.1-0.2mol/m3The concentration of hydrogen chloride is 20-30mol/m3The volume of the mixed gas is 100-150m3The temperature is 70-90 ℃, the temperature of the mixed gas is changed into 20-40 ℃ after passing through the heat exchanger 2, and the mixed gas is pumped into the first-stage spray absorption tower 3 and then is used for 1-2m3Absorbing with water to obtain aldehyde-containing waste acid L1Adding aldehyde-containing waste acid L1Pumping the mixture to a material liquid mixing reaction kettle 5, adding 50-200mol of manganese dioxide, mixing and stirring for 40-300min, and adding a material liquid L2Pumping to a solid-liquid separator 7 for solid-liquid separation to obtain a solution L3Is 0.8-0.98m3And a mass of unreacted manganese dioxide, wherein the solution L3Pumping the mixture to an aeration tank 9 for aeration, wherein the aeration flow is 0.2-1.5m3Min, solution L3Staying in the aeration tank for 10-200min, and after aeration, remaining solution L4Pumping into a first-stage spray absorption tower 3 for the absorption of the hydrogen chloride and formaldehyde mixed gas in the next round, and enabling the gas to enter a second stageThe spray absorption tower 11 regulates and controls the final hydrochloric acid concentration by adjusting the volume of the clear water used by the secondary spray absorption tower 11, the clear water is pumped into the hydrochloric acid storage tank 13 after absorption, the tail gas is treated by the second tail gas treater 22 and then is discharged after reaching the standard, and the solution L is4And circulating for 10-20 times, pumping into a salt solution storage tank 17, and performing evaporation crystallization according to conditions to obtain manganese chloride solid and a manganese chloride solution with a certain concentration, so that the treatment of the aldehyde-containing waste acid is realized, and a hydrochloric acid solution with a certain concentration and a manganese chloride solution close to or reaching saturation are finally obtained, so that the utilization value and the economic benefit of the aldehyde-containing waste acid can be improved.
The invention has been described in connection with the accompanying drawings, it is to be understood that the invention is not limited to the specific embodiments disclosed, but is intended to cover various modifications, adaptations or uses of the invention, and all such modifications and variations are within the scope of the invention.

Claims (9)

