CN110683693A - Method for treating sodium sulfate type wastewater by electrodialysis and reverse osmosis integrated conversion method - Google Patents
Method for treating sodium sulfate type wastewater by electrodialysis and reverse osmosis integrated conversion method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 87
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 61
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 57
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 57
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 46
- 238000000909 electrodialysis Methods 0.000 title claims abstract description 42
- 239000002351 wastewater Substances 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 190
- 239000012528 membrane Substances 0.000 claims abstract description 73
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 44
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 36
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 36
- 239000010842 industrial wastewater Substances 0.000 claims abstract description 18
- 239000012141 concentrate Substances 0.000 claims abstract description 15
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 11
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 84
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 78
- 239000013505 freshwater Substances 0.000 claims description 69
- 239000001103 potassium chloride Substances 0.000 claims description 43
- 235000011164 potassium chloride Nutrition 0.000 claims description 41
- 239000011780 sodium chloride Substances 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 16
- 239000007832 Na2SO4 Substances 0.000 claims description 6
- 238000005192 partition Methods 0.000 claims description 5
- YAGXZDADEJXXMM-UHFFFAOYSA-M potassium chloride hydrate Chemical compound [OH-].Cl.[K+] YAGXZDADEJXXMM-UHFFFAOYSA-M 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 83
- 239000002994 raw material Substances 0.000 abstract description 20
- 239000012267 brine Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000010354 integration Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 20
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 239000012266 salt solution Substances 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005341 cation exchange Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 208000028659 discharge Diseases 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000010446 mirabilite Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003011 anion exchange membrane Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
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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
- 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
- C02F1/44—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
- 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
- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
- C02F2301/046—Recirculation with an external loop
Abstract
The invention relates to a method for treating sodium sulfate type wastewater by an electrodialysis and reverse osmosis integrated conversion method. The method applies the conversion method electrodialysis technology to wastewater treatment, combines the conversion method electrodialysis and reverse osmosis, realizes the continuous operation of the whole process by arranging a circulating water tank with overflow and connecting the circulating water tank with each compartment of the membrane stack and matching the process, has stable product parameters and meets the requirements of industrial production; meanwhile, the integration with reverse osmosis is adopted, the dilute brine produced in the electrodialysis process is concentrated and reused, and the utilization rate of raw materials is improved. The method can convert and concentrate the sodium sulfate wastewater with low concentration and low economic value into the potassium sulfate solution with high concentration and high economic value, realizes high-value conversion of products in the wastewater treatment process while concentrating and separating, and greatly improves the economy of sodium sulfate type industrial wastewater treatment.
Description
Technical Field
The invention relates to a treatment method of sodium sulfate type industrial wastewater, in particular to a method for treating sodium sulfate type industrial wastewater by adopting a displacement electrodialysis and reverse osmosis integrated conversion method, belonging to the technical field of wastewater treatment.
Background
With the development of industry, the discharge amount of industrial wastewater is increasing. Sodium sulfate is an important constituent substance in natural water bodies and some industrial production, and thus a large amount of sodium sulfate is present in discharged industrial wastewater. Like other types of salt-containing wastewater, if not properly treated, it causes serious environmental pollution.
The traditional wastewater zero-discharge treatment method is to perform concentration and crystallization on the wastewater to obtain fresh water and crystallized salt, for example, patent CN 109205866 a discloses an electrodialysis concentration system and method for high-salt-content industrial wastewater without chemical softening pretreatment, wherein the electrodialysis concentration system comprises the steps of treating filtered wastewater through electrodialysis to obtain concentrated solution, and crystallizing the concentrated solution into salt. For sodium sulfate, the economic value is low, and the difficulty is brought to the sale and the disposal of the sodium sulfate. If low-value sodium sulfate can be converted into potassium sulfate with higher value, the by-product with higher value is produced while the wastewater is treated, and the advantages are more obvious.
The main routes for synthesizing potassium sulfate at present are: (1) mannheim method: putting potassium chloride and concentrated sulfuric acid into a reaction furnace according to a certain proportion, firstly carrying out exothermic reaction at low temperature, carrying out the second step of reaction after 268 ℃, completely reacting at about 600 ℃, and generating a byproduct hydrochloric acid in the reaction process. For example, patent CN 108926965 a discloses a method for separating tail gas from potassium sulfate produced by mannheim process, which utilizes concentrated sulfuric acid to separate the tail gas discharged from mannheim furnace, and the method has reliable process and high product purity, but because strong acid is used in the reaction process, the equipment is corroded, and the energy consumption is also high. (2) A mirabilite conversion method: it is prepared by reacting mirabilite with potassium chloride. Firstly, reacting at 25 ℃ to generate glaserite, and then continuously reacting with potassium chloride at 60-100 ℃ to generate potassium sulfate. For example, patent CN 107857282 a discloses a method for preparing potassium sulfate from mirabilite, which has the advantages of simple process, low energy consumption and no pollution. But the separation of potassium ions and sodium ions is not thorough, so that the purity of the product is low. (3) A gypsum conversion method: the method uses calcium sulfate and potassium chloride to react, and utilizes the characteristic that potassium sulfate is low in solubility and crystallized and precipitated in an ethanol solution of ammonia to react at low temperature to generate a product and simultaneously generate a byproduct calcium chloride. For example, patent CN 104046380 a discloses a method for preparing potassium sulfate from gypsum, which has the main advantages of easily available raw materials, simple process and easy operation. But requires control of low temperature operating conditions and by-products are difficult to handle. (4) Ammonium sulfate conversion: the main principle of the method is to use ammonium sulfate and potassium chloride to react, and to separate potassium sulfate from ammonium chloride by controlling the conditions of temperature, solution concentration, reaction time and the like according to the difference of product solubility. For example, the method adopted in patent CN 106629781A is energy-saving and environment-friendly, and takes the by-product ammonium sulfate of some chemical products as raw material. But the product purity is lower due to the low recovery rate of potassium ions. In a device and a method for preparing potassium sulfate disclosed by the patent CN105177619B, the device mainly comprises a membrane stack, a first electrolyte sample injection device, a second electrolyte sample injection device, a first salt solution sample injection device, a second salt solution sample injection device, a third salt solution generation device and a fourth salt solution generation device, and potassium sulfate and ammonium sulfate are prepared by adopting a conversion method electrodialysis technology; however, the process of the invention is intermittent operation which can not be continuously carried out, higher conversion effect can not be achieved, and the product is more stable; secondly, the invention does not address how low concentrations of starting materials are handled after conversion is complete and is not practically feasible in industry.
Disclosure of Invention
The invention aims to provide a method for treating sodium sulfate type wastewater by an electrodialysis and reverse osmosis integrated conversion method aiming at the problems in the prior art. The method applies the conversion method electrodialysis technology to wastewater treatment, and compared with a simple substance concentration process in the traditional water treatment process, the method combines the conversion method electrodialysis and reverse osmosis, can convert and concentrate the low-concentration low-economic-value sodium sulfate wastewater into a high-concentration high-economic-value potassium sulfate solution, realizes high-value conversion of a product in the wastewater treatment process while concentrating and separating, and greatly improves the economy of sodium sulfate type industrial wastewater treatment. Compared with the intermittent operation of the electrodialysis process by other process conversion methods, the process realizes the continuous operation of the whole process by arranging the circulating water tank with overflow, connecting the circulating water tank with each compartment of the membrane stack and matching the process, has stable product parameters and meets the requirements of industrial production; meanwhile, the integration with reverse osmosis is adopted, the dilute brine produced in the electrodialysis process is concentrated and reused, and the utilization rate of raw materials is improved.
The technical scheme adopted by the invention is as follows:
a method for treating sodium sulfate type wastewater by electrodialysis and reverse osmosis integrated conversion comprises the following steps:
(1) adding corresponding solution into each water tank;
wherein, the first concentration chamber water tank C1 is filled with potassium sulfate solution, the concentration of potassium sulfate is 0.2-0.4 mol/L; a sodium chloride solution is filled in the second concentration chamber water tank C2, and the concentration of the sodium chloride is 0.5-1 mol/L; sodium sulfate type industrial wastewater, Na, is filled in the first fresh water chamber D12SO4The concentration of the wastewater is 10-100 g/L; the second fresh water chamber D2 is filled with potassium chloride solution, and the concentration of KCl solution is 10-100 g/L; the polar liquid in the polar chamber water tank is NaCl solution and Na2SO4One of the solutions with the mass concentration of 1-3 percent;
(2) opening the magnetic circulating pumps of the water tanks, and adjusting the flow velocity of the membrane surface of each water tank flowing into the membrane stack to be 1-10cm/s, wherein the flow rates of the circulating pumps are consistent; simultaneously, adding solutions with the same components in the initial concentration (namely the set concentration in the step (1)) of the water tank into the first fresh water tank D1 and the second fresh water tank D2 at a constant speed, and keeping the liquid level unchanged;
(3) turning on the direct current power supply, adjusting the voltage, wherein the range of the adjusted voltage is as follows: d.c. voltage is membrane stack membrane logarithm x (0.1-1) V;
the sodium chloride solution is continuously overflowed from the second concentration chamber water tank C2 during the operation, the concentration of NaCl of an overflowed product is 60-150 g/L, the potassium sulfate solution is continuously overflowed from the first concentration chamber water tank C1, and an overflowed product K is obtained2SO4The concentration of the solution is 80-100 g/L, and the solution is collected as two product solutions respectively; na overflowing from a first fresh water chamber D12SO4The concentration of the low concentrated water is 5-30 g/L, and the low concentrated water enters a first reverse osmosis device; the concentration of the low-concentration potassium chloride solution overflowing from the second fresh water tank D2 is 5-30 g/L and enters the second reverse osmosis device.
The flow rates (inter-membrane flow rates) of the five groups of feed channels are the same. The flow velocity on the surface of the clapboard is 1-10 cm/s.
The device for treating the sodium sulfate type wastewater by the electrