CN115448525A - High-salinity mine water recycling treatment process - Google Patents
High-salinity mine water recycling treatment process Download PDFInfo
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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
- 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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of water treatment, and discloses a high-salinity mine water recycling treatment process. Compared with the traditional process, the high-salt mine water recycling treatment process omits a nanofiltration salt separation process, simplifies the process flow, adopts the ingenious combination of a monovalent selective ion exchange membrane and a bipolar membrane, improves the purity of the produced acid-alkali liquor, enlarges the utilization range of the product, improves the utilization rate, realizes the recycling of the high-salt mine water under the condition of no phase change, greatly reduces the addition of chemical agents, saves the production cost of enterprises, and simultaneously well protects the natural environment of a coal mine production place.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a high-salt mine water recycling treatment process.
Background
China belongs to a poor water country, coal mine water is one of important water resources, and nearly 40% of the coal mine water is high-salt mine water, so that the problem of discharge of the high-salt mine water is obvious. The direct discharge causes ecological environmental pollution in the drainage basin, mainly manifested by rising of salt content in river water, breeding of salinization in soil, weakening of tree species without salinization, yield reduction of crops and the like, and causes difficulty in reasonable utilization of limited water resources.
The recycling of high-salt mine water is to carry out desalting treatment to achieve water quality meeting production or living requirements except that the conventional process is adopted for pretreatment to remove suspensions, the main methods for desalting comprise a distillation method, an ion exchange method, electrodialysis and a reverse osmosis method, and the reverse osmosis method is most applied at present. The high-salt mine water is desalted by a reverse osmosis method, the recovery rate of fresh water is 50-70%, meanwhile, a large amount of high-salt wastewater with higher concentration is generated, strong brine is usually heated, evaporated and crystallized to generate a large amount of miscellaneous salts, and the miscellaneous salts are treated according to solid wastes, so that the risks of large dosage of various acid-base chemical agents, high operation cost, resource waste, difficulty in handling miscellaneous salts and secondary pollution in the process are existed. With the increasing environmental protection pressure, the policy for mine water treatment is becoming more and more strict, and an effective and low-cost method for treating high-salinity mine water is urgently needed. Therefore, a system method for zero discharge of high-salt mine water becomes a research hotspot in recent years.
CN113896370A discloses a novel mine water zero discharge system and method, and the system comprises a deep magnesium removal reaction unit, a first filtering unit, a first ultrafiltration unit, a reverse osmosis unit, a deep calcium removal unit, a second filtering unit, a second ultrafiltration unit, a high-salt reverse osmosis unit, an evaporation crystallization unit and a strong brine solidification unit. The process still belongs to the traditional process, and has the problems of large dosage of various acid-base chemical agents, large energy consumption and high operation cost in the process. CN114212938A discloses a mine water recycling zero-emission system and method, and the system comprises a pretreatment unit, a nanofiltration salt separation unit, a reverse osmosis concentration unit, a high-pressure nanofiltration unit and a bipolar membrane electrodialysis unit. CN114349207A discloses a zero-emission-oriented high-salt and high-fluorine mine water purification system and process, wherein a bipolar membrane device is adopted to prepare mixed acid liquor and alkali liquor, a filtrate-mixture preparation device is adopted to prepare acidic mixture and alkaline filtrate, the alkaline filtrate is added into a high-density sedimentation tank, the acidic mixture is added into a membrane coagulation reactor, and then decarburization and electrodeionization treatment are carried out to finally prepare mixed purified effluent. CN215855456U discloses a contain salt mine water high efficiency and reuse processing system, and the system includes hollow fiber nanofiltration membrane system, concentration system and nanofiltration and divides the salt system in proper order, and the concentration system includes one-level reverse osmosis unit, chemical induction crystallization device and water storage water tank, utilizes bipolar membrane technology to handle the high salt concentrate and obtains the acid-base solution of retrieval and utilization simultaneously. The processes all adopt a bipolar membrane electrodialysis technology, or adopt a nanofiltration salt separation technology or produce mixed acid liquor, and the produced acid-alkali liquor is not pure enough, so that the recycling range is limited.
Therefore, how to provide a treatment process of high-salinity mine water, which can obtain high-purity acid-alkali liquor and realize zero emission, has important significance on resource utilization of mine water in coal mines.
