WO2018177222A1 - Système et procédé de traitement d'eaux usées contenant du chrome - Google Patents

Système et procédé de traitement d'eaux usées contenant du chrome Download PDF

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WO2018177222A1
WO2018177222A1 PCT/CN2018/080320 CN2018080320W WO2018177222A1 WO 2018177222 A1 WO2018177222 A1 WO 2018177222A1 CN 2018080320 W CN2018080320 W CN 2018080320W WO 2018177222 A1 WO2018177222 A1 WO 2018177222A1
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tank
chromium
solid
liquid separation
containing wastewater
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PCT/CN2018/080320
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English (en)
Chinese (zh)
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余章军
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福建欣宇卫浴科技股份有限公司
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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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/001—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals for sludges or waste products from water treatment installations
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • 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

Definitions

  • the present application relates to the field of wastewater treatment technology, and in particular to a chromium-containing wastewater treatment system.
  • the sources of electroplating wastewater are generally: (1) plating water for cleaning; (2) waste plating solution; (3) other wastewater, including scouring workshop floor, scrubbing plate washing water, ventilating equipment condensate, and leakage due to plating tank Or the operation and management of various "run, run, drip, leak" of various tanks and drainage; (4) equipment cooling water, cooling water in the course of use in addition to temperature rise, not contaminated.
  • the water quality and quantity of electroplating wastewater are related to the process conditions, production load, operation management and water use mode of electroplating production.
  • the water quality of electroplating wastewater is complex and the composition is difficult to control. It contains heavy metal ions such as chromium, cadmium, nickel, copper, zinc, gold and silver, and cyanide. Some of them are highly toxic substances that are carcinogenic, teratogenic and mutagenic.
  • Chromium-containing wastewater is the most common type of electroplating wastewater.
  • the main components of chromium-containing wastewater are sulfuric acid and Cr 6+ , and a small amount of other metal ions such as Cu 2+ , Ni 2+ , Co 2+ , Fe 3+ , Zn .
  • One or more impurities such as 2+ , Fe 2+ , Cr 3+ , and Ca 2+ .
  • the existing chromium-containing wastewater treatment system has a complicated structure, low processing efficiency, poor treatment effect, and can not efficiently separate and treat Cr 6+ , and consumes labor, has low automation, and has a short service life. Therefore, it is necessary to improve the current chromium-containing wastewater treatment system.
  • the present application provides a chromium-containing wastewater treatment system, which better overcomes the problems and shortcomings of the prior art described above, and can effectively separate and treat Cr 6+ , has a simple structure and high processing efficiency. The advantage of good processing effect.
  • a chromium-containing wastewater treatment system comprising a pH adjustment tank connected in sequence, a filtering device, a cationic resin exchange system, a storage tank, and a first solid-liquid separation system;
  • the water outlet of the cationic resin exchange system is in communication with the reservoir, the desorption liquid outlet of the cationic resin exchange system is connected to a desorption liquid reservoir, and the desorption liquid reservoir is connected to a second solid-liquid separation system.
  • a wastewater storage tank is further included, and the wastewater storage tank is connected to the pH adjusting tank by a water pump.
  • the first solid-liquid separation system includes a reduction reaction tank, a first precipitation reaction tank, a first concentration membrane device, a first sedimentation tank, a first collection tank, and a first nanofiltration-microfiltration combination device that are sequentially connected.
  • a first clear water tank the concentrated water outlet of the first concentration membrane device is in communication with the first sedimentation tank, and the sludge outlet of the first sedimentation tank is connected to a first centrifuge or a filter press, the first The water outlet of the concentrated membrane device and the water outlet of the first sedimentation tank are both in communication with the first collection tank, and the water outlet of the first nanofiltration-microfiltration combination device is in communication with the first clear water tank,
  • the sludge outlet of the first nanofiltration-microfiltration combination device is in communication with the first precipitation tank, and the sludge outlet of the first centrifuge or filter press is connected to the first calcining furnace.
  • the second solid-liquid separation system includes a second precipitation reaction tank, a second concentration membrane device, a second sedimentation tank, a second collection tank, a second nanofiltration-microfiltration combination device, and a second clean water that are sequentially connected.
