CN109879477B - Arsenic-containing wastewater treatment method - Google Patents
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Abstract
The invention provides a method for treating arsenic-containing wastewater, which has good arsenic removal effect and can meet increasingly strict arsenic emission standards. Which comprises the following steps: firstly, after the wastewater is collected, adding acid and alkali agents to adjust the pH value, and adding an oxidant to oxidize trivalent arsenic into pentavalent arsenic; secondly, carrying out coagulation reaction on the mixed solution obtained by the treatment in the step one by adding an iron salt coagulant and adjusting the pH value; thirdly, introducing the mixed liquor obtained by the treatment in the second step into a concentration tank, adding an arsenic removal agent into the concentration tank, and removing insoluble particles through a tubular microfiltration membrane system; fourthly, adding iron salt into the mixed solution obtained by the treatment in the third step, and further reducing the arsenic concentration through a catalytic arsenic removal tower; fifthly, adding a reducing agent into the mixed liquid obtained by the fourth treatment to enable the oxidation-reduction potential ORP to be less than 300mV, adjusting the pH value to be 5-6, and then deeply removing arsenic through arsenic removing resin or arsenic removing filter material and discharging.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for treating arsenic-containing wastewater.
Background
Arsenic-containing wastewater in the semiconductor industry generally comes from two parts, wherein one part comes from the chip production process, such as cleaning, stripping, etching, grinding and polishing, chip cutting and other processes; the other part is derived from arsenic-containing and phosphorus-containing wastewater generated by gallium arsenide epitaxial waste gas treatment. As a pollutant, the discharge of arsenic is strictly controlled, and the arsenic is required to be less than 0.5mg/L in the integrated wastewater discharge standard (GB 8978-1996) Table 1. The requirement of arsenic in table 2 of the emission Standard of pollutants for the electronic industry (draft of second order comments) is less than 0.1 mg/L; in the semiconductor industry pollutant emission standard of Shanghai city (DB 31-2006), the A standard in Table 1 is arsenic less than 0.05 mg/L; the special emission standard is arsenic less than 0.05 mg/L. However, the partial environment capacity is small or the arsenic emission is controlled in total, and the arsenic emission concentration is even required to be < 2. mu.g/L. The common methods for removing arsenic in industry include chemical precipitation, adsorption with arsenic-removing resin or adsorbent, reverse osmosis and evaporative concentration.
In the practical engineering case, the arsenic-containing waste water is treated by adopting a chemical precipitation method, the method has mature process and simple and convenient operation, and the concentration of the arsenic in the effluent can be less than 0.5 mg/L. For example, chinese patent CN103408162A discloses a method for treating arsenic-containing wastewater, which adopts processes of adding iron and two-stage chemical precipitation filtration, and has a good treatment effect on arsenic-containing wastewater with different concentrations. However, the method depends on excessive addition of chemical reagents, so that the problems of large sludge amount and high yielding water soluble solids are easily caused. The process can only treat the arsenic-containing wastewater to be less than 0.5mg/L, and can not meet increasingly strict discharge standards.
In the case of high emission requirements, a coagulation-binding resin removal process is often adopted, for example, chinese patent CN106517577A discloses an acidic arsenic-containing wastewater treatment process, which adopts a two-stage coagulation-precipitation binding resin adsorption process, and the effluent can reach arsenic less than 0.05mg/L for different inlet water concentrations. But the process adopts two-stage coagulation and precipitation, and the floor area of facilities is large; meanwhile, the effluent water after coagulation has relatively high arsenic content, and the increasingly strict discharge standard cannot be met.
Increasingly strict water quality management standards put higher demands on the treatment process of arsenic-containing wastewater, and a method for treating arsenic-containing wastewater, which is low in cost, efficient and stable and is suitable for high discharge standards, is urgently required.
Disclosure of Invention
Aiming at the problem of high discharge standard of the existing arsenic-containing wastewater, the invention provides the arsenic-containing wastewater treatment method which has good arsenic removal effect and can meet increasingly strict arsenic discharge standard.
