CN113336379A - Treatment method of chlorine-containing sewage with high salinity - Google Patents

Treatment method of chlorine-containing sewage with high salinity Download PDF

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CN113336379A
CN113336379A CN202110594907.5A CN202110594907A CN113336379A CN 113336379 A CN113336379 A CN 113336379A CN 202110594907 A CN202110594907 A CN 202110594907A CN 113336379 A CN113336379 A CN 113336379A
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sewage
chlorine
salinity
hco
mgco
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CN113336379B (en
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张海兵
杜春安
沈蓉
吕秀丽
王青
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China University of Petroleum Beijing
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China University of Petroleum Beijing
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B11/00—Oxides or oxyacids of halogens; Salts thereof
    • C01B11/04—Hypochlorous acid
    • C01B11/06—Hypochlorites
    • C01B11/062—Hypochlorites of alkali metals
    • 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
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/02—Temperature
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/05—Conductivity or salinity
    • C02F2209/055—Hardness
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/29—Chlorine compounds
    • 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
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/02—Softening water by precipitation of the hardness

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

The invention relates to a water treatment process, in particular to a treatment method of high-salinity chlorine-containing sewage. The treatment method utilizes electrochemical reaction to convert chloride ions into hypochlorous acid, and proper amount of carbon dioxide is introduced to lead Ca2+、Mg2+Conversion to CaCO3、MgCO3Precipitating, filtering to remove, heating to convert hypochlorous acid in sewage into chlorine, and absorbing with NaOH solution to obtain disinfectant solution as by-product, Ca (HCO)3)2And Mg (HCO)3)2Conversion to CaCO3And MgCO3Removing the precipitate by filtration; namely, the mineralization of the sewage and the removal of chloride ions are realized. Compared with the multi-effect evaporation technology, the processing method of the invention has the advantages that the adopted voltage is lower, the heating temperature is also within 40 ℃, the energy consumption can be greatly reduced, and the investment cost is reduced; the treatment method of the invention has the mineralization degree and the removal rate of chloride ions reaching more than 85 percent.

Description

Treatment method of chlorine-containing sewage with high salinity
Technical Field
The invention relates to a water treatment process, in particular to a treatment method of high-salinity chlorine-containing sewage.
Background
At present, in the sewage treatment process, although no strict requirements are provided for the mineralization degree and chloride ions in water, the mineralization degree and the chloride ions of the sewage are often required to be reduced in the actual treatment process, so that the problems of scaling and corrosion in the subsequent recycling process are solved; in addition, the excessive mineralization degree and the existence of chloride ions also influence the recycling range of the sewage, and particularly, strong brine obtained by the currently and commonly adopted reverse osmosis membrane process can have the possibility of high mineralization degree and high chloride ions. Therefore, the treatment of the chlorine-containing sewage with high salinity is a prominent important link in the current sewage treatment.
In recent years, with the continuous improvement of environmental protection requirements and the continuous innovation of technologies, the treatment technology of high-salinity chlorine-containing sewage is gradually mature, the technology which can be adopted for the high-salinity chlorine-containing sewage is mainly a physical evaporation method, more than 90% of water in the sewage is evaporated by the method, then the water is condensed to obtain pure water for recycling, and crystallized inorganic salt can be sold as a byproduct.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a treatment method of chlorine-containing sewage with high salinity, which has the advantages of strong pertinence, easy implementation, low energy consumption and good removal effect of the salinity and the chloride ions.
Specifically, the invention provides the following technical scheme:
the invention provides a method for treating chlorine-containing sewage with high salinity, which comprises the following steps:
(1) carrying out electrochemical reaction on the high-salinity chlorine-containing sewage to be treated to convert chloride ions in the high-salinity chlorine-containing sewage into hypochlorous acid so as to obtain sewage containing the hypochlorous acid; in the high-salinity chlorine-containing sewage to be treated, the content of chloride ions is not lower than 5000 mg/L;
(2) introducing CO into the sewage containing hypochlorous acid2To make Ca therein2+、Mg2+Conversion to Ca (HCO)3)2、Mg(HCO3)2、CaCO3And MgCO3Filtering off CaCO3And MgCO3Taking the filtrate;
(3) heating the filtrate to convert hypochlorous acid therein to chlorine gas and simultaneously to convert Ca (HCO) therein3)2And Mg (HCO)3)2Conversion to CaCO3And MgCO3Filtering off CaCO3And MgCO3。
The invention discovers that the electrochemical reaction process is adopted, and then CO is introduced2The sewage is softened and dechlorinated by heating; namely, the high-salinity chlorine-containing sewage is treated by adopting the mode, so that the salinity and the chloride ions can be effectively removed; the content of chloride ions in the high-salinity chlorine-containing sewage to be treated is not lower than 5000mg/L, so that on one hand, the current efficiency in the electrochemical process is improved, and on the other hand, the treatment cost of the process can be reduced.
Preferably, if the content of chloride ions in the highly mineralized chlorine-containing wastewater to be treated is too low, the wastewater may be pretreated to enrich the chloride ions in the wastewater.
Specifically, when the content of chloride ions in the chlorine-containing sewage with high salinity to be treated is lower than 5000mg/L, pretreating the chlorine-containing sewage with high salinity to be treated to increase the content of the chloride ions in the chlorine-containing sewage to be treated to be not lower than 5000 mg/L;
further, the pretreatment is selected from one or more of a permeable membrane process, a nanofiltration process, an electrodialysis process and an evaporation process.
In addition, in order to further reduce the mineralization degree of the sewage and improve the removal rate of chloride ions in the sewage, the invention optimizes the steps as follows:
preferably, in the step (1), the time of the electrochemical reaction is not less than 2 h.
Furthermore, the time of the electrochemical reaction is 2.5-3.5 h.
Further, the electrochemical reaction is carried out in an electrochemical reactor, and the electrochemical reactor is 1 group of reaction chambers or consists of a plurality of groups of reaction chambers which are connected in series; in the reaction chamber, the voltage is 3-10V, and the distance between the electrodes is 2-10 cm.
Furthermore, in the reaction chamber, the voltage is 5-8V, and the distance between the electrodes is 3-7 cm.
Further, when the electrochemical reactor is composed of a plurality of groups of reaction chambers connected in series, the voltage of each reaction chamber gradually increases along with the sequence of entering the sewage, and the distance between the electrodes in each reaction chamber gradually decreases along with the sequence of entering the sewage.
Further, in the reaction chamber, the electrode is a plate-shaped electrode; active carbon, iron carbon particles, ceramic particles and the like can be added between the electrodes.
Aiming at the high-salinity chlorine-containing sewage, when the electrochemical reaction is carried out under the conditions, the conversion of chloride ions into hypochlorous acid is facilitated, and the conversion rate is improved.
Preferably, in step (2), the CO is2Is added in an amount greater than the Ca2+And Mg2+Total molar amount of (a);
further, the CO is2Is the Ca2+And Mg2+The total molar amount of the component (a) is 1.2 to 1.8 times.
Treating the sewage containing hypochlorous acid prepared in the step (1) with CO2Is added in an amount greater than Ca2+And Mg2+The total molar amount (especially 1.2-1.8 times) of the total amount of the component (B) is favorable for Ca2+And Mg2+Conversion to Ca (HCO)3)2、Mg(HCO3)2、CaCO3And MgCO3The conversion rate is improved, and the mineralization degree of the sewage is reduced.
Preferably, in the step (3), NaOH solution is adopted to absorb the chlorine gas to obtain sodium hypochlorite; the sodium hypochlorite can be used as a disinfectant.
Preferably, in step (3), the heating is: heating at a rate not exceeding 5 deg.C/min to a maximum temperature of no more than 40 deg.C.
Further, the heating is: heating to 35-38 ℃ at a speed of 2-4 ℃/min.
The slow heating mode is favorable for converting hypochlorous acid into chlorine and Ca (HCO)3)2And Mg (HCO)3)2Conversion to CaCO3And MgCO3The conversion rate is improved, and the mineralization degree of the sewage is further reduced.
Preferably, if the salinity and the chloride ion content of the sewage treated by the method do not meet the requirement of recycling, the filtrate obtained in the step (3) can be repeatedly subjected to the steps (1) to (3) until the finally obtained filtrate meets the requirement of water quality.
As a preferred technical solution of the present invention, the processing method includes the steps of:
(1) carrying out electrochemical reaction on the high-salinity chlorine-containing sewage to be treated for 2.5-3.5 h to convert chloride ions in the high-salinity chlorine-containing sewage into hypochlorous acid, so as to obtain sewage containing the hypochlorous acid; in the high-salinity chlorine-containing sewage to be treated, the content of chloride ions is not lower than 5000 mg/L;
wherein the electrochemical reaction is carried out in an electrochemical reactor, and the electrochemical reactor is 1 group of reaction chambers or consists of a plurality of groups of reaction chambers which are connected in series; in the reaction chamber, the voltage is 5-8V, and the distance between the electrodes is 3-7 cm; when the electrochemical reactor is formed by connecting a plurality of groups of reaction chambers in series, the voltage of each reaction chamber is gradually increased along with the sequence of entering the sewage, and the distance between electrodes in each reaction chamber is gradually reduced along with the sequence of entering the sewage;
(2) introducing CO into the sewage containing hypochlorous acid2To make Ca therein2+、Mg2+Conversion to Ca (HCO)3)2、Mg(HCO3)2、CaCO3And MgCO3Filtering off CaCO3And MgCO3Taking the filtrate;
the CO is2Is the Ca2+And Mg2+1.2 to 1.8 times of the total molar amount of the component (A);
(3) heating the filtrate to 35-38 deg.C at a rate of 2-4 deg.C/min to convert hypochlorous acid into chlorine gas and Ca (HCO) therein3)2And Mg (HCO)3)2Conversion to CaCO3And MgCO3Filtering off CaCO3And MgCO3；
(4) And (4) repeating the steps (1) to (3) on the filtrate obtained in the step (3) until the final filtrate meets the water quality requirement.
In the invention, chlorine ions are converted into hypochlorous acid by electrochemical reaction, and Ca is converted by introducing proper amount of carbon dioxide2+、Mg2+Conversion to CaCO3、MgCO3Precipitating, filtering to remove, heating to convert hypochlorous acid in sewage into chlorine, and absorbing with NaOH solution to obtain disinfectant solution as by-product, Ca (HCO)3)2And Mg (HCO)3)2Conversion to CaCO3And MgCO3Removing the precipitate by filtration; namely, the mineralization of the sewage and the removal of chloride ions are realized.
The invention has the beneficial effects that:
(1) compared with the multi-effect evaporation technology, the processing method of the invention has the advantages of lower voltage, heating temperature within 40 ℃, greatly reduced energy consumption and reduced investment cost.
(2) The chloride ions can be converted into disinfectant to be sold as a byproduct, and the cost of the whole treatment process can be further reduced.
(3) The treatment method of the invention has the mineralization degree and the removal rate of chloride ions reaching more than 85 percent.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or instruments used are conventional products available from regular distributors, not indicated by the manufacturer.
Example 1
The embodiment provides a method for treating chlorine-containing sewage with high salinity, which comprises the following specific steps:
the properties of sewage produced from a certain oil field after oil removal and sludge removal are shown in Table 1; further processing is required to generate steam for flooding the oil field.
TABLE 1 properties of produced water after oil and sludge removal in certain oil field
Figure BDA0003090758640000051
The method comprises the steps of enabling oil field sewage (properties are shown in table 1) after oil removal and sludge removal to enter an electrodialysis treatment process to obtain concentrated sewage with chloride ions larger than 5000mg/l, enabling the rest fresh water to be directly recycled, enabling the concentrated sewage to enter an electrochemical reactor, enabling the concentrated sewage to pass through 3 electrochemical reaction chambers, enabling the voltage of each reaction chamber to be 5V, 6V and 7V respectively, enabling the electrodes to be plate-type electrodes, enabling the plate intervals to be 5cm, 4cm and 3cm respectively, enabling the concentrated sewage to enter a carbon dioxide reactor after 2.5-hour reaction, and blowing carbon dioxide (the adding amount is 1.5 times of the total molar amount of calcium and magnesium ions in the sewage) into the sewage through a gas distributor to enable Ca in the sewage to be Ca2+、Mg2+Conversion to Ca (HCO)3)2、Mg(HCO3)2、CaCO3And MgCO3Filtering off CaCO3And MgCO3Heating the filtrate to 38 deg.C at 2 deg.C/min, absorbing chlorine gas generated during heating with NaOH to generate sodium hypochlorite as disinfectant, and adding Ca (HCO) therein3)2And Mg (HCO)3)2Conversion to CaCO3And MgCO3Filtering off CaCO3And MgCO3。
After the treatment by the process, Ca in the sewage2+Reduced to 215Mg/l, Mg2+The concentration is reduced to 112mg/l, the chloride ions are reduced to 308mg/l, the COD is reduced to 39mg/l, the total mineralization of calcium and magnesium ions is reduced by more than 85%, the removal rate of the chloride ions reaches 87%, the treated sewage can enter a boiler again for use, and the aim of zero discharge of the oilfield produced water is fulfilled.
Example 2
The embodiment provides a method for treating chlorine-containing sewage with high salinity, which comprises the following specific steps:
the sewage (same as the example 1) after oil field oil removal and mud removal enters a reverse osmosis treatment process to obtain chloridionThe concentrated sewage with the ion concentration larger than 5000mg/l and the rest fresh water can be directly recycled, the concentrated sewage enters an electrochemical reactor, passes through 4 electrochemical reaction chambers, the voltage of each reaction chamber is 5V, 6V, 7V and 8V, the electrodes adopt plate electrodes, the plate distances are 5cm, 4cm, 3cm and 2cm respectively, after 3.5 hours of reaction, the concentrated sewage enters a carbon dioxide reactor, carbon dioxide is blown into the sewage through a gas distributor (the adding amount is 1.7 times of the total molar amount of calcium and magnesium ions in the sewage), and Ca in the concentrated sewage is enabled to be Ca2+、Mg2+Conversion to Ca (HCO)3)2、Mg(HCO3)2、CaCO3And MgCO3Filtering off CaCO3And MgCO3Heating the filtrate to 37 deg.C at 3 deg.C/min, absorbing chlorine gas generated during heating with NaOH to generate sodium hypochlorite as disinfectant, and adding Ca (HCO) therein3)2And Mg (HCO)3)2Conversion to CaCO3And MgCO3Filtering off CaCO3And MgCO3。
After the treatment by the process, Ca in the sewage2+Reduced to 178Mg/l, Mg2+The concentration is reduced to 86mg/l, the chloride ion concentration is reduced to 227mg/l, the COD is reduced to 26mg/l, the total mineralization degree of calcium and magnesium ions is reduced by more than 90%, the removal rate of the chloride ion reaches 90%, the treated sewage can enter a boiler again for use, and the aim of zero discharge of oilfield produced water is fulfilled.
Example 3
The embodiment provides a method for treating chlorine-containing sewage with high salinity, which comprises the following specific steps:
the method comprises the steps of adopting certain gas field sewage, removing oil and mud, passing through a multi-stage reverse osmosis membrane to obtain concentrated sewage (properties are shown in table 2), directly entering an electrochemical reactor, passing through 3 electrochemical reaction chambers, enabling the voltage of each reaction chamber to be 6V, 7V and 8V respectively, adopting plate-type electrodes as electrodes, enabling the plate intervals to be 4cm, 3cm and 2cm respectively, reacting for 3 hours, entering a carbon dioxide reactor, and blowing carbon dioxide (the adding amount is 1.6 times of the total molar amount of calcium and magnesium ions in sewage) into the sewage through a gas distributor to enable Ca in the sewage to be Ca2+、Mg2+Conversion to Ca (HCO)3)2、Mg(HCO3)2、CaCO3And MgCO3Filtering off CaCO3And MgCO3Heating the filtrate to 36 deg.C at 4 deg.C/min, absorbing chlorine gas generated during heating with NaOH to generate sodium hypochlorite as disinfectant solution, converting hypochlorous acid into chlorine gas, and simultaneously converting Ca (HCO) therein3)2And Mg (HCO)3)2Conversion to CaCO3And MgCO3Filtering off CaCO3And MgCO3。
After the treatment of the process, Ca in the concentrated sewage2+Reduced to 455Mg/l, Mg2+The concentration is reduced to 321mg/l, the chloride ions are reduced to 586mg/l, the COD is reduced to 137mg/l, the total mineralization of calcium and magnesium ions is reduced by more than 85%, the removal rate of the chloride ions reaches 87%, the treated sewage can enter a boiler again for use, and the aim of zero discharge of the produced water of the gas field is fulfilled.
TABLE 2 Properties of concentrated wastewater after reverse osmosis membrane treatment in a certain gas field
Figure BDA0003090758640000071
Example 4
The embodiment provides a method for treating chlorine-containing sewage with high salinity, which comprises the following specific steps:
before a certain thermal power plant enters a boiler, ion exchange resin is utilized to soften water, chlorine-containing sewage with high mineralization is generated during the regeneration of the ion exchange resin (the basic properties are shown in table 3), the sewage directly enters an electrochemical reactor and passes through 4 electrochemical reaction chambers, the voltage of each reaction chamber is respectively 5V, 6V, 7V and 8V, plate electrodes are adopted as the electrodes, the plate distance is respectively 5cm, 4cm, 3cm and 2cm, the sewage enters a carbon dioxide reactor after 3.5 hours of reaction, carbon dioxide is blown into the sewage through a gas distributor (the adding amount is 1.6 times of the total molar amount of calcium and magnesium ions in the sewage), and Ca in the sewage is enabled to be in a state that the total molar amount of the calcium and magnesium ions is 1.6 times of the total molar amount2+、Mg2+Conversion to Ca (HCO)3)2、Mg(HCO3)2、CaCO3And MgCO3Filtering off CaCO3And MgCO3Heating the filtrate to 37 deg.C at 3 deg.C/min, absorbing chlorine gas generated during heating with NaOH to generate sodium hypochlorite as disinfectant, and adding Ca (HCO) therein3)2And Mg (HCO)3)2Conversion to CaCO3And MgCO3Filtering off CaCO3And MgCO3。
After the treatment by the process, Ca in the sewage2+Reduced to 413Mg/l, Mg2+The concentration is reduced to 303mg/l, the chloride ions are reduced to 566mg/l, the COD is reduced to 107mg/l, the total mineralization degree of calcium and magnesium ions is reduced by more than 90%, the removal rate of the chloride ions reaches 92%, the treated sewage can enter a circulating system again for use, and the aim of zero discharge of the sewage of the thermal power plant is fulfilled.
TABLE 3 Properties of ion exchange resin regenerated wastewater of certain thermal power plant
Figure BDA0003090758640000081
Comparative example 1
The comparative example provides a method for treating chlorine-containing sewage with high salinity, which is different from the method in the example 1 only in that: directly feeding the oil field oil-removed and mud-removed sewage into an electrochemical reactor without an electrodialysis treatment process.
After the treatment by the process, Ca in the sewage2+Reduced to 636Mg/l, Mg2+The concentration is reduced to 322mg/l, the chloride ion concentration is reduced to 973mg/l, the COD is reduced to 150mg/l, the total mineralization of calcium and magnesium ions is reduced by 56.2 percent, and the removal rate of the chloride ion is 57.3 percent.
Comparative example 2
The comparative example provides a method for treating chlorine-containing sewage with high salinity, which is different from the method in the example 1 only in that: the time of the electrochemical reaction was 1.5 h.
After the treatment by the process, Ca in the sewage2+Reduced to 537Mg/l, Mg2+The concentration is reduced to 283mg/l, the chloride ion concentration is reduced to 1132mg/l, the COD is reduced to 173mg/l, the total mineralization of calcium and magnesium ions is reduced by 62.5 percent, and the removal rate of the chloride ion is 50.3 percent.
Comparative example 3
The comparative example provides a method for treating chlorine-containing sewage with high salinity, which is different from the method in the example 1 only in that: the filtrate was heated to 40 ℃ at a rate of 10 ℃/min.
After the treatment by the process, Ca in the sewage2+Reduced to 837Mg/l, Mg2+Reducing the concentration to 433mg/l, reducing the concentration of chloride ions to 1567mg/l, reducing the COD to 155mg/l, reducing the total mineralization of calcium and magnesium ions by 42 percent, and achieving the removal rate of chloride ions of 31 percent.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A treatment method of chlorine-containing sewage with high salinity is characterized by comprising the following steps:
(1) carrying out electrochemical reaction on the high-salinity chlorine-containing sewage to be treated to convert chloride ions in the high-salinity chlorine-containing sewage into hypochlorous acid so as to obtain sewage containing the hypochlorous acid; in the high-salinity chlorine-containing sewage to be treated, the content of chloride ions is not lower than 5000 mg/L;
(2) introducing CO into the sewage containing hypochlorous acid2To make Ca therein2+、Mg2+Conversion to Ca (HCO)3)2、Mg(HCO3)2、CaCO3And MgCO3Filtering off CaCO3And MgCO3Taking the filtrate;
(3) heating the filtrate to convert hypochlorous acid therein to chlorine gas and simultaneously to convert Ca (HCO) therein3)2And Mg (HCO)3)2Conversion to CaCO3And MgCO3Filtering off CaCO3And MgCO3。
2. The treatment method according to claim 1, wherein when the content of chloride ions in the high-salinity chlorine-containing sewage to be treated is lower than 5000mg/L, the high-salinity chlorine-containing sewage to be treated is pretreated so that the content of chloride ions in the high-salinity chlorine-containing sewage is increased to be not lower than 5000 mg/L;
preferably, the pretreatment is selected from one or more of a permeable membrane process, a nanofiltration process, an electrodialysis process and an evaporation process.
3. The treatment method according to claim 1 or 2, wherein in the step (1), the time of the electrochemical reaction is not less than 2 h;
preferably, the time of the electrochemical reaction is 2.5-3.5 h.
4. The process of claim 3, wherein the electrochemical reaction is carried out in an electrochemical reactor consisting of 1 set of reaction chambers or a plurality of sets of reaction chambers connected in series; in the reaction chamber, the voltage is 3-10V, and the distance between electrodes is 2-10 cm;
preferably, in the reaction chamber, the voltage is 5-8V, and the distance between the electrodes is 3-7 cm.
5. The treatment method according to claim 4, wherein when the electrochemical reactor is composed of a plurality of reaction chambers connected in series, the voltage of each reaction chamber is gradually increased along with the sequence of wastewater entering, and the distance between the electrodes in each reaction chamber is gradually decreased along with the sequence of wastewater entering.
6. The process according to any one of claims 1 to 5, wherein in the step (2), the CO is introduced into the reaction vessel2Is added in an amount greater than the Ca2+And Mg2+Total molar amount of (a);
preferably, the CO is2Is the Ca2+And Mg2+The total molar amount of the component (a) is 1.2 to 1.8 times.
7. The process according to any one of claims 1 to 6, wherein in step (3), the chlorine gas is absorbed by NaOH solution to obtain sodium hypochlorite.
8. The process according to any one of claims 1 to 7, wherein in the step (3), the heating is: heating at a rate not exceeding 5 deg.C/min to a maximum temperature of no more than 40 deg.C.
9. The process of claim 8, wherein the heating is: heating to 35-38 ℃ at a speed of 2-4 ℃/min.
10. The treatment method according to any one of claims 1 to 9, wherein the filtrate obtained in step (3) is subjected to steps (1) to (3) repeatedly until the final filtrate meets the water quality requirement.
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