NL2029939A - Treatment process for purifying chlorine-containing wastewater by crystallization of ammonium salt - Google Patents
Treatment process for purifying chlorine-containing wastewater by crystallization of ammonium salt Download PDFInfo
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- NL2029939A NL2029939A NL2029939A NL2029939A NL2029939A NL 2029939 A NL2029939 A NL 2029939A NL 2029939 A NL2029939 A NL 2029939A NL 2029939 A NL2029939 A NL 2029939A NL 2029939 A NL2029939 A NL 2029939A
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0259—Compounds of N, P, As, Sb, Bi
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0296—Nitrates of compounds other than those provided for in B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
-
- 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
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F2001/5218—Crystallization
-
- 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
- C02F2101/12—Halogens or halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Removal Of Specific Substances (AREA)
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Abstract
The invention relates to the technical field of wastewater treatment, and proposes a treatment process for purifying chlorine - containing wastewater by crystallization of ammonium salt, comprising the following steps: 81, simultaneously feeding a chloride ion absorbent and wastewater into a primary stirring tank to be stirred uniformly, and then standing for layering to separate the chloride ion absorbent and primary wastewater from the mixture; 82, feeding the primary wastewater obtained after the primary stirring treatment into a secondary stirring tank, filling a novel chloride ion absorbent into the secondary stirring tank at the same time to be stirred uniformly, and then standing for layering to obtain the treated clean water for reuse; S3, feeding the chlorine ion absorbent separated from the primary stirring tank into a regeneration tank to recover the chloride ion absorbent, and feeding the recovered chloride ion absorbent into the secondary stirring tank; and S4, feeding the chloride ion absorbent separated from the secondary stirring tank into the primary stirring tank, thereby forming a cycle. By adopting the above technical solution, a series of problems such as complicated desalting process, high energy consumption, large land occupation, high investment and production of hazardous wastes in the prior art are solved.
Description
CRYSTALLIZATION OF AMMONIUM SALT Technical Field The present invention relates to the technical field of wastewater treatment, in particular to a treatment process for purifying chlorine - containing wastewater by crystallization of ammonium salt. Background With the rapid development of industry, the volume of discharged wastewater has been increased sharply. Nowadays, natural water bodies, including rivers, lakes and oceans, are inevitably affected by industrial and agricultural wastewater and domestic sewage. Extremely high concentration of chloride ions in industrial circulating water will cause pitting corrosion, crevice corrosion and stress corrosion of heat exchange equipment, thereby threatening the production safety. Chloride ions in the solution may destroy passivation films on surfaces of various metals and alloys thereof, thereby easily causing various local corrosions to metal equipment, and bringing various troubles and hidden dangers to the normal operation of equipment, the realization of novel processes and the quality of products. With the increasingly strict requirements of environmental protection, in the trend of continuously strengthening the upgrading and transformation of industrial technologies and vigorously advocating energy conservation and emission reduction, the traditional methods for removing chlorine from industrial wastewater, including the chemical precipitation method, the membrane separation method, the electrochemical method, the ion exchange method and the traditional flocculation precipitation method, cannot meet the requirements of the industry due to easy secondary environmental pollution, high energy consumption and poor treatment effect. Summary The present invention proposes a treatment process for purifying chlorine - containing wastewater by crystallization of ammonium salt, to solve a series of problems such as complicated desalting process, high energy consumption, large land occupation, high investment and production of hazardous wastes in the prior art. The following technical solution is adopted by the present invention: A treatment process for purifying chlorine - containing wastewater by the crystallization of ammonium salt comprises the following steps: S1, simultaneously feeding a chloride ion absorbent and wastewater into a primary stirring tank to be stirred uniformly, and then standing for layering to separate the chloride ion absorbent and primary wastewater from the mixture;
S2, feeding the primary wastewater obtained after the primary stirring treatment into a secondary stirring tank, filling a novel chloride ion absorbent into the secondary stirring tank at the same time to be stirred uniformly, and then standing for layering to obtain the treated clean water for reuse; S3, feeding the chlorine ion absorbent separated from the primary stirring tank into a regeneration tank to recover the chloride ion absorbent, and feeding the recovered chloride ion absorbent into the secondary stirring tank; S4, feeding the chloride ion absorbent separated from the secondary stirring tank into the primary stirring tank, thereby forming a cycle.
As a further technical solution, the chloride ion absorbent comprises the following components in parts by weight: 100 - 150 parts of water - soluble chitosan, 50 - 80 parts of bismuth nitrate, 10 - 20 parts of polyvinyl alcohol, 5 - 10 parts of p - hydroxyacetophenone and 5 - 10 parts of 1 - methoxy - 2 - propanol.
As a further technical solution, a preparation method of the chloride ion absorbent comprises the following steps: S1, weighing and preparing materials; S2, adding water - soluble chitosan into water, heating up to 100°C, and adding bismuth nitrate while stirring, wherein the dosage of water is 1.5 - 2 times the mass of the water - soluble chitosan; S3, keeping the temperature at 100 - 120°C, sequentially adding polyvinyl alcohol, p - hydroxyacetophenone and 1 - methoxy - 2 - propanol into the mixture in step S2, and stirring for 2 h to obtain the chloride ion absorbent.
As a further technical solution, liquid ammonia or ammonium carbonate solution is placed in the regeneration tank in step S3.
As a further technical solution, the step S3 specifically comprises: feeding the chloride ion absorbent separated from the primary stirring tank into the regeneration tank to recover the chloride ion absorbent; taking out the saturated crystals after standing; centrifuging to separate salt and water; feeding the recovered chloride ion absorbent into the secondary stirring tank; and feeding the recovered clean water into the regeneration tank for recovery.
As a further technical solution, the treatment process for purifying chlorine - containing wastewater by the crystallization of ammonium salt comprises: absorbing the wastewater for three times by adding the wastewater into a tertiary stirring tank after the secondary stirring tank when the wastewater treated by the secondary stirring tank still fails to meet requirements.
Application of any of the above treatment process for purifying chlorine - containing wastewater by crystallization of ammonium salt in the treatment of electrical and steel wastewater is provided.
The present invention has principles and beneficial effects as follows.
1. The dechlorination process of the present invention has simple flow and few procedures, can adsorb the chloride ions by stirring twice, has good purification effect, can remove more than 95% of chloride ions, and usually can be completed within 0.5 h to achieve time saving and high efficiency.
2. The chloride ion absorbent in the present invention is prepared from a plurality of organic compounds and rare metal bismuth in strict proportion, so that chlorine can be removed efficiently by utilizing the relatively strong electronegativity of bismuth compounds in aqueous solution. Meanwhile, antichlor in the present invention contains a large number of hydroxyl groups, methoxy groups and carbonyl groups; the above functional groups can be taken as adsorption sites of various ions; therefore, besides the effect of adsorbing the chlorine ions, the present invention can also cooperatively remove calcium and magnesium ions in water, reduce the hardness of water, and prevent pipes from hazards due to corrosion and scaling.
3. The regeneration tank in the present invention generates an alkaline environment by utilizing ammonium carbonate or liquid ammonia, regenerates and recovers the chlorine ion absorbent which has absorbed chloride ions, and then replaces the chloride ions in the alkaline environment, thereby reducing the cost and recovering the resources. Since the concentration of chloride ions in the wastewater treated by the primary stirring tank is already very low, the chloride ion absorbent treated by the secondary stirring tank can directly enter the primary stirring tank, and the clean water treated by the secondary stirring tank can be directly reused.
Description of Drawings The present invention will be further described in detail below in combination with the accompanying drawings and specific embodiments.
Fig. 1 is a process flow chart of the present invention.
Detailed Description The technical solutions in embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Apparently, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those ordinary skilled in the art based on the embodiments of the present invention without contributing creative effort shall be involved in the protection scope of the present invention.
Embodiment 1 Preparation of a chloride ion absorbent: 10 kg of water - soluble chitosan was added into 15 kg of water; the mixture was heated up to 100°C and was added with 5 kg of bismuth nitrate while stirring; the temperature was kept at 100 - 120°C; and then, 1 kg of polyvinyl alcohol, 0.5 kg of p
- hydroxyacetophenone and 0.5 kg of 1 - methoxy - 2 - propanol were added and stirred for 2 h to obtain the chloride ion absorbent.
The chloride ion absorbent in the present embodiment is used for treating the industrial wastewater collected from a power plant in Tangshan according to the following steps: S1, the chlorine ion absorbent and wastewater were simultaneously fed into a primary stirring tank, stirred uniformly and then stood for layering; S2, the wastewater treated by the primary stirring was fed into a secondary stirring tank; and a novel chlorine ion absorbent was filled into the secondary stirring tank at the same time, stirred uniformly and then stood for layering to obtain the treated wastewater; S3, the chloride ion absorbent separated from the primary stirring tank was fed into a regeneration tank containing liquid ammonia to recover the chloride ion absorbent; the saturated crystals were taken out after standing; salt and water were separated through centrifugation; the recovered chloride ion absorbent was fed into the secondary stirring tank; and the recovered clean water was fed into the regeneration tank for recovery; S4, the chloride ion absorbent separated from the secondary stirring tank was fed into the primary stirring tank, thereby forming a cycle.
Embodiment 2 Preparation of a chloride ion absorbent: 15 kg of water - soluble chitosan was added into 30 kg of water; the mixture was heated up to 100°C and was added with 8 kg of bismuth nitrate while stirring; the temperature was kept at 100 - 120°C; and then, 2 kg of polyvinyl alcohol, 1 kg of p - hydroxyacetophenone and 1 kg of 1 - methoxy - 2 - propanol were added and stirred for 2 h to obtain the chloride ion absorbent.
The chloride ion absorbent in the present embodiment is used for treating the industrial wastewater collected from a power plant in Baoding according to the following steps: S1, the chlorine ion absorbent and wastewater were simultaneously fed into a primary stirring tank, stirred uniformly and then stood for layering; S2, the wastewater treated by the primary stirring was fed into a secondary stirring tank; and a novel chlorine ion absorbent was filled into the secondary stirring tank at the same time, stirred uniformly and then stood for layering to obtain the treated wastewater; S3, the chloride ion absorbent separated from the primary stirring tank was fed into a regeneration tank containing ammonium carbonate solution to recover the chloride ion absorbent; the saturated crystals were taken out after standing; salt and water were separated through centrifugation; the recovered chloride ion absorbent was fed into the secondary stirring tank; and the recovered clean water was fed into the regeneration tank for recovery; S4, the chloride ion absorbent separated from the secondary stirring tank was fed into the primary stirring tank, thereby forming a cycle.
Embodiment 3 Preparation of a chloride ion absorbent: 12 kg of water - soluble chitosan was added into 20 5 kg of water; the mixture was heated up to 100°C and was added with 7 kg of bismuth nitrate while stirring; the temperature was kept at 100 - 120°C; and then, 1.5 kg of polyvinyl alcohol, 0.8 kg of p - hydroxyacetophenone and 0.8 kg of 1 - methoxy - 2 - propanol were added and stirred for 2 h to obtain the chloride ion absorbent. The chloride ion absorbent in the present embodiment is used for treating the industrial wastewater used in embodiment 2 according to the following steps: S1, the chlorine ion absorbent and wastewater were simultaneously fed into a primary stirring tank, stirred uniformly and then stood for layering; S2, the wastewater treated by the primary stirring was fed into a secondary stirring tank; and a novel chlorine ion absorbent was filled into the secondary stirring tank at the same time, stirred uniformly and then stood for layering to obtain the treated wastewater; S3, the chloride ion absorbent separated from the primary stirring tank was fed into a regeneration tank containing ammonium carbonate solution to recover the chloride ion absorbent; the saturated crystals were taken out after standing; salt and water were separated through centrifugation; the recovered chloride ion absorbent was fed into the secondary stirring tank; and the recovered clean water was fed into the regeneration tank for recovery; S4, the chloride ion absorbent separated from the secondary stirring tank was fed into the primary stirring tank, thereby forming a cycle.
Reference example 1 Preparation of a chloride ion absorbent: 12 kg of water - soluble chitosan was added into 20 kg of water; the mixture was heated up to 100°C, was added with 7 kg of bismuth nitrate while stirring, and then was stirred for 2 h to obtain the chloride ion absorbent.
The same batch of wastewater in embodiment 3 was treated by the same process.
Reference example 2 Preparation of a chloride ion absorbent: 12 kg of water - soluble chitosan was added into 20 kg of water; the mixture was heated up to 100°C, and was added with 7 kg of bismuth nitrate while stirring; the temperature was kept at 100 - 120°C; and then, 0.8 kg of p - hydroxyacetophenone and 0.8 kg of 1 - methoxy - 2 - propanol were added and stirred for 2 h to obtain the chloride ion absorbent. The same batch of wastewater in embodiment 3 was treated by the same process. Reference example 3
A chlorine ion absorbent (Beijing Zhongyouya Environmental Science and Technology Co., Ltd.) was used to treat the same batch of wastewater in embodiment 3. The content of chloride ions was determined by a chloride ion analyzer; and the COD was determined by a COD rapid tester. The data obtained are as shown in Table 1.
Table 1 Chloride ion and COD values in embodiments 1 - 3 and reference examples 1-3 The chloride ion removal rates in the embodiments and the reference examples were calculated and counted as shown in Table 2 below.
Table 2 Chloride ion removal rates in the embodiments and the reference examples Embodiment Embodiment | Embodiment | Embodiment| Reference | Reference | Reference ee En er | ores | canes Chloride ion 85.00 97.27 97.00 74.15 83.59 89.07 orn | | TTT In treating chloride ions in the industrial sewage, the chloride ion absorbent in the embodiments of the present invention has a removal rate of up to 97.27%, which is much higher than that of the same type of chloride ion absorbents of other companies. When polyvinyl alcohol, p - hydroxyacetophenone and 1 - methoxy - 2 - propanol are not added in reference example 1, only chitosan and bismuth nitrate achieve the effects, thereby lowering the chloride ion absorption effect in comparison with embodiment 3. When polyvinyl alcohol is not added in reference example 2, the content of hydroxyl groups in the chloride ion absorbent is greatly reduced, thereby weakening the chloride ion absorption effect.
The above are only the preferred embodiments of the present invention, which are not intended to limit the present invention.
Any modification, equivalent replacement, improvement and the like made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.
Claims (7)
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CN202011462954.6A CN112723513B (en) | 2020-12-14 | 2020-12-14 | Treatment process for purifying chlorine-containing wastewater by ammonium salt crystallization |
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AU2011219469A1 (en) * | 2010-02-24 | 2012-10-18 | Ockert Tobias Van Niekerk | Water desalination and treatment system and method |
CN104479056B (en) * | 2014-11-14 | 2017-12-29 | 上海岚淼水处理科技有限公司 | A kind of macromolecule bismuth organic compound antichlor and preparation method thereof |
CN106699925B (en) * | 2016-12-29 | 2019-05-28 | 山西振东安特生物制药有限公司 | A kind of molten type chitosan-bismuth of acid and its preparation method and application |
CN107892375B (en) * | 2017-10-19 | 2021-08-06 | 上海交通大学 | Method for removing chloride ions in chlorine-containing solution |
CN108993391A (en) * | 2018-08-14 | 2018-12-14 | 长沙华盛新材料科技有限责任公司 | A kind of fluorine adsorbent and from fluorinated water removing recycling fluorine method |
CN110894113A (en) * | 2019-12-18 | 2020-03-20 | 镇江泽润环境科技有限公司 | Desulfurization wastewater dechlorination treatment method and desulfurization wastewater treatment equipment |
CN111908672A (en) * | 2020-06-29 | 2020-11-10 | 西安交通大学 | Method and system for adsorbing, removing and recycling chloride ions in chlorine-containing wastewater |
CN111620481B (en) * | 2020-07-29 | 2020-10-16 | 湖南大青生态科技有限公司 | Recycling treatment method of industrial wastewater containing chlorine and arsenic |
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