CN111635050A - Method and device for treating high-salinity mine water - Google Patents
Method and device for treating high-salinity mine water Download PDFInfo
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Abstract
The invention provides a device and a method for treating high-salinity mine water. The treatment device and the method comprise a regulating tank, a pretreatment system, an ultrafiltration system, a first-stage membrane system, a first-stage concentrated water reaction tank, a tubular membrane system, a second-stage membrane system, an ion exchanger, a three-stage salt extraction system and an evaporative crystallization salt separation system which are sequentially connected. The first-stage concentrated water reaction tank and the second-stage concentrated water reaction tank are communicated with a dispenser. The invention has reasonable structure, small occupied area of the device, flexible operation and low cost, and can adjust the water production index of the mine water according to local or national standards and the needs of owners, thereby realizing the standard discharge or recycling of the mine water.
Description
Technical Field
The invention relates to a device and a method for treating high-salinity mine water, belonging to the field of water treatment.
Background
The mine water with high mineralization degree is directly discharged without being treated, and certain harm is brought to the ecological environment. The method mainly comprises the steps of rising the salt content of river water, raising the shallow underground water level, breeding salinization in soil, weakening the tree vigor of salt and alkali resistance, reducing the yield of crops and the like. It also affects the industrial production in the region, because many industrial processes cannot use water with high salt content, and if the industrial processes are used, the salt content in the water must be reduced, so that the cost is increased. If the underground water is not used, a large amount of underground water is exploited, underground water resources are in short supply, and the economic development of the region is seriously influenced.
With the increasing environmental protection pressure, the national policy is gradually changed, and the mine water with high mineralization degree cannot be directly discharged at present, so that an effective and low-cost method for treating the mine water with high mineralization degree is urgently needed.
Disclosure of Invention
The purpose of the invention is: the method solves the problem that the prior art has no better treatment method for the mine water with high mineralization degree. The method can effectively treat the mine wastewater, remove impurity ions in the mine wastewater, and simultaneously recover and obtain sodium sulfate as a byproduct.
The technical scheme is as follows:
a method for treating high-salinity mine water comprises the following steps:
step 1, adding a coagulant into the high-salinity mine water to perform coagulation reaction;
step 2, filtering the wastewater obtained in the step 1 by adopting a solid-liquid separation membrane to remove solid suspended matters;
step 3, performing first reverse osmosis concentration treatment on the filtrate obtained in the step 2 to improve the salt concentration;
step 4, adding NaOH and Na into the concentrated solution obtained in the step 32CO3Precipitating impurity cations;
step 6, carrying out second reverse osmosis concentration treatment on the filtrate obtained in the step 5;
step 7, carrying out ion exchange treatment on the concentrated solution obtained in the step 6 to remove impurity cations;
step 8, carrying out third reverse osmosis concentration treatment on the wastewater obtained in the step 7, and then carrying out concentration and crystallization to obtain recovered Na2SO4。
In one embodiment, a flocculating agent is added after the coagulation reaction in step 1.
In one embodiment, the coagulant is polyaluminum chloride and is added in an amount of 40mg/L to 80 mg/L.
In one embodiment, the flocculant is polyacrylamide and is added in an amount of 4-8 mg/L.
In one embodiment, a flocculation nucleating agent is also added during the coagulation in step 1.
In one embodiment, the flocculation nucleating agent is selected from bentonite, powdered activated carbon, activated silicic acid, ferroferric oxide subjected to surface hydrophobic modification treatment; the addition amount is 400mg/L-500 mg/L.
In one embodiment, Na2CO3The adding concentration of (1) is 4g/L-8 g/L; NaOH is added in the pH range of 10-12.
In one embodiment, the ion exchange process may employ a weakly acidic cation exchange resin.
In one embodiment, the third reverse osmosis concentration is Disc Tube Reverse Osmosis (DTRO).
In one embodiment, the crystallization temperature is from-5 ℃ to 5 ℃ and the crystallization mode is fractional crystallization.