The technical scheme is as follows: a method for treating arsenic-containing wastewater comprises the following steps:
a method for treating arsenic-containing wastewater comprises the following steps:
firstly, after the wastewater is collected, adding acid and alkali agents to adjust the pH value, and adding an oxidant to oxidize trivalent arsenic into pentavalent arsenic;
secondly, carrying out coagulation reaction on the mixed solution obtained by the treatment in the step one by adding an iron salt coagulant and adjusting the pH value;
the method is characterized in that: it also includes the following steps:
thirdly, introducing the mixed liquor obtained by the treatment in the second step into a concentration tank, adding an arsenic removal agent into the concentration tank, and removing insoluble particles through a tubular microfiltration membrane system;
fourthly, adding iron salt into the mixed solution obtained by the treatment in the third step, and further reducing the arsenic concentration through a catalytic arsenic removal tower;
fifthly, adding a reducing agent into the mixed liquid obtained by the treatment in the fourth step to enable the oxidation-reduction potential to be less than 300mV, adjusting the pH value, and then deeply removing arsenic through arsenic removing resin or arsenic removing filter material and discharging.
It is further characterized in that:
in the first step, the pH is adjusted to 6-9, an oxidant is added, and the ORP is controlled to be more than 400 mV;
in the second step, the ferric salt coagulant contains ferric iron, so that the molar ratio of iron to arsenic in the solution is 2: 1-10: 1;
in the second step, adding an iron salt coagulant, wherein the adding amount is that the molar ratio of iron to phosphorus is 1: 1-3: 1, adding an alkaline agent, adjusting the pH value to 6.5-9.5, and reacting for 30-60 min;
adding an arsenic removal agent into the solution to enable the molar ratio of iron to arsenic in the solution to be 1: 1-10: 1; the preparation method of the arsenic removal medicament comprises the following steps: adding every 10-20 g of activated carbon powder into 200 mL of 0.25 mol/L ferric chloride solution, stirring for 30-120 min, ultrasonically oscillating for 40-90 min, adding 1mol/L sodium hydroxide solution into the mixed solution at the speed of 1-5 mL/min until the pH value is 6.5-8.0, aging for 24h at room temperature, filtering, washing with pure water until the supernatant is colorless, and drying at 60 ℃;
in the fourth step, the filter material of the catalytic arsenic removal tower is manganese sand or a medium containing a manganese dioxide coating;
in the fourth step, the ferric salt is an iron composite reagent, the molar ratio of ferric ions to ferrous ions is 0.5: 1-2: 1, the molar ratio of iron to arsenic in the solution is 10: 1-50: 1, and the water inlet flow rate of the arsenic removal tower is 10-25 bv/h;
in the fifth step, the water inflow velocity of the deep arsenic removal device is 10-30 bv/h, and the adsorption material is a reproducible strong-base anion exchange resin loaded with iron oxyhydroxide or a nonrenewable arsenic removal filter material based on titanium and iron oxyhydroxide;
and fifthly, before deep arsenic removal is carried out through the arsenic removal resin or the arsenic removal filter material, firstly adjusting the pH value to 5-9, then adjusting the pH value through the phosphorus removal resin, and then removing phosphorus from the wastewater.
The arsenic-containing wastewater treatment method disclosed by the invention has the following advantages:
(1) tubular microfiltration membrane filters and replaces traditional filtering pond, practices thrift the space and under the effect of concentrator tank, improves medicament availability factor, improves and removes arsenic effect.
(2) The arsenic removal filter can remove 90% of residual arsenic after chemical precipitation, the service life of the terminal arsenic removal resin/filter material is prolonged, the filter material coated with manganese sand and manganese dioxide is applied, chemical regeneration is not needed, the application cost is saved, and the arsenic removal effect is improved.
(3) The competitive adsorption of phosphate and arsenic is fully considered when the arsenic removal resin/filter material is used, and the problem of unstable arsenic removal effect caused by phosphorus is avoided, so that the arsenic removal effect is further improved.
(4) After the method is adopted, the effluent has extremely low arsenic concentration, and the arsenic can be less than 2 mug/L.
Drawings
FIG. 1 is a flow chart of the present invention.
Detailed Description
The method for treating the arsenic-containing wastewater as shown in figure 1 comprises the following steps:
firstly, after the wastewater is collected, adding acid and alkali agents to adjust the pH value to 6-9, and adding an oxidant to oxidize trivalent arsenic into pentavalent arsenic, wherein the oxidant such as hypochlorite, ozone, ferrate, permanganate and the like makes the oxidation-reduction potential ORP more than 400 mV;
and II, carrying out coagulation reaction on the mixed solution obtained by the treatment in the step I by adding an iron salt coagulant for 15-30min, adjusting the pH to 6.5-9.5, and reacting for 15-30min, wherein the iron salt coagulant is a ferric salt coagulant, and the molar ratio of iron to arsenic in the solution is 2: 1-10: 1; if the water contains phosphate, adding an iron salt coagulant, wherein the adding amount is that the molar ratio of iron to phosphorus is 1: 1-3: 1, adding alkaline agents (sodium hydroxide and potassium hydroxide), adjusting the pH value to 6.5-9.5, and reacting for 30-60 min;
thirdly, introducing the mixed solution obtained by the treatment in the second step into a concentration tank, adding an arsenic removal agent into the concentration tank to enable the molar ratio of iron to arsenic in the solution to be 1: 1-10: 1, removing insoluble particles through a tubular microfiltration membrane system, enabling the filtrate to enter a relay tank, and returning the concentrated solution to the concentration tank; regularly discharging mud from the concentration tank; the preparation method of the arsenic removal medicament comprises the following steps: adding 200-mesh activated carbon powder per 10-20 g into 200 mL of 0.25 mol/L ferric chloride solution, stirring for 30-120 min, ultrasonically oscillating for 40-90 min, adding 1mol/L sodium hydroxide solution into the mixed solution at the speed of 1-5 mL/min until the pH value is 6.5-8.0, aging for 24h at room temperature, filtering, washing with pure water until the supernatant is colorless, and drying at 60 ℃;
adding ferric salt into the mixed solution obtained by the treatment in the step three, wherein the ferric salt is an iron composite reagent, the molar ratio of ferric ions to ferrous ions is 0.5: 1-2: 1, the molar ratio of iron to arsenic in the solution is 10: 1-50: 1, and the water inlet flow rate of the arsenic removal tower is 10-25 bv/h; then a catalytic arsenic removal tower with manganese sand as a filter material is used for carrying out catalytic coprecipitation arsenic removal, so that the arsenic concentration is further reduced, the water inlet load of the deep arsenic removal device is reduced, and the produced water enters a secondary relay tank;
fifthly, adding a reducing agent into the mixed solution obtained by the fourth treatment step to enable the oxidation-reduction potential ORP to be less than 300mV, adjusting the pH to be 5-9, then removing phosphorus through phosphorus removal resin, adjusting the pH, then deeply adsorbing and removing arsenic through arsenic removal resin, and then discharging, wherein the arsenic removal resin is reproducible strong-base anion exchange resin loaded with iron oxyhydroxide arranged in a resin tower, or is a nonrenewable titanium-based and iron oxyhydroxide arsenic removal filter material arranged in a filter tank, and the water inlet flow rate of the resin tower or the filter tank is 10-30 bv/h.
The arsenic removal effect is demonstrated below in connection with the examples:
example 1: water quality of arsenic-containing wastewater of a certain gallium arsenide semiconductor enterprise: there are two different concentrations of arsenic-containing wastewater for this enterprise: (1) arsenic acid and alkali containing wastewater: the pH value is 3-9.5, the arsenic content TAs in the wastewater is less than 100mg/L, the suspended matter content SS in the wastewater is less than 10mg/L, and the discharge amount is 120m 3/d; (2) arsenic-containing grinding wastewater: the pH value is 3-9.5, TAs is less than 100mg/L, SS is less than 300mg/L, and the discharge amount is 120m 3/d. The two kinds of waste water are collected together to a regulating reservoir for post-treatment, and the embodiment comprises the following steps:
the first step is as follows: adjusting the pH value of the collected arsenic-containing wastewater to 6.5-7.5, and reacting for 30 min; then adding 10% sodium hypochlorite, maintaining ORP more than 400mV, and reacting for 30 min;
the second step is that: adding 20% ferric chloride at a flow rate of 60L/h, adjusting the pH value to 7.5-9.5, and carrying out coagulation reaction for 30 min. Then the mixture enters a concentration tank;
the third step: adding 20g/h of arsenic removal agent into the concentration tank, and enabling outlet water to enter a DF membrane, wherein the inlet pressure is 0.2MPa, the average water inlet flow is 82t/h, and the average water yield is 12 t/h;
the preparation method of the arsenic removal medicament comprises the following steps: adding 200 g of 200-mesh activated carbon powder into 200 mL of 0.25 mol/L ferric chloride solution, stirring for 30-120 min, ultrasonically shaking for 40-90 min, slowly adding 1mol/L NaOH (1-5 mL/min) into the mixed solution until the pH value is 6.5-8.0, aging for 24h at room temperature, filtering, washing with pure water until the supernatant is colorless, and drying at 60 ℃.
The fourth step: adding an iron compound medicament (Fe 2 +: Fe3+ =1: 2) 1.8L/h into the effluent after the filtration of the relay tank 1, adjusting the pH to 7.5-9.0, and then feeding the effluent into a catalytic arsenic removal tower at the flow rate of 15 bv/h;
the fifth step: the pH of the effluent of the relay pool 2 is adjusted to 7, and 10 percent sodium bisulfite is added for reduction, so that orp is less than 300 mV. Entering a deep arsenic removal tower, wherein an unrecoverable filter material is used in the tower, the flow rate is 10bv/h, and the arsenic concentration of the effluent is less than 2 mug/L.
Example 2: in a certain LED semiconductor production enterprise, the high-concentration arsenic-containing wastewater quality of the enterprise is as follows: the designed water discharge is 20m 3/h, COD is 10-150 mg/L, SS is 0-400 mg/L, TAs is 50-250 mg/L, TP is 10-20 mg/L, and pH is 3-7. The process steps before modification are as follows:
the first step is as follows: adjusting the pH value of the collected arsenic-containing wastewater to 6.5-7.5, and reacting for 30 min; then the mixture enters an oxidation tank, 10% sodium hypochlorite is added, the ORP is maintained to be more than 400mV, the reaction time is 30min, and the effluent enters a reaction tank;
the second step is that: adding 20% ferric chloride into the reaction tank, adjusting the flow rate to be 288L/h and the pH value to be 7.5-9.5, carrying out coagulation reaction for 60min, then adding PAM, reacting for 30min, and entering a sedimentation tank. The hydraulic retention time of the sedimentation tank is 4.5h, the supernatant enters a relay water tank, and the hydraulic retention time of the relay water tank is 3 h;
the third step: the water from the relay tank enters a pH adjusting tank, the reaction time is 20min, and the pH is adjusted to 7.5; then adding sodium bisulfite (10 percent) to make the ORP less than 300mV, and then entering a resin tower; the resin tower adopts special arsenic-removing resin with the flow rate of 10bV/h, and the final arsenic concentration of the effluent is less than 50 mug/L.
The following problems exist in the operation process:
(1) due to untimely sludge discharge, the problem that sludge enters a subsequent working section along with effluent frequently occurs in a sedimentation tank, so that an inlet filter of a resin tower is blocked, and the service life of a filter element is shortened;
(2) the resin tower is regenerated frequently, and the arsenic removal resin needs to be regenerated every 1-2 weeks;
(3) the COD fluctuation of the inlet water is large, and the COD of the outlet water exceeds the standard (COD is more than 100 mg/L) in certain time periods.
The process comprises the following steps:
the first step is as follows: adjusting the pH value of the collected arsenic-containing wastewater to 7, and reacting for 30 min; then the mixture enters an oxidation tank, 10% sodium hypochlorite is added, the ORP is maintained to be more than 400mV, the reaction time is 30min, and the effluent enters a reaction tank;
the second step is that: adding 20% ferric chloride into the reaction tank, adjusting the flow rate to 216L/h and the pH value to 7, carrying out coagulation reaction for 30min, and feeding the mixture into a DF concentration tank;
the third step: 50g/L of arsenic removal agent is added into the wastewater of the concentration tank, and then the wastewater enters a DF membrane for filtration; after solid-liquid separation, clear liquid enters a relay tank, the average water inlet flow is 164t/h, and the average water yield is 24 t/h;
the fourth step: after being filtered by the relay tank 1, the effluent is supplemented with an iron compound medicament (Fe 2 +: Fe3+ =1: 2) for 3.6L/h, the pH is adjusted to 7.5-9.0, and then the effluent enters a catalytic arsenic removal tower at the flow rate of 15 bv/h;
the fifth step: adjusting the pH value of the effluent of the relay tank 2 to 6, adding 10% sodium bisulfite for reduction to make orp less than 300mV, and then entering a dephosphorization resin tower; the effluent of the dephosphorization resin tower is subjected to pH adjustment to 7.5 by a pipeline mixer, and then enters an arsenic removal resin adsorption filter material tower through a security filter, wherein the special arsenic removal resin is used in the tower, the flow rate is 20bv/h, and the arsenic concentration of the effluent is less than 2 mug/L;
compared with the prior art, the method has the following advantages:
(1) the problem of SS rising does not exist in the effluent filtered by the tubular microfiltration membrane, and meanwhile, part of COD can be removed by the activated carbon, so that the effluent is stable and reaches the standard; meanwhile, the tubular microfiltration membrane is combined with an arsenic removal medicament, so that the consumption of ferric chloride is reduced by 25%, and the TDS of the effluent is reduced by over 25%.
(2) The regeneration period of the terminal arsenic-removing resin is prolonged from 1 week to 80 days, and the emission of high-concentration arsenic-containing regeneration waste liquid is reduced by 90%;
(3) the arsenic concentration of the effluent is less than 2 mug/L, and the arsenic concentration of the effluent is reduced by 96 percent compared with the original arsenic concentration.
In summary, the present application has the following advantages;
1. the natural manganese sand is used for catalyzing, co-precipitating and removing arsenic, so that the adsorption effect of iron oxyhydroxide on arsenic is enhanced, and the removal effect of arsenic in a reactor is greatly improved. After absorbing arsenic, the iron oxyhydroxide is intercepted in the device by the filter material and can be removed by simple backwashing without regenerated chemical agents. And residual iron in water is removed synchronously, and resin poisoning is prevented.
2. The tubular microfiltration membrane system replaces the traditional sedimentation tank, saves facilities and land occupation, and is particularly suitable for projects with limited site space and high water outlet requirements. And the tubular microfiltration membrane is arranged, and the conventional sedimentation tank can be separated from water flow when the downward sedimentation time of suspended matters in liquid is shorter than the time of water flow flowing out of the sedimentation tank, so that a polyacrylamide polymer coagulant aid is required to be used for capturing fine flocs to form large and compact flocs, and the sinking speed of the large and compact flocs is increased. The tubular micro-filtration membrane uses a porous membrane (micro-filtration membrane) as a filtration medium, and suspended substances, micro-particles, bacteria and the like in a solution are trapped under the pushing of pressure. Thus, no coagulant aid is required. Thereby avoiding the use of high molecular organic flocculants such as polyacrylamide and the like, and effectively preventing the weakening of the adsorption effect of the high molecular organic matters on the resin.
3. The adsorption arsenic removal material is limited by adsorption capacity, and the high concentration of inlet water can cause frequent regeneration and shorten the service life. After the catalytic coprecipitation arsenic removal treatment, the regeneration frequency of the adsorption arsenic removal material is greatly reduced, and the service life is prolonged by more than 10 times.
4. Aiming at the arsenic-containing wastewater containing phosphate, the content of phosphate is reduced by adding the dephosphorization resin, so that the competition of high-concentration phosphate on the adsorption of arsenic is avoided.
5. The whole process has stable treatment effect and simple and convenient operation, the concentration of arsenic in the effluent is stabilized below 2 mug/L, the requirement of the special emission limit value of 0.04mg/L in the Integrated Water pollution discharge Standard of Beijing (DB 11/307-2013) is met, and even the high emission standard of less than 2 mug/L provided by some regions with serious environmental pollution is met.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (3)
1. A method for treating arsenic-containing wastewater comprises the following steps:
firstly, after the wastewater is collected, adding acid and alkali agents to adjust the pH value, and adding an oxidant to oxidize trivalent arsenic into pentavalent arsenic;
secondly, carrying out coagulation reaction on the mixed solution obtained by the treatment in the step one by adding an iron salt coagulant and adjusting the pH value;
the method is characterized in that: it also includes the following steps:
in the second step, the ferric salt coagulant contains ferric iron, so that the molar ratio of iron to arsenic in the solution is 2: 1-10: 1, after the coagulation reaction is finished and the pH is adjusted, supplementing an iron salt coagulant according to the content of phosphate in the wastewater, wherein the addition amount is that the molar ratio of iron to phosphorus is 1: 1-3: 1, then adjusting the pH value to 6.5-9.5;
thirdly, introducing the mixed solution obtained by the treatment in the second step into a concentration tank, wherein an arsenic removal medicament is added into the concentration tank, and the preparation method of the arsenic removal medicament comprises the following steps: adding every 10-20 g of activated carbon powder into 200 mL of 0.25 mol/L ferric chloride solution, stirring for 30-120 min, ultrasonically oscillating for 40-90 min, then adding sodium hydroxide solution, adjusting the pH value to 6.5-8.0, aging at room temperature, filtering, washing with pure water until the supernatant is colorless, drying, and adding an arsenic removal agent to enable the molar ratio of iron to arsenic in the solution to be 1: 1-10: 1; removing insoluble particulate matters through a tubular microfiltration membrane system;
fourthly, adding ferric salt into the mixed solution obtained by the treatment in the third step, wherein the ferric salt is an iron composite reagent, and the molar ratio of ferric ions to ferrous ions is 0.5: 1-2: 1, so that the molar ratio of iron to arsenic in the solution is 10: 1-50: 1; the arsenic concentration is further reduced by a catalytic arsenic removal tower, and a filter material of the catalytic arsenic removal tower is manganese sand or a medium containing a manganese dioxide coating;
fifthly, adding a reducing agent into the mixed liquid obtained by the treatment in the fourth step to enable the oxidation-reduction potential to be less than 300mV, adjusting the pH value to 5-9, then removing phosphorus through phosphorus removal resin, adjusting the pH value again, and then deeply removing arsenic through arsenic removal resin or arsenic removal filter material and discharging.
2. The method for treating arsenic-containing wastewater according to claim 1, wherein: in the first step, the pH is adjusted to 6-9, an oxidant is added, and the ORP is controlled to be more than 400 mV.
3. The method for treating arsenic-containing wastewater according to claim 1, wherein: in the fifth step, the water inflow velocity of the deep arsenic removal device is 10-30 bv/h, and the adsorption material is a reproducible strong-base anion exchange resin loaded with the hydroxyl iron oxide or a nonrenewable arsenic removal filter material based on titanium and hydroxyl iron oxide.
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| CN112299588A (en) * | 2019-07-25 | 2021-02-02 | 东泰高科装备科技有限公司 | Method for treating industrial wastewater with high content of organic matters and arsenic |
| CN110592806B (en) * | 2019-07-29 | 2021-09-07 | 同济大学 | Double-nanometer functional core-loaded arsenic-removing nanofiber membrane and preparation method thereof |
| CN110642460A (en) * | 2019-09-19 | 2020-01-03 | 济南大学 | Method for removing nitrogen and phosphorus by ferrate enhanced denitrification phosphorus removal biological filter |
| CN110498644B (en) * | 2019-09-26 | 2022-03-29 | 常熟理工学院 | Arsenic slag treatment method |
| CN112678987A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Treatment method and application of high-COD high-phosphorus heavy metal-containing sewage |
| CN113289573A (en) * | 2020-02-21 | 2021-08-24 | 苏州崇越工程有限公司 | Arsenic adsorbent, method for producing arsenic adsorbent, and system for treating arsenic-containing wastewater |
| CN113716775B (en) * | 2021-08-31 | 2022-05-03 | 四川恒泰环境技术有限责任公司 | Comprehensive treatment method for high-arsenic high-salt wastewater and arsenic-containing grinding wastewater of gallium arsenide chip |
| CN115893698A (en) * | 2021-09-30 | 2023-04-04 | 山东华光光电子股份有限公司 | Treatment process of high-concentration arsenic-phosphorus-containing wastewater generated by III-V compound semiconductor epitaxial process |
| CN116282699B (en) * | 2023-03-06 | 2023-12-05 | 武汉天源环保股份有限公司 | Semiconductor wastewater treatment method and system |
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| CN101423277A (en) * | 2008-12-01 | 2009-05-06 | 上海西恩化工设备有限公司 | Water purification process with arsenic removal function |
| CN104815611A (en) * | 2015-04-13 | 2015-08-05 | 北京工业大学 | Preparation method of iron oxide modified quartz sand filter material for adsorption removal of arsenic and phosphorus |
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| CN101423277A (en) * | 2008-12-01 | 2009-05-06 | 上海西恩化工设备有限公司 | Water purification process with arsenic removal function |
| CN104815611A (en) * | 2015-04-13 | 2015-08-05 | 北京工业大学 | Preparation method of iron oxide modified quartz sand filter material for adsorption removal of arsenic and phosphorus |
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