CN113336379B - Treatment method of chlorine-containing sewage with high salinity - Google Patents
Treatment method of chlorine-containing sewage with high salinity Download PDFInfo
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- CN113336379B CN113336379B CN202110594907.5A CN202110594907A CN113336379B CN 113336379 B CN113336379 B CN 113336379B CN 202110594907 A CN202110594907 A CN 202110594907A CN 113336379 B CN113336379 B CN 113336379B
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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
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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- 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
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/05—Conductivity or salinity
- C02F2209/055—Hardness
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/29—Chlorine compounds
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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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
- 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
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 convert Ca 2+ 、Mg 2+ Conversion to CaCO 3 、MgCO 3 Precipitating, filtering to remove, heating to convert hypochlorous acid in sewage into chlorine, and absorbing with NaOH solution to obtain sterilized water as byproduct, ca (HCO) 3 ) 2 And Mg (HCO) 3 ) 2 Conversion to CaCO 3 And MgCO 3 Removing 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
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 prevented; 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 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 5000mg/L;
(2) Introducing CO into the sewage containing hypochlorous acid 2 To make Ca therein 2+ 、Mg 2+ Conversion to Ca (HCO) 3 ) 2 、Mg(HCO 3 ) 2 、CaCO 3 And MgCO 3 Filtering off CaCO 3 And MgCO 3 Taking the filtrate;
(3) Heating the filtrate to convert hypochlorous acid into chlorine gas and simultaneously to convert Ca (HCO) into 3 ) 2 And Mg (HCO) 3 ) 2 Conversion to CaCO 3 And MgCO 3 Filtering off CaCO 3 And MgCO 3 。
The invention discovers that the electrochemical reaction process is adopted, and then CO is introduced 2 The sewage is softened and dechlorinated by heating; namely, the high-salinity chlorine-containing sewage is treated by adopting the above mode, so that the salinity and chloride ions can be effectively removed; wherein, the content of chloride ions in the high-salinity chlorine-containing sewage to be treated is not less than 5000mg/L, on one hand, the method is beneficial to improving the content of chloride ions in the electrochemical processCurrent efficiency, on the other hand, can reduce the processing cost of the process.
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 5000mg/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 2h.
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.
Further, 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 is 2 Is added in an amount greater than the Ca 2+ And Mg 2+ Total molar amount of (a);
further, the CO is 2 Is the Ca 2+ And Mg 2+ 1.2 to 1.8 times of the total molar weight of the components.
Treating the sewage containing hypochlorous acid prepared in the step (1) with CO 2 Is added in an amount greater than Ca 2+ And Mg 2+ The total molar amount of (C) is 1.2 to 1.8 times, in particular, ca is favorably contained 2+ And Mg 2+ Conversion to Ca (HCO) 3 ) 2 、Mg(HCO 3 ) 2 、CaCO 3 And MgCO 3 The 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 ℃/min to a maximum temperature, said maximum temperature being not higher than 40 ℃.
Further, the heating is: heating to 35-38 ℃ at the speed of 2-4 ℃/min.
The slow heating mode is favorable for converting hypochlorous acid into chlorine and Ca (HCO) 3 ) 2 And Mg (HCO) 3 ) 2 Conversion to CaCO 3 And MgCO 3 The 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 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 5000mg/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 acid 2 To make Ca therein 2+ 、Mg 2+ Conversion to Ca (HCO) 3 ) 2 、Mg(HCO 3 ) 2 、CaCO 3 And MgCO 3 Filtering off CaCO 3 And MgCO 3 Taking the filtrate;
said CO 2 Is the Ca 2+ And Mg 2+ 1.2 to 1.8 times of the total molar amount of the active carbon;
(3) Heating the filtrate to 35-38 deg.C at 2-4 deg.C/min to convert hypochlorous acid into chlorine gas and Ca (HCO) therein 3 ) 2 And Mg (HCO) 3 ) 2 Conversion to CaCO 3 And MgCO 3 Filtering off CaCO 3 And MgCO 3 ；
(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 dioxide 2+ 、Mg 2+ Conversion to CaCO 3 、MgCO 3 Precipitating, 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 ) 2 And Mg (HCO) 3 ) 2 Conversion to CaCO 3 And MgCO 3 Removing 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 reducing energy consumption and reducing 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 the displacement of the oil field.
TABLE 1 Properties of produced Water after oil field oil removal and mud removal
The method comprises the steps of enabling oil field oil-removed and sludge-removed sewage (properties are shown in table 1) 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 and pass through 3 electrochemical reaction chambers, enabling the voltage of each reaction chamber to be 5V, 6V and 7V respectively, enabling the electrodes to adopt 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 the sewage to be subjected to oil removal and sludge removalWherein Ca 2+ 、Mg 2+ Conversion to Ca (HCO) 3 ) 2 、Mg(HCO 3 ) 2 、CaCO 3 And MgCO 3 Filtering off CaCO 3 And MgCO 3 Heating the filtrate to 38 deg.C at a speed of 2 deg.C/min, absorbing chlorine gas generated during heating with NaOH to generate sodium hypochlorite as disinfectant, and adding Ca (HCO) to the disinfectant 3 ) 2 And Mg (HCO) 3 ) 2 Conversion to CaCO 3 And MgCO 3 Filtering off CaCO 3 And MgCO 3 。
After the treatment by the process, ca in the sewage 2+ Reduced to 215Mg/l, mg 2+ 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 embodiment 1) after oil field oil removal and mud removal enters a reverse osmosis treatment process to obtain concentrated sewage with chloride ions larger than 5000mg/l, the rest fresh water can be directly recycled, the concentrated sewage enters an electrochemical reactor and passes through 4 electrochemical reaction chambers, the voltage of each reaction chamber is 5V, 6V, 7V and 8V, plate electrodes are adopted as the electrodes, the plate intervals are 5cm, 4cm, 3cm and 2cm respectively, the concentrated sewage enters a carbon dioxide reactor after 3.5 hours of reaction, carbon dioxide is blown into the sewage through a gas distributor (the total adding amount is 1.7 times of the total adding amount of calcium and magnesium ions in the sewage), and Ca in the concentrated sewage is enabled to be in a state that the total adding amount of the calcium and magnesium ions is 1.7 times of the total adding amount of the calcium and magnesium ions in the sewage 2+ 、Mg 2+ Conversion to Ca (HCO) 3 ) 2 、Mg(HCO 3 ) 2 、CaCO 3 And MgCO 3 Filtering off CaCO 3 And MgCO 3 Heating 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) therein 3 ) 2 And Mg (HCO) 3 ) 2 Conversion to CaCO 3 And MgCO 3 Filtering off CaCO 3 And MgCO 3 。
After the treatment of the process, ca in the sewage 2+ Reduced to 178Mg/l, mg 2+ 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 high-salinity chlorine-containing sewage, which specifically comprises the following 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 Ca 2+ 、Mg 2+ Conversion to Ca (HCO) 3 ) 2 、Mg(HCO 3 ) 2 、CaCO 3 And MgCO 3 Filtering off CaCO 3 And MgCO 3 Heating 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) therein 3 ) 2 And Mg (HCO) 3 ) 2 Conversion to CaCO 3 And MgCO 3 Filtering off CaCO 3 And MgCO 3 。
After the treatment of the process, ca in the concentrated sewage 2+ Reduced to 455Mg/l, mg 2+ 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 emission 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
Example 4
The embodiment provides a method for treating high-salinity chlorine-containing sewage, which specifically comprises the following 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 amount 2+ 、Mg 2+ Conversion to Ca (HCO) 3 ) 2 、Mg(HCO 3 ) 2 、CaCO 3 And MgCO 3 Filtering to remove CaCO 3 And MgCO 3 Heating 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) to the disinfectant 3 ) 2 And Mg (HCO) 3 ) 2 Conversion to CaCO 3 And MgCO 3 Filtering off CaCO 3 And MgCO 3 。
After the treatment by the process, ca in the sewage 2+ Reduced to 413Mg/l, mg 2+ 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 regeneration wastewater of certain thermal power plant
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 sewage 2+ Reduced to 636Mg/l, mg 2+ 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 1.5h.
After the treatment by the process, ca in the sewage 2+ Reduced to 537Mg/l, mg 2+ 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 of the process, ca in the sewage 2+ Reduced to 837Mg/l, mg 2+ The content of the calcium ions and the magnesium ions is reduced to 433mg/l, the content of the chloride ions is reduced to 1567mg/l, the COD is reduced to 155mg/l, the total mineralization of the calcium ions and the magnesium ions is reduced by 42 percent, and the removal rate of the chloride ions is 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 (9)
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 5000mg/L;
(2) Introducing CO into the sewage containing hypochlorous acid 2 To make Ca therein 2+ 、Mg 2+ Conversion to Ca (HCO) 3 ) 2 、Mg(HCO 3 ) 2 、CaCO 3 And MgCO 3 Filtering off CaCO 3 And MgCO 3 Taking the filtrate;
(3) Heating the filtrate to convert hypochlorous acid therein to chlorine gas and simultaneously to convert Ca (HCO) therein 3 ) 2 And Mg (HCO) 3 ) 2 Conversion to CaCO 3 And MgCO 3 Filtering off CaCO 3 And MgCO 3 ；
The electrochemical reaction in the step (1) is carried out in an electrochemical reactor, 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 entering sequence of the sewage, and the distance between electrodes in each reaction chamber is gradually reduced along with the entering sequence of the sewage;
in the reaction chamber, the voltage is 3 to 10V, and the distance between electrodes is 2 to 10 cm; the time of the electrochemical reaction is 2.5 to 3.5 hours;
in the step (3), the heating is as follows: heating to a maximum temperature at a rate of no more than 5 ℃/min, said maximum temperature being no greater than 40 ℃;
when the content of chloride ions in the high-salinity chlorine-containing sewage to be treated is lower than 5000mg/L, pretreating the high-salinity chlorine-containing sewage to be treated to increase the content of the chloride ions to be not lower than 5000mg/L;
the pretreatment is one or more selected from a permeable membrane process, a nanofiltration process, an electrodialysis process and an evaporation process.
2. The process according to claim 1, wherein the voltage in the reaction chamber is from 5 to 8V, and the distance between the electrodes is from 3 to 7cm.
3. The process according to claim 1 or 2, wherein in step (2), the CO is 2 Is added in an amount greater than the Ca 2+ And Mg 2+ Total molar amount of (a).
4. The process of claim 3 wherein said CO is 2 Is the Ca 2+ And Mg 2+ The total molar amount of (a) is 1.2 to 1.8 times.
5. The process according to any one of claims 1, 2 and 4, wherein in the step (3), the chlorine gas is absorbed by NaOH solution to obtain sodium hypochlorite.
6. The process of claim 3, wherein in step (3), the chlorine gas is absorbed by NaOH solution to obtain sodium hypochlorite.
7. The process according to claim 1, characterized in that the heating is: heating to 35-38 ℃ at the speed of 2-4 ℃/min.
8. The treatment method according to any one of claims 1, 2, 4, 6 and 7, characterized in that the filtrate obtained in the step (3) is repeatedly subjected to the steps (1) - (3) until the finally obtained filtrate meets the water quality requirement.
9. The treatment method according to claim 3, wherein the filtrate obtained in the step (3) is subjected to the steps (1) - (3) repeatedly until the final filtrate meets the water quality requirement.
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| RU2389687C2 (en) * | 2004-07-19 | 2010-05-20 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | CaCO3 OR MgCO3 SYNTHESIS METHOD |
| JP5085027B2 (en) * | 2005-10-17 | 2012-11-28 | 住友大阪セメント株式会社 | Method and apparatus for treating chlorine-containing waste |
| CN105016541B (en) * | 2015-07-29 | 2017-04-26 | 凯姆德（北京）能源环境科技有限公司 | Method for separating and recovering salts from high-salt wastewater |
| CN107298489A (en) * | 2017-07-25 | 2017-10-27 | 武汉轻工大学 | The method that high calcium high chloride ion coexists in electrochemical reactor and removal waste water |
| CN208700815U (en) * | 2018-08-09 | 2019-04-05 | 西安正元环保技术咨询有限公司 | A kind of high slat-containing wastewater zero-discharge treatment system |
| CN110255799A (en) * | 2019-06-11 | 2019-09-20 | 中国科学院生态环境研究中心 | A kind of dechlorination medicament and the methods and applications that are dechlorinated using it to acid water |
| CN110904466B (en) * | 2019-11-12 | 2021-03-12 | 江苏乾宝生物科技有限公司 | Electrolytic sodium hypochlorite generator system and operation method |
| CN111268771A (en) * | 2020-02-17 | 2020-06-12 | 北京科技大学 | Electrochemical method for dechlorinating and removing heavy metals from incineration fly ash water washing liquid |
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