Disclosure of Invention
The invention aims to provide a high-salinity mine water recycling treatment process, which solves the problems of mine water treatment methods in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a high-salinity mine water recycling treatment process, which comprises the following steps of:
(1) Pretreatment: sequentially carrying out coagulating sedimentation, filtration and ion exchange softening and silicon removal on the high-salt mine water to obtain pretreated high-salt mine water;
(2) And (3) membrane concentration: sequentially carrying out reverse osmosis, high-pressure reverse osmosis and electrodialysis on the pretreated high-salt mine water to obtain concentrated high-salt mine water;
(3) First-stage bipolar membrane electrodialysis: performing first-stage bipolar membrane electrodialysis on the concentrated high-salt mine water to respectively obtain hydrochloric acid solution, sodium hydroxide alkali solution and mixed salt solution;
(4) And (3) second-stage bipolar membrane electrodialysis: performing two-stage bipolar membrane electrodialysis on the mixed salt solution to respectively obtain a mixed acid solution, a sodium hydroxide alkali solution and a low-salt solution;
(5) Stripping by blowing: and blowing off the mixed acid liquor to obtain carbon dioxide gas and sulfuric acid liquor.
Preferably, in the above process for recycling high-salt mine water, the step (1) further comprises adding a softening agent while performing coagulation precipitation; ion exchange resin is used for softening and removing silicon by ion exchange; the regeneration method of the ion exchange resin comprises the steps of firstly using acid liquor for regeneration and then using alkali liquor for neutralization.
Preferably, in the above process for recycling high-salt mine water, the softening agent in step (1) is the sodium hydroxide lye of step (3) and/or the sodium hydroxide lye of step (4); the acid solution in the regeneration method of the ion exchange resin is the hydrochloric acid solution in the step (3); and (3) the alkali liquor in the regeneration method of the ion exchange resin is the sodium hydroxide alkali liquor in the step (3) and/or the sodium hydroxide alkali liquor in the step (4).
Preferably, in the above process for recycling high-salt mine water, the ratio of the concentration of salt in the concentrated high-salt mine water in step (2) to the concentration of salt in the pretreated high-salt mine water is 8 to 12:1.
preferably, in the above process for recycling high-salt mine water, the membrane stack for the first-stage bipolar membrane electrodialysis in step (3) includes an anode, an anode chamber, a repeating membrane group unit, a monovalent selective anion exchange membrane, a salt chamber, a monovalent selective cation exchange membrane, a cathode chamber, and a cathode, which are sequentially arranged;
the repeated membrane module unit comprises a monovalent selective anion exchange membrane, a salt chamber, a monovalent selective cation exchange membrane, an alkali chamber, a bipolar membrane and an acid chamber which are sequentially arranged; the cathode membrane of the bipolar membrane in the repeated membrane group unit and the monovalent selective cation exchange membrane form an alkali chamber; an anode membrane of the bipolar membrane in the repeated membrane group unit and a monovalent selective anion exchange membrane form an acid chamber; the number of the repeating groups of the repeating membrane group unit is 10 to 100.
Preferably, in the above process for recycling high-salt mine water, the separation function of the valence selective anion exchange membrane in step (3) is: under the action of an electric field, monovalent anions pass through, and divalent anions are intercepted;
the separation function of the monovalent selective cation exchange membrane is: under the action of an electric field, monovalent cations pass through, and divalent cations are intercepted.
Preferably, in the above high-salt mine water resource treatment process, the membrane stack composition of the two-stage bipolar membrane electrodialysis in step (4) includes an anode, an anode chamber, a repeated membrane group unit, an anion exchange membrane, a salt chamber, a monovalent selective cation exchange membrane, a cathode chamber, and a cathode, which are sequentially arranged;
the repeated membrane group unit comprises an anion exchange membrane, a salt chamber, a monovalent selective cation exchange membrane, an alkali chamber, a bipolar membrane and an acid chamber which are sequentially arranged; the cathode membrane of the bipolar membrane in the repeated membrane group unit and the monovalent selective cation exchange membrane form an alkali chamber; an anode membrane and an anion exchange membrane of the bipolar membrane in the repeated membrane group unit form an acid chamber; the number of the repeating groups of the repeating membrane group unit is 10 to 100.
Preferably, in the above process for recycling high-salinity mine water, the separation function of the cation exchange membrane with valence selectivity in the step (4) is as follows: under the action of an electric field, monovalent cations pass through, and divalent cations are intercepted.