  • a tank; the concentrated water outlet of the second concentration membrane device is in communication with the second sedimentation tank, and the sludge outlet of the second sedimentation tank is connected to a second centrifuge or a filter press, and the second concentrated membrane device is The water outlet of the fresh water outlet and the second sedimentation tank are both connected to the second collection tank, and the water outlet of the second nanofiltration-microfiltration combination device is in communication with the second clear water tank, the second nanofiltration
  • the sludge outlet of the microfiltration combination device is in communication with the second sedimentation tank, and the sludge outlet of the second centrifuge or filter press is connected to the second calciner.
  • the first solid-liquid separation system further includes a first dosing device and a second dosing device in communication with the reduction reaction tank, the first dosing device being configured to add to the reduction reaction pool The acidic substance, the second dosing device is configured to add a reducing agent to the reduction reaction tank.
  • the reduction reaction tank is provided with a first pH monitoring device and a potential controller, the first pH monitoring device is connected to the first medicating device, and the potential controller and the second medicating device connection.
  • the first solid-liquid separation system further includes a third dosing device in communication with the first precipitation reaction tank, the third dosing device configured to add an alkaline substance to the precipitation reaction tank;
  • the first precipitation reaction tank is provided with a second pH monitoring device, and the second pH monitoring device is connected to the third medicating device.
  • the second solid-liquid separation system further includes a fourth dosing device in communication with the second precipitation reaction tank, the fourth dosing device configured to add alkalinity to the second precipitation reaction tank a substance; the second precipitation reaction tank is provided with a third pH monitoring device, and the third pH monitoring device is connected to the fourth dosing device.
  • the first sedimentation tank is connected to the first centrifuge or the filter press through the first sludge storage tank; the water outlet of the first centrifuge or the filter press and the first concentration membrane device Connected.
  • the second sedimentation tank is connected to the second centrifuge or the filter press through the second sludge storage tank; the water outlet of the second centrifuge or the filter press and the second concentrated membrane device Connected.
  • the cationic resin exchange system comprises a plurality of cationic resin exchangers.
  • the filtering device comprises a quartz sand filter, an activated carbon filter, a ceramic filter, a multi-media filter or a fiber filter.
  • the chromium-containing wastewater treatment system of the present application effectively uses Cr 6+ and other metal ions such as Cu 2+ , Ni 2+ , Co 2+ , Fe 3+ , Zn 2+ , Fe 2 by using a cationic resin exchange system. + , one or more impurities such as Cr 3+ and Ca 2+ are separated, and then the wastewater containing Cr 6+ and other metal ions such as Cu 2+ , Ni 2+ , Co 2+ are separately separated by a solid-liquid separation system.
  • the desorption liquid of one or more impurities such as Fe 3+ , Zn 2+ , Fe 2+ , Cr 3+ , Ca 2+ is subjected to solid-liquid separation treatment, and it is not necessary to add organic substances such as PAC and PAM, thereby saving cost and avoiding Water again causes pollution.
  • the solid-liquid separation system of the present application forms a precipitate by causing a metal ion in the wastewater to precipitate with a basic substance such as sodium hydroxide in a precipitation reaction tank, and then is concentrated by a concentration membrane device to precipitate the particles.
  • concentration and concentration increase and increase, accelerate the sedimentation, and then carry out solid-liquid separation in the sedimentation tank.
  • the collected water in the collection tank is further filtered by the nanofiltration-microfiltration combination device for microfiltration and nanofiltration, and the water can be removed more thoroughly.
  • a small amount of fine solid suspension, the precipitate obtained by filtration is discharged into the sedimentation tank in batches, and the precipitate in the sedimentation tank is dehydrated by a centrifuge or a filter press, and the obtained solid waste residue does not contain PAC, PAM.
  • the organic impurities, the water content is also low, and then calcined in the calcining furnace, the obtained metal oxides and other compounds can not only be recycled, but also achieve zero pollutant emissions, and the related technology eventually generates dangerous solid waste, and needs to be Compared with the system for treating dangerous solid waste, it effectively reduces the sludge treatment cost and load, and solves the problem of waste of resources, and greatly reduces The production cost of the enterprise has great social and economic benefits.
  • the solid-liquid separation system of the present application monitors the pH value in the reaction tank in real time by setting a pH monitoring device on the precipitation reaction tank, and controls the dosing device to automatically add the medicine according to the corresponding pH value, so that the system is automated. High, safe, stable, easy to operate, easy to manage and better.
  • Another aspect of the present application provides a chromium-containing wastewater treatment process for treating chromium-containing wastewater by using the chromium-containing wastewater treatment system described above, including:
  • the chromium-containing wastewater is pumped into the pH adjusting tank, the pH is adjusted to 3.0-7.0, filtered through a filtering device, and the filtrate is subjected to ion exchange through two tandem cationic resin exchangers to separate Cr 6+ in the wastewater, containing Cr. 6+ of the waste water is discharged into the storage tank, and the cation exchange resin adsorbing the remaining metal ions enters the regeneration device to regenerate the resin, and the obtained desorbed liquid containing the remaining metal ions is discharged into the desorption liquid storage tank;
  • the Cr 6+ -containing wastewater discharged into the reservoir is subjected to solid-liquid separation by the first solid-liquid separation system, and the desorbed liquid containing the remaining metal ions discharged into the desorption liquid reservoir is subjected to solid-liquid separation by the second solid-liquid separation system.
  • the waste water discharged into the storage tank containing Cr 6+ passes through the reduction reaction tank in the first solid-liquid separation system, and after the Cr 6+ in the waste water is reduced to Cr 3+ , the Cr is reacted through the first precipitation reaction tank to form Cr.
  • (OH) 3 precipitates, and then concentrated by the first concentration membrane device; then enters the first sedimentation tank for solid-liquid separation, and the obtained supernatant liquid is discharged into the first collection tank; the sediment is discharged into the first sludge storage tank After the amount of sludge in the first sludge storage tank reaches a set amount, the sludge is pumped to the first centrifuge or the filter press for dehydration separation, and the obtained wastewater is recovered into the first concentrated membrane device to continue the second time. After the treatment, the obtained solid waste residue is automatically sent to the first calcining furnace for direct high-temperature calcination or after being placed, and calcined intermittently to obtain chromium oxide.
  • the supernatant collected in the first collection tank is further subjected to the first nanofiltration-microfiltration combination device to further remove the solid suspension in the supernatant collected in the first collection tank, and the precipitate obtained by filtration is discharged in batches.
  • the secondary treatment is continued in the first sedimentation tank, and the filtered water is discharged into the first clear water tank for recycling.
  • the desorbed liquid discharged into the desorption liquid reservoir is first reacted by the second precipitation reaction tank to form a metal hydroxide precipitate, and then concentrated by a second concentration membrane device; and then enters a second sedimentation tank for solid-liquid separation.
  • the supernatant liquid is discharged into the second collection tank; the sediment is discharged into the second sludge storage tank, and the amount of sludge in the second sludge storage tank reaches a set amount, and is pumped to the second centrifuge through the sludge pump or The filter press performs dehydration separation, and the obtained wastewater is recovered into the second concentration membrane device to continue the secondary treatment, and the obtained solid waste residue is automatically sent to the second calcination furnace for direct high-temperature calcination or intermittently calcined to obtain a metal oxide. And a mixture of compounds.
  • FIG. 1 is a first structural schematic view of a chromium-containing wastewater treatment system of the present application
  • FIG. 2 is a schematic view showing the second structure of the first solid-liquid separation system of the present application.
  • FIG. 3 is a schematic view showing the third structure of the second solid-liquid separation system of the present application.
  • 1-chromium-containing wastewater treatment system 100-wastewater storage tank; 200-pump pump; 300-pH adjustment tank; 400-filter device; 500-cationic resin exchanger; 600-reservoir; 700-first solid-liquid separation system 701-reduction reaction cell; 7011-first dosing device; 7012-second dosing device; 7013-first pH monitoring device; 7014-potential controller; 702-first precipitation reaction cell; 7021-third plus Drug device; 7022 - second pH monitoring device; 703 - first concentration membrane device; 704 - first sedimentation tank; 705 - first collection tank; 706 - first nanofiltration - microfiltration combination device; 707 - first clear water Pool; 708-first sludge storage tank; 709-first centrifuge or filter press; 710-first calciner; 800-desorbent reservoir; 900-second solid-liquid separation system; 901-second precipitation Reaction cell; 9011-fourth dosing device; 9012-third pH monitoring device; 902-second concentration membrane device; 90
  • a chromium-containing wastewater treatment system will now be described more fully with reference to the associated drawings.
  • a preferred embodiment of a chromium-containing wastewater treatment system is given in the accompanying drawings.
  • the chromium-containing wastewater treatment system can be implemented in many different forms and is not limited to the embodiments described herein. Rather, the purpose of providing these embodiments is to make the disclosure of chromium-containing wastewater treatment systems more thorough and comprehensive.
  • the present application provides a chromium-containing wastewater treatment system 1 comprising a pH adjustment tank 300, a filtration device 400, a cationic resin exchange system, a reservoir 600, and a first solid-liquid separation system 700 that are sequentially connected.
  • the outlet of the cationic resin exchange system is in communication with the reservoir 600, the desorption liquid outlet of the cationic resin exchange system is connected to a desorption liquid reservoir 800, and the desorption liquid reservoir 800 is connected to the second solid-liquid separation system. 900.
  • the filtering device 400 is configured to filter out impurities such as solid particulate matter in the chromium-containing wastewater to avoid affecting the adsorption performance of the cation exchange resin in the subsequent cationic resin exchange system.
  • the filtration device 400 may be exemplified by a quartz sand filter, an activated carbon filter, a ceramic filter, a multi-media filter, or a fiber filter.
  • the cationic resin exchange system of the present application is configured to adsorb a metal ion other than Cr 6+ such as Cu 2+ , Ni 2+ , Co 2+ , Fe by loading a cation exchange resin into the cation resin exchanger 500.
  • a metal ion other than Cr 6+ such as Cu 2+ , Ni 2+ , Co 2+ , Fe
  • One or more impurities such as 3+ , Zn 2+ , Fe 2+ , Cr 3+ , Ca 2+ , etc., thereby Cr 6+ and other metal ions such as Cu 2+ , Ni 2+ , Co 2+ , Fe 3
  • One or more impurities such as + , Zn 2+ , Fe 2+ , Cr 3+ , and Ca 2+ are separated.
  • the wastewater containing Cr 6+ is discharged into the reservoir 600 through the water outlet; and other metal ions such as Cu 2+ , Ni 2+ , Co 2+ , Fe 3+ , Zn 2+ , Fe 2+ , Cr 3+ are adsorbed.
  • a cation exchange resin of one or more impurities such as Ca 2+ enters the regeneration device through a desorption and regeneration process to regenerate the resin, and the obtained other metal ions such as Cu 2+ , Ni 2+ , Co 2+ , Fe 3+
  • the desorbed liquid of one or more impurities such as Zn 2+ , Fe 2+ , Cr 3+ , Ca 2+ is discharged into the desorption liquid reservoir 800 through the desorbent outlet.
  • the first solid-liquid separation system 700 is configured to perform solid-liquid separation of the Cr 6+ -containing wastewater discharged into the storage tank 600; the second solid-liquid separation system 900 is configured to discharge the desorption
  • the liquid storage tank 800 contains one or more impurities such as Cu 2+ , Ni 2+ , Co 2+ , Fe 3+ , Zn 2+ , Fe 2+ , Cr 3+ , Ca 2+ , etc.
  • the desorbed liquid is subjected to solid-liquid separation.
  • the chromium-containing wastewater treatment system 1 of the present application further includes a wastewater storage tank 100 that communicates with the pH adjustment tank 300 through a water pump 200.
  • the first solid-liquid separation system 700 includes a reduction reaction tank 701, a first precipitation reaction tank 702, a first concentration membrane device 703, which are sequentially connected, a first sedimentation tank 704, a first collection tank 705, a first nanofiltration-microfiltration combination device 706, a first clear water tank 707; a concentrated water outlet of the first concentration membrane device 703 is in communication with the first precipitation tank 704,
  • the sludge outlet of the first sedimentation tank 704 is connected to a first centrifuge or a filter press 709, and the water outlet of the first concentration membrane device 703 and the water outlet of the first sedimentation tank 704 are both the first
  • the collection tank 705 is in communication
  • the water outlet of the first nanofiltration-microfiltration combination device 706 is in communication with the first clear water tank 707
  • the sludge outlet of the first nanofiltration-microfiltration combination device 706 and the first A sedimentation tank 704 is in communication, and the sludge outlet of the first centrion of the first centrion of the first centr
  • the reduction reaction tank 701 Cr 6+ in the wastewater is reduced to Cr 3+ by adding a reducing agent
  • the reducing agent may, for example, be sodium sulfite, sodium metabisulfite or sodium hydrogen sulfite.
  • the embodiment The amount of reducing agent is slightly larger than the theoretical amount of the reaction, so that a sufficient reaction can occur.
  • the first solid-liquid separation system 700 further includes a first dosing device 7011 and a second dosing device 7012 that are in communication with the reduction reaction cell 701, and the first dosing device 7011 is configured to An acidic substance is added to the reduction reaction tank 701, and the second dosing device 7012 is configured to add a reducing agent to the reduction reaction tank 701; the reduction reaction tank 701 is provided with a first pH monitoring device 7013 and a potential The controller 7014 is connected to the first dosing device 7011, and the potential controller 7014 is connected to the second dosing device 7012.
  • the first pH monitoring device 7013 is configured to monitor the pH value of the wastewater in the reduction reaction tank 701 in real time. When the monitored pH value is greater than 3.0, the first pH monitoring device 7013 automatically controls.
  • the first dosing device 7011 adds an acidic substance to the reduction reaction tank 701; when the monitored pH value is lower than 2.5, the first pH monitoring device 7013 automatically controls the first dosing device 7011 to reduce the reaction.
  • the addition of acidic substances in the tank 701 is stopped.
  • the acidic substance may, for example, be sulfuric acid or hydrochloric acid.
  • the potential controller 7014 (ORP meter) is configured to monitor the potential of the wastewater in the reduction reaction tank 701 in real time.
  • the potential controller 7014 (ORP meter) Automatically controlling the second dosing device 7012 to add a reducing agent to the reduction reaction cell 701; when the monitored pH value is lower than 220 mV, the potential controller 7014 (ORP meter) automatically controls the second dosing The device 7012 stops adding the reducing agent to the reduction reaction cell 701.
  • the pH of the Cr 3+ -containing wastewater obtained by reduction through the reduction reaction tank 701 is adjusted to a certain range, and a Cr(OH) 3 precipitate is formed by reacting a basic substance with Cr 3+ .
  • the alkaline substance is sodium hydroxide in the present embodiment, and of course, the alkaline substance may also be exemplified by lime or a mixture of lime and sodium hydroxide.
  • the specific reaction formula is:
  • the first solid-liquid separation system 700 further includes a third dosing device 7021 in communication with the first precipitation reaction cell 702, and the third dosing device 7021 is configured to react to the precipitation.
  • the pool is doped with an alkaline substance; the first precipitation reaction tank 702 is provided with a second pH monitoring device 7022, and the second pH monitoring device 7022 is connected to the third dosing device 7021.
  • the second pH monitoring device 7022 is configured to monitor the pH value of the wastewater in the first precipitation reaction tank 702 in real time. When the monitored pH value is less than 10, the second pH monitoring device 7022 Automatically controlling the third dosing device 7021 to add alkaline substances to the first precipitation reaction tank 702; when the monitored pH value is greater, the third pH monitoring device 9012 automatically controls the fourth dosing device 9011 The addition of the alkaline substance to the first precipitation reaction tank 702 is stopped.
  • the second solid-liquid separation system 900 includes a second precipitation reaction tank 901, a second concentration membrane device 902, and a second sedimentation tank 903 that are sequentially connected.
  • the sludge outlet of the tank 903 is connected to the second centrifuge or the filter press 908, and the water outlet of the second concentration membrane device 902 and the water outlet of the second sedimentation tank 903 are both connected to the second collection tank 904.
  • the water outlet of the second nanofiltration-microfiltration combination device 905 is in communication with the second clear water tank 906, and the sludge outlet of the second nanofiltration-microfiltration combination device 905 is connected to the second precipitation tank 903.
  • the sludge outlet of the second centrifuge or filter press 908 is connected to a second calciner 909.
  • the first precipitation reaction tank 702 is provided by containing other metal ions such as Cu 2+ , Ni 2+ , Co 2+ , Fe 3+ , Zn 2+ , Fe 2+ , Cr 3+ , Ca 2+ or the like or
  • the pH of wastewater with various impurities is adjusted to a certain range, and alkaline substances and other metal ions such as Cu 2+ , Ni 2+ , Co 2+ , Fe 3+ , Zn 2+ , Fe 2+ , Cr 3 are utilized.
  • One or more reactions such as + and Ca 2+ form a metal hydroxide precipitate to remove other metal ions such as Cu 2+ , Ni 2+ , Co 2+ , Fe 3+ , Zn 2+ , Fe 2 in the wastewater.
  • the alkaline substance is sodium hydroxide in the present embodiment, and of course, the alkaline substance may also be exemplified by lime or a mixture of lime and sodium hydroxide. Specific reaction formulas can be listed as follows:
  • Ni 2+ +2OH - Ni(OH) 2 ⁇ .
  • the second solid-liquid separation system 900 further includes a fourth dosing device 9011 in communication with the second precipitation reaction tank 901, and the fourth dosing device 9011 is configured to be toward the second
  • the precipitation reaction tank 901 is added with a basic substance; the second precipitation reaction tank 901 is provided with a third pH monitoring device 9012, and the third pH monitoring device 9012 is connected to the fourth dosing device 9011.
  • the third pH monitoring device 9012 has the same working principle as the second pH monitoring device 7022 described above, that is, configured to monitor the pH value in the second precipitation reaction tank 901 in real time, and control the fourth dosing device 9011 according to the corresponding pH value. Start or stop adding alkaline substances.
  • the first concentrated membrane device 703 and the second concentrated membrane device 902 can be exemplified by a high pressure reverse osmosis roll membrane or a high pressure reverse osmosis disc membrane or a vibrating membrane or a forward osmosis membrane.
  • the first concentration membrane device 703 and the second concentration membrane device 902 can also be exemplified by a nanofiltration membrane, an ultrafiltration membrane, a microfiltration membrane, or a general filter cartridge.
  • the hydroxide precipitated particles are further concentrated, aggregated, and thickened by membrane separation.
  • the first settling tank 704 is in communication with the first centrifuge or filter press 709 through a first sludge storage tank 708; the water outlet of the first centrifuge or filter press 709 is The first concentration membrane device 703 is in communication.
  • the second sedimentation tank 903 is in communication with the second centrifuge or filter press 908 through the second sludge storage tank 907; the water outlet of the second centrifuge or filter press 908 is The second concentrated membrane device 902 is in communication.
  • the sludge storage tank is configured to store the sludge discharged from the sludge outlet of the sedimentation tank, and after being accumulated to a certain amount, it is sent to a centrifuge or a filter press for dehydration separation, thereby avoiding intermittent provision of the sedimentation tank.
  • the sludge is sent to a centrifuge or filter press to affect the service life of the centrifuge or filter press.
  • the solid-liquid separation system of the embodiment of the present application recovers the waste water obtained by dehydration and separation by a centrifuge or a filter press to a concentrated membrane device, thereby realizing secondary recovery treatment and utilization of the wastewater, thereby reducing emission pollution.
  • the cationic resin exchange system includes a plurality of cationic resin exchangers 500.
  • two or three parallel or series cation resin exchangers 500 can be set to make Cr 6+ and other metal ions such as Cu 2+ , Ni 2+ , Co 2+ , One or more impurities such as Fe 3+ , Zn 2+ , Fe 2+ , Cr 3+ , and Ca 2+ are completely separated.
  • the cationic resin exchange system of the present application includes two tandem cation resin exchangers 500.
  • the process flow of the chromium-containing wastewater treatment system 1 of the present application is:
  • the chromium-containing wastewater in the wastewater storage tank 100 is pumped into the pH adjusting tank 300 through the pump 200, and the pH is adjusted to 3.0 to 7.0, and filtered by the filtering device 400 to remove solid particles in the chromium-containing wastewater.
  • the filtrate is further ion-exchanged through two tandem cation resin exchangers 500, and the Cr 6+ and other metal ions in the wastewater such as Cu 2+ , Ni 2+ , Co 2+ , Fe 3+ , Zn 2
  • One or more impurities such as + , Fe 2+ , Cr 3+ , and Ca 2+ are separated.
  • the wastewater containing Cr 6+ is discharged into the reservoir 600 through the water outlet, and adsorbs other metal ions such as Cu 2+ , Ni 2+ , Co 2+ , Fe 3+ , Zn 2+ , Fe 2+ , Cr 3+ .
  • the cation exchange resin of one or more impurities such as Ca 2+ undergoes a desorption and regeneration process to regenerate the resin, and the obtained metal ions such as Cu 2+ , Ni 2+ , Co 2+ , Fe 3+ , Zn 2 are obtained.
  • the desorbed solution of one or more impurities such as + , Fe 2+ , Cr 3+ , Ca 2+ is discharged into the desorbent reservoir 800 through the desorbent outlet.
  • the wastewater containing Cr6 + discharged into the storage tank 600 passes through the reduction reaction tank 701 in the first solid-liquid separation system 700, and the Cr 6+ in the wastewater is reduced to Cr 3+ and then passes through the first precipitation.
  • the reaction cell 702 reacts to form a Cr(OH) 3 precipitate, and is concentrated by the first concentration membrane device 703 to concentrate and aggregate the Ni(OH) 2 precipitated particles to increase and increase; then enter the first precipitation tank 704 for solid-liquid separation.
  • the obtained supernatant liquid is discharged into the first collection tank 705 through the water outlet of the first sedimentation tank 704; the sediment is discharged into the first sludge storage tank 708 through the sludge outlet of the first sedimentation tank 704, and the first sewage is to be treated.
  • the amount of sludge in the mud storage tank 708 reaches a certain amount, and is pumped to the first centrifuge or the filter press 709 through a sludge pump (not shown) for dehydration separation, and the obtained wastewater is recovered to the first concentrated membrane device 703.
  • the secondary treatment is continued, and the obtained solid waste residue is automatically sent to the first calcining furnace 710 for direct high-temperature calcination or intermittently calcined after being placed to obtain chromium oxide having higher purity. Further, hydrogen gas and nitrogen gas may be further introduced into the first calcining furnace 710 to further reduce chromium oxide into elemental chromium, and finally chromium or chromium oxide is recycled.
  • the supernatant collected in the first collection tank 705 is further subjected to the first nanofiltration-microfiltration combination device 706 to further remove traces of fine solid suspension in the supernatant collected in the first collection tank 705, and the precipitate obtained by filtration is filtered.
  • the material is discharged into the first sedimentation tank 704 in batches to continue the secondary treatment, and the filtered water is discharged into the first clear water tank 707 for recycling.
  • the supernatant collected in the second collection tank 904 is further removed by the second nanofiltration-microfiltration combination device 905 to further remove traces of fine solid suspension in the supernatant collected in the second collection tank 904, and the precipitate obtained by filtration is filtered.
  • the material is discharged into the second sedimentation tank 903 in batches to continue the secondary treatment, and the filtered water is discharged into the second clear water tank 906 for recycling.
  • the chromium-containing wastewater treatment system of the present application effectively uses Cr 6+ and other metal ions such as Cu 2+ , Ni 2+ , Co 2+ , Fe 3+ , Zn 2+ , Fe 2 by using a cationic resin exchange system. + , one or more impurities such as Cr 3+ and Ca 2+ are separated, and then the wastewater containing Cr 6+ and other metal ions such as Cu 2+ , Ni 2+ , Co 2+ are separately separated by a solid-liquid separation system.
  • the desorption liquid of one or more impurities such as Fe 3+ , Zn 2+ , Fe 2+ , Cr 3+ , Ca 2+ is subjected to solid-liquid separation treatment, and it is not necessary to add organic substances such as PAC and PAM, thereby saving cost and avoiding Water again causes pollution.
  • the solid-liquid separation system of the present application forms a precipitate by causing a metal ion in the wastewater to precipitate with a basic substance such as sodium hydroxide in a precipitation reaction tank, and then is concentrated by a concentration membrane device to precipitate the particles.
  • concentration and concentration increase and increase, accelerate the sedimentation, and then carry out solid-liquid separation in the sedimentation tank.
  • the collected water in the collection tank is further filtered by the nanofiltration-microfiltration combination device for microfiltration and nanofiltration, and the water can be removed more thoroughly.
  • a small amount of fine solid suspension, the precipitate obtained by filtration is discharged into the sedimentation tank in batches, and the precipitate in the sedimentation tank is dehydrated by a centrifuge or a filter press, and the obtained solid waste residue does not contain PAC, PAM.
  • the organic impurities, the water content is also low, and then calcined in the calcining furnace, the obtained metal oxides and other compounds can not only be recycled, but also achieve zero pollutant emissions, and the related technology eventually generates dangerous solid waste, and needs to be Compared with the system for treating dangerous solid waste, it effectively reduces the sludge treatment cost and load, and solves the problem of waste of resources, and greatly reduces The production cost of the enterprise has great social and economic benefits.
  • the solid-liquid separation system of the present application monitors the pH value in the reaction tank in real time by setting a pH monitoring device on the precipitation reaction tank, and controls the dosing device to automatically add the medicine according to the corresponding pH value, so that the system is automated. High, safe, stable, easy to operate, easy to manage and better.
  • the metal oxides and other compounds obtained by the chromium-containing wastewater treatment system provided by the present application can not only be recycled, but also realize zero pollutant discharge, effectively reduce sludge treatment cost and load, and solve the problem of resource waste, and greatly reduce The production cost of the enterprise has great social and economic benefits.

Landscapes

  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

L'invention concerne un système de traitement (1) d'eaux usées contenant du chrome, le système comprenant un réservoir de réglage de pH (300), un dispositif de filtration (400), un système à résine échangeuse de cations, un réservoir de stockage d'eau (600) et un premier système de séparation solide-liquide (700), qui sont disposés successivement et en communication, une sortie d'eau du système à résine échangeuse de cations étant en communication avec le réservoir de stockage d'eau (600), une sortie de liquide de désorption du système à résine échangeuse de cations étant en communication avec un réservoir de stockage de liquide de désorption (800), et le réservoir de stockage de liquide de désorption (800) étant en communication avec un second système de séparation solide-liquide (900). L'invention concerne également un procédé de traitement d'eaux usées contenant du chrome : - d'une part, les eaux usées contenant du chrome sont réglées à un pH compris entre 3,0 et 7,0 et filtrées par l'intermédiaire d'un dispositif de filtration (400) ; un filtrat est soumis à un échange d'ions par l'intermédiaire d'une résine échangeuse de cations (500) ; les eaux usées contenant du Cr6 + sont évacuées vers un réservoir de stockage d'eau (600) et sont soumises à une séparation solide-liquide au moyen d'un premier système de séparation solide-liquide (700), d'autre part, la résine échangeuse de cations qui a absorbé des ions métalliques résiduels, entre dans un dispositif de régénération destiné à la régénération de la résine ; et le liquide de désorption est évacué vers un réservoir de stockage de liquide de désorption (800), et est soumis à une séparation solide-liquide à l'aide d'un second système de séparation solide-liquide (900), et les déchets solides résultants issus de la séparation solide-liquide sont soumis à un traitement de calcination.
PCT/CN2018/080320 2017-03-27 2018-03-23 Système et procédé de traitement d'eaux usées contenant du chrome WO2018177222A1 (fr)

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