A device for treating high-salinity mine water comprises:
the coagulation reaction tank is used for carrying out coagulation reaction on the mine water;
the coagulant adding tank is connected with the coagulation reaction tank and is used for adding a coagulant into the coagulation reaction tank;
the first solid-liquid separation membrane is connected to the coagulation reaction tank and is used for carrying out solid-liquid separation treatment on the wastewater subjected to coagulation reaction in the coagulation reaction tank;
the first reverse osmosis membrane is connected to the filtrate side of the first solid-liquid separation membrane and is used for performing reverse osmosis concentration treatment on the filtrate of the first solid-liquid separation membrane;
the precipitation reaction tank is connected to the concentration side of the first reverse osmosis membrane and is used for carrying out precipitation reaction on the concentrated solution of the first reverse osmosis membrane to remove impurity cations;
NaOH is added into the tank and Na2CO3Adding tanks respectively connected to the precipitation reaction tank for adding NaOH and Na into the precipitation reaction tank 72CO3；
The second solid-liquid separation membrane is connected to the precipitation reaction tank and is used for carrying out solid-liquid separation treatment on the wastewater obtained by the reaction in the precipitation reaction tank;
the second reverse osmosis membrane is connected to the filtrate side of the second solid-liquid separation membrane and is used for concentrating the penetrating fluid of the second solid-liquid separation membrane;
the ion exchange resin column is connected to the concentration side of the second reverse osmosis membrane and is used for carrying out ion exchange treatment on the concentrated solution of the second reverse osmosis membrane to remove impurity cations;
the third reverse osmosis membrane is connected with the ion exchange resin column and is used for concentrating the produced water of the ion exchange resin column;
an evaporative crystallization device connected to the concentration side of the third reverse osmosis membrane for carrying out evaporative crystallization treatment on the concentrated solution of the third reverse osmosis membrane to obtain recovered Na2SO4。
In one embodiment, further comprising: and the nucleating agent adding tank is connected to the coagulation reaction tank and is used for adding the coagulation nucleating agent into the coagulation reaction tank.
In one embodiment, further comprising: and the flocculating agent adding tank is connected to the coagulation reaction tank and is used for adding the flocculating agent into the coagulation reaction tank.
In one embodiment, the average pore size of the first solid-liquid separation membrane and/or the second solid-liquid separation membrane is in the range of 50 to 2000 nm.
In one embodiment, the ion exchange resin column is packed with a weakly acidic cation exchange resin.
In one embodiment, the third reverse osmosis membrane is a Disc Tube Reverse Osmosis (DTRO).
In one embodiment, the evaporative crystallization device consists of an MVR evaporator and a cryocrystallizer.
The device for treating the high-salinity mine water is applied to treating the mine water.
Advantageous effects
In conclusion, the invention adopts the membrane integration technology as the core to solve the treatment problem of the high-salinity mine water, reduces the environmental protection pressure, and the desalted produced water reaches the standard and is discharged or used for replacing and exploiting underground water for recycling water used by power plants, bathing and the like, thereby greatly reducing the water resource cost and having considerable economic benefit. Compared with other similar patents, the method has the following advantages:
1. the pretreatment can adopt special pretreatment technology, and the advantage is that the required sedimentation tank is only 1/10 traditional sedimentation tank. Greatly saves a sedimentation tank required by the traditional coagulating sedimentation and reduces the cost and the space. The used iron powder can be recycled, and the recovery rate can reach 99 percent;
2. the process can be flexibly adjusted according to the water production requirement reuse or discharge index, and the technical transformation is convenient;
3. when the nanofiltration process is adopted, the operation cost can be effectively reduced, the pressure of a subsequent reverse osmosis membrane system is reduced, and the production cost is further reduced;
4. the three-section salt extraction system can select DTRO or electrodialysis to realize the improvement of salt concentration according to the front-end process, and reduce the subsequent steam consumption or power consumption;
5. with the increase of environmental protection pressure, the national requirements on environmental protection are higher and higher, the indexes of sewage treatment are stricter and stricter, and the process can select a proper membrane system according to the change of policies in the future.
Drawings
FIG. 1 is a system set-up diagram of the present invention. FIG. 2 is a comparison of the turbidity effect of the coagulation treatment. FIG. 3 is a flux decay curve for a ceramic membrane
Wherein, 1, a coagulation reaction tank; 2. adding a coagulant into a tank; 3. a nucleating agent adding tank; 4. a flocculant adding tank; 5. a first solid-liquid separation membrane; 6. a first reverse osmosis membrane; 7. a precipitation reaction tank; 8. adding NaOH into the tank; 9. na (Na)2CO3Adding into a tank; 10. a second solid-liquid separation membrane; 11. a second reverse osmosis membrane; 12. ion exchange resin column; 13. a third reverse osmosis membrane; 14. and (4) an evaporation crystallization device.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments. It will be understood by those skilled in the art that the following examples are illustrative of the present invention only and should not be taken as limiting the scope of the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Approximating language, as used herein throughout the specification and claims, may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as "about," is not to be limited to the precise value specified. In at least some instances, the approximating language may correspond to the precision of an instrument for measuring the value. Unless context or language indicates otherwise, range limitations may be combined and/or interchanged, and such ranges are identified and include all the sub-ranges included herein. Other than in the operating examples, or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as modified in all instances by the word "about".
The recitation of values by ranges is to be understood in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a concentration range of "about 0.1% to about 5%" should be interpreted to include not only the explicitly recited concentration of about 0.1% to about 5%, but also include individual concentrations (e.g., 1%, 2%, 3%, and 4%) and sub-ranges (e.g., 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%) within the indicated range.
The term "removal" in the present specification includes not only a case where a target substance is completely removed but also a case where the target substance is partially removed (the amount of the substance is reduced). "purification" in this specification includes the removal of any or specific impurities.
The words "include," "have," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The mine water produced in the coal mining process needs to be treated by the invention, the water quality of the mine water contains organic matters, generally COD is about 5-100ppm, and in addition, the mine water has higher salt content, generally contains Total Dissolved Solids (TDS) 200-5000ppm, total nitrogen 1-20ppm, total hardness 200-5000ppm and sulfate radical 100-3000 ppm.
As mine wastewater contains more suspended impurities and organic pollution, the process of the invention firstly carries out coagulation reaction on the mine wastewater, and the adopted coagulant can be polyaluminium chloride, and the addition amount can be 40mg/L-80 mg/L; in addition, in order to further improve the coagulation effect, a coagulation nucleating agent can be added, the nucleating agent can be used in the invention without special limitation, and the nucleating agent has the function of leading the colloid to be mixed in the coagulation processThe surface of the condensed nucleus grows and condenses to enlarge the aggregate, and the aggregate can be separated by subsequent sedimentation and filtration, wherein the nucleating agent can be bentonite, powdered activated carbon, activated silicic acid and the like, preferably ferroferric oxide nucleating agent subjected to surface hydrophobic modification treatment, and the preparation process can be that the nucleating agent contains 5wt% of Fe3O4Adding oleic acid into the absolute ethyl alcohol solution, wherein the addition amount of the oleic acid is Fe3O4About 3 times of the amount of the acid-modified ferroferric oxide nucleating agent, reacting at 80 ℃ for about 1 hour after uniformly stirring, filtering out precipitates, washing with ethanol and drying to obtain the oleic acid-modified ferroferric oxide nucleating agent, which can effectively adsorb organic impurities in mine water and improve the flocculation effect; the addition amount of the nucleating agent can be controlled between 400mg/L and 500 mg/L.
In order to further improve the coagulation effect, a flocculating agent can be added after the coagulation reaction, so that the concrete can be further grown and is easier to settle and separate. The flocculant used herein may be Polyacrylamide (PAM), and its addition amount may be controlled to 4-8 mg/L.
After the coagulation reaction is carried out, the flocculating constituent can be filtered and removed by a solid-liquid separation mode, wherein the solid-liquid separation mode can adopt a conventional microfiltration membrane or an ultrafiltration membrane, and the average pore diameter is in a range of 50-2000 nm.
After solid-liquid separation, the filtrate needs to be subjected to reverse osmosis concentration treatment for the first time, the reverse osmosis treatment for the first time aims to improve the concentration of inorganic salt ions in the filtrate, so that the subsequent precipitation reaction by adding a precipitator is facilitated, and when the filtrate enters a section of reverse osmosis membrane system, a scale inhibitor needs to be added to prevent calcium scaling. The added concentration of the scale inhibitor is 1mg/L-50 mg/L.
Then NaOH and Na are added2CO3The aim of the method is to ensure that most of hardness ions in the solution are generated into colloidal precipitate, mainly calcium and magnesium ions and other heavy metal ions, the adding concentration of sodium carbonate is 4g/L-8g/L, the adding concentration of sodium hydroxide is calculated by the pH value, the pH value is 10-12, after the precipitate is generated, the precipitate is filtered again through a subsequent solid-liquid separation membrane, and the generated colloidal precipitate can be obtainedFor filtration separation, the solid-liquid separation can be carried out by using a conventional microfiltration membrane or ultrafiltration membrane, and the average pore diameter is in the range of 50 to 2000 nm.
The filtrate obtained after the solid-liquid separation is subjected to a concentration treatment by a reverse osmosis membrane for the second time, whereby the salt concentration can be further increased and the amount of wastewater can be reduced.
Because all impurity metal ions cannot be removed in the process of precipitation reaction, the impurity metal ions can be deeply removed by adopting an ion exchange method for the concentrated solution after the concentrated solution is concentrated by the reverse osmosis membrane for the second time, and the ion exchange process used here can adopt weak acid cation exchange resin, and can exchange the impurity metal ions into sodium ions.
The wastewater obtained by the ion exchange resin treatment is concentrated by a third reverse osmosis membrane, the reverse osmosis membrane used in the step can be a disc tube type reverse osmosis (DTRO), the wastewater amount can be further reduced, and the recovered Na can be obtained by subsequent evaporative concentration crystallization2SO4The freezing crystallization temperature is-5 ℃, and the crystallization mode is fractional crystallization.
Based on the method, the invention also provides a device for treating the high-salinity mine water, which comprises the following steps:
the coagulation reaction tank 1 is used for carrying out coagulation reaction on mine water;
a coagulant adding tank 2 connected to the coagulation reaction tank 1 and used for adding a coagulant into the coagulation reaction tank 1;
the first solid-liquid separation membrane 5 is connected to the coagulation reaction tank 1 and is used for performing solid-liquid separation treatment on the wastewater subjected to coagulation reaction in the coagulation reaction tank 1;
a first reverse osmosis membrane 6 connected to the filtrate side of the first solid-liquid separation membrane 5, for performing reverse osmosis concentration treatment on the filtrate of the first solid-liquid separation membrane 5;
the precipitation reaction tank 7 is connected to the concentration side of the first reverse osmosis membrane 6 and is used for carrying out precipitation reaction on the concentrated solution of the first reverse osmosis membrane 6 to remove impurity cations;
NaOH addition tank 8 and Na2CO3The adding tanks 9 are respectively connected with the precipitation reaction tank 7 and are respectively used for adding NaOH and Na into the precipitation reaction tank 72CO3；
The second solid-liquid separation membrane 10 is connected to the precipitation reaction tank 7 and is used for performing solid-liquid separation treatment on the wastewater obtained by the reaction in the precipitation reaction tank 7;
a second reverse osmosis membrane 11 connected to the filtrate side of the second solid-liquid separation membrane 10, for concentrating the permeate of the second solid-liquid separation membrane 10;
an ion exchange resin column 12 connected to the concentration side of the second reverse osmosis membrane 11 for performing ion exchange treatment to remove impurity cations from the concentrated solution of the second reverse osmosis membrane 11;
the third reverse osmosis membrane 13 is connected to the ion exchange resin column 12 and is used for concentrating the produced water of the ion exchange resin column 12;
an evaporative crystallization device 14 connected to the concentration side of the third reverse osmosis membrane 13 for subjecting the concentrated solution of the third reverse osmosis membrane 13 to evaporative crystallization treatment to obtain recovered Na2SO4。
In one embodiment, further comprising: and the nucleating agent adding tank 3 is connected to the coagulation reaction tank 1 and is used for adding the coagulation nucleating agent into the coagulation reaction tank 1.
In one embodiment, further comprising: and the flocculating agent adding tank 4 is connected to the coagulation reaction tank 1 and is used for adding the flocculating agent into the coagulation reaction tank 1.
In one embodiment, the average pore size of the first solid-liquid separation membrane and/or the second solid-liquid separation membrane is in the range of 50 to 2000 nm.
In one embodiment, ion exchange resin column 12 is packed with a weakly acidic cation exchange resin.
In one embodiment, the third reverse osmosis membrane 13 is a Disc Tube Reverse Osmosis (DTRO).
In one embodiment, the evaporative crystallization device 14 consists of an MVR evaporator and a cryocrystallizer.
The water quality of the high-salinity mine water to be treated in the following process is as follows: turbidity 45NTU, COD65ppm, TDS3300ppm, total nitrogen 12ppm, total hardness 1660 ppm, sulfate 1450 ppm.
Example 1
When the treatment device and the treatment method are adopted in a certain coal mine, mine water is firstly buffered in the flow and water quality adjusting tank.
The water in the regulating tank is conveyed to a superconducting magnetic separator, and 400mg/L Fe is added by an adding device3O4Coagulating 40mg/L PAC, flocculating, and adding 4mg/L PAM; after flocculation treatment, a superconductive magnetic separator is used for separating and removing floccules, effluent is filtered by a ceramic membrane with the aperture of 50nm, the filtering pressure is 0.3MPa, the cross flow velocity is 2m/s, and mine water is further clarified.
The filtrate of the ceramic membrane enters a section of reverse osmosis membrane system to separate salt and water in the mine water, the operation pressure is 1.0Mpa, and the water recovery rate is 60%.
Adding sodium carbonate and sodium hydroxide into concentrated water of the first-stage reverse osmosis membrane system for softening, wherein the concentration of the added sodium carbonate is 4 g/L. Sodium hydroxide was added to ph10 and then treated with a 0.2um tubular microfiltration membrane to remove suspended matter.
And the effluent of the tubular microfiltration membrane enters a two-stage reverse osmosis membrane system to further separate salt and water in the mine water, the membrane system is used by combining an ordinary pressure reverse osmosis membrane and a seawater desalination membrane, the operating pressure of the ordinary pressure reverse osmosis membrane is 1.0MPa, and the operating pressure of the seawater desalination membrane is 3.0 MPa. The water recovery rate was 50%.
The concentrated water of the two-stage reverse osmosis system is treated by an ion exchanger to remove the residual calcium and magnesium ions, and the ion exchanger is filled with weak acid cation exchange resin.
The effluent of the ion exchanger enters a three-section salt extraction system for concentration, the system adopts a disc tube type reverse osmosis membrane, and the operating pressure is 7.0 MPa. The water recovery was 30%.
The concentration of the concentrated water of the three-section reverse osmosis membrane system is increased to 150g/L by an MVR evaporator, and then sodium sulfate crystals are obtained by freezing and crystallizing, wherein the crystallization temperature is-5 ℃. And drying the sodium sulfate crystals.
Example 2
When the treatment device and the treatment method are adopted in a certain coal mine, mine water is firstly buffered in the flow and water quality adjusting tank.
Conveying the water in the regulating tank to a superconducting magnetic separator, and adding 450mg/L Fe through a feeder3O4Coagulating 60mg/L PAC, flocculating, and adding 6mg/L PAM; after flocculation treatment, a superconductive magnetic separator is used for separating and removing floccules, effluent is filtered by a ceramic membrane with the aperture of 50nm, the filtering pressure is 0.2MPa, the cross flow velocity is 3m/s, and mine water is further clarified.
The filtrate of the ceramic membrane enters a section of nanofiltration membrane system to separate salt and water in the mine water, the operating pressure is 1.5Mpa, and the water recovery rate is 70%.
Adding sodium carbonate and sodium hydroxide into concentrated water of the first-stage reverse osmosis membrane system for softening, wherein the concentration of the added sodium carbonate is 5 g/L. Sodium hydroxide was added to ph11 and then treated with a 0.5um tubular microfiltration membrane to remove suspended matter.
The effluent of the tubular microfiltration membrane enters a two-stage nanofiltration membrane system to further separate salt and water in the mine water, the operating pressure of the nanofiltration membrane is 1.5Mpa, and the water recovery rate is 60%.
The concentrated water of the two-stage nanofiltration membrane system is treated by an ion exchanger to remove the residual calcium and magnesium ions, and the ion exchanger is filled with weak acid cation exchange resin.
The effluent of the ion exchanger enters a three-section salt extraction system for concentration, the system adopts a disc tube type reverse osmosis membrane, and the operating pressure is 8.0 MPa. The water recovery was 40%.
The concentration of the concentrated water of the three-section reverse osmosis membrane system is increased to 150g/L by an MVR evaporator, and then sodium sulfate crystals are obtained by freezing and crystallizing, wherein the crystallization temperature is 0 ℃. And drying the sodium sulfate crystals.
Example 3
The differences from example 2 are: no nucleating agent is added in the coagulation process.
When the treatment device and the treatment method are adopted in a certain coal mine, mine water is firstly buffered in the flow and water quality adjusting tank.
Conveying the water in the regulating tank to a superconducting magnetic separator, adding 60mg/L PAC (polyaluminium chloride) through a feeder for coagulation treatment, then performing flocculation treatment, and adding 6mg/L PAM (polyacrylamide); after flocculation treatment, the effluent is filtered by a ceramic membrane with the aperture of 50nm, the filtering pressure is 0.2MPa, the cross flow velocity is 3m/s, and the mine water is further clarified.
And (3) allowing the ceramic membrane filtrate to enter a nanofiltration membrane system, separating salt and water in the mine water, wherein the operation pressure is 2Mpa, and the water recovery rate is 80%.
Adding sodium carbonate and sodium hydroxide into concentrated water of the first-stage nanofiltration membrane system for softening, wherein the concentration of the added sodium carbonate is 8 g/L. Sodium hydroxide was added to ph12 and then treated with a 1um tubular microfiltration membrane to remove suspended matter.
And (3) enabling the effluent of the tubular microfiltration membrane to enter a two-stage reverse osmosis membrane system to further separate salt and water in the mine water, wherein the membrane system adopts a normal-pressure reverse osmosis membrane, and the operating pressure of the normal-pressure reverse osmosis membrane is 2.0 Mpa. The water recovery rate was 70%.
The concentrated water of the two-stage reverse osmosis system is treated by an ion exchanger to remove the residual calcium and magnesium ions, and the ion exchanger is filled with weak acid cation exchange resin.
The effluent of the ion exchanger enters a three-stage salt extraction system for concentration, and the system adopts electrodialysis.
The concentration of the concentrated water of the three-section electrodialysis system is increased to 150g/L by an MVR evaporator, and then sodium sulfate crystals are obtained by freezing and crystallizing, wherein the crystallization temperature is 5 ℃. And drying the sodium sulfate crystals.
Example 4
The differences from example 2 are: the coagulating nucleating agent adopts Fe subjected to surface oleic acid modification treatment3O4。
When the treatment device and the treatment method are adopted in a certain coal mine, mine water is firstly buffered in the flow and water quality adjusting tank.
Conveying the water in the regulating tank to a superconducting magnetic separator, and adding 450mg/L Fe through a feeder3O4Coagulating 60mg/L PAC, flocculating, and adding 6mg/L PAM; after flocculation treatment, a superconductive magnetic separator is used for separating and removing floccules, effluent is filtered by a ceramic membrane with the aperture of 50nm, the filtering pressure is 0.2MPa, the cross flow velocity is 3m/s, and mine water is further clarified.
The filtrate of the ceramic membrane enters a section of nanofiltration membrane system to separate salt and water in the mine water, the operating pressure is 1.5Mpa, and the water recovery rate is 70%.