Preferably, in the above high-salt mine water resource treatment process, the low-salt solution in step (4) is refluxed to step (2) for membrane concentration.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
compared with the traditional process, the high-salt mine water recycling treatment process provided by the invention omits a nanofiltration salt separation process, simplifies the process flow, adopts the ingenious combination of a monovalent selective ion exchange membrane and a bipolar membrane, improves the purity of the produced acid-alkali liquor, enlarges the utilization range of the product, improves the utilization rate, realizes the recycling of the high-salt mine water under the condition of no phase change, greatly reduces the addition of chemical agents, saves the production cost of enterprises, and can well protect the natural environment of a coal mine production place.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a flow chart of the high salt mine water resource treatment process of the invention;
FIG. 2 is a schematic view of a membrane stack for one-stage bipolar membrane electrodialysis according to the present invention;
FIG. 3 is a schematic view of a two-stage bipolar membrane electrodialysis stack according to the present invention;
FIG. 4 is a flow chart of a one-stage bipolar membrane electrodialysis process according to the present invention;
FIG. 5 is a flow diagram of a two-stage bipolar membrane electrodialysis process of the present invention;
FIG. 6 is a specific process flow diagram of the high salt mine water reclamation treatment of the present invention;
the method comprises the following steps of 1-pretreatment, 2-membrane concentration, 3-first-stage bipolar membrane electrodialysis, 4-second-stage bipolar membrane electrodialysis, 5-air stripping, 21-anode, 22-monovalent selective anion exchange membrane, 23-monovalent selective cation exchange membrane, 24-bipolar membrane, 25-cathode, 32-anion exchange membrane, 41-anode chamber, 42-salt chamber, 43-alkali chamber, 44-acid chamber, 45-cathode chamber, 51-anode chamber, 52-salt chamber, 53-alkali chamber, 54-acid chamber, 55-cathode chamber, 56-polar water circulation tank, 57-brine circulation tank, 58-alkali liquid circulation tank, 59-acid liquid circulation tank, 60-direct current power supply, 61-polar water circulation pump, 62-brine circulation pump, 63-alkali liquid circulation pump, 64-acid liquid circulation pump, 66-polar water circulation tank, 67-brine circulation tank, 68-alkali liquid circulation tank, 69-acid liquid circulation tank, 70-direct current power supply, 71-polar water circulation pump, 72-brine circulation pump, 73-acid liquid circulation pump, and 74-acid liquid circulation pump.
Detailed Description
The invention provides a high-salinity mine water recycling treatment process, as shown in figure 1, the sequence of the treatment process is as follows: pretreatment 1, membrane concentration 2, first-stage bipolar membrane electrodialysis 3, second-stage bipolar membrane electrodialysis 4 and stripping 5.
The specific process flow of the treatment process is shown in fig. 6, and comprises the following steps:
(1) Pretreatment: sequentially carrying out coagulating sedimentation, filtration and ion exchange softening and silicon removal on the high-salt mine water to obtain pretreated high-salt mine water;
(2) And (3) membrane concentration: sequentially carrying out reverse osmosis, high-pressure reverse osmosis and electrodialysis on the pretreated high-salt mine water to obtain concentrated high-salt mine water;
(3) First-stage bipolar membrane electrodialysis: carrying out first-stage bipolar membrane electrodialysis on the concentrated high-salt mine water to respectively obtain hydrochloric acid solution, sodium hydroxide alkali solution and mixed salt solution;
(4) And (3) second-stage bipolar membrane electrodialysis: performing two-stage bipolar membrane electrodialysis on the mixed salt solution to respectively obtain a mixed acid solution, a sodium hydroxide alkali solution and a low-salt solution;
(5) Stripping by blowing: and blowing off the mixed acid liquor to obtain carbon dioxide gas and sulfuric acid liquor.
In the invention, the pretreatment of the step (1) can remove suspended matters and calcium and magnesium hardness in the high-salinity mine water and prevent the suspended matters and the calcium and magnesium hardness from entering equipment of a subsequent treatment process. The suspended matters are removed by adopting the traditional process of coagulating sedimentation and filtering, and simultaneously, the process is organically combined with the softening process, namely, alkali liquor is added while coagulating, and the hardness of carbonate in high-salt mine water reacts with the alkali to generate calcium carbonate sediment and magnesium hydroxide sediment. The high-salt mine water generally contains Ca as cation 2+ 、Mg 2+ 、Na + In the pretreatment, more than 99 percent of calcium and magnesium are removed by medicament softening and ion exchange softening, and cations in the pretreated water are mainly Na + . The anion contained in the high-salt mine water is SO 4 2- 、Cl - 、HCO 3 - The pretreatment process has less anion removal and only a small amount of HCO 3 - Is removed, and HCO in water is generated due to the increase of pH value of water after the softening of the agent 3 - Conversion to CO 3 2- 。
In the invention, the agent added in the step (1) by coagulating sedimentation is PAC. The present invention is not limited to the coagulation sedimentation and filtration, and may be carried out by a method known to those skilled in the art.
In the invention, the coagulating sedimentation in the step (1) is carried out while adding a softening agent; ion exchange resin is used for softening and removing silicon by ion exchange; the ion exchange resin is coupling resin suitable for high salt condition; the regeneration method of the ion exchange resin comprises the steps of firstly using acid liquor for regeneration and then using alkali liquor for neutralization.
In the invention, the softening agent in the step (1) is the sodium hydroxide lye in the step (3) and/or the sodium hydroxide lye in the step (4); the acid solution in the regeneration method of the ion exchange resin is the hydrochloric acid solution in the step (3); and (3) the alkali liquor in the regeneration method of the ion exchange resin is the sodium hydroxide alkali liquor in the step (3) and/or the sodium hydroxide alkali liquor in the step (4).
In the invention, the membrane concentration in the step (2) concentrates the salinity of the high-salinity well water by about 10 times, and the fresh water obtained in the concentration process is recycled to the first-stage bipolar membrane electrodialysis and the second-stage bipolar membrane electrodialysis, so that the resource utilization rate is improved. The method of reverse osmosis, high pressure reverse osmosis and electrodialysis is not limited in the present invention, and any method known to those skilled in the art to achieve the purpose of concentration may be used.
In the present invention, the fresh water produced by reverse osmosis in the step (2) is used for the first-stage bipolar membrane electrodialysis and the second-stage bipolar membrane electrodialysis; the concentrated solution generated by the high-pressure reverse osmosis is used for the first-stage bipolar membrane electrodialysis and the second-stage bipolar membrane electrodialysis.
In the present invention, the ratio of the concentration of the salt in the concentrated high-salt well water in the step (2) to the concentration of the salt in the pretreated high-salt well water is preferably 8 to 12:1, more preferably 8.7 to 11.2:1, more preferably 10.3:1.
in the present invention, the composition of the membrane stack of the first-stage bipolar membrane electrodialysis in step (3) is shown in fig. 2, and specifically:
the membrane stack composition of the first-stage bipolar membrane electrodialysis comprises an anode 21, an anode chamber 41, a repeated membrane group unit, a monovalent selective anion exchange membrane 22, a salt chamber 42, a monovalent selective cation exchange membrane 23, a cathode chamber 45 and a cathode 25 which are sequentially arranged;
wherein, the repeated membrane group unit comprises a monovalent selective anion-exchange membrane 22, a salt chamber 42, a monovalent selective cation-exchange membrane 23, an alkali chamber 43, a bipolar membrane 24 and an acid chamber 44 which are arranged in sequence; the cathode membrane of the bipolar membrane 24 in the repeating membrane group unit and the monovalent selective cation exchange membrane 23 form an alkali chamber 43; the anode membrane of the bipolar membrane 24 in the repeating membrane group unit and the monovalent selective anion exchange membrane 22 form an acid chamber 44; the number of the repeating groups of the repeating membrane group unit is 10-100, and the number of the repeating groups of the repeating membrane group unit can be adjusted according to the amount of water to be treated.
In the present invention, the separation function of the valence selective anion exchange membrane 22 in the step (3) is: under the action of an electric field, monovalent anions pass through, and divalent anions are intercepted; the separation function of the monovalent selective cation exchange membrane 23 is: under the action of an electric field, monovalent cations pass through, and divalent cations are intercepted. The sources of the monovalent selective anion exchange membrane and the monovalent selective cation exchange membrane are not limited in the present invention, and the monovalent selective anion exchange membrane and the monovalent selective cation exchange membrane can be obtained from commercial products available to those skilled in the art or from previous studies by the inventors (for example, patent 202110156619.1, 202011610615.8).
In the present invention, the process flow of performing the bipolar membrane electrodialysis in step (3) is shown in fig. 4, and specifically includes:
introducing the concentrated high-salinity mine water obtained by membrane concentration in the step (2) into a brine circulating water tank 57 of first-stage bipolar membrane electrodialysis; introducing the concentrated solution generated by high-pressure reverse osmosis in the membrane concentration in the step (2) into an electrode water circulating water tank 56 of primary bipolar membrane electrodialysis, namely preparing about 5% of saline water as electrode water; respectively introducing fresh water generated by reverse osmosis in the membrane concentration in the step (2) into an alkali liquor circulating water tank 58 and an acid liquor circulating water tank 59 of the first-stage bipolar membrane electrodialysis; simultaneously starting a polar water circulating pump 61, a brine circulating pump 62, an alkali liquor circulating pump 63, an acid liquor circulating pump 64 and a direct-current power supply 60 to perform electrodialysis; under the action of an electric field, ions in high-salt mine water are subjected to directional migration: chloride ions penetrate through the monovalent selective anion exchange membrane 22 to enter an anode side flow channel of the bipolar membrane 24, and are dissociated with H generated by the bipolar membrane 24 in water + Finally, HCl solution with certain concentration flows out; sodium ions penetrate through the monovalent selective cation exchange membrane 23 to enter a cathode side flow channel of the bipolar membrane 24, and are dissociated with OH generated by the bipolar membrane 24 in water - Finally, flowing out with NaOH solution with certain concentration; SO in high salinity mine water due to the interception of monovalent selective anion and cation exchange membranes 22, 23 4 2- 、CO 3 2- Divalent anions and small amount of Ca remaining after softening 2+ 、Mg 2+ Cation is interceptedThe solution is left in the salt chamber 42, so that the purity of HCl and NaOH solution is improved; after the operation is carried out for a certain time, the salt concentration in the brine circulation water tank 57 is reduced, the NaOH concentration in the alkali liquor circulation water tank 58 reaches more than 5 percent and can be reused for the pretreatment and downstream industrial chains in the step (1), and the HCl concentration in the acid liquor circulation water tank 59 reaches more than 5 percent and can be reused for the pretreatment and downstream industrial chains in the step (1); when the salt concentration in the brine circulating water tank 57 does not decrease after a period of operation, the remaining main anion in the high-salt mine water is SO 4 2- 、CO 3 2- And obtaining mixed salt solution.
In the present invention, the composition of the membrane stack of the two-stage bipolar membrane electrodialysis in step (4) is shown in fig. 3, and specifically:
the membrane stack composition of the two-stage bipolar membrane electrodialysis comprises an anode 21, an anode chamber 41, a repeated membrane group unit, an anion exchange membrane 32, a salt chamber 42, a monovalent selective cation exchange membrane 23, a cathode chamber 45 and a cathode 25 which are sequentially arranged;
wherein, the repeated membrane group unit comprises an anion exchange membrane 32, a salt chamber 42, a monovalent selective cation exchange membrane 23, an alkali chamber 43, a bipolar membrane 24 and an acid chamber 44 which are arranged in sequence; the cathode membrane of the bipolar membrane 24 in the repeating membrane group unit and the monovalent selective cation exchange membrane 23 form an alkali chamber 43; the anode membrane of the bipolar membrane 24 in the repeating membrane group unit and the anion exchange membrane 32 form an acid chamber 44; the number of the repeating groups of the repeating membrane group unit is 10-100, and the number of the repeating groups of the repeating membrane group unit can be adjusted according to the amount of water to be treated.
In the present invention, the separation function of the valence selective cation exchange membrane 23 in the step (4) is: under the action of an electric field, monovalent cations pass through, and divalent cations are intercepted.
In the present invention, the process flow of performing the two-stage bipolar membrane electrodialysis in step (4) is shown in fig. 5, and specifically includes:
introducing the mixed salt solution generated by the first-stage bipolar membrane electrodialysis in the step (3) into a brine circulating water tank 67 for the second-stage bipolar membrane electrodialysis; introducing the concentrated solution generated by high-pressure reverse osmosis in the membrane concentration in the step (2) into a polar water circulation water tank 66 of the second-stage bipolar membrane electrodialysis, which is equivalent to the preparation ofPutting about 5% of saline water as polar water; respectively introducing fresh water generated by reverse osmosis in the membrane concentration in the step (2) into an alkali liquor circulating water tank 68 and an acid liquor circulating water tank 69 for two-stage bipolar membrane electrodialysis; simultaneously starting an electrode water circulating pump 71, a brine circulating pump 72, an alkali liquor circulating pump 73, an acid liquor circulating pump 74 and a direct-current power supply 70 to perform electrodialysis; mixing SO in the salt solution under the action of an electric field 4 2- 、CO 3 2- Divalent anions penetrate through the anion exchange membrane 32 to enter the anode side flow channel of the bipolar membrane 24, and are dissociated with the bipolar membrane 24 to generate H + Finally at a certain concentration of H 2 SO 4 、CO 2 The mixed acid liquid flows out; sodium ions penetrate through the monovalent selective cation exchange membrane 23 to enter a cathode side flow channel of the bipolar membrane 24, and are dissociated with OH generated by the bipolar membrane 24 in water - Finally, flowing out with NaOH solution with certain concentration; a small amount of Ca remaining due to the entrapment by the monovalent selective cation exchange membrane 23 2+ 、Mg 2+ The cations are trapped in the salt chamber 42, thereby raising H 2 SO 4 And the purity of NaOH solution; after the operation is carried out for a certain time, the salt concentration in the brine circulating water tank 67 is reduced, the NaOH concentration in the alkali liquor circulating water tank 68 reaches more than 5 percent and can be reused in the pretreatment and downstream industrial chains in the step (1), and the mixed acid liquor in the acid liquor circulating water tank 69 reaches more than 5 percent and can enter a stripping tower for stripping; the salt concentration in the brine circulating water tank 67 is reduced to less than 1%, and the brine is refluxed to the front end of the membrane concentration in the step (2) to carry out the membrane concentration.
In the present invention, the H in the acid solution is mixed under acidic conditions in the step (5) 2 CO 3 With CO 2 Is blown into the atmosphere in a stripping tower to finally obtain pure H 2 SO 4 And (3) solution. Compared with the traditional stripping method, the stripping method of the invention omits the regulation of pH value and avoids adding a large amount of acid and alkali.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The embodiment provides a high-salinity well water recycling treatment process, which comprises the following steps of:
(1) Pretreatment: the salt content of high-salt mine water is 3172mg/L, wherein Ca 2+ 、Mg 2+ 、Na + The contents are 212mg/L, 48mg/L and 675mg/L respectively, HCO 3 - 、SO 4 2- 、Cl - The content is 582mg/L, 991mg/L and 664mg/L respectively;
adding PAC and sodium hydroxide into the high-salt mine water for coagulating sedimentation, filtering, and then carrying out ion exchange softening and desilicication to obtain pretreated high-salt mine water, wherein Ca 2+ 、Mg 2+ 、Na + Respectively in the content of<1mg/L、<1mg/L、1382mg/L，CO 3 2- 、SO 4 2- 、Cl - The content is 276mg/L, 984mg/L and 665mg/L respectively;
(2) And (3) membrane concentration: sequentially carrying out reverse osmosis, high-pressure reverse osmosis and electrodialysis on the pretreated high-salt mine water to obtain concentrated high-salt mine water, wherein Ca 2+ 、Mg 2+ 、Na + The contents are respectively 8mg/L, 3.5mg/L and 11350mg/L, CO 3 2- 、SO 4 2- 、Cl - The content is 2730mg/L, 9710mg/L and 6540mg/L respectively;
(3) First-stage bipolar membrane electrodialysis: performing primary bipolar membrane electrodialysis on the concentrated high-salt mine water, wherein the number of repeated groups of repeated membrane group units in a membrane stack is 10, the concentration of NaOH in an alkali liquor circulating water tank 58 reaches 5.2%, the concentration of HCl in an acid liquor circulating water tank 59 reaches 5.1% after the operation for 120min, and the main residual anions in a brine circulating water tank 57 are SO 4 2- 、CO 3 2- Obtaining mixed salt solution;
(4) And (3) second-stage bipolar membrane electrodialysis: performing two-stage bipolar membrane electrodialysis on the mixed salt solution, wherein the number of repeating groups of repeating membrane group units in the membrane stack is 10, the concentration of NaOH in the alkali liquor circulating water tank 68 reaches 5.1%, the concentration of mixed acid in the acid liquor circulating water tank 69 reaches 5.4% after the membrane stack is operated for 120min, and the brine circulatesThe remaining major cation in the annular water tank 67 is Ca 2+ 、Mg 2+ Obtaining low-salt liquid, and refluxing the low-salt liquid to the step (2) for membrane concentration;
(5) Stripping by blowing: introducing the mixed acid liquid into a stripping tower for stripping, and removing H in the mixed acid liquid under acidic condition 2 CO 3 With CO 2 Is blown into the atmosphere in a stripping tower to finally obtain 3.4 percent pure H 2 SO 4 And (3) solution.
Ca in NaOH solution produced by first-stage bipolar membrane electrodialysis and bipolar membrane electrodialysis due to action of monovalent selective cation-anion exchange membrane 2+ 、Mg 2+ SO in HCl solution produced by first-stage bipolar membrane electrodialysis without content detection 4 2- The content ratio is less than 5 percent.
Example 2
The embodiment provides a high-salinity mine water recycling treatment process, which comprises the following steps:
(1) Pretreatment: the salt content of high-salt mine water is 4115mg/L, wherein Ca 2+ 、Mg 2+ 、Na + The contents are 340mg/L, 83mg/L and 736mg/L respectively, HCO 3 - 、SO 4 2- 、Cl - The content is 915mg/L, 1008mg/L and 1030mg/L respectively;
adding PAC and sodium hydroxide into the high-salt mine water for coagulating sedimentation, filtering, and then carrying out ion exchange softening and desilicication to obtain pretreated high-salt mine water, wherein Ca 2+ 、Mg 2+ 、Na + Respectively in an amount of<1mg/L、<1mg/L、1560mg/L，CO 3 2- 、SO 4 2- 、Cl - The contents are 460mg/L, 992mg/L and 1010mg/L respectively;
(2) And (3) membrane concentration: sequentially carrying out reverse osmosis, high-pressure reverse osmosis and electrodialysis on the pretreated high-salt mine water to obtain concentrated high-salt mine water, wherein Ca 2+ 、Mg 2+ 、Na + The contents are respectively 7mg/L, 3mg/L and 16170mg/L, CO 3 2- 、SO 4 2- 、Cl - The content is 4675mg/L, 10700mg/L and 10990mg/L respectively;
(3) First-order bipolar membraneElectrodialysis: performing first-stage bipolar membrane electrodialysis on the concentrated high-salt mine water, wherein the number of repeating groups of repeating membrane group units in a membrane stack is 15, the concentration of NaOH in an alkali liquor circulating water tank 58 reaches 5.5%, the concentration of HCl in an acid liquor circulating water tank 59 reaches 5.3% after the membrane stack is operated for 120min, and the main residual anions in a brine circulating water tank 57 are SO 4 2- 、CO 3 2- Obtaining mixed salt solution;
(4) And (3) electrodialysis by using a two-stage bipolar membrane: performing secondary bipolar membrane electrodialysis on the mixed salt solution, wherein the number of repeating groups of repeating membrane group units in a membrane stack is 15, the concentration of NaOH in an alkali liquor circulating water tank 68 reaches 5.2 percent after the membrane stack is operated for 120min, the concentration of mixed acid in an acid liquor circulating water tank 69 reaches 5.6 percent, and the main cations remained in a brine circulating water tank 67 are Ca 2+ 、Mg 2+ Obtaining low-salt liquid, and refluxing the low-salt liquid to the step (2) for membrane concentration;
(5) Stripping by blowing: introducing the mixed acid liquid into a stripping tower for stripping, and removing H in the mixed acid liquid under acidic condition 2 CO 3 With CO 2 In the form of pure H of 3.6% by blowing into the atmosphere in a stripping column 2 SO 4 And (3) solution.
Ca in NaOH solution produced by first-stage bipolar membrane electrodialysis and bipolar membrane electrodialysis due to action of monovalent selective anion-cation exchange membrane 2+ 、Mg 2+ SO in HCl solution produced by first-stage bipolar membrane electrodialysis with undetected content 4 2- The content ratio is less than 5%.
Example 3
The embodiment provides a high-salinity mine water recycling treatment process, which comprises the following steps:
(1) Pretreatment: the salt content of high-salt mine water is 2270mg/L, and the conductivity is 3.24mS/cm;
adding PAC and sodium hydroxide into the high-salt mine water for coagulating sedimentation, filtering, and then carrying out ion exchange softening to remove silicon to obtain pretreated high-salt mine water with the conductivity of 3.53mS/cm;
(2) And (3) membrane concentration: sequentially carrying out reverse osmosis, high-pressure reverse osmosis and electrodialysis on the pretreated high-salt mine water to obtain concentrated high-salt mine water with the conductivity of 90.5mS/cm;
(3) First-stage bipolar membrane electrodialysis: performing first-stage bipolar membrane electrodialysis on the concentrated high-salt mine water, wherein the concentration of NaOH in the alkali liquor circulating water tank 58 reaches 5.6%, the concentration of HCl in the acid liquor circulating water tank 59 reaches 5.1%, and the main anions remained in the brine circulating water tank 57 are SO after the operation for 120min 4 2- 、CO 3 2- Obtaining mixed salt solution;
(4) And (3) second-stage bipolar membrane electrodialysis: performing two-stage bipolar membrane electrodialysis on the mixed salt solution, wherein after the operation for 120min, the concentration of NaOH in the alkali liquor circulating water tank 68 reaches 5.1%, the concentration of the mixed acid in the acid liquor circulating water tank 69 reaches 5.0%, and the main cations left in the brine circulating water tank 67 are Ca 2+ 、Mg 2+ Obtaining low-salt liquid, and refluxing the low-salt liquid to the step (2) for membrane concentration;
(5) Stripping by blowing: introducing the mixed acid liquid into a stripping tower for stripping, and removing H in the mixed acid liquid under acidic condition 2 CO 3 With CO 2 In the form of pure H of 3.3% purity is obtained by blowing into the atmosphere in a stripping tower 2 SO 4 And (3) solution.
Ca in NaOH solution produced by first-stage bipolar membrane electrodialysis and bipolar membrane electrodialysis due to action of monovalent selective anion-cation exchange membrane 2+ 、Mg 2+ SO in HCl solution produced by first-stage bipolar membrane electrodialysis without content detection 4 2- The content ratio is less than 5%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A high-salinity mine water recycling treatment process is characterized by comprising the following steps:
(1) Pretreatment: sequentially carrying out coagulating sedimentation, filtration and ion exchange softening and silicon removal on the high-salt mine water to obtain pretreated high-salt mine water;
(2) And (3) membrane concentration: sequentially carrying out reverse osmosis, high-pressure reverse osmosis and electrodialysis on the pretreated high-salt mine water to obtain concentrated high-salt mine water;
(3) First-stage bipolar membrane electrodialysis: performing first-stage bipolar membrane electrodialysis on the concentrated high-salt mine water to respectively obtain hydrochloric acid solution, sodium hydroxide alkali solution and mixed salt solution;
(4) And (3) electrodialysis by using a two-stage bipolar membrane: performing two-stage bipolar membrane electrodialysis on the mixed salt solution to respectively obtain a mixed acid solution, a sodium hydroxide alkali solution and a low-salt solution;
(5) Stripping by blowing: and blowing off the mixed acid liquor to obtain carbon dioxide gas and sulfuric acid liquor.
2. The high-salinity mine water recycling treatment process according to claim 1, characterized in that the step (1) further comprises adding a softening agent while performing coagulating sedimentation; ion exchange softening and silicon removal by using ion exchange resin; the regeneration method of the ion exchange resin comprises the steps of firstly using acid liquor for regeneration and then using alkali liquor for neutralization.
3. The high-salinity mine water recycling treatment process according to claim 2, characterized in that the softening agent in the step (1) is the sodium hydroxide lye of the step (3) and/or the sodium hydroxide lye of the step (4); the acid solution in the regeneration method of the ion exchange resin is the hydrochloric acid solution in the step (3); and (3) the alkali liquor in the regeneration method of the ion exchange resin is the sodium hydroxide alkali liquor in the step (3) and/or the sodium hydroxide alkali liquor in the step (4).
4. The high-salinity mine water recycling treatment process according to claim 1 or 2, wherein the ratio of the concentration of the salt in the concentrated high-salinity mine water in the step (2) to the concentration of the salt in the pretreated high-salinity mine water is 8-12: 1.
5. the high-salt mine water resource treatment process according to any one of claims 1 to 3, characterized in that the membrane stack composition of the first-stage bipolar membrane electrodialysis in the step (3) comprises an anode, an anode chamber, a repeated membrane group unit, a monovalent selective anion exchange membrane, a salt chamber, a monovalent selective cation exchange membrane, a cathode chamber and a cathode which are arranged in sequence;
the repeated membrane module unit comprises a monovalent selective anion exchange membrane, a salt chamber, a monovalent selective cation exchange membrane, an alkali chamber, a bipolar membrane and an acid chamber which are sequentially arranged; the cathode membrane of the bipolar membrane in the repeated membrane group unit and the monovalent selective cation exchange membrane form an alkali chamber; an acid chamber is formed by an anode membrane of the bipolar membrane in the repeated membrane group unit and a monovalent selective anion exchange membrane; the number of the repeating groups of the repeating membrane group unit is 10 to 100.
6. The high-salinity mine water recycling treatment process according to claim 5, wherein the separation function of the valence selective anion exchange membrane in the step (3) is as follows: under the action of an electric field, monovalent anions pass through, and divalent anions are intercepted;
the separation function of the monovalent selective cation exchange membrane is as follows: under the action of an electric field, monovalent cations pass through, and divalent cations are intercepted.
7. The high-salinity mine water resource treatment process according to claim 1, characterized in that the membrane stack composition of the two-stage bipolar membrane electrodialysis in the step (4) comprises an anode, an anode chamber, a repeating membrane group unit, an anion exchange membrane, a salt chamber, a monovalent selective cation exchange membrane, a cathode chamber and a cathode which are arranged in sequence;
the repeated membrane group unit comprises an anion exchange membrane, a salt chamber, a monovalent selective cation exchange membrane, an alkali chamber, a bipolar membrane and an acid chamber which are sequentially arranged; the cathode membrane of the bipolar membrane in the repeated membrane group unit and the monovalent selective cation exchange membrane form an alkali chamber; an anode membrane and an anion exchange membrane of the bipolar membrane in the repeated membrane group unit form an acid chamber; the number of repeating groups of the repeating membrane group unit is 10 to 100.
8. The high-salinity mine water recycling treatment process according to claim 7, wherein the separation function of the valence selective cation exchange membrane in the step (4) is as follows: under the action of an electric field, monovalent cations pass through, and divalent cations are intercepted.
9. The high-salt mine water resource treatment process according to claim 1 or 7, characterized in that the low-salt solution in the step (4) flows back to the step (2) for membrane concentration.
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