CN113666561A - High-salt sulfur-containing fluorine-containing wastewater treatment process - Google Patents
High-salt sulfur-containing fluorine-containing wastewater treatment process Download PDFInfo
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Abstract
The invention relates to a high-salt sulfur-containing fluorine-containing wastewater treatment process, which comprises the following steps: firstly, oxidizing sulfite into sulfate by forced oxidation of high-salt sulfur-containing fluorine-containing wastewater, and then adjusting the pH to be below 4 to remove carbonate in the wastewater; secondly, adjusting the pH value of the wastewater back to 5-10, adding a defluorinating agent to remove fluoride ions in the solution, separating and removing solid impurities from the generated suspension by a ceramic membrane, finally, adsorbing and removing calcium ions in the wastewater by ion exchange resin after the wastewater is subjected to solid removal, returning the wastewater generated by the regeneration of the ion exchange resin to a defluorinating reaction kettle to be used as the defluorinating agent, allowing the wastewater after the decalcification to enter MVR, recovering crude salt, performing filter pressing and separation on the solid impurities separated by the ceramic membrane by a box filter press, and returning the separated wastewater to a membrane separation tank. The invention improves the process flow of the traditional high-salt fluorine-containing wastewater, reduces the addition amount of the medicament and the generation amount of sludge, and solves the technical problem of overproof sewage discharge.
Description
Technical Field
The invention relates to a high-salt sulfur-containing fluorine-containing wastewater treatment process, and belongs to the technical field of fluorine chemical wastewater treatment.
Background
With the development of modern industry, a large amount of fluorine-containing industrial wastewater is generated in the production process of fluorine-related industry, the composition of the fluorine-containing wastewater is relatively complex, but fluorine elements in the fluorine-containing wastewater still exist in the forms of oxyfluormic acid, fluosilicic acid and soluble fluoride salt, a large amount of fluorine-containing wastewater is generated in various industries due to the development of industrial technology, and the fluorine ion concentration difference of the fluorine-containing wastewater is relatively large due to different characteristics of various industries. Because the wastewater is industrial wastewater, the fluorine-containing wastewater is accompanied by other pollutants such as inorganic salts and organic matters besides fluorine, and many enterprises do not have perfect water treatment facilities to treat the wastewater and then discharge the wastewater into the nature. Will seriously pollute the environment for human life and will pose a great threat to the human health. The adoption of the method for removing fluorine is comprehensively considered according to the water quality, water quantity and discharge standard of industrial wastewater, the characteristics, cost, recovery economic value and the like of a treatment method. The conventional industrial wastewater treatment methods are classified into physical treatment, chemical treatment, biochemical treatment, and physicochemical treatment according to the principle.
At present, a great deal of work has been carried out in the aspect of researching the treatment of the fluorine-containing wastewater at home and abroad, and CN201910865251.9 discloses the resource utilization of a deep defluorination resin desorption solution, wherein the defluorination resin is firstly used for carrying out adsorption treatment on the fluorine-containing wastewater, and then alkali liquor is used for desorption; adding alkali liquor into the produced desorption solution for carbonization, then adding a small amount of calcium oxide or calcium hydroxide into the desorption solution for precipitation and defluorination, and carrying out solid-liquid separation; calcium oxide or calcium hydroxide is added into the solution obtained after the solid-liquid separation for causticization reaction, then the supernatant after the solid-liquid separation is softened by resin to remove calcium, and the high-concentration alkali obtained by the causticization reaction can be used as a desorption agent, so that the resource recycling of the resin desorption solution for the advanced treatment of the fluorine-containing wastewater is effectively realized; CN202010690536.6 utilizes an external electric field to gather fluorine ions, separates waste water in a fluorine ion-enriched area from waste water in a few fluorine ion areas, removes fluorine from the waste water in the fluorine ion-enriched area by chemical precipitation, and separates, chemically precipitates and circulates the waste water after fluorine removal by using an external electrostatic field to enrich and separate the fluorine ions, thereby improving the fluorine removal efficiency and reducing the fluorine removal cost.
CN202010472584.8 discloses that the pH value of fluorine-containing waste water is adjusted to 3-8, chemical defluorinating agent is added for reaction, alkali is added for adjusting the pH value of reaction liquid to 6-9 after the reaction, polyacrylamide is added for flocculation reaction, and primary purified liquid and primary filter residue are obtained after solid-liquid separation; deeply removing fluorine from the primary purified liquid by using modified strong-base anion resin, and then deeply treating the fluorine in the wastewater by using a chemical precipitation method and the modified strong-base anion resin, wherein the fluorine content of the final effluent is stably lower than 1 mg/L.
In recent years, the national requirements for environmental protection are more and more strict, and the development of enterprises is restricted by the obvious long process and large dosage of medicaments of each treatment process at present, so that the development of a deep treatment method with simple process and excellent effect is urgently needed.
Disclosure of Invention
The invention aims to provide a high-salt sulfur-containing fluorine-containing wastewater treatment process to solve the problems of long process flow or large dosage of medicament in each treatment process in the prior art.
The purpose of the invention can be realized by the following technical scheme:
a high-salt sulfur-containing fluorine-containing wastewater treatment process comprises the following steps:
(1) forcibly oxidizing the high-salt sulfur-containing fluorine-containing wastewater, adjusting the pH to be less than 4, and then adjusting the pH back to 5-10;
(2) adding a fluorine removal agent into the treated wastewater with the pH adjusted back in the step (1), and performing fluorine removal precipitation reaction;
(3) carrying out solid-liquid separation (ceramic membrane filtration can be adopted) on the suspension obtained in the step (2) after the reaction, and sending the obtained liquid phase into an ion exchange resin tower for ion exchange adsorption to obtain softened wastewater; concentrating and filter-pressing the solid phase to obtain a mixture of calcium fluoride and calcium sulfate; (4) and (5) feeding the obtained softened wastewater into an MVR system, and separating out crude salt and water to finish the process.
Further, in the step (1), the forced oxidation method is one or a combination of two methods of blowing air, blowing ozone or adding hydrogen peroxide;
when the mode of blowing air or ozone is adopted, the aeration time is controlled to be 14-18 hours, and the aeration rate is 200-800 ml/min;
when the mode of adding hydrogen peroxide is adopted, the addition amount of the hydrogen peroxide meets the following requirements: the concentration of the catalyst in the wastewater is 1.5-3.0 wt%, and the reaction time after adding hydrogen peroxide is 30-50 min.
Further, in the step (2), the defluorinating agent is calcium chloride.
In the step (2), when the pH value of the treated wastewater is adjusted back to 5-7, the addition amount of the fluorine removal agent meets the following requirements: the molar ratio of calcium ions to fluoride ions in the wastewater is (1.5-2.0): 1;
when the pH value of the treated wastewater is adjusted back to 7-10, the molar ratio of calcium ions contained in the wastewater to fluorine ions in the wastewater is (2.0-3.0): 1.
Further, in the step (2), the solid-liquid separation process is carried out in a ceramic membrane separation tank, a ceramic membrane component for solid-liquid separation is arranged in the ceramic membrane separation tank, and an aeration component is arranged at a position 30-50mm away from the bottom of the ceramic membrane component.
Furthermore, in the step (2), the solid phase obtained by solid-liquid separation is concentrated and then sent to a filter press for filter pressing, and the liquid discharged by the filter press is returned to the step (2) for defluorination reaction.
Furthermore, in the step (2), after the ceramic membrane separation tank operates for a set time, the ceramic membrane component is subjected to back flush regeneration or chemical cleaning.
More preferably, in the step (2), EDTA or aluminum trichloride is used as the cleaning reagent in the chemical cleaning process.
Further, in the step (3), the ion exchange resin is a chelating resin (used when the TDS is more than 50000) for removing calcium and magnesium from high-salinity water, and a product which is conventional in the field and is commercially available is adopted.
Further, in the step (3), the ion exchange resin needs to be regenerated by using 4% -8% hydrochloric acid after being saturated by adsorption, the using amount of a regenerant hydrochloric acid is 2-5 times of the volume of the resin, the regenerated resin is neutralized by using sodium hydroxide, and the H-type resin is converted into the Na-type resin.
The invention utilizes forced oxidation to convert sulfite in the high-salt sulfur-containing fluorine-containing wastewater into normal salt, thereby preventing SO when the pH is adjusted, acidified and carbonate is removed2Overflowing to pollute the environment, then acidifying the wastewater obtained after forced oxidation to remove carbon, adjusting the pH value back, adding a defluorinating agent, and chemically precipitating to remove fluorine to generate suspension. The suspension enters a ceramic membrane separation tank, an aeration device is arranged at the position 30-50mm away from the bottom of a membrane component of the ceramic membrane separation tank, the surface of the membrane is cleaned through aeration disturbance, and solid phase and liquid phase are separated by the ceramic membrane. The solid phase obtained by ceramic membrane separation enters a box type filter press for recycling after being concentrated by a concentration tank, the solid phase is mainly calcium fluoride and can be recycled, and the liquid discharged from the filter press returns to a defluorination reaction kettle; and (3) introducing the obtained liquid-phase wastewater into an ion exchange resin tower for decalcification treatment, removing excessive calcium ions added in the defluorination reaction, and exchanging and adsorbing calcium and magnesium ions in the wastewater in the ion exchange resin tower to ensure that the wastewater reaches the softened water index. And (3) the obtained softened wastewater enters an MVR system, crude salt is separated out, one part of separated water is recycled, and the other part of separated water is directly discharged. And performing back flushing regeneration or chemical cleaning after the ceramic membrane separation operation for a period of time, and returning wastewater generated by ion exchange resin regeneration to the defluorination reaction kettle to serve as a defluorination agent. The invention utilizes the coupling process technology of 'forced oxidation + ceramic membrane separation + ion exchange resin', shortens the process flow, reduces the addition of chemical agents and the generation of solid wastes, recycles calcium ions, enables MVR to run for a long period and reduces energy consumption.
The limit of hydrogen peroxide is determined according to the content of sulfite in the wastewater, and chlorineThe addition amount of calcium chloride is determined by the concentration of fluoride ions in the wastewater after the defluorination reaction, excessive calcium chloride is added, calcium chloride medicament is wasted, the operation cost is increased, and Ca is added2+And the scale can be formed in the subsequent MVR evaporation and desalination, and the energy consumption is increased.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts 'ceramic membrane and ion exchange resin' to recycle green and environment-friendly materials, reduces the addition of the medicament, reduces the generation amount of sludge, and is green and economic.
(2) The invention creatively combines the integration of 'forced oxidation, chemical precipitation and fluorine removal, ceramic membrane separation and ion exchange and calcium removal', shortens the traditional process flow and improves the efficiency.
(3) The solid phase of the ceramic membrane separation method is mainly calcium fluoride, so that the ceramic membrane separation method can be used as a resource, the utilization rate of byproducts is improved, and the generation of solid waste is reduced.
(4) The solution obtained by regenerating the ion exchange resin with hydrochloric acid mainly contains calcium chloride, can be returned to the defluorination reaction kettle and used as a defluorination agent, and improves the utilization rate of calcium ions.
Drawings
FIG. 1 is a schematic flow diagram of the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
As shown in figure 1, the invention provides a high-salt sulfur-containing fluorine-containing wastewater treatment process, which comprises the following steps:
(1) the sulfite in the wastewater is converted into normal salt by forced oxidation of the sulfur-containing and fluorine-containing wastewater;
(2) forcibly adjusting the pH value of the wastewater after oxidation to be less than 4, removing carbonate ions in the wastewater, and then adjusting the pH value of the wastewater back to 5-10;
(3) pumping the wastewater with the adjusted pH value into a defluorination reaction kettle, and injecting a defluorination agent into the defluorination reaction kettle to generate calcium fluoride, calcium sulfate and the like;
(4) the suspension generated by defluorination reaction enters a ceramic membrane separation tank, an aeration device is arranged at the position 30-50mm away from the bottom of a membrane component of the ceramic membrane separation tank, the surface of the membrane is disturbed and cleaned by aeration, the solid phase and the liquid phase are separated by the ceramic membrane, and the solid phase enters a chamber type filter press after being concentrated by a concentration tank; the effluent phase wastewater separated by the ceramic membrane enters an ion exchange resin tower for decalcification treatment, and the liquid discharged from the filter press returns to the defluorination reaction kettle; performing back flushing regeneration or chemical cleaning for a period of time by ceramic membrane separation operation;
(5) calcium and magnesium ions in the wastewater are exchanged and adsorbed in an ion exchange resin tower, so that the wastewater reaches the softened water index;
(6) and (3) the wastewater softened by the ion exchange resin enters an MVR system, crude salt is separated out, and part of the separated water is recycled and part of the separated water is directly discharged.
The invention utilizes the coupling process technology of 'forced oxidation + ceramic membrane separation + ion exchange resin', shortens the process flow, reduces the addition of chemical agents and the generation of solid wastes, recycles calcium ions, enables MVR to run for a long period and reduces energy consumption. The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
The process flow is described below with reference to more specific examples.
In the following examples, unless otherwise specified, it is assumed that the starting materials or the treatment steps used are conventional commercial products or conventional techniques.
Example 1
On the basis of the above process flow shown in fig. 1, the process parameters of this embodiment are as follows:
the sulfate radical concentration in the wastewater containing sulfur and fluorine is 1.5%, the fluorine ion concentration is 499mg/L, 2% hydrogen peroxide (2% refers to the mass content of the added hydrogen peroxide in the wastewater) is added for reaction for 30min, the conversion rate of the sulfite radical ions is 99%, then hydrochloric acid is added, the pH value is adjusted to 3.5, the carbonate radical in the wastewater is removed, the pH value is adjusted to 5.5, and then, the hydrochloric acid is addedCalcium chloride is added to satisfy [ Ca ]2+/F-]1.5, F in the waste water after ceramic membrane separation-1The concentration is 20mg/L, calcium ions in the wastewater after the ceramic membrane separation are removed through ion exchange resin exchange, and the calcium ion concentration of the wastewater after calcium removal is 25mg/L, so that the softened water index is reached.
Example 2
On the basis of the above process flow shown in fig. 1, the process parameters of this embodiment are as follows:
the sulfate radical concentration in the wastewater containing sulfur and fluorine is 1.5%, the fluorine ion concentration is 499mg/L, 2.5% hydrogen peroxide (wherein 2.5% refers to the mass content of the added hydrogen peroxide in the wastewater) is added for reaction for 30min, the conversion rate of sulfite ions is 100%, then hydrochloric acid is added, the pH value is adjusted to 3.5, carbonate radicals in the wastewater are removed, the pH value is adjusted back to 5.5, calcium chloride is added, and the condition that [ Ca is satisfied2+/F-]1.5, F in the waste water after ceramic membrane separation-1The concentration is 18mg/L, calcium ions in the wastewater after the ceramic membrane separation are removed through ion exchange resin exchange, and the calcium ion concentration of the wastewater after calcium removal is 27mg/L, thereby reaching the index of softened water.
Embodiment 3
On the basis of the above process flow shown in fig. 1, the process parameters of this embodiment are as follows:
the sulfate radical concentration in the wastewater containing sulfur and fluorine is 2 percent, the fluorine ion concentration is 604mg/L, 3 percent hydrogen peroxide is added for reaction for 40min, the conversion rate of the sulfite radical ions is 100 percent, hydrochloric acid is added, the pH value is adjusted to 3, carbonate radicals in the wastewater are removed, the pH value is adjusted to 6.5, calcium chloride is added, and the requirement of [ Ca2+/F-]2.0, F in the waste water after ceramic membrane separation-1The concentration is 12mg/L, calcium ions in the wastewater after the ceramic membrane separation are removed through ion exchange resin exchange, and the calcium ion concentration of the wastewater after calcium removal is 35mg/L, so that the softened water index is reached.
Example 4
On the basis of the above process flow shown in fig. 1, the process parameters of this embodiment are as follows:
the sulfate radical concentration in the wastewater containing sulfur and fluorine is 1.5 percent, the fluorine ion concentration is 800mg/L, the aeration oxidation is carried out for 14 hours, and the aeration quantity is 200ml/min, 99% of sulfite ion conversion rate, adding hydrochloric acid, adjusting the pH value to 3.5, removing carbonate in the wastewater, adjusting the pH value to 7, adding calcium chloride and Ca2+/F-]2, F in the waste water after ceramic membrane separation-1The concentration is 20mg/L, calcium ions are removed through ion exchange resin exchange, and the calcium ion concentration of the waste water after calcium removal is 40mg/L, thereby reaching the index of softened water.
Example 5
On the basis of the above process flow shown in fig. 1, the process parameters of this embodiment are as follows:
the sulfate radical concentration in the wastewater containing sulfur and fluorine is 2.0 percent, the fluorine ion concentration is 800mg/L, aeration oxidation is carried out for 14 hours, the aeration amount is 200ml/min, the sulfite ion conversion rate is 99 percent, then hydrochloric acid is added, the pH value is adjusted to 3.5, carbonate radical in the wastewater is removed, the pH value is adjusted back to 7, calcium chloride and Ca are added2+/F-]2, F in the waste water after ceramic membrane separation-1The concentration is 20mg/L, calcium ions are removed through ion exchange resin exchange, and the calcium ion concentration of the waste water after calcium removal is 42mg/L, so that the index of softened water is reached.
Example 6
On the basis of the above process flow shown in fig. 1, the process parameters of this embodiment are as follows:
the sulfate radical concentration in the wastewater containing sulfur and fluorine is 2.0 percent, the fluorine ion concentration is 800mg/L, aeration oxidation is carried out for 14 hours, the aeration amount is 200ml/min, the sulfite ion conversion rate is 99 percent, then hydrochloric acid is added, the pH value is adjusted to 3.5, carbonate radical in the wastewater is removed, the pH value is adjusted back to 8, calcium chloride and Ca are added2+/F-]2, F in the waste water after ceramic membrane separation-1The concentration is 28mg/L, calcium ions are removed through ion exchange resin exchange, and the calcium ion concentration of the waste water after calcium removal is 45mg/L, so that the index of softened water is reached.
Example 7
On the basis of the above process flow shown in fig. 1, the process parameters of this embodiment are as follows:
the sulfate radical concentration in the wastewater containing sulfur and fluorine is 2.0 percent, the fluorine ion concentration is 800mg/L, the aeration oxidation is carried out for 14 hours, the aeration amount is 200ml/min, and sulfurous acidThe conversion rate of the root ions is 99 percent, hydrochloric acid is added, the pH value is adjusted to 3.5, carbonate in the wastewater is removed, the pH value is adjusted back to 8, calcium chloride and Ca are added2+/F-]2.5, F in the waste water after ceramic membrane separation-1The concentration is 21mg/L, calcium ions are removed through ion exchange resin exchange, and the calcium ion concentration of the waste water after calcium removal is 48mg/L, so that the index of softened water is reached.
Example 8
On the basis of the above process flow shown in fig. 1, the process parameters of this embodiment are as follows:
the sulfate radical concentration in the wastewater containing sulfur and fluorine is 2.0 percent, the fluorine ion concentration is 800mg/L, aeration oxidation is carried out for 14 hours, the aeration amount is 200ml/min, the sulfite ion conversion rate is 99 percent, then hydrochloric acid is added, the pH value is adjusted to 3.5, carbonate radical in the wastewater is removed, the pH value is adjusted back to 9, calcium chloride and Ca are added2+/F-]3, F in the waste water after ceramic membrane separation-1The concentration is 15mg/L, calcium ions are removed through ion exchange resin exchange, and the calcium ion concentration of the waste water after calcium removal is 52mg/L, so that the water softening index is reached.
Example 9
Compared with the embodiment 1, most of the method is the same, except that 1.5 percent of hydrogen peroxide is added.
Example 10
Compared to example 1, most of the same except that the pH was adjusted back to 5 before the addition of calcium chloride.
Example 11
Compared to example 8, most of the same was done, except that the pH was adjusted back to 10 before the addition of calcium chloride.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A high-salt sulfur-containing fluorine-containing wastewater treatment process is characterized by comprising the following steps:
(1) forcibly oxidizing the high-salt sulfur-containing fluorine-containing wastewater, adjusting the pH to be less than 4, and then adjusting the pH back to 5-10;
(2) adding a fluorine removal agent into the treated wastewater with the pH adjusted back in the step (1), and performing fluorine removal precipitation reaction;
(3) carrying out solid-liquid separation on the suspension obtained in the step (2) after the reaction, and sending the liquid phase into an ion exchange resin tower for ion exchange to adsorb calcium and magnesium ions to obtain softened wastewater; the solid phase is concentrated and pressed to obtain a mixture of calcium fluoride and calcium sulfate and then sent out;
(4) and (5) sending the obtained softened wastewater into an MVR system, and evaporating and separating out crude salt and water to finish the process.
2. The high-salt sulfur-containing fluorine-containing wastewater treatment process according to claim 1, wherein in the step (1), the forced oxidation method is one or a combination of two methods of blowing air, blowing ozone or adding hydrogen peroxide;
when the mode of blowing air or ozone is adopted, the aeration time is controlled to be 14-18 hours, and the aeration rate is 200-;
when the mode of adding hydrogen peroxide is adopted, the addition amount of the hydrogen peroxide meets the following requirements: the concentration of the catalyst in the wastewater is 1.5-3.0 wt%, and the reaction time after adding hydrogen peroxide is 30-50 min.
3. The process of claim 1, wherein in the step (2), the defluorinating agent is calcium chloride.
4. The process for treating high-salt sulfur-containing fluorine-containing wastewater according to claim 1 or 3, wherein in the step (2), when the pH of the wastewater is adjusted back to 5-7, the addition amount of the fluorine removal agent satisfies the following requirements: the molar ratio of calcium ions to fluoride ions in the wastewater is (1.5-2.0): 1;
when the pH value of the treated wastewater is adjusted back to 7-10, the molar ratio of calcium ions contained in the wastewater to fluorine ions in the wastewater is (2.0-3.0): 1.
5. The process for treating high-salt sulfur-and fluorine-containing wastewater according to claim 1, wherein in the step (2), the solid-liquid separation process is carried out in a ceramic membrane separation tank, a ceramic membrane module for solid-liquid separation is arranged in the ceramic membrane separation tank, and an aeration module is arranged at a position 30-50mm from the bottom of the ceramic membrane module.
6. The process for treating high-salt sulfur-containing fluorine-containing wastewater according to claim 5, wherein in the step (2), the solid phase obtained by solid-liquid separation is concentrated and then sent to a filter press for filter pressing, and the liquid discharged from the filter press is returned to the step (2) for defluorination reaction.
7. The process of claim 5, wherein in the step (2), the ceramic membrane module is subjected to back flush regeneration or chemical cleaning after the ceramic membrane separation tank is operated for a set time.
8. The process of claim 7, wherein EDTA or aluminum trichloride with a concentration of 0.1-0.2 mol/L is used as a cleaning agent in the step (2).
9. The process of claim 1, wherein in the step (3), the ion exchange resin is a chelating resin for removing calcium and magnesium from the high-salt water.
10. The process for treating high-salt sulfur-containing fluorine-containing wastewater according to claim 1, wherein in the step (3), the ion exchange resin is regenerated by using 4-8% hydrochloric acid after being saturated by adsorption, the amount of the hydrochloric acid used for regeneration is 2-5 times of the volume of the ion exchange resin, and the regenerated ion exchange resin is neutralized by using sodium hydroxide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115340221A (en) * | 2022-09-14 | 2022-11-15 | 深圳市环境科学研究院 | Deep defluorination treatment process and recycling system |
| CN115448522A (en) * | 2022-10-17 | 2022-12-09 | 北京国润伟业科技中心(有限合伙) | System and method for purifying high-salinity wastewater |
Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5609767A (en) * | 1994-05-11 | 1997-03-11 | Eisenmann; Erhard T. | Method for regeneration of electroless nickel plating solution |
| WO2012141896A1 (en) * | 2011-04-13 | 2012-10-18 | Molycorp Minerals, Llc | Rare earth removal of hydrated and hydroxyl species |
| US20140045248A1 (en) * | 2012-08-13 | 2014-02-13 | Enviro Water Minerals Company, Inc. | System for removing selenium from a feed stream |
| US20140069821A1 (en) * | 2012-05-23 | 2014-03-13 | High Sierra Energy, LP | System and method for treatment of produced waters |
| CN104445717A (en) * | 2014-11-13 | 2015-03-25 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | Synchronous fluorine-calcium removal treatment process for reverse osmosis concentrated liquor of waste water from lead-zinc smelting |
| CN105502782A (en) * | 2015-12-07 | 2016-04-20 | 湖南湘牛环保实业有限公司 | Technology for recovering water resources and salt from coking wastewater in coal chemical industry |
| CN105800885A (en) * | 2016-05-23 | 2016-07-27 | 北京今大禹环境技术股份有限公司 | Resource recycling and treatment system of high-concentration degradation-resistant salt-containing organic waste water |
| CN105800886A (en) * | 2016-05-23 | 2016-07-27 | 北京今大禹环境技术股份有限公司 | Resource recycling and treatment technology of high-concentration degradation-resistant salt-containing organic waste water |
| SE1551685A1 (en) * | 2015-12-21 | 2017-06-22 | Easymining Sweden Ab | Method and arrangement for recovery of salt |
| CN110204123A (en) * | 2019-04-16 | 2019-09-06 | 南京工业大学 | A kind of Resource comprehensive utilization method of Fipronil production abraum salt |
| CN110590012A (en) * | 2019-09-12 | 2019-12-20 | 南京大学 | Resource utilization method of deep defluorination resin desorption solution |
| CN110606612A (en) * | 2019-11-04 | 2019-12-24 | 江苏中电创新环境科技有限公司 | Coal coking high-salinity wastewater recycling treatment process |
| CN110683709A (en) * | 2019-07-15 | 2020-01-14 | 衢州市鼎盛化工科技有限公司 | Zero-discharge treatment method for fluorine-containing wastewater |
| CN111170544A (en) * | 2020-02-29 | 2020-05-19 | 北京中航泰达环保科技股份有限公司 | Zero discharge system and method for pretreatment wastewater of active coke desulfurization and denitrification and salt preparation from rich gas |
| CN111362283A (en) * | 2018-12-26 | 2020-07-03 | 广州金科水务工程有限公司 | Viscose waste water recycling treatment method |
| CN111762963A (en) * | 2020-06-23 | 2020-10-13 | 烟台金正环保科技有限公司 | High-salt high-COD sewage treatment zero-discharge process |
| CN112266099A (en) * | 2020-10-12 | 2021-01-26 | 内蒙古晶泰环境科技有限责任公司 | Mine fluorine-containing wastewater resource utilization system and process |
| CN112624447A (en) * | 2020-12-21 | 2021-04-09 | 杭州蓝然环境技术股份有限公司 | Zero-discharge comprehensive utilization treatment process for graphite wastewater |
| CN112939321A (en) * | 2021-02-04 | 2021-06-11 | 上海宝汇环境科技有限公司 | Steel wastewater zero-discharge treatment technology |
| CN113003845A (en) * | 2019-12-19 | 2021-06-22 | 山东理工大学 | Zero-emission treatment process and system for sewage with high sulfate content and high COD (chemical oxygen demand) |
-
2021
- 2021-08-26 CN CN202110988489.8A patent/CN113666561B/en active Active
Patent Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5609767A (en) * | 1994-05-11 | 1997-03-11 | Eisenmann; Erhard T. | Method for regeneration of electroless nickel plating solution |
| WO2012141896A1 (en) * | 2011-04-13 | 2012-10-18 | Molycorp Minerals, Llc | Rare earth removal of hydrated and hydroxyl species |
| US20140069821A1 (en) * | 2012-05-23 | 2014-03-13 | High Sierra Energy, LP | System and method for treatment of produced waters |
| US20140045248A1 (en) * | 2012-08-13 | 2014-02-13 | Enviro Water Minerals Company, Inc. | System for removing selenium from a feed stream |
| CN104445717A (en) * | 2014-11-13 | 2015-03-25 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | Synchronous fluorine-calcium removal treatment process for reverse osmosis concentrated liquor of waste water from lead-zinc smelting |
| CN105502782A (en) * | 2015-12-07 | 2016-04-20 | 湖南湘牛环保实业有限公司 | Technology for recovering water resources and salt from coking wastewater in coal chemical industry |
| SE1551685A1 (en) * | 2015-12-21 | 2017-06-22 | Easymining Sweden Ab | Method and arrangement for recovery of salt |
| CN105800885A (en) * | 2016-05-23 | 2016-07-27 | 北京今大禹环境技术股份有限公司 | Resource recycling and treatment system of high-concentration degradation-resistant salt-containing organic waste water |
| CN105800886A (en) * | 2016-05-23 | 2016-07-27 | 北京今大禹环境技术股份有限公司 | Resource recycling and treatment technology of high-concentration degradation-resistant salt-containing organic waste water |
| CN111362283A (en) * | 2018-12-26 | 2020-07-03 | 广州金科水务工程有限公司 | Viscose waste water recycling treatment method |
| CN110204123A (en) * | 2019-04-16 | 2019-09-06 | 南京工业大学 | A kind of Resource comprehensive utilization method of Fipronil production abraum salt |
| CN110683709A (en) * | 2019-07-15 | 2020-01-14 | 衢州市鼎盛化工科技有限公司 | Zero-discharge treatment method for fluorine-containing wastewater |
| CN110590012A (en) * | 2019-09-12 | 2019-12-20 | 南京大学 | Resource utilization method of deep defluorination resin desorption solution |
| CN110606612A (en) * | 2019-11-04 | 2019-12-24 | 江苏中电创新环境科技有限公司 | Coal coking high-salinity wastewater recycling treatment process |
| CN113003845A (en) * | 2019-12-19 | 2021-06-22 | 山东理工大学 | Zero-emission treatment process and system for sewage with high sulfate content and high COD (chemical oxygen demand) |
| CN111170544A (en) * | 2020-02-29 | 2020-05-19 | 北京中航泰达环保科技股份有限公司 | Zero discharge system and method for pretreatment wastewater of active coke desulfurization and denitrification and salt preparation from rich gas |
| CN111762963A (en) * | 2020-06-23 | 2020-10-13 | 烟台金正环保科技有限公司 | High-salt high-COD sewage treatment zero-discharge process |
| CN112266099A (en) * | 2020-10-12 | 2021-01-26 | 内蒙古晶泰环境科技有限责任公司 | Mine fluorine-containing wastewater resource utilization system and process |
| CN112624447A (en) * | 2020-12-21 | 2021-04-09 | 杭州蓝然环境技术股份有限公司 | Zero-discharge comprehensive utilization treatment process for graphite wastewater |
| CN112939321A (en) * | 2021-02-04 | 2021-06-11 | 上海宝汇环境科技有限公司 | Steel wastewater zero-discharge treatment technology |
Non-Patent Citations (2)
| Title |
|---|
| 牛健南: "第十五届国际水道会议专题", 《青岛理工大学学报》 * |
| 王晓晖;徐晓;卜二军;朱文玲;: "化学沉淀法处理离子交换含盐废水试验", 化工生产与技术 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115340221A (en) * | 2022-09-14 | 2022-11-15 | 深圳市环境科学研究院 | Deep defluorination treatment process and recycling system |
| CN115448522A (en) * | 2022-10-17 | 2022-12-09 | 北京国润伟业科技中心(有限合伙) | System and method for purifying high-salinity wastewater |
| CN115448522B (en) * | 2022-10-17 | 2024-01-30 | 北京国润伟业科技中心(有限合伙) | System and method for purifying water quality of high-salt wastewater |
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