CN110877945A - Treatment method of high-salt high-organic matter industrial wastewater - Google Patents
Treatment method of high-salt high-organic matter industrial wastewater Download PDFInfo
- Publication number
- CN110877945A CN110877945A CN201911174711.XA CN201911174711A CN110877945A CN 110877945 A CN110877945 A CN 110877945A CN 201911174711 A CN201911174711 A CN 201911174711A CN 110877945 A CN110877945 A CN 110877945A
- Authority
- CN
- China
- Prior art keywords
- industrial wastewater
- ion exchange
- salt
- filtering
- oxidation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
Abstract
The invention relates to a method for treating high-salt high-organic matter industrial wastewater. The treatment method comprises the main steps of standing sedimentation, ion exchange, catalytic oxidation, secondary oxidation, evaporation concentration and the like, combines the technical characteristics of sedimentation, ion exchange, catalytic oxidation, secondary oxidation and physical evaporation, can realize effective separation and purification of inorganic salt through mutual synergistic action among the steps, finally obtains solid salt, can be used for raw saline water required by the ion membrane caustic soda industry, and really realizes harmless treatment and zero discharge of high-salt high-organic matter industrial wastewater. In addition, the treatment method is wide in application range, and can be used for treating high-salinity high-organic-matter industrial wastewater with TOC content of 10-100000 mg/L and inorganic salt content of 15-300 g/L.
Description
Technical Field
The invention relates to the field of wastewater treatment, in particular to a method for treating high-salt high-organic matter industrial wastewater.
Background
Due to the shortage of water resources, seawater is increasingly used in production and life, for example, in marine processing plants, toilets and the like are flushed with water, so that the resulting wastewater contains a large amount of inorganic salts. In addition, organic wastewater with high salinity can be generated in the production process of industries such as printing and dyeing, leather making, papermaking, chemical industry, pesticide and the like. The industrial wastewater with high salt content and high organic matter content is common wastewater which is difficult to treat, and generally refers to wastewater with the total salt content of more than 1 percent, high organic matter content and complex components. The high-salinity high-organic matter industrial wastewater can cause harm to the growth of microorganisms due to high salinity, and is difficult to be directly treated by a biological method; in addition, the organic matter content is high, the components are complex, the boiling point of some organic matters is lower than that of water, and the boiling point of some organic matters is higher than that of water, so that the organic matters are more difficult to effectively treat. Once entering the environment, the high-salt high-organic matter industrial wastewater can cause great damage to surrounding ecosystems, and is a well-recognized problem in the field of domestic and foreign wastewater treatment at present.
Compared with high-salt high-organic matter industrial wastewater containing other inorganic salts, the high-sodium chloride high-organic matter industrial wastewater is one of the most difficult to treat, and the main reasons are as follows: 1) the high sodium chloride wastewater has strong corrosivity, so that the temperature-resistant and corrosion-resistant investment of equipment is increased, and the service life is shortened; 2) the solubility of the sodium chloride has small change along with the temperature, and the adoption of the evaporation concentration process can cause large amount of evaporated water and high operation energy consumption; 3) compared with other inorganic salts, the sodium chloride has limited market demand, and the domestic by-product sodium chloride has large waste salt amount, extremely limited market path and deviation of waste salt recycling effect; 4) the existing process for treating the industrial wastewater with high sodium chloride and high organic matters is difficult to effectively remove the organic matters in the sodium chloride aqueous solution or the sodium chloride wet salt, so that the downstream applicable field is extremely limited. Therefore, compared with the high-salt high-organic industrial wastewater containing other inorganic salts, the high-sodium chloride high-organic industrial wastewater not only further improves the treatment requirement, but also greatly improves the development difficulty of the treatment process.
Researchers have conducted a great deal of research based on high-salt and high-organic industrial wastewater and disclosed various treatment methods, for example, CN105461157A discloses a zero discharge method of high-salt and high-organic industrial wastewater, which adopts a mode of 'submerged membrane bioreactor + nanofiltration + high-efficiency reverse osmosis + membrane distillation + evaporative crystallization' to treat high-salt and high-organic industrial wastewater. Although the method can be used for maximally recovering water resources while solving the problem of wastewater discharge and basically realizing zero discharge of high-salt high-organic matter industrial wastewater, nanofiltration concentrated water generated in the treatment process of the method is difficult to further treat, and nanofiltration membranes are easy to pollute and increase the input cost. CN106186537A discloses a new evaporative crystallization process for high-salt high-concentration organic wastewater, which is characterized in that the high-salt high-concentration organic wastewater is subjected to simple pretreatment of oil removal and high-efficiency filtration, and then is directly subjected to evaporative crystallization, and NaCl crystals generated by solid-liquid separation are treated or refined as hazardous waste. Although the method has simple process flow, the method has no obvious effect of removing high-concentration organic matters, and the NaCl crystals are used as hazardous wastes for treatment or refining, so that the operation cost is increased, and inorganic salt resources are wasted.
Although the above prior art discloses a treatment method for high-salt high-organic matter industrial wastewater, the method still has the problems of high equipment input cost or process operation cost, insufficient organic matter removal, ineffective utilization of inorganic salt resources and the like. Therefore, how to develop an effective method for treating industrial wastewater with high salt and high organic matter content, which can remove organic matter with complex components and difficult treatment and can realize effective utilization of inorganic salt resources, is a problem to be solved at present.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a method for treating high-salt high-organic matter industrial wastewater, which comprises the steps of standing and settling, ion exchange, catalytic oxidation, secondary oxidation, evaporation concentration and the like, and solid salt obtained by evaporation concentration is dissolved by pure water to obtain raw material salt water meeting the chlor-alkali industry standard. The treatment method provided by the invention is used for carrying out step-by-step treatment on the salt and organic matters in the industrial wastewater, so that the high-salt and high-organic-matter industrial wastewater can be effectively treated.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a method for treating high-salinity high-organic matter industrial wastewater, which comprises the following steps:
(1) standing and settling the high-salt high-organic matter industrial wastewater and filtering;
(2) carrying out ion exchange on the industrial wastewater filtered in the step (1);
(3) adjusting the industrial wastewater subjected to ion exchange in the step (2) to acidity, and then carrying out catalytic oxidation;
(4) adjusting the industrial wastewater subjected to catalytic oxidation in the step (3) to be alkaline, cooling and filtering, and performing secondary oxidation;
(5) and (4) purifying the industrial wastewater subjected to secondary oxidation in the step (4) by using resin, evaporating and concentrating, and filtering to obtain solid salt.
The high-salt high-organic-matter industrial wastewater mentioned in the invention refers to industrial wastewater with TOC content of 10-100000 mg/L and inorganic salt content of 15-300 g/L, and especially refers to industrial wastewater with TOC content of 1000-100000 mg/L and inorganic salt content of 50-250 g/L. Specifically, the TOC content may be 10mg/L, 100mg/L, 500mg/L, 1000mg/L, 5000mg/L, 10000mg/L, 30000mg/L, 50000mg/L, 70000mg/L, 100000mg/L, or the like, and the inorganic salt content may be 15g/L, 25g/L, 50g/L, 70g/L, 100g/L, 130g/L, 150g/L, 180g/L, 200g/L, 250g/L, or 300g/L or the like, but is not limited to the recited values, and other values not recited in the above numerical ranges are also applicable.
The treatment method provided by the invention combines sedimentation, ion exchange, catalytic oxidation, secondary oxidation and physical evaporation, and the steps are mutually synergistic, so that inorganic salt can be effectively separated and purified, and solid salt can be finally obtained and can be used as raw material brine required by the ionic membrane caustic soda industry.
The treatment method provided by the invention can realize the high-efficiency removal of organic matters under the synergistic oxidation action by sequentially carrying out catalytic oxidation on the industrial wastewater subjected to ion exchange under an acidic condition and then adjusting the industrial wastewater to be alkaline for secondary oxidation, and meanwhile, most of the catalyst introduced in the catalytic oxidation step can be removed by alkaline adjustment of the secondary oxidation, thereby providing favorable conditions for greatly improving the extraction rate of inorganic salts by subsequent evaporation and concentration.
In a preferred embodiment of the present invention, the time for standing and settling in step (1) is 0.5-100 h, for example, 0.5h, 1h, 5h, 10h, 24h, 30h, 36h, 48h, 60h, 70h or 100h, preferably 24-48 h.
Preferably, the temperature of the standing and settling in the step (1) is-15 to 100 ℃, for example, -15 ℃, 5 ℃, 0 ℃, 10 ℃, 25 ℃, 35 ℃, 50 ℃, 60 ℃, 70 ℃, 90 ℃ or 100 ℃, preferably 25 to 60 ℃.
Preferably, the filtration pore size of the filtration in the step (1) is 10 to 15000 meshes, such as 10 meshes, 30 meshes, 50 meshes, 100 meshes, 300 meshes, 500 meshes, 2000 meshes, 5000 meshes, 10000 meshes or 15000 meshes, and the like, and preferably 50 to 500 meshes.
The treatment method provided by the invention can effectively remove suspended matters in the high-salt high-organic matter industrial wastewater through standing sedimentation and filtration operation, thereby creating good conditions for subsequent ion exchange.
In a preferred embodiment of the present invention, the pH environment of the ion exchange in step (2) is 9 to 14, for example, 9, 10, 11, 12, 13, or 14, preferably 12 to 14.
The treatment method provided by the invention needs to perform proper pH adjustment according to the acidity and alkalinity of the industrial wastewater filtered in the step (1), and then performs the step (2), namely, when the industrial wastewater filtered in the step (1) is acidic or alkaline, the pH of the industrial wastewater is adjusted to be 9-14 in an alkaline environment by adopting an alkaline or acidic solution according to needs, so that the treatment method is more beneficial to ion exchange treatment.
Preferably, the ion exchange of step (2) is carried out using an ion exchange resin.
Preferably, the ion exchange resin is an acidic ion exchange resin, preferably a sulfonic acid type strongly acidic ion exchange resin.
The treatment method provided by the invention can better realize the exchange and separation of corresponding substances in the high-salt high-organic matter industrial wastewater by adopting the sulfonic acid type strong-acid ion exchange resin, and is more beneficial to subsequent related operations.
Preferably, the treatment temperature of the ion exchange in the step (2) is-15 to 100 ℃, for example, -15 ℃, -5 ℃, 0 ℃, 10 ℃, 30 ℃, 50 ℃, 60 ℃, 70 ℃, 90 ℃ or 100 ℃, and the like, and preferably 30 to 60 ℃.
Preferably, the adsorption feeding space velocity of the ion exchange in the step (2) is 0.1-100 h-1E.g. 0.1h-1、0.3h-1、0.5h-1、1h-1、5h-1、10h-1、30h-1、50h-1Or 100h-1Etc., preferably 0.5 to 10 hours-1。
In a preferred embodiment of the present invention, the acidic pH range in step (3) is 1 to 6, for example, 1, 2, 3, 4, 5, or 6, preferably 3 to 4.
Preferably, the adjustment to acidity in step (3) is adjusted with hydrochloric acid.
Preferably, the mass concentration of the hydrochloric acid is 1 to 35.5%, for example, 1%, 5%, 10%, 18%, 28%, 31%, 33%, 35.5%, etc., preferably 28 to 31%.
As a preferable technical scheme of the invention, the catalyst adopted in the catalysis in the step (3) is soluble transition metal chloride.
Preferably, the catalyst is any one or a mixture of at least two of ferric chloride, cobalt chloride, copper chloride, zinc chloride or manganese chloride, typical but non-limiting examples of which are: mixtures of ferric chloride and cobalt chloride, mixtures of ferric chloride and copper chloride, mixtures of zinc chloride and manganese chloride or mixtures of cobalt chloride and manganese chloride, and the like.
Preferably, the mass ratio of the catalyst to the industrial wastewater after the acidity adjustment in the step (3) is 1:100 to 100000, for example, 1:100, 1:500, 1:1000, 1:3000, 1:5000, 1:7000, 1:10000, 1:20000, 1:50000, 1:80000 or 1:100000, and preferably 1:5000 to 20000.
Preferably, the oxidizing agent used in the oxidation in step (3) is any one or a mixture of at least two of air, oxygen, hydrogen peroxide or sodium hypochlorite, and typical but non-limiting examples of the mixture are: a mixture of air and oxygen, a mixture of air and hydrogen peroxide, a mixture of air and sodium hypochlorite or a mixture of hydrogen peroxide and sodium hypochlorite, etc.
Preferably, the mass ratio of the available oxygen in the oxidant to the COD content in the industrial wastewater after the acidity adjustment in step (3) is 1-20: 1, such as 1:1, 5:1, 7:1, 10:1, 15:1, 18:1 or 20:1, and preferably 1-10: 1.
Preferably, the reaction temperature of the catalytic oxidation in the step (3) is 50 to 500 ℃, for example, 50 ℃, 100 ℃, 150 ℃, 200 ℃, 300 ℃, 400 ℃ or 500 ℃, and the like, and preferably 230 to 300 ℃.
Preferably, the reaction pressure of the catalytic oxidation in the step (3) is 0 to 100MPa gauge pressure, for example, 0MPa, 2MPa, 4MPa, 6MPa, 10MPa, 20MPa, 30MPa, 50MPa or 100MPa gauge pressure, and preferably 4 to 10MPa gauge pressure.
Preferably, the reaction residence time of the catalytic oxidation in the step (3) is 0.001 to 10 hours, such as 0.001 hour, 0.005 hour, 0.01 hour, 0.05 hour, 0.1 hour, 0.5 hour, 1 hour, 5 hours or 10 hours, and the like, and preferably 0.01 to 1 hour.
Preferably, the reactor for catalytic oxidation in step (3) is any one of a tank reactor, a tubular reactor, a tower reactor or a microchannel reactor or a combination of at least two of them, and typical but non-limiting examples of the combination are: a combination of a tank reactor and a tubular reactor, a combination of a tubular reactor and a tower reactor, a combination of a tower reactor and a microchannel reactor, a combination of a microchannel reactor and a tank reactor, and the like, preferably a microchannel reactor.
In a preferred embodiment of the present invention, the alkaline pH range in step (4) is 9 to 14, for example, 9, 10, 11, 12, 13, or 14, preferably 9 to 12.
Preferably, the temperature after the temperature reduction in the step (4) is-15 to 100 ℃, for example, -15 ℃, -5 ℃, 0 ℃, 10 ℃, 30 ℃, 40 ℃, 50 ℃, 70 ℃ or 100 ℃, and the like, and preferably 30 to 50 ℃.
Preferably, the filtration pore size of the filtration in the step (4) is 10 to 15000 meshes, such as 10 meshes, 50 meshes, 100 meshes, 300 meshes, 500 meshes, 1000 meshes, 5000 meshes, 10000 meshes or 15000 meshes, and the like, and preferably 50 to 500 meshes.
Preferably, the oxidant used in the secondary oxidation in step (4) is any one or a mixture of at least two of air, oxygen, ozone, hydrogen peroxide or sodium hypochlorite, and typical but non-limiting examples of the mixture are: a mixture of air and oxygen, a mixture of air and ozone, a mixture of ozone and hydrogen peroxide or a mixture of hydrogen peroxide and sodium hypochlorite, preferably ozone.
Preferably, the feeding molar ratio of the available oxygen in the oxidizing agent to the industrial wastewater after alkaline adjustment in the step (4) and temperature reduction and filtration is 0.0001-1: 1, such as 0.0001:1, 0.0005:1, 0.001:1, 0.005:1, 0.01:1, 0.05:1, 0.1:1, 0.5:1 or 1:1, and preferably 0.001-0.005: 1.
Preferably, the reaction temperature of the secondary oxidation in the step (4) is-15 to 150 ℃, for example, -15 ℃, -5 ℃, 0 ℃, 10 ℃, 30 ℃, 40 ℃, 50 ℃, 70 ℃, 100 ℃ or 150 ℃, and the like, and preferably 30 to 50 ℃.
Preferably, the reaction pressure of the secondary oxidation in the step (4) is 0 to 10MPa gauge pressure, such as 0MPa, 0.5MPa, 1MPa, 3MPa, 5MPa, 7MPa, 8MPa or 10MPa gauge pressure, and preferably 0 to 1MPa gauge pressure.
Preferably, the reaction residence time of the secondary oxidation in the step (4) is 1-3600 s, such as 1s, 10s, 100s, 300s, 500s, 1000s, 2000s, 3000s or 3600s, preferably 10-300 s.
Preferably, the reactor for the secondary oxidation in step (4) is any one of a tank reactor, a tubular reactor, a tower reactor or a microchannel reactor or a combination of at least two of them, and typical but non-limiting examples of the combination are: a combination of a tank reactor and a tubular reactor, a combination of a tubular reactor and a tower reactor, a combination of a tower reactor and a microchannel reactor, a combination of a microchannel reactor and a tank reactor, and the like, preferably a microchannel reactor.
The treatment method provided by the invention adopts the operation of firstly carrying out catalytic oxidation and then carrying out secondary oxidation, the firstly carrying out catalytic oxidation can accelerate the oxidation of easily-decomposed organic matters under the action of a catalyst, and then carrying out secondary oxidation can oxidize the remaining difficultly-decomposed organic matters and catalytic oxidation products, so that the efficient removal of the organic matters under the synergistic oxidation effect provides favorable conditions for the subsequent evaporation and concentration and the substantial improvement of the extraction rate of inorganic salts.
As a preferable technical scheme of the invention, chelating resin is adopted for the resin purification in the step (5).
Preferably, the resin purification temperature in step (5) is-15 to 100 ℃, such as-15 ℃, -5 ℃, 0 ℃, 10 ℃, 30 ℃, 50 ℃, 60 ℃, 70 ℃ or 100 ℃, preferably 30 to 60 ℃.
The chelating resin can remove heavy metal ions in industrial wastewater, can fully remove residual catalyst introduced in the catalytic oxidation step, and provides favorable conditions for greatly improving the extraction rate of inorganic salt by subsequent evaporation and concentration.
Preferably, the concentration ratio of the evaporation concentration in the step (5) is 40-90%, such as 40%, 50%, 65%, 70%, 80%, 85%, 90%, etc., preferably 80-85%.
Preferably, after the solid salt in the step (5) is dissolved by pure water, raw material brine meeting the requirements of the ionic membrane caustic soda industry is obtained.
Preferably, the concentrated mother liquor obtained by the evaporation and concentration in the step (5) is recycled to the step (1).
Preferably, the condensed water obtained by the evaporation and concentration in the step (5) is purified and then is reused in the preparation process of the raw material brine.
Preferably, the condensed water purification employs an ionic exchange resin, preferably a strongly basic anion exchange resin.
Preferably, the condensed water is purified at a temperature of 0 to 100 ℃, for example, 0 ℃, 10 ℃, 30 ℃, 50 ℃, 60 ℃, 70 ℃ or 100 ℃, preferably 30 to 60 ℃.
The treatment method provided by the invention can not only recover the solid salt containing sodium chloride, but also directly use the solid salt as the raw material saline water meeting the requirements of the ionic membrane caustic soda industry after being dissolved by pure water, thereby realizing high-efficiency recovery and reutilization; meanwhile, concentrated mother liquor obtained by evaporation and concentration can be directly refluxed and applied to the step (1) to realize recycling; and purifying the condensed water obtained by evaporation and concentration, and reusing the purified condensed water in the preparation process of the raw material brine. Therefore, the invention realizes the high-efficiency treatment and recovery of high-salt and high-organic matters. As a preferred technical solution of the present invention, the processing method comprises the steps of:
(1) standing and settling the high-salt high-organic matter industrial wastewater at a temperature of-15-100 ℃ for 0.5-100 h, and then filtering with a filtering aperture of 10-15000 meshes;
(2) carrying out ion exchange treatment on the industrial wastewater filtered in the step (1) at-15-100 ℃ by using sulfonic acid type strong-acid ion exchange resin, wherein the adsorption feeding airspeed is 0.1-100 h-1；
(3) Adjusting the pH of the industrial wastewater subjected to ion exchange in the step (2) to 1-6 by adopting hydrochloric acid with the mass concentration of 1-35.5%, adding a catalyst and an oxidant, and performing catalytic oxidation at 50-500 ℃ and the gauge pressure of 0-100 MPa, wherein the reaction residence time is 0.001-10 h;
(4) adjusting the pH of the industrial wastewater subjected to catalytic oxidation in the step (3) to 9-14, cooling to-15-100 ℃, filtering with a filtering pore size of 10-15000 meshes, adding an oxidant, and performing secondary oxidation at-15-150 ℃ and a gauge pressure of 0-10 MPa, wherein the reaction residence time is 1-3600 s;
(5) purifying the industrial wastewater subjected to secondary oxidation in the step (4) by using chelating resin at a temperature of-15-100 ℃, evaporating and concentrating the treated wastewater by 40-90%, and filtering to obtain solid salt;
dissolving the solid salt in the step (5) by using pure water to obtain raw material salt water meeting the requirements of the ionic membrane caustic soda industry;
refluxing and recycling the concentrated mother liquor obtained by the evaporation and concentration in the step (5) to the step (1);
and (5) purifying the condensate obtained by evaporation and concentration in the step (5) by using strongly basic anion exchange resin at the temperature of 0-100 ℃, and reusing the purified condensate in the preparation process of the raw material brine.
The second object of the present invention is to provide a solid salt obtained by the treatment method described in the first object.
As a preferred technical scheme of the invention, the solid salt is used for preparing raw material brine meeting the requirements of the ionic membrane caustic soda industry.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the method for treating the high-salt high-organic matter industrial wastewater has a wide application range, and can be used for treating the high-salt high-organic matter industrial wastewater with TOC content of 10-100000 mg/L and inorganic salt content of 15-300 g/L;
(2) the treatment method has the advantages of simple operation, short reaction period and low energy consumption, does not produce secondary pollution, and basically realizes 100 percent recycling and harmless treatment;
(3) according to the treatment method, the industrial wastewater after ion exchange is subjected to catalytic oxidation under an acidic condition in sequence, and then is adjusted to be alkaline for secondary oxidation, so that not only is the efficient removal of organic matters under the synergistic oxidation effect realized, but also most of catalysts introduced in the catalytic oxidation step can be removed through alkaline adjustment of secondary oxidation, and favorable conditions are provided for greatly improving the extraction rate of inorganic salts through subsequent evaporation and concentration;
(4) the treatment method can obtain solid salt through evaporation and concentration, and the solid salt can be used for raw material brine meeting the requirements of the ionic membrane caustic soda industry after being dissolved by pure water, thereby providing an effective way for harmlessness of inorganic salt and resource recycling.
Drawings
FIG. 1 is a flow chart of the method for treating high-salinity high-organic-content industrial wastewater provided by the invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The flow of the method for treating high-salt high-organic matter industrial wastewater provided by the invention is shown in figure 1, and the method specifically comprises the following steps:
(1) standing and settling the high-salt high-organic matter industrial wastewater and filtering;
(2) carrying out ion exchange on the industrial wastewater filtered in the step (1);
(3) adjusting the industrial wastewater subjected to ion exchange in the step (2) to acidity, and then carrying out catalytic oxidation;
(4) adjusting the industrial wastewater subjected to catalytic oxidation in the step (3) to be alkaline, cooling and filtering, and performing secondary oxidation;
(5) purifying the industrial wastewater subjected to secondary oxidation in the step (4) by using resin, evaporating and concentrating, and filtering to obtain solid salt;
dissolving the solid salt in the step (5) by using pure water to obtain raw material salt water meeting the requirements of the ionic membrane caustic soda industry;
refluxing and recycling the concentrated mother liquor obtained by the evaporation and concentration in the step (5) to the step (1);
and (5) purifying the condensed water obtained by evaporation and concentration in the step (5) and reusing the purified condensed water in the preparation process of the raw material brine.
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples.
Example 1
A treatment method of industrial wastewater generated in the production of a rubber accelerator CBS comprises the following steps:
(1) standing and settling industrial wastewater generated in the production of the rubber accelerator CBS at 30 ℃ for 3h, and then filtering with the filter aperture of 500 meshes;
(2) performing ion exchange treatment on the industrial wastewater filtered in the step (1) at the temperature of 30 ℃ and the pH of 13 by adopting a blue-Dai scientific and technological XDA-200 type sulfonic acid strongly acidic ion exchange resin, and adsorbing the industrial wastewater intoThe space velocity of the material is 4h-1；
(3) Adjusting the pH value of the industrial wastewater subjected to ion exchange in the step (2) to 4 by adopting hydrochloric acid with the mass concentration of 30%, adding copper chloride and cobalt chloride which are used as catalysts in the mass ratio of 1:1, adjusting the mass ratio of the catalysts to the industrial wastewater subjected to acidity adjustment in the step (3) to 1:10000, uniformly stirring, pumping into a microchannel reactor, performing catalytic oxidation reaction by using oxygen as an oxidant at 300 ℃ and 10MPa gauge pressure, adjusting the mass ratio of the oxygen feeding mass to the COD content in the industrial wastewater subjected to acidity adjustment in the step (3) to 1.5:1, and keeping the reaction time to 0.01 h;
(4) adjusting the pH value of the industrial wastewater subjected to catalytic oxidation in the step (3) to 12, then cooling to 35 ℃, filtering with the filter pore size of 500 meshes, pumping into a microchannel reactor, performing secondary oxidation by using ozone as an oxidant at the temperature of 35 ℃ and the gauge pressure of 0.03MPa, adjusting the feeding molar ratio of the ozone to the industrial wastewater subjected to cooling filtration in the step (4) to be alkaline, wherein the feeding molar ratio of the ozone to the industrial wastewater subjected to catalytic oxidation in the step (4) is 0.005:1, and the reaction residence time is 300 s;
(5) purifying the industrial wastewater subjected to secondary oxidation in the step (4) by adopting blue-known scientific and technological LSC500 chelating resin at 35 ℃, evaporating and concentrating the treated wastewater by 80%, and filtering to obtain solid salt;
wherein, the solid salt in the step (5) is added with pure water according to the weight ratio of the solid salt: dissolving pure water in a mass ratio of 3:10 to obtain raw material brine meeting the requirements of the ionic membrane caustic soda industry;
refluxing and recycling the concentrated mother liquor obtained by the evaporation and concentration in the step (5) to the step (1);
and (5) purifying the condensate obtained by evaporation and concentration in the step (5) by adopting blue-well-know technology XDA-1 type strongly-basic anion exchange resin at 35 ℃, and reusing the purified condensate in the preparation process of the raw material brine.
The rubber accelerator CBS of example 1 gives the relevant composition of the industrial waste water from the production of CBS and the raw brine obtained after treatment, as shown in Table 1.
TABLE 1
Example 2
A treatment method of industrial wastewater generated in rubber antioxidant TMQ production comprises the following steps:
(1) standing and settling industrial wastewater generated in the production of the rubber antioxidant TMQ at 25 ℃ for 48h, and then filtering with the filtering aperture of 50 meshes;
(2) carrying out ion exchange treatment on the industrial wastewater filtered in the step (1) at the temperature of 60 ℃ and the pH value of 14 by adopting AMBERJET 1000NA sulfonic acid type strong-acid ion exchange resin, wherein the adsorption feeding airspeed is 1h-1；
(3) Adjusting the pH value of the industrial wastewater subjected to ion exchange in the step (2) to 3 by adopting hydrochloric acid with the mass concentration of 28%, adding copper chloride as a catalyst, uniformly stirring the copper chloride and the industrial wastewater subjected to acidity adjustment in the step (3) to obtain a mass ratio of 1:100000, pumping the mixture into a microchannel reactor, performing catalytic oxidation reaction by using air as an oxidant at 230 ℃ and at a gauge pressure of 4MPa, wherein the mass ratio of the available oxygen in the air to the COD content in the industrial wastewater subjected to acidity adjustment in the step (3) is 2:1, and the reaction residence time is 1 h;
(4) adjusting the pH value of the industrial wastewater subjected to catalytic oxidation in the step (3) to 12, then cooling to 50 ℃, filtering with the filter pore size of 500 meshes, pumping into a microchannel reactor, performing secondary oxidation by using ozone as an oxidant at the temperature of 30 ℃ and the gauge pressure of 0.3MPa, adjusting the feeding molar ratio of the ozone to the industrial wastewater subjected to cooling filtration in the step (4) to be alkaline, and keeping the reaction time at 10 s;
(5) purifying the industrial wastewater subjected to secondary oxidation in the step (4) by adopting blue-known scientific and technological LSC500 chelating resin at 30 ℃, evaporating and concentrating the treated wastewater by 85%, and filtering to obtain solid salt;
wherein, the solid salt in the step (5) is added with pure water according to the weight ratio of the solid salt: dissolving pure water in a mass ratio of 3:10 to obtain raw material brine meeting the requirements of the ionic membrane caustic soda industry;
refluxing and recycling the concentrated mother liquor obtained by the evaporation and concentration in the step (5) to the step (1);
and (5) purifying the condensed water obtained by evaporation and concentration in the step (5) by adopting AMBERJET 4000CL strongly-basic anion exchange resin at the temperature of 30 ℃, and then reusing the purified condensed water in the preparation process of the raw material brine.
The relative compositions of the industrial wastewater from the production of rubber antioxidant TMQ of example 2 and the raw brine obtained after the treatment are shown in Table 2.
TABLE 2
Example 3
A method for treating industrial wastewater generated in the production of N-tert-butyl-2-benzothiazole sulfonamide comprises the following steps:
(1) standing and settling industrial wastewater generated in the production of the N-tert-butyl-2-benzothiazole sulfonamide for 24 hours at the temperature of 60 ℃, and then filtering with the filter aperture of 5000 meshes;
(2) the industrial wastewater filtered in the step (1) is treated at the temperature of 70 ℃ under the condition that the pH value is 12
MonoPlus S100 sulfonic acid type strong acid ion exchange resin is subjected to ion exchange treatment, and the adsorption feeding airspeed is 0.5h-1；
(3) Adjusting the pH of the industrial wastewater subjected to ion exchange in the step (2) to 3.5 by adopting hydrochloric acid with the mass concentration of 31%, adding copper chloride, ferric chloride and cobalt chloride which are used as catalysts in the mass ratio of 20:1:1, adjusting the mass ratio of the catalysts to the industrial wastewater subjected to acidity in the step (3) to 1:20000, uniformly stirring, pumping into a microchannel reactor, performing catalytic oxidation reaction by using oxygen as an oxidant at 270 ℃ and 6MPa gauge pressure, adjusting the mass ratio of the oxygen feeding mass to the COD content in the industrial wastewater subjected to acidity in the step (3) to 10:1, and keeping the reaction time to 0.1 h;
(4) adjusting the pH value of the industrial wastewater subjected to catalytic oxidation in the step (3) to 14, then cooling to 40 ℃, filtering with the filter pore size of 800 meshes, pumping into a microchannel reactor, performing secondary oxidation by using ozone as an oxidant at 50 ℃ and under 0.01MPa of gauge pressure, adjusting the feeding molar ratio of the ozone to the industrial wastewater subjected to cooling and filtration in the step (4) to be alkaline, wherein the feeding molar ratio of the ozone to the industrial wastewater subjected to catalytic oxidation is 0.005:1, and the reaction retention time is 100 s;
(5) the industrial wastewater after the secondary oxidation in the step (4) is firstly adopted
Purifying MonoPlus TP 207 chelate resin at 60 ℃, evaporating and concentrating the treated wastewater by 90%, and filtering to obtain solid salt;
wherein, the solid salt in the step (5) is added with pure water according to the weight ratio of the solid salt: dissolving pure water in a mass ratio of 3:10 to obtain raw material brine meeting the requirements of the ionic membrane caustic soda industry;
refluxing and recycling the concentrated mother liquor obtained by the evaporation and concentration in the step (5) to the step (1);
condensing water obtained by evaporation and concentration in the step (5) adopts
The M + MP 800 strongly basic anion exchange resin is purified at 60 ℃ and then reused in the preparation process of the raw material brine.
The relative composition of the industrial waste water from the production of N-tert-butyl-2-benzothiazolesulfenamide of example 3 and the raw brine obtained after treatment are shown in Table 3.
TABLE 3
Example 4
A treatment method of rubber vulcanization accelerator DCBS industrial wastewater comprises the following steps:
(1) standing and settling the rubber vulcanization accelerator DCBS industrial wastewater for 10h at 20 ℃, and then filtering with the filtering aperture of 30 meshes;
(2) adjusting the pH of the industrial wastewater filtered in the step (1) to 13 by adopting a sodium hydroxide solution with the mass concentration of 29%, and then carrying out ion exchange treatment by adopting AMBERJET 1000NA sulfonic acid type strong-acid ion exchange resin at the temperature of 30 ℃, wherein the adsorption feeding airspeed is 3h-1；
(3) Adjusting the pH of the industrial wastewater subjected to ion exchange in the step (2) to 4 by adopting hydrochloric acid with the mass concentration of 10%, adding copper chloride and cobalt chloride which are used as catalysts in the mass ratio of 5:1, adjusting the mass ratio of the catalysts to the industrial wastewater subjected to acidity in the step (3) to 1:15000, uniformly stirring, pumping into a microchannel reactor, performing catalytic oxidation reaction by using oxygen as an oxidant at 260 ℃ and under the gauge pressure of 5.5MPa, adjusting the mass ratio of the oxygen feeding mass to the COD content in the industrial wastewater subjected to acidity in the step (3) to 5:1, and keeping the reaction time to 0.2 h;
(4) adjusting the pH value of the industrial wastewater subjected to catalytic oxidation in the step (3) to 13, then cooling to 40 ℃, filtering with the filter aperture of 5000 meshes, pumping into a microchannel reactor, performing secondary oxidation by using ozone as an oxidant at 40 ℃ and under the gauge pressure of 0.1MPa, adjusting the feeding molar ratio of the ozone to the industrial wastewater subjected to cooling and filtration in the step (4) to be alkaline, wherein the feeding molar ratio of the ozone to the industrial wastewater subjected to catalytic oxidation is 0.05:1, and the reaction retention time is 200 s;
(5) the industrial wastewater after the secondary oxidation in the step (4) is firstly adopted
Purifying MonoPlus TP 207 chelate resin at 35 ℃, evaporating and concentrating the treated wastewater by 70%, and filtering to obtain solid salt;
wherein, the solid salt in the step (5) is added with pure water according to the weight ratio of the solid salt: dissolving pure water in a mass ratio of 3:10 to obtain raw material brine meeting the requirements of the ionic membrane caustic soda industry;
refluxing and recycling the concentrated mother liquor obtained by the evaporation and concentration in the step (5) to the step (1);
condensing water obtained by evaporation and concentration in the step (5) adopts
The M + MP 800 strongly basic anion exchange resin is purified at 35 ℃ and then reused in the preparation process of the raw material brine.
The rubber vulcanization accelerator DCBS industrial waste water of example 4 and the composition of the raw material brine obtained after the treatment are shown in table 4.
TABLE 4
Comparative example 1
In the comparative example, the step (3) is adjusted as follows, other process conditions are the same as those in the example 1, and the specific operation is as follows:
(3) adjusting the pH of the industrial wastewater subjected to ion exchange in the step (2) to 4 by adopting hydrochloric acid with the mass concentration of 30%, and then pumping the industrial wastewater into a microchannel reactor to react for 0.01h at the temperature of 300 ℃ and the gauge pressure of 10 MPa.
Comparative example 2
In the comparative example, the step (4) is adjusted as follows, other process conditions are the same as those in the example 1, and the specific operation is as follows:
(4) adjusting the pH value of the industrial wastewater subjected to catalytic oxidation in the step (3) to 12, cooling to 35 ℃, filtering with the filter pore size of 500 meshes, pumping into a microchannel reactor, and reacting at 35 ℃ and a gauge pressure of 0.03MPa for a retention time of 300 s.
The raw brine obtained after the above examples and comparative examples is now summarized in table 5.
TABLE 5
The test results in table 5 show that: in examples 1 to 4, the raw material brine obtained by the treatment method provided by the invention has the characteristics that the NaCl content is 300g/L, the metal cation content is low, the content of suspended solid is less than 1mg/L, TOC and less than 10mg/L, pH, and the content is between 9 and 11, and can meet the requirements of the ionic membrane caustic soda industry. Comparative example 1 the treatment method did not completely decompose the organic substances by oxidation because no catalytic oxidation operation was performed in step (3), and the obtained raw brine had an organic nitrogen content as high as 55mg/L and a TOC content as high as 842 mg/L. Comparative example 2 because the secondary oxidation operation was not performed in step (4), the treatment method failed to oxidatively decompose residual catalytic oxidation products and hardly decomposed organic substances in the industrial wastewater, and the TOC content in the raw brine reached as high as 350 mg/L. Therefore, the treatment method can effectively treat various high-salt high-organic matter industrial wastewater, and the obtained solid salt is used for preparing raw material brine meeting the requirements of the ionic membrane caustic soda industry.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A treatment method of high-salt high-organic matter industrial wastewater is characterized by comprising the following steps:
(1) standing and settling the high-salt high-organic matter industrial wastewater and filtering;
(2) carrying out ion exchange on the industrial wastewater filtered in the step (1);
(3) adjusting the industrial wastewater subjected to ion exchange in the step (2) to acidity, and then carrying out catalytic oxidation;
(4) adjusting the industrial wastewater subjected to catalytic oxidation in the step (3) to be alkaline, cooling and filtering, and performing secondary oxidation;
(5) and (4) purifying the industrial wastewater subjected to secondary oxidation in the step (4) by using resin, evaporating and concentrating, and filtering to obtain solid salt.
2. The treatment method according to claim 1, wherein the standing and settling time in the step (1) is 0.5-100 h, preferably 24-48 h;
preferably, the temperature of the standing and sedimentation in the step (1) is-15 to 100 ℃, and preferably 25 to 60 ℃;
preferably, the filtration pore size of the filtration in the step (1) is 10-15000 meshes, preferably 50-500 meshes.
3. The treatment according to claim 1 or 2, wherein the pH environment of the ion exchange in step (2) is 9 to 14, preferably 12 to 14;
preferably, the ion exchange of step (2) is treated with an ion exchange resin;
preferably, the ion exchange resin is an acidic ion exchange resin, preferably a sulfonic acid type strongly acidic ion exchange resin;
preferably, the treatment temperature of the ion exchange in the step (2) is-15-100 ℃, and preferably 30-60 ℃;
preferably, the adsorption feeding space velocity of the ion exchange in the step (2) is 0.1-100 h-1Preferably 0.5 to 10 hours-1。
4. The treatment according to any one of claims 1 to 3, wherein the acidic pH in step (3) is in the range of 1 to 6, preferably 3 to 4;
preferably, the acidity adjustment in the step (3) is adjusted by hydrochloric acid;
preferably, the mass concentration of the hydrochloric acid is 1-35.5%, and preferably 28-31%.
5. The process according to any one of claims 1 to 4, wherein the catalyst used in the catalysis of step (3) is a soluble transition metal chloride;
preferably, the catalyst is any one or a mixture of at least two of ferric chloride, cobalt chloride, copper chloride, zinc chloride or manganese chloride;
preferably, the mass ratio of the catalyst to the industrial wastewater which is adjusted to be acidic in the step (3) is 1: 100-100000, preferably 1: 5000-20000;
preferably, the oxidant used in the oxidation in the step (3) is any one or a mixture of at least two of air, oxygen, hydrogen peroxide or sodium hypochlorite;
preferably, the mass ratio of the available oxygen in the oxidant to the COD content in the industrial wastewater which is adjusted to be acidic in the step (3) is 1-20: 1, and preferably 1-10: 1;
preferably, the reaction temperature of the catalytic oxidation in the step (3) is 50-500 ℃, and preferably 230-300 ℃;
preferably, the reaction pressure of the catalytic oxidation in the step (3) is 0-100 MPa gauge pressure, preferably 4-10 MPa gauge pressure;
preferably, the reaction residence time of the catalytic oxidation in the step (3) is 0.001-10 h, preferably 0.01-1 h;
preferably, the reactor for catalytic oxidation in step (3) is any one or a combination of at least two of a tank reactor, a tubular reactor, a tower reactor and a microchannel reactor, and is preferably a microchannel reactor.
6. The treatment according to any one of claims 1 to 5, wherein the alkaline pH in step (4) is in the range of 9 to 14, preferably 9 to 12;
preferably, the temperature after the temperature reduction in the step (4) is-15 to 100 ℃, and preferably 30 to 50 ℃;
preferably, the filtering pore size of the filtering in the step (4) is 10-15000 meshes, preferably 50-500 meshes;
preferably, the oxidant used in the secondary oxidation in the step (4) is any one or a mixture of at least two of air, oxygen, ozone, hydrogen peroxide or sodium hypochlorite, and is preferably ozone;
preferably, the feeding molar ratio of the available oxygen in the oxidant to the industrial wastewater subjected to alkaline adjustment in the step (4) and temperature reduction and filtration is 0.0001-1: 1, preferably 0.001-0.005: 1;
preferably, the reaction temperature of the secondary oxidation in the step (4) is-15 to 150 ℃, and preferably 30 to 50 ℃;
preferably, the reaction pressure of the secondary oxidation in the step (4) is 0-10 MPa gauge pressure, preferably 0-1 MPa gauge pressure;
preferably, the reaction residence time of the secondary oxidation in the step (4) is 1-3600 s, preferably 10-300 s;
preferably, the reactor for the secondary oxidation in the step (4) is any one or a combination of at least two of a tank reactor, a tubular reactor, a tower reactor and a microchannel reactor, and is preferably a microchannel reactor.
7. The process of any one of claims 1 to 6, wherein the resin purification of step (5) employs a chelating resin;
preferably, the resin purification temperature in the step (5) is-15-100 ℃, and preferably 30-60 ℃;
preferably, the concentration proportion of the evaporation concentration in the step (5) is 40-90%, and preferably 80-85%;
preferably, after the solid salt in the step (5) is dissolved by pure water, raw material salt water meeting the requirements of the ionic membrane caustic soda industry is obtained;
preferably, the concentrated mother liquor obtained by the evaporation and concentration in the step (5) is recycled to the step (1);
preferably, the condensed water obtained by the evaporation and concentration in the step (5) is purified and then is reused in the preparation process of the raw material brine;
preferably, the condensed water purification employs an ionic exchange resin, preferably a strongly basic anion exchange resin;
preferably, the temperature of the condensed water purification is 0-100 ℃, and preferably 30-60 ℃.
8. The processing method according to any one of claims 1 to 7, characterized in that it comprises the steps of:
(1) standing and settling the high-salt high-organic matter industrial wastewater at a temperature of-15-100 ℃ for 0.5-100 h, and then filtering with a filtering aperture of 10-15000 meshes;
(2) carrying out ion exchange treatment on the industrial wastewater filtered in the step (1) at-15-100 ℃ by using sulfonic acid type strong-acid ion exchange resin, wherein the adsorption feeding airspeed is 0.1-100 h-1；
(3) Adjusting the pH of the industrial wastewater subjected to ion exchange in the step (2) to 1-6 by adopting hydrochloric acid with the mass concentration of 1-35.5%, adding a catalyst and an oxidant, and performing catalytic oxidation at 50-500 ℃ and the gauge pressure of 0-100 MPa, wherein the reaction residence time is 0.001-10 h;
(4) adjusting the pH of the industrial wastewater subjected to catalytic oxidation in the step (3) to 9-14, cooling to-15-100 ℃, filtering with a filtering pore size of 10-15000 meshes, adding an oxidant, and performing secondary oxidation at-15-150 ℃ and a gauge pressure of 0-10 MPa, wherein the reaction residence time is 1-3600 s;
(5) purifying the industrial wastewater subjected to secondary oxidation in the step (4) by using chelating resin at a temperature of-15-100 ℃, evaporating and concentrating the treated wastewater by 40-90%, and filtering to obtain solid salt;
dissolving the solid salt in the step (5) by using pure water to obtain raw material salt water meeting the requirements of the ionic membrane caustic soda industry;
refluxing and recycling the concentrated mother liquor obtained by the evaporation and concentration in the step (5) to the step (1);
and (5) purifying the condensate obtained by evaporation and concentration in the step (5) by using strongly basic anion exchange resin at the temperature of 0-100 ℃, and reusing the purified condensate in the preparation process of the raw material brine.
9. A solid salt obtained by the treatment method according to any one of claims 1 to 8.
10. The solid salt of claim 9, wherein the solid salt is used to formulate a raw brine meeting ionic membrane caustic soda industry requirements.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911174711.XA CN110877945A (en) | 2019-11-26 | 2019-11-26 | Treatment method of high-salt high-organic matter industrial wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911174711.XA CN110877945A (en) | 2019-11-26 | 2019-11-26 | Treatment method of high-salt high-organic matter industrial wastewater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110877945A true CN110877945A (en) | 2020-03-13 |
Family
ID=69729440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911174711.XA Pending CN110877945A (en) | 2019-11-26 | 2019-11-26 | Treatment method of high-salt high-organic matter industrial wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110877945A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112239264A (en) * | 2020-09-30 | 2021-01-19 | 宜宾天原集团股份有限公司 | Method for treating carbon-containing organic matters in waste brine |
| CN112374637A (en) * | 2020-10-22 | 2021-02-19 | 泰兴市扬子医药化工有限公司 | Method for preparing refined brine from high-salt phenol-containing wastewater |
| CN112517604A (en) * | 2020-11-16 | 2021-03-19 | 新中天环保股份有限公司 | Harmless treatment process for industrial waste salt |
| CN114409171A (en) * | 2022-02-18 | 2022-04-29 | 科迈化工股份有限公司 | Process for deeply treating and recycling BT (BT) from rubber accelerator DCBS (dichlorodifluoromethane) mother liquor wastewater |
| CN114920387A (en) * | 2022-05-18 | 2022-08-19 | 浙江奇彩环境科技股份有限公司 | Method for recycling waste salt in monosultap production process |
| CN115108669A (en) * | 2022-06-28 | 2022-09-27 | 宁夏信广和新材料科技有限公司 | Method for treating nitrifying wastewater |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628205A (en) * | 2015-01-30 | 2015-05-20 | 苏州聚智同创环保科技有限公司 | High-salt organic wastewater zero discharge treatment process |
| CN104876380A (en) * | 2015-05-26 | 2015-09-02 | 浙江奇彩环境科技有限公司 | Method for treating high-concentration organic copper-containing wastewater and recycling copper |
| CN106587476A (en) * | 2016-12-21 | 2017-04-26 | 科迈化工股份有限公司 | Method for treatment of mixed wastewater produced during production of rubber accelerator NS\CZ\DZ |
| CN110117115A (en) * | 2019-06-05 | 2019-08-13 | 南京大学盐城环保技术与工程研究院 | A kind of processing method and equipment of industrial waste salt recycling |
| CN110255773A (en) * | 2019-07-04 | 2019-09-20 | 浙江德强科技有限公司 | A kind of processing method of the high salt organic waste water generated in epoxy resin production process |
-
2019
- 2019-11-26 CN CN201911174711.XA patent/CN110877945A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628205A (en) * | 2015-01-30 | 2015-05-20 | 苏州聚智同创环保科技有限公司 | High-salt organic wastewater zero discharge treatment process |
| CN104876380A (en) * | 2015-05-26 | 2015-09-02 | 浙江奇彩环境科技有限公司 | Method for treating high-concentration organic copper-containing wastewater and recycling copper |
| CN106587476A (en) * | 2016-12-21 | 2017-04-26 | 科迈化工股份有限公司 | Method for treatment of mixed wastewater produced during production of rubber accelerator NS\CZ\DZ |
| CN110117115A (en) * | 2019-06-05 | 2019-08-13 | 南京大学盐城环保技术与工程研究院 | A kind of processing method and equipment of industrial waste salt recycling |
| CN110255773A (en) * | 2019-07-04 | 2019-09-20 | 浙江德强科技有限公司 | A kind of processing method of the high salt organic waste water generated in epoxy resin production process |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112239264A (en) * | 2020-09-30 | 2021-01-19 | 宜宾天原集团股份有限公司 | Method for treating carbon-containing organic matters in waste brine |
| CN112239264B (en) * | 2020-09-30 | 2023-06-02 | 宜宾天原集团股份有限公司 | Method for treating carbon-containing organic matters in waste brine |
| CN112374637A (en) * | 2020-10-22 | 2021-02-19 | 泰兴市扬子医药化工有限公司 | Method for preparing refined brine from high-salt phenol-containing wastewater |
| CN112517604A (en) * | 2020-11-16 | 2021-03-19 | 新中天环保股份有限公司 | Harmless treatment process for industrial waste salt |
| CN114409171A (en) * | 2022-02-18 | 2022-04-29 | 科迈化工股份有限公司 | Process for deeply treating and recycling BT (BT) from rubber accelerator DCBS (dichlorodifluoromethane) mother liquor wastewater |
| CN114920387A (en) * | 2022-05-18 | 2022-08-19 | 浙江奇彩环境科技股份有限公司 | Method for recycling waste salt in monosultap production process |
| CN115108669A (en) * | 2022-06-28 | 2022-09-27 | 宁夏信广和新材料科技有限公司 | Method for treating nitrifying wastewater |
| CN115108669B (en) * | 2022-06-28 | 2023-11-21 | 宁夏信广和新材料科技有限公司 | Treatment method of nitrified wastewater |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110877945A (en) | Treatment method of high-salt high-organic matter industrial wastewater | |
| Rajoria et al. | Treatment of electroplating industry wastewater: a review on the various techniques | |
| CN104386874B (en) | A kind of wiring board industry high-concentration waste liquor treating process | |
| CN208429966U (en) | A kind of processing unit of effluent brine | |
| CN108793551B (en) | Treatment method and treatment device for high-salt high-COD organic wastewater | |
| CN112960817A (en) | Comprehensive treatment method and system for hydrazine hydrate waste salt | |
| CN109293148B (en) | Treatment device and treatment method for sulfur-containing and salt-containing wastewater | |
| CN110590034A (en) | Process treatment method for lithium iron wastewater of lithium battery anode material | |
| CN110665370A (en) | Method for improving acid-base concentration in bipolar membrane electrodialysis regeneration | |
| CN105174532A (en) | Pretreatment system for prevention of scaling of high ammonia-nitrogen industrial wastewater before ammonia distillation and treatment method thereof | |
| CN111362480A (en) | Method for treating reverse osmosis strong brine | |
| CN104291500B (en) | A kind of lower concentration NH containing Mo 4the recycling treatment system of Cl waste water and method thereof | |
| CN113003829A (en) | Treatment method of high-salinity organic wastewater | |
| CN110963595A (en) | Coal chemical industry salt-containing wastewater treatment system and treatment method | |
| CN114455750A (en) | Method and system for treating high-salt refractory wastewater | |
| CN112239264B (en) | Method for treating carbon-containing organic matters in waste brine | |
| CN114804456A (en) | Recovery system and method for alkaline washing wastewater generated in chloroethylene production by oxychlorination method | |
| CN116040826A (en) | Treatment method and treatment system for coal chemical industry mixed salt mother liquor | |
| CN103420520A (en) | Processing method of vanadium-containing aluminum-containing wastewater | |
| CN210214990U (en) | Zero discharge system for cyclic and comprehensive utilization of waste water of chlor-alkali enterprise | |
| CN110835195A (en) | Process for treating wastewater of sulfenamide accelerator production process | |
| CN114906973A (en) | Coking sewage advanced treatment zero-discharge process | |
| CN204981419U (en) | Be used for preventing before high ammonia -nitrogen concentration industrial waste water ammonia still process scale deposit pretreatment systems | |
| CN219136566U (en) | Electroplating wastewater treatment system | |
| CN111847742A (en) | Industrial wastewater treatment system and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200313 |
|
| RJ01 | Rejection of invention patent application after publication |