1. The process system for treating the aldehyde-containing waste acid by using the manganese dioxide is characterized by comprising a heat exchange unit, a primary spraying absorption unit, a feed liquid mixing reaction unit, a solid-liquid separation unit, an aeration unit, a secondary spraying absorption unit and an acid liquid storage unit which are sequentially connected, wherein the primary spraying absorption unit and the secondary spraying absorption unit are both connected with a tail gas treatment unit, and the aeration unit is connected with an air purification unit and a salt liquid storage unit.
2. The process system for treating waste acid containing aldehyde by using manganese dioxide as claimed in claim 1,
the heat exchange unit comprises a heat exchanger (2), a cooling medium inlet, a cooling medium outlet, a gas inlet and a gas outlet are arranged on the heat exchanger (2), and the gas inlet of the heat exchanger (2) is connected with a mixed gas inlet pipe (1) of hydrogen chloride and formaldehyde;
the primary spray absorption unit comprises a primary spray absorption tower (3), a gas inlet is formed in the lower end of the side wall of the primary spray absorption tower (3), a liquid outlet is formed in the bottom of the side wall of the primary spray absorption tower, a liquid inlet is formed in the top of the side wall of the primary spray absorption tower, an exhaust port is formed in the upper end of the side wall of the primary spray absorption tower (3), the gas inlet of the primary spray absorption tower (3) is connected with the gas outlet of the heat exchanger (2), and the liquid inlet of the primary spray absorption tower (3;
the feed liquid mixing reaction unit comprises a feed liquid mixing reaction kettle (5), a manganese dioxide feed inlet (23) is formed in the top of the side wall of the feed liquid mixing reaction kettle (5), an inlet of the feed liquid mixing reaction kettle (5) is connected with a liquid outlet of the primary spray absorption tower (3) through a first acid-resistant pump (4), the feed liquid mixing reaction kettle (5) is connected with an exhaust port of the primary spray absorption tower (3) through a pipeline, and a pressure reducing valve (18) is arranged on the pipeline;
the solid-liquid separation unit comprises a solid-liquid separator (7), a mixture inlet, a solid outlet and a liquid outlet are formed in the solid-liquid separator (7), the mixture inlet of the solid-liquid separator (7) is connected with the outlet of the feed liquid mixing reaction kettle (5) through a second acid-resistant pump (6), and the solid outlet of the solid-liquid separator (7) is connected with the feed liquid mixing reaction kettle (5) through a solid medicament return pump (21);
the aeration unit comprises an aeration tank (9), the inlet of the aeration tank (9) is connected with the liquid outlet of the solid-liquid separator (7) through a third acid-resistant pump (8), and an aeration head is arranged in the aeration tank (9);
the air purification unit comprises an air purifier (15), and the air purifier (15) is connected with an aeration head in the aeration tank (9) through an aeration pump (16);
the salt solution storage unit comprises a salt solution storage tank (17), and an outlet at the bottom of the aeration tank (9) is connected with the salt solution storage tank (17);
the secondary spray absorption unit comprises a secondary spray absorption tower (11), a gas inlet is formed in the lower end of the side wall of the secondary spray absorption tower (11), a liquid outlet is formed in the bottom of the side wall of the secondary spray absorption tower, a liquid inlet is formed in the top of the side wall of the secondary spray absorption tower, an exhaust port is formed in the upper end of the side wall of the secondary spray absorption tower, the gas inlet of the secondary spray absorption tower (11) is connected with a gas outlet in the top of the aeration tank (9) through a fourth acid-resistant pump (10), and the liquid inlet of the secondary spray absorption tower;
the acid liquid storage unit comprises a hydrochloric acid storage tank (13), and the hydrochloric acid storage tank (13) is connected with a liquid outlet of the secondary spray absorption tower (11) through a fifth acid-resistant pump (12);
the tail gas treatment unit comprises a first tail gas processor (19) and a second tail gas processor (22), the first tail gas processor (19) is connected with a pipeline where a pressure reducing valve (18) between the primary spray absorption tower (3) and the feed liquid mixing reaction kettle (5) is located, and the second tail gas processor (22) is connected with an exhaust port of the secondary spray absorption tower (11).
3. The process system for treating waste acid containing aldehyde by using manganese dioxide as claimed in claim 2, wherein the aeration tank (9) is provided with a liquid foam filter plate layer at the upper part inside.
4. The process system for treating aldehyde-containing waste acid by using manganese dioxide as claimed in claim 3, wherein a circulating liquid port is arranged below the liquid foam filtering plate layer on the aeration tank (9), and the circulating liquid port is connected with a top liquid inlet of the primary spray absorption tower (3) through a sixth acid-proof pump (24).
5. The process system for treating waste acid containing aldehyde by using manganese dioxide as claimed in claim 4, wherein a stirring device is arranged in the feed liquid mixing reaction kettle (5), and the stirring device is connected with a stirring motor.
6. The process system for treating waste acid containing aldehyde by using manganese dioxide as claimed in claim 5, wherein a serpentine heat exchange tube is arranged in the heat exchanger (2), and the serpentine heat exchange tube is connected with a cooling medium inlet and a cooling medium outlet.
7. A treatment method of a process system for treating aldehyde-containing waste acid by using manganese dioxide is characterized by comprising the following specific steps:
s1, enabling the mixed gas of hydrogen chloride and formaldehyde to enter a heat exchanger (2) through a hydrogen chloride and formaldehyde mixed gas inlet pipe (1), and achieving reduction of the temperature of the mixed gas by heat exchange with a cooling medium flowing inside the heat exchanger (2);
s2, allowing the cooled mixed gas to enter a primary spray absorption tower (3), continuously spraying an absorption liquid downwards from a liquid inlet at the top of the primary spray absorption tower (3), and absorbing the mixed gas of hydrogen chloride and formaldehyde to form aldehyde-containing waste acid feed liquid L1The tail gas is discharged after being treated by a first tail gas treater (19);
s3 aldehyde-containing waste acid feed liquid L1Pumping into a feed liquid mixing reaction kettle (5), adding manganese dioxide into the feed liquid mixing reaction kettle (5), adding the manganese dioxide and the aldehyde-containing waste acid feed liquid L1The mass ratio of the formaldehyde in the waste acid liquid is 1.5-5.0, and the waste acid liquid containing the formaldehyde L1The retention time in the feed liquid mixing reaction kettle (5) is 10min-300min, the formaldehyde can be completely consumed, and finally the feed liquid L for removing the formaldehyde is obtained2；
S4 feed liquid L for removing formaldehyde2Pumping into a solid-liquid separator (7) to realize solid-liquid separation to obtain a solution L3The unreacted manganese dioxide and the unreacted manganese dioxide are returned to the material liquid mixing reaction kettle (5) through a solid medicament return pump (21) for reutilization;
s5 solution L3Aeration is carried out by utilizing clean air after entering the aeration tank (9), a liquid foam filtering laminate is arranged on the upper part of the aeration tank (9), the separation of gas and liquid foam can be realized, and the solution L3The retention time in the aeration tank (9) is 10min-300min, the aeration volume flow is 0.1-200L/min, and the solution L from which the hydrogen chloride is removed4Pumping to a first-stage spray absorption tower (3) for cyclic utilization, and obtaining a solution L4Recycling the solution L when the saturation of manganese chloride is approached or reached4Pumping the salt solution into a salt solution storage tank (17) for storage;
s6, enabling the gas flowing out of the aeration tank (9) to enter a secondary spraying absorption tower (11), controlling the concentration of hydrochloric acid by controlling the using amount of spraying clear water, storing the finally obtained hydrochloric acid solution into a hydrochloric acid storage tank (13), and treating the tail gas generated by the secondary spraying absorption tower (11) by a second tail gas processor (22) to achieve the standard and discharge.
8. The process for treating waste acid containing aldehyde by using manganese dioxide as claimed in claim 7The processing method of the process system is characterized in that in the step S2, when the primary spray absorption tower (3) works, the aldehyde-containing waste acid feed liquid L is controlled1The concentration of the hydrogen chloride is between 1mol/L and 5 mol/L.
9. The method for processing a process system for treating waste acid containing aldehyde by using manganese dioxide as claimed in claim 8, wherein in step S3, manganese dioxide is supplemented at the manganese dioxide feed inlet (23) in time according to the consumption of manganese dioxide.
CN202011171238.2A 2020-10-28 2020-10-28 Process system for treating aldehyde-containing waste acid by using manganese dioxide and treatment method thereof Pending CN112221314A (en)

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