CN116062937A - Acid wastewater arsenic removal system and method - Google Patents
Acid wastewater arsenic removal system and method Download PDFInfo
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- CN116062937A CN116062937A CN202310083713.8A CN202310083713A CN116062937A CN 116062937 A CN116062937 A CN 116062937A CN 202310083713 A CN202310083713 A CN 202310083713A CN 116062937 A CN116062937 A CN 116062937A
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 135
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000002253 acid Substances 0.000 title claims abstract description 54
- 239000002351 wastewater Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 142
- 238000006243 chemical reaction Methods 0.000 claims abstract description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000007872 degassing Methods 0.000 claims abstract description 49
- 239000002893 slag Substances 0.000 claims abstract description 47
- 239000002562 thickening agent Substances 0.000 claims abstract description 47
- 239000002002 slurry Substances 0.000 claims abstract description 45
- 238000003860 storage Methods 0.000 claims abstract description 26
- 238000010517 secondary reaction Methods 0.000 claims abstract description 14
- 239000003814 drug Substances 0.000 claims abstract description 4
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 169
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 46
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 46
- 239000012295 chemical reaction liquid Substances 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 23
- 230000002378 acidificating effect Effects 0.000 claims description 17
- CUGMJFZCCDSABL-UHFFFAOYSA-N arsenic(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[As+3].[As+3] CUGMJFZCCDSABL-UHFFFAOYSA-N 0.000 claims description 15
- 230000001105 regulatory effect Effects 0.000 claims description 14
- 239000007921 spray Substances 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 230000009471 action Effects 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 1
- 239000002699 waste material Substances 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 239000002920 hazardous waste Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052958 orpiment Inorganic materials 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D25/00—Filters formed by clamping together several filtering elements or parts of such elements
- B01D25/12—Filter presses, i.e. of the plate or plate and frame type
-
- 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
-
- 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
- B01D53/1468—Removing hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Hydrology & Water Resources (AREA)
- Dispersion Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses an acid wastewater arsenic removal system, which comprises: an acid water storage tank; the inlet end of the first-stage closed tubular reactor is connected with the outlet end of the acid water storage tank; the inlet end of the gas-liquid separator is connected with the outlet end of the first-stage closed tubular reactor; the inlet end of the secondary reaction tank is connected with the outlet end of the gas-liquid separator; the inlet end of the third-stage reaction tank is connected with the outlet end of the second-stage reaction tank; the inlet end of the thickener is connected with the outlet end of the three-stage reaction tank; the inlet end of the slag slurry degassing tower is connected with a liquid outlet at the bottom of the thickener; the inlet end of the filter press is connected with a bottom liquid outlet of the slag slurry degassing tower; the liquid tank after arsenic removal is respectively connected with the top overflow port of the thickener and the outlet end of the filter press. The invention also discloses an arsenic removal method for the acid wastewater, which comprises the following steps: step A, preparing a medicament; step B, removing arsenic at a first stage; step C, secondary arsenic removal; step D, three-stage arsenic removal; and E, separating slag and liquid.
Description
Technical Field
The invention relates to the technical field of chemical environment-friendly equipment, in particular to an acid wastewater arsenic removal system and method.
Background
Certain amount of arsenic-containing acidic wastewater can be generated in the nonferrous metal smelting process, the common practice in industry is to add a vulcanizing agent into a reaction tank to remove arsenic, the defect of external escape of hydrogen sulfide exists, the safety and the environment of operators are adversely affected, the escape of the hydrogen sulfide is reduced in a vulcanizing agent shortage mode in production, the arsenic removal efficiency is reduced, and the environment protection requirement cannot be met. Therefore, there is a need to develop a safe arsenic removal technique that is efficient in removing arsenic and avoids hydrogen sulfide escaping.
Disclosure of Invention
Aiming at the technical problems, the invention provides an acid wastewater arsenic removal system.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
an acidic wastewater arsenic removal system comprising:
an acid water storage tank;
the inlet end of the first-stage closed tubular reactor is connected with the outlet end of the acid water storage tank;
the inlet end of the gas-liquid separator is connected with the outlet end of the first-stage closed tubular reactor;
the inlet end of the secondary reaction tank is connected with the outlet end of the gas-liquid separator;
the inlet end of the third-stage reaction tank is connected with the outlet end of the second-stage reaction tank;
the inlet end of the thickener is connected with the outlet end of the three-stage reaction tank;
the inlet end of the slag slurry degassing tower is connected with a liquid outlet at the bottom of the thickener;
the inlet end of the filter press is connected with a bottom liquid outlet of the slag slurry degassing tower;
the liquid tank after arsenic removal is respectively connected with a top overflow port of the thickener and an outlet end of the filter press;
a NaHS reservoir;
the inlet end of the NaHS configuration tank is connected with the outlet end of the NaHS storage tank, and the outlet end of the NaHS configuration tank is respectively connected with a first-stage NaHS feeding pipe on the first-stage closed tubular reactor, a second-stage NaHS feeding pipe on the second-stage reaction tank and a third-stage NaHS feeding pipe on the third-stage reaction tank.
The acid water storage tank is connected with the first-stage closed tubular reactor through a first-stage acid water conveying pipe, and an acid water pump, an acid water regulating valve and an acid water check valve are sequentially arranged on the first-stage acid water conveying pipe.
The secondary NaHS feeding pipe is provided with a secondary NaHS feeding valve, the outlet end of the secondary reaction tank is provided with a secondary ORP meter, and the secondary NaHS feeding valve is interlocked with the secondary ORP meter; the three-stage NaHS feeding pipe is provided with a three-stage NaHS feeding valve, the outlet end of the three-stage reaction tank is provided with a three-stage ORP meter, and the three-stage NaHS feeding valve is interlocked with the three-stage ORP meter.
The slag slurry degassing tower is internally provided with a degassing tower nozzle, and the degassing tower nozzle is connected with a bottom liquid outlet of the thickener through an underflow pump of the thickener.
And a bottom liquid outlet of the slag slurry degassing tower is connected with an inlet end of the filter press through a filter press liquid inlet pump.
The outlet end of the NaHS storage tank is connected with the inlet end of the NaHS configuration tank through a NaHS configuration pump, and the outlet end of the NaHS configuration tank is provided with a NaHS feeding pump.
The NaHS feeding pump is connected with the first-stage NaHS feeding pipe sequentially through a first-stage NaHS feeding valve and a NaHS check valve, the first-stage NaHS feeding valve is interlocked with a first-stage ORP meter on the outlet end of the first-stage closed pipe reactor, and the NaHS feeding pump is also connected with the second-stage NaHS feeding pipe.
The gas-liquid separator is internally provided with a gas-liquid separator nozzle.
The top of the gas-liquid separator, the top of the secondary reaction tank, the top of the tertiary reaction tank, the top of the thickener and the top of the slag slurry degasser are respectively provided with an exhaust port, and the exhaust ports are connected with a degassing fan through pipelines, and the air outlet end of the degassing fan is connected with a hydrogen sulfide absorbing device.
The invention also provides an arsenic removal method for the acidic wastewater, which comprises the following steps:
step A, preparation of a medicament: opening a water adding valve at the upper part of the NaHS configuration tank, adding water, starting a NaHS configuration pump, sending high-concentration NaHS in a NaHS storage tank into the NaHS configuration tank, opening a stirring device in the NaHS configuration tank, uniformly mixing NaHS solution, and preparing 10% concentration NaHS solution;
step B, primary arsenic removal: the high arsenic wastewater in the acid water storage tank is pumped into a first-stage closed tubular reactor through an acid water pump, the opening of a first-stage NaHS feeding valve is regulated through the ORP value of the reaction liquid at the outlet of the first-stage closed tubular reactor, the flow rate of NaHS entering the first-stage closed tubular reactor is controlled, and most of arsenic reacts with NaHS to generate As 2 S 3 The precipitation is completed, the primary arsenic removal reaction is completed in a primary closed tubular reactor, the escape of hydrogen sulfide is avoided, the reaction liquid at the outlet of the primary closed tubular reactor enters a gas-liquid separator, the reaction liquid is sprayed from top to bottom through a nozzle of the gas-liquid separator under the negative pressure operation condition, and the hydrogen sulfide gas in the reaction liquid is separated out and is sent to a hydrogen sulfide absorption device through a degassing fan;
step C, secondary arsenic removal: the first-stage arsenic removal liquid at the outlet of the gas-liquid separator enters the bottom of the second-stage reaction tank, the opening of a second-stage NaHS feeding valve is regulated according to the ORP value of the reaction liquid at the outlet of the second-stage reaction tank, the flow rate of NaHS entering the second-stage reaction tank is controlled, the first-stage arsenic removal liquid and NaHS are uniformly mixed under the action of a stirring paddle of the reaction tank, arsenic in wastewater is further removed, the second-stage arsenic removal is completed, and hydrogen sulfide gas in the second-stage reaction tank is sent into a hydrogen sulfide tail gas absorbing device through a degassing fan;
step D, three-stage arsenic removal: the method comprises the steps that secondary arsenic removal liquid at the outlet of a secondary reaction tank enters the bottom of a tertiary reaction tank, the opening of a tertiary NaHS (sodium hydrogen sulfide) feeding valve is regulated according to the ORP value of the reaction liquid at the outlet of the tertiary reaction tank, the flow rate of NaHS entering the tertiary reaction tank is controlled, the secondary arsenic removal liquid and the NaHS are uniformly mixed under the action of a stirring paddle of the reaction tank, residual arsenic in wastewater is finally removed, tertiary arsenic removal is completed, and hydrogen sulfide gas in the tertiary reaction tank is sent into a hydrogen sulfide tail gas absorption device through a degassing fan;
step E, slag-liquid separation: the three-stage arsenic removal liquid at the outlet of the three-stage reaction tank enters a thickener for sedimentation, solid-liquid separation is carried out, overflow clear liquid at the upper part of the thickener enters an arsenic removal post-liquid tank, arsenic sulfide slag slurry settled at the bottom of the thickener enters a slag slurry degassing tower, is sprayed from top to bottom through a nozzle of the degassing tower, is absorbed by a hydrogen sulfide tail gas absorbing device through the sulfhydrylation in the slag slurry under the negative pressure condition, the slag slurry after the removal of hydrogen sulfide is pumped to a filter press for filter pressing through a liquid inlet pump of the filter press, clear liquid of the filter press enters an arsenic removal post-liquid tank and can be sent to a water unit for recycling, and the arsenic sulfide slag is sent to a hazardous waste disposal unit for treatment.
The beneficial effects of the invention are as follows: the method has simple flow and reliable operation, realizes the high-efficiency and safe arsenic removal of the acid wastewater, forms a three-stage gradient arsenic removal system by arranging a first-stage closed tubular reactor, a gas-liquid separator, a second-stage reaction tank, a third-stage reaction tank, a thickener, a degasser, a filter press and an arsenic removal post-liquid tank, and can treat the high-arsenic wastewater; firstly, carrying out primary arsenic removal by using a primary closed tubular reactor, wherein the primary reaction of arsenic removal is completed in the primary closed tubular reactor, so that hydrogen sulfide escaping is avoided; then the secondary reaction tank is utilized to carry out secondary arsenic removal, and arsenic in the wastewater is further removed; finally, three-stage arsenic removal is carried out by utilizing a three-stage reaction tank, so that residual arsenic in the wastewater is further removed; settling the arsenic removal reaction liquid by a thickener, and removing generated arsenic sulfide slag from the system after filter pressing by a filter press; the top of the second-stage reaction tank, the third-stage reaction tank, the gas-liquid separator, the thickener and the degassing tower are provided with degassing pipelines, and the degassing pipelines are sent into a hydrogen sulfide tail gas absorption system through a degassing fan to avoid the escape of hydrogen sulfide outside the body.
Drawings
Fig. 1 is a schematic diagram of the present invention.
Wherein, 1, an acid water storage tank; 2. an acid water pump; 3. a first-stage closed tubular reactor; 4. a gas-liquid separator; 5. a second-stage reaction tank; 6. a third-stage reaction tank; 7. a thickener; 8. a slag slurry degassing tower; 9. a filter press; 10. a liquid tank after arsenic removal; 11. an underflow pump of the thickener; 12. a NaHS reservoir; 13. configuring a pump by using NaHS; 14. a NaHS configuration tank; 15. a NaHS adding pump; 16. a first-stage NaHS adding valve; 17. a NaHS check valve; 18. an acid water regulating valve; 19. an acid water check valve; 20. a second-stage NaHS adding valve; 21. three-stage NaHS adding valves; 22. a gas-liquid separator spray head; 23. a degasser spray head; 24. a primary acid water conveying pipe; 25. a first-stage NaHS feeding pipe; 26. a secondary NaHS feeding pipe; 27. three-stage NaHS feeding pipes; 28. a primary ORP meter; 29. a secondary ORP meter; 30. a three stage ORP meter; 31. a liquid inlet pump of the filter press; 32. a degassing fan.
Detailed Description
The objects, technical solutions and advantages of the present invention will become more apparent by the following detailed description of the present invention with reference to the accompanying drawings. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
As shown in fig. 1, an acidic wastewater arsenic removal system comprises: an acid water storage tank 1; the inlet end of the first-stage closed tubular reactor 3 is connected with the outlet end of the acid water storage tank 1; the inlet end of the gas-liquid separator 4 is connected with the outlet end of the first-stage closed tubular reactor 3; the inlet end of the secondary reaction tank 5 is connected with the outlet end of the gas-liquid separator 4; the inlet end of the third-stage reaction tank 6 is connected with the outlet end of the second-stage reaction tank 5; the inlet end of the thickener 7 is connected with the outlet end of the three-stage reaction tank 6; the inlet end of the slag slurry degasser 8 is connected with a liquid outlet at the bottom of the thickener 7; the inlet end of the filter press 9 is connected with a bottom liquid outlet of the slag slurry degassing tower 8; the arsenic-removed liquid tank 10 is respectively connected with a top overflow port of the thickener 7 and an outlet end of the filter press 9; a NaHS reservoir 12; the inlet end of the NaHS configuration tank 14 is connected with the outlet end of the NaHS storage tank 12, and the outlet end of the NaHS configuration tank is respectively connected with a first-stage NaHS feeding pipe 25 on the first-stage closed tubular reactor 3, a second-stage NaHS feeding pipe 26 on the second-stage reaction tank 5 and a third-stage NaHS feeding pipe 27 on the third-stage reaction tank 6.
As shown in fig. 1, an acid water pump 2, an acid water regulating valve 18 and an acid water check valve 19 are sequentially arranged on a primary acid water conveying pipe 24 between an acid water storage tank 1 and a primary closed tubular reactor 3.
As shown in fig. 1, a secondary NaHS feeding valve 20 is arranged on a secondary NaHS feeding pipe 26, a secondary ORP meter 29 is arranged on the outlet end of the secondary reaction tank 5, and the secondary NaHS feeding valve 20 is interlocked with the secondary ORP meter 29; the three-stage NaHS feeding pipe 27 is provided with a three-stage NaHS feeding valve 21, the outlet end of the three-stage reaction tank 6 is provided with a three-stage ORP meter 30, and the three-stage NaHS feeding valve 21 is interlocked with the three-stage ORP meter 30.
As shown in fig. 1, a degasser nozzle 23 is arranged in the slurry degasser 8, and the degasser nozzle 23 is connected with a bottom liquid outlet of the thickener 7 through a thickener underflow pump 11.
As shown in fig. 1, the bottom liquid outlet of the slurry degasser 8 is connected with the inlet end of the filter press 9 through a filter press liquid inlet pump 31.
As shown in fig. 1, the outlet end of the NaHS storage tank 12 is connected with the inlet end of the NaHS configuration tank 14 through the NaHS configuration pump 13, and the outlet end of the NaHS configuration tank 14 is provided with a NaHS feeding pump 15.
As shown in fig. 1, the NaHS feeding pump 15 is connected with a primary NaHS feeding pipe 25 sequentially through a primary NaHS feeding valve 16 and a NaHS check valve 17, the primary NaHS feeding valve 16 is interlocked with a primary ORP meter 28 on the outlet end of the primary closed tubular reactor 3, and the NaHS feeding pump 15 is also connected with a secondary NaHS feeding pipe 26.
As shown in fig. 1, the gas-liquid separator 4 is internally provided with a gas-liquid separator shower head 22.
As shown in fig. 1, the top parts of the gas-liquid separator 4, the secondary reaction tank 5, the tertiary reaction tank 6, the thickener 7 and the slurry degasser 8 are respectively provided with an exhaust port, the exhaust ports are connected with a degassing fan 32 through pipelines, and the air outlet end of the degassing fan 32 is connected with a hydrogen sulfide absorbing device.
The slag slurry degassing tower 8 is connected with an inlet of a degassing fan 32 through a degassing pipe at the top, negative pressure operation conditions are provided for the slag slurry degassing tower 8 through the action of the degassing fan 32, arsenic sulfide slag slurry settled at the bottom of the thickener 7 enters a degassing tower spray head 23 to spray from top to bottom, hydrogen sulfide in the slag slurry is desorbed under the negative pressure conditions and enters a hydrogen sulfide tail gas absorption system to absorb, and the phenomenon that the concentration of hydrogen sulfide in a filter pressing factory building is high due to direct filter pressing of the arsenic sulfide slag slurry is prevented from influencing the operation environment.
The number of the filter presses 7 is two and the filter presses are arranged in parallel, the number of the filter presses is 2, the pressure gauge and the valve are arranged on the liquid inlet pipe, 2 filter presses 7 alternately run, the liquid inlet pressure of one filter press reaches 0.6MPa, and the liquid inlet valve is closed to stop feeding; and the liquid inlet valve of the other filter press is opened to start feeding, so that uninterrupted filter pressing operation is ensured.
The acid water storage tank 1, the arsenic-removing liquid tank 10, the NaHS storage tank 12 and the NaHS configuration tank 14 are all provided with liquid level meters, and the liquid level is monitored to prevent the tank from overflowing.
The thickener 7 and the slag slurry degassing tower 8 are of cone bottom structures, the cone bottom is provided with a short section, the short section is provided with a manual valve, the manual valve is opened during maintenance, and internal feed liquid is emptied, so that the maintenance is convenient.
The gas-liquid separator 4, the secondary reaction tank 5, the tertiary reaction tank 6 and the thickener 7 have gradient high-level differences, and the adjacent devices convey the feed liquid through the high-level differences without pump power facilities.
The invention also provides an arsenic removal method for the acidic wastewater, which comprises the following steps:
step A, preparation of a medicament: opening a water adding valve at the upper part of the NaHS configuration tank 14, adding water, starting a NaHS configuration pump 13, feeding high-concentration NaHS in the NaHS storage tank 12 into the NaHS configuration tank 14, opening a stirring device in the NaHS configuration tank 14, uniformly mixing the NaHS solution, and preparing 10% concentration NaHS solution;
step B, primary arsenic removal: the high arsenic wastewater in the acid water storage tank 1 is sent into the first-stage closed tubular reactor 3 through the acid water pump 2, the opening of the first-stage NaHS feeding valve 16 is regulated according to the ORP value of the reaction liquid at the outlet of the first-stage closed tubular reactor 3, the flow rate of NaHS entering the first-stage closed tubular reactor 3 is controlled, and most of arsenic reacts with NaHS to generate As 2 S 3 The primary arsenic removal is completed by precipitation, the primary arsenic removal reaction is completed in the primary closed tubular reactor 3, hydrogen sulfide is prevented from escaping, reaction liquid at the outlet of the primary closed tubular reactor 3 enters the gas-liquid separator 4, the reaction liquid is sprayed from top to bottom through the gas-liquid separator spray head 22 under the negative pressure operation condition, and the hydrogen sulfide gas in the reaction liquid is separated out and is sent to the hydrogen sulfide absorption device through the degassing fan 32;
step C, secondary arsenic removal: the first-stage arsenic removal liquid at the outlet of the gas-liquid separator 4 enters the bottom of the second-stage reaction tank 5, the opening of a second-stage NaHS feeding valve 20 is regulated according to the ORP value of the reaction liquid at the outlet of the second-stage reaction tank 5, the flow rate of NaHS entering the second-stage reaction tank 5 is controlled, the first-stage arsenic removal liquid and NaHS are uniformly mixed under the action of a stirring paddle of the reaction tank, arsenic in wastewater is further removed, the second-stage arsenic removal is completed, and hydrogen sulfide gas in the second-stage reaction tank 5 is sent into a hydrogen sulfide tail gas absorbing device through a degassing fan 32;
step D, three-stage arsenic removal: the second-stage arsenic removal liquid at the outlet of the second-stage reaction tank 5 enters the bottom of the third-stage reaction tank 6, the opening of a third-stage NaHS feeding valve 21 is regulated according to the ORP value of the reaction liquid at the outlet of the third-stage reaction tank 6, the NaHS flow entering the third-stage reaction tank 6 is controlled, the second-stage arsenic removal liquid and the NaHS are uniformly mixed under the action of a stirring paddle of the reaction tank, residual arsenic in the wastewater is finally removed, the third-stage arsenic removal is completed, and hydrogen sulfide gas in the third-stage reaction tank 6 is sent into a hydrogen sulfide tail gas absorption device through a degassing fan 32;
step E, slag-liquid separation: the three-stage arsenic removal liquid at the outlet of the three-stage reaction tank 6 enters a thickener 7 for sedimentation, solid-liquid separation is carried out, overflow clear liquid at the upper part of the thickener 7 enters an arsenic removal liquid tank 10, arsenic sulfide slag slurry settled at the bottom of the thickener 7 enters a slag slurry degassing tower 8, is sprayed from top to bottom through a degassing tower spray head 23, is absorbed by a hydrogen sulfide tail gas absorbing device through sulfhydrylation in the slag slurry under the negative pressure condition, the slag slurry after hydrogen sulfide removal is sent to a filter press 9 for filter pressing through a filter press liquid inlet pump 31, the clear liquid of the filter press enters the arsenic removal liquid tank 10 and can be sent to a water unit for recycling, and the arsenic sulfide slag is sent to hazardous waste disposal unit for treatment.
Example 1
The system and the method for removing arsenic from the acidic wastewater are applied to a certain production system, and the working conditions are as follows: the acid wastewater amount is 30m3/h, the As concentration is 5232mg/l, and the specific steps are As follows: preparing 10% concentration NaHS solution, feeding acid wastewater into a first-stage closed tubular reactor 3 through an acid water pump 2, adjusting the opening of a first-stage NaHS feeding valve 16, controlling the flow rate of NaHS entering the first-stage closed tubular reactor 3 to be 1.64m < 3 >/h, controlling the ORP value of reaction liquid at the outlet of the first-stage closed tubular reactor 3 to be about 100mv, detecting the concentration 784.8mg/l of As in the first-stage arsenic removal liquid at the outlet of the first-stage closed tubular reactor 3, wherein the As removal rate reaches 85%, and most of arsenic reacts with NaHS to generate As2S3 sediment, thereby completing the first-stage arsenic removal; after the reaction liquid at the outlet of the first-stage closed tubular reactor 3 enters a gas-liquid separator 4 and is sprayed and analyzed from top to bottom through a spray head under the negative pressure operation condition to obtain hydrogen sulfide gas, the first-stage arsenic removal liquid enters the bottom of a second-stage reaction tank 5, the opening of a second-stage NaHS (sodium hydrogen sulfide) adding valve 20 is regulated, the flow rate of NaHS entering the second-stage reaction tank 5 is controlled to be 0.28m < 3 >/h, the ORP value of the reaction liquid at the outlet of the second-stage reaction tank 5 is controlled to be about 40mv, the concentration of As in the second-stage arsenic removal liquid at the outlet of the second-stage reaction tank is detected to be 39.24mg/l, and the As removal rate reaches 95%; the second-level arsenic removal liquid enters the bottom of the three-level reaction tank 6, the opening of a three-level NaHS feeding valve 21 is adjusted, the flow rate of NaHS entering the three-level reaction tank 6 is controlled to be 0.02m < 3 >/h, the ORP value of the reaction liquid at the outlet of the three-level reaction tank 6 is controlled to be about-20 mv, the concentration of As in the three-level arsenic removal liquid at the outlet of the three-level reaction tank 6 is detected to be 0.39mg/l, and the As removal rate reaches 99%; the three-stage arsenic removal liquid at the outlet of the three-stage reaction tank 6 enters a thickener 7 to be settled for solid-liquid separation, overflow clear liquid at the upper part of the thickener 7 enters a post-arsenic removal liquid tank 10, arsenic sulfide slag slurry settled at the bottom of the thickener 7 enters a slag slurry degassing tower 8, slag slurry after hydrogen sulfide removal is sent to a filter press 9 for filter pressing through a filter press liquid inlet pump 31, clear liquid of the filter press enters the post-arsenic removal liquid tank 10 and can be sent to a water unit for recycling, and arsenic sulfide slag is sent to a hazardous waste disposal unit for treatment. The total As removal rate of the example reaches 99.99%, the As content of the arsenic-removed liquid reaches the requirement of arsenic (As < 0.5 mg/l) in the emission standard of industrial pollutants of copper, nickel and cobalt, and the arsenic removal effect is obvious.
Example 2
The system and the method for removing arsenic from the acidic wastewater are applied to a certain production system, and the working conditions are as follows: the acid wastewater amount is 30m3/h, the As concentration is 8764mg/l, and the specific steps are As follows: preparing 10% concentration NaHS solution, feeding acid wastewater into a first-stage closed tubular reactor 3 through an acid water pump 2, adjusting the opening of a first-stage NaHS feeding valve 16, controlling the flow rate of NaHS entering the first-stage closed tubular reactor 3 to be 1.88m < 3 >/h, controlling the ORP value of reaction liquid at the outlet of the first-stage closed tubular reactor 3 to be about 100mv, detecting the concentration 1139.32mg/l of As in the first-stage arsenic removal liquid at the outlet of the first-stage closed tubular reactor 3, wherein the As removal rate reaches 87%, and most of arsenic reacts with NaHS to generate As2S3 sediment, thereby completing the first-stage arsenic removal; after the reaction liquid at the outlet of the first-stage closed tubular reactor 3 enters a gas-liquid separator 4 and is sprayed and analyzed from top to bottom through a spray head under the negative pressure operation condition to obtain hydrogen sulfide gas, the first-stage arsenic removal liquid enters the bottom of a second-stage reaction tank 5, the opening of a second-stage NaHS (sodium hydrogen sulfide) adding valve 20 is adjusted, the flow rate of NaHS entering the second-stage reaction tank 5 is controlled to be 0.27m < 3 >/h, the ORP value of the reaction liquid at the outlet of the second-stage reaction tank 5 is controlled to be about 40mv, the concentration of As in the second-stage arsenic removal liquid at the outlet of the second-stage reaction tank 5 is detected to be 45.57mg/l, and the As removal rate reaches 96%; the second-level arsenic removal liquid enters the bottom of the three-level reaction tank 6, the opening of a three-level NaHS feeding valve 21 is adjusted, the flow rate of NaHS entering the three-level reaction tank 6 is controlled to be 0.01m < 3 >/h, the ORP value of the reaction liquid at the outlet of the three-level reaction tank 6 is controlled to be about-20 mv, the concentration of As in the three-level arsenic removal liquid at the outlet of the three-level reaction tank 6 is detected to be 0.45mg/l, and the As removal rate reaches 99%; the three-stage arsenic removal liquid at the outlet of the three-stage reaction tank 6 enters a thickener 7 to be settled for solid-liquid separation, overflow clear liquid at the upper part of the thickener 7 enters a post-arsenic removal liquid tank 10, arsenic sulfide slag slurry settled at the bottom of the thickener 7 enters a slag slurry degassing tower 8, slag slurry after hydrogen sulfide removal is sent to a filter press 7 for filter pressing through a filter press liquid inlet pump 31, clear liquid of the filter press enters the post-arsenic removal liquid tank 10 and can be sent to a water unit for recycling, and arsenic sulfide slag is sent to a hazardous waste disposal unit for treatment. The total As removal rate of the example reaches 99.99%, the As content of the arsenic-removed liquid reaches the requirement of arsenic (As < 0.5 mg/l) in the emission standard of industrial pollutants of copper, nickel and cobalt, and the arsenic removal effect is obvious.
Example 3
The system and the method for removing arsenic from the acidic wastewater are applied to a certain production system, and the working conditions are as follows: the acid wastewater quantity is 30m3/h, the As concentration is 12055mg/l, and the specific steps are As follows: preparing 10% concentration NaHS solution, feeding acid wastewater into a first-stage closed tubular reactor 3 through an acid water pump 2, adjusting the opening of a first-stage NaHS feeding valve 16, controlling the flow rate of NaHS entering the first-stage closed tubular reactor 3 to be 2.00m < 3 >/h, controlling the ORP value of reaction liquid at the outlet of the first-stage closed tubular reactor 3 to be about 100mv, detecting the concentration 1205.52mg/l of As in the first-stage arsenic removal liquid at the outlet of the first-stage closed tubular reactor 3, wherein the As removal rate reaches 90%, and most of arsenic reacts with NaHS to generate As2S3 sediment, thereby completing the first-stage arsenic removal; after the reaction liquid at the outlet of the first-stage closed tubular reactor 3 enters a gas-liquid separator 4 and is sprayed and analyzed from top to bottom through a spray head under the negative pressure operation condition to obtain hydrogen sulfide gas, the first-stage arsenic removal liquid enters the bottom of a second-stage reaction tank 5, the opening of a second-stage NaHS (sodium hydrogen sulfide) adding valve 20 is adjusted, the flow rate of NaHS entering the second-stage reaction tank 5 is controlled to be 0.22m < 3 >/h, the ORP value of the reaction liquid at the outlet of the second-stage reaction tank 5 is controlled to be about 40mv, the concentration of As in the second-stage arsenic removal liquid at the outlet of the second-stage reaction tank is detected to be 36.17mg/l, and the As removal rate reaches 97%; the second-level arsenic removal liquid enters the bottom of the three-level reaction tank 6, the opening of a three-level NaHS feeding valve 21 is adjusted, the flow rate of NaHS entering the three-level reaction tank 6 is controlled to be 0.01m < 3 >/h, the ORP value of the reaction liquid at the outlet of the three-level reaction tank 6 is controlled to be about-20 mv, the concentration of As in the three-level arsenic removal liquid at the outlet of the three-level reaction tank 6 is detected to be 0.36mg/l, and the As removal rate reaches 99%; the three-stage arsenic removal liquid at the outlet of the three-stage reaction tank 6 enters a thickener 7 to be settled for solid-liquid separation, overflow clear liquid at the upper part of the thickener 7 enters a post-arsenic removal liquid tank 10, arsenic sulfide slag slurry settled at the bottom of the thickener 7 enters a slag slurry degassing tower 8, slag slurry after hydrogen sulfide removal is sent to a filter press 7 for filter pressing through a filter press liquid inlet pump 31, clear liquid of the filter press enters the post-arsenic removal liquid tank 10 and can be sent to a water unit for recycling, and arsenic sulfide slag is sent to a hazardous waste disposal unit for treatment. The total As removal rate of the example reaches 99.99%, the As content of the arsenic-removed liquid reaches the requirement of arsenic (As < 0.5 mg/l) in the emission standard of industrial pollutants of copper, nickel and cobalt, and the arsenic removal effect is obvious.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explanation of the principles of the present invention and are in no way limiting of the invention. Accordingly, any modification, equivalent replacement, improvement, etc. made without departing from the spirit and scope of the present invention should be included in the scope of the present invention. Furthermore, the appended claims are intended to cover all such changes and modifications that fall within the scope and boundary of the appended claims, or equivalents of such scope and boundary.
Claims (10)
1. An acidic wastewater arsenic removal system, comprising:
an acid water storage tank (1);
the inlet end of the first-stage closed tubular reactor (3) is connected with the outlet end of the acid water storage tank (1);
the inlet end of the gas-liquid separator (4) is connected with the outlet end of the first-stage closed tubular reactor (3);
the inlet end of the secondary reaction tank (5) is connected with the outlet end of the gas-liquid separator (4);
the inlet end of the third-stage reaction tank (6) is connected with the outlet end of the second-stage reaction tank (5);
the inlet end of the thickener (7) is connected with the outlet end of the three-stage reaction tank (6);
the inlet end of the slag slurry degassing tower (8) is connected with a liquid outlet at the bottom of the thickener (7);
the inlet end of the filter press (9) is connected with a bottom liquid outlet of the slag slurry degassing tower (8);
the liquid tank (10) after arsenic removal is respectively connected with a top overflow port of the thickener (7) and an outlet end of the filter press (9);
a NaHS reservoir (12);
the inlet end of the NaHS configuration tank (14) is connected with the outlet end of the NaHS storage tank (12), and the outlet end of the NaHS configuration tank is respectively connected with a first-stage NaHS feeding pipe (25) on the first-stage closed tubular reactor (3), a second-stage NaHS feeding pipe (26) on the second-stage reaction tank (5) and a third-stage NaHS feeding pipe (27) on the third-stage reaction tank (6).
2. The arsenic removal system for acidic wastewater according to claim 1, wherein the acid water storage tank (1) is connected with the primary closed tubular reactor (3) through a primary acid water conveying pipe (24), and an acid water pump (2), an acid water regulating valve (18) and an acid water check valve (19) are sequentially arranged on the primary acid water conveying pipe (24).
3. The arsenic removal system for acidic wastewater according to claim 1, wherein a secondary NaHS feeding valve (20) is arranged on the secondary NaHS feeding pipe (26), a secondary ORP meter (29) is arranged on the outlet end of the secondary reaction tank (5), and the secondary NaHS feeding valve (20) is interlocked with the secondary ORP meter (29); the three-level NaHS adding pipe (27) is provided with a three-level NaHS adding valve (21), the outlet end of the three-level reaction tank (6) is provided with a three-level ORP meter (30), and the three-level NaHS adding valve (21) is interlocked with the three-level ORP meter (30).
4. The arsenic removal system for acidic wastewater according to claim 1, wherein a degasser nozzle (23) is arranged in the slurry degasser (8), and the degasser nozzle (23) is connected with a bottom liquid outlet of the thickener (7) through a thickener underflow pump (11).
5. The arsenic removal system for acidic wastewater according to claim 1, wherein a bottom outlet of the slurry degasser (8) is connected with an inlet end of a filter press (9) through a filter press liquid inlet pump (31).
6. The acid wastewater arsenic removal system according to claim 1, wherein the outlet end of the NaHS storage tank (12) is connected with the inlet end of the NaHS configuration tank (14) through a NaHS configuration pump (13), and a NaHS feeding pump (15) is arranged on the outlet end of the NaHS configuration tank (14).
7. The arsenic removal system for acidic wastewater according to claim 6, wherein the NaHS feeding pump (15) is connected with a primary NaHS feeding pipe (25) sequentially through a primary NaHS feeding valve (16) and a NaHS check valve (17), and the primary NaHS feeding valve (16) is interlocked with a primary ORP meter (28) on the outlet end of the primary closed tubular reactor (3), and the NaHS feeding pump (15) is also connected with a secondary NaHS feeding pipe (26).
8. An acidic wastewater arsenic removal system according to claim 1, characterized in that the gas-liquid separator (4) is internally provided with a gas-liquid separator spray head (22).
9. The arsenic removal system for acidic wastewater according to claim 1, wherein the top parts of the gas-liquid separator (4), the secondary reaction tank (5), the tertiary reaction tank (6), the thickener (7) and the slurry degassing tower (8) are respectively provided with an exhaust port, the exhaust ports are respectively connected with a degassing fan (32) through pipelines, and the exhaust end of the degassing fan (32) is connected with a hydrogen sulfide absorbing device.
10. The method for removing arsenic from the acidic wastewater is characterized by comprising the following steps of:
step A, preparation of a medicament: opening a water adding valve at the upper part of a NaHS configuration tank (14), adding water, starting a NaHS configuration pump (13), conveying high-concentration NaHS in a NaHS storage tank (12) into the NaHS configuration tank (14), and opening a stirring device in the NaHS configuration tank (14) to uniformly mix NaHS solution and prepare 10% concentration NaHS solution;
step B, primary arsenic removal: the high arsenic wastewater in the acid water storage tank (1) is sent into the first-stage closed tubular reactor (3) through the acid water pump (2), the opening of the first-stage NaHS feeding valve (16) is regulated through the ORP value of the reaction liquid at the outlet of the first-stage closed tubular reactor (3), the flow rate of NaHS entering the first-stage closed tubular reactor (3) is controlled, and most of arsenic reacts with NaHS to generate As 2 S 3 The primary arsenic removal is completed by precipitation, the primary arsenic removal reaction is completed in a primary closed tubular reactor (3), hydrogen sulfide is prevented from escaping, reaction liquid at the outlet of the primary closed tubular reactor (3) enters a gas-liquid separator (4), the reaction liquid is sprayed from top to bottom through a gas-liquid separator spray head (22) under the negative pressure operation condition, and the hydrogen sulfide gas in the reaction liquid is separated out and is sent to a hydrogen sulfide absorption device through a degassing fan (32);
step C, secondary arsenic removal: the first-stage arsenic removal liquid at the outlet of the gas-liquid separator (4) enters the bottom of the second-stage reaction tank (5), the opening of a second-stage NaHS (sodium hydrogen sulfide) feeding valve (20) is regulated through the ORP value of the reaction liquid at the outlet of the second-stage reaction tank (5), the flow rate of NaHS entering the second-stage reaction tank (5) is controlled, the first-stage arsenic removal liquid and NaHS are uniformly mixed under the action of a stirring paddle of the reaction tank, arsenic in wastewater is further removed, the second-stage arsenic removal is completed, and hydrogen sulfide gas in the second-stage reaction tank (5) is sent into a hydrogen sulfide tail gas absorption device through a degassing fan (32);
step D, three-stage arsenic removal: the method comprises the steps that secondary arsenic removal liquid at the outlet of a secondary reaction tank (5) enters the bottom of a tertiary reaction tank (6), the opening of a tertiary NaHS (sodium hydrogen sulfide) feeding valve (21) is regulated through the ORP value of the reaction liquid at the outlet of the tertiary reaction tank (6), the flow rate of NaHS entering the tertiary reaction tank (6) is controlled, the secondary arsenic removal liquid and the NaHS are uniformly mixed under the action of a stirring paddle of the reaction tank, residual arsenic in wastewater is finally removed, tertiary arsenic removal is completed, and hydrogen sulfide gas in the tertiary reaction tank (6) is sent into a hydrogen sulfide tail gas absorption device through a degassing fan (32);
step E, slag-liquid separation: the three-stage arsenic removal liquid at the outlet of the three-stage reaction tank (6) enters a thickener (7) for sedimentation, solid-liquid separation is carried out, overflow clear liquid at the upper part of the thickener (7) enters a post-arsenic removal liquid tank (10), arsenic sulfide slag slurry settled at the bottom of the thickener (7) enters a slag slurry degassing tower (8), spray from top to bottom through a degassing tower spray head (23), the hydrogen sulfide in the slag slurry is absorbed by a hydrogen sulfide tail gas absorption device under the negative pressure condition, the slag slurry after hydrogen sulfide removal is sent to a filter press (9) for filter pressing through a filter press liquid inlet pump (31), the clear liquid of the filter press enters the post-arsenic removal liquid tank (10) and can be sent to a water unit for recycling, and the arsenic sulfide slag is sent to a dangerous waste disposal unit for treatment.
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