Adding sodium carbonate and sodium hydroxide into concentrated water of the first-stage reverse osmosis membrane system for softening, wherein the concentration of the added sodium carbonate is 5 g/L. Sodium hydroxide was added to ph11 and then treated with a 0.5um tubular microfiltration membrane to remove suspended matter.
The effluent of the tubular microfiltration membrane enters a two-stage nanofiltration membrane system to further separate salt and water in the mine water, the operating pressure of the nanofiltration membrane is 1.5Mpa, and the water recovery rate is 60%.
The concentrated water of the two-stage nanofiltration membrane system is treated by an ion exchanger to remove the residual calcium and magnesium ions, and the ion exchanger is filled with weak acid cation exchange resin.
The effluent of the ion exchanger enters a three-section salt extraction system for concentration, the system adopts a disc tube type reverse osmosis membrane, and the operating pressure is 8.0 MPa. The water recovery was 40%.
The concentration of the concentrated water of the three-section reverse osmosis membrane system is increased to 150g/L by an MVR evaporator, and then sodium sulfate crystals are obtained by freezing and crystallizing, wherein the crystallization temperature is 0 ℃. And drying the sodium sulfate crystals.
The results of the above procedure are shown in the following table:
as can be seen from the table above, the method of the invention can deeply treat the mine water and recover and obtain industrial-grade sodium sulfate; the flocculation process can obviously reduce the turbidity of the mine water, and the comparison between the example 2 and the example 3 shows that the addition of the nucleating agent in the coagulation process can improve the agglomeration effect of the coagulation process on the colloid, so that the coagulation treatment effect is improved, and the comparison result of the turbidity is shown in figure 2; it can be seen from comparison between example 4 and example 2 that the ferroferric oxide subjected to surface oil acidification treatment is used as a coagulation nucleating agent, so that hydrophobic groups on the surface can adsorb organic matters in mine water, the effect in the coagulation process is better, the turbidity removal rate is improved, and the stable flux of a membrane during subsequent ceramic membrane filtration treatment can be improved, and as can be seen from the flux attenuation curve of the ceramic membrane in fig. 3, when the ferroferric oxide subjected to oleic acid acidification treatment is used as the coagulation nucleating agent in example 4, the flux reduction trend of the ceramic membrane can be remarkably slowed down. After the subsequent hardness removal step treatment and the concentration treatment of the reverse osmosis membrane, the purity of the recovered sodium sulfate is more than 98 percent, and the whiteness is more than 90 percent.
Claims (10)
1. A method for treating high-salinity mine water is characterized by comprising the following steps:
step 1, adding a coagulant into the high-salinity mine water to perform coagulation reaction;
step 2, filtering the wastewater obtained in the step 1 by adopting a solid-liquid separation membrane to remove solid suspended matters;
step 3, performing first reverse osmosis concentration treatment on the filtrate obtained in the step 2 to improve the salt concentration;
step 4, adding NaOH and Na into the concentrated solution obtained in the step 32CO3Precipitating impurity cations;
step 5, filtering the wastewater obtained in the step 4 by adopting a solid-liquid separation membrane to remove solid suspended matters;
step 6, carrying out second reverse osmosis concentration treatment on the filtrate obtained in the step 5;
step 7, carrying out ion exchange treatment on the concentrated solution obtained in the step 6 to remove impurity cations;
step 8, carrying out third reverse osmosis concentration treatment on the wastewater obtained in the step 7, and then carrying out concentration and crystallization to obtain recovered Na2SO4。
2. The method for treating hypersalinity mine water according to claim 1, wherein in one embodiment, a flocculating agent is added after the coagulation reaction in the step 1; in one embodiment, the coagulant is polyaluminum chloride, and the addition amount is 40mg/L-80 mg/L; the flocculating agent is polyacrylamide, and the adding amount is 4-8 mg/L.
3. The method for treating the hypersalinity mine water according to claim 1, characterized in that, in one embodiment, a flocculation nucleating agent is further added in the coagulation process in the step 1; in one embodiment, the flocculation nucleating agent is selected from bentonite, powdered activated carbon, activated silicic acid, ferroferric oxide subjected to surface hydrophobic modification treatment; the addition amount is 400mg/L-500 mg/L.
4. The method of treating hypersalinity mine water according to claim 1, characterized in that, in one embodiment, Na2CO3The adding concentration of (1) is 4g/L-8 g/L; NaOH is added, and the pH range is 10-12 calculated by pH; in one embodiment, the ion exchange process may employ a weakly acidic cation exchange resin; in one embodiment, the third reverse osmosis concentration employs disc-tube reverse osmosis (DTRO); in one embodiment, the crystallization temperature is from-5 ℃ to 5 ℃ and the crystallization mode is fractional crystallization.
5. A device for treating high-salinity mine water is characterized by comprising:
the coagulation reaction tank (1) is used for carrying out coagulation reaction on mine water;
the coagulant adding tank (2) is connected with the coagulation reaction tank (1) and is used for adding a coagulant into the coagulation reaction tank (1);
the first solid-liquid separation membrane (5) is connected to the coagulation reaction tank (1) and is used for carrying out solid-liquid separation treatment on the wastewater subjected to coagulation reaction in the coagulation reaction tank (1);
a first reverse osmosis membrane (6) connected to the filtrate side of the first solid-liquid separation membrane (5) and used for performing reverse osmosis concentration treatment on the filtrate of the first solid-liquid separation membrane (5);
the precipitation reaction tank (7) is connected to the concentration side of the first reverse osmosis membrane (6) and is used for carrying out precipitation reaction on the concentrated solution of the first reverse osmosis membrane (6) to remove impurity cations;
NaOH is added into a tank (8) and Na2CO3The adding tanks (9) are respectively connected with the precipitation reaction tank (7) and are respectively used for adding NaOH and Na into the precipitation reaction tank (7)2CO3；
The second solid-liquid separation membrane (10) is connected to the precipitation reaction tank (7) and is used for carrying out solid-liquid separation treatment on the wastewater obtained by the reaction in the precipitation reaction tank (7);
a second reverse osmosis membrane (11) connected to the filtrate side of the second solid-liquid separation membrane (10) and used for concentrating the permeate of the second solid-liquid separation membrane (10);
an ion exchange resin column (12) connected to the concentration side of the second reverse osmosis membrane (11) and used for performing ion exchange treatment for removing impurity cations on the concentrated solution of the second reverse osmosis membrane (11);
the third reverse osmosis membrane (13) is connected with the ion exchange resin column (12) and is used for concentrating the produced water of the ion exchange resin column (12);
an evaporative crystallization device (14) connected to the concentration side of the third reverse osmosis membrane (13) for subjecting the concentrated solution of the third reverse osmosis membrane (13) to evaporative crystallization treatment to obtain recovered Na2SO4。
6. The apparatus for treating highly mineralized mine water according to claim 5, further comprising, in one embodiment: the nucleating agent adding tank (3) is connected to the coagulation reaction tank (1) and is used for adding the coagulation nucleating agent into the coagulation reaction tank (1); in one embodiment, further comprising: the flocculant adding tank (4) is connected to the coagulation reaction tank (1) and is used for adding a flocculant into the coagulation reaction tank (1); in one embodiment, the average pore size of the first solid-liquid separation membrane (5) and/or the second solid-liquid separation membrane (10) is in the range of 50 to 2000 nm.
7. The apparatus for treating highly mineralized mine water according to claim 5, wherein in one embodiment, the ion exchange resin column (12) is filled with a weakly acidic cation exchange resin.
8. An installation for the treatment of hypersalinity mine water according to claim 5, characterized in that in one embodiment the third reverse osmosis membrane (13) is a Disc Tube Reverse Osmosis (DTRO).
9. The apparatus for treating highly mineralized mine water according to claim 5, characterized in that the evaporative crystallization apparatus (14) consists of an MVR evaporator and a cryocrystallizer in one embodiment.
10. Use of the apparatus for treating highly mineralized mine water according to claim 5 for treating mine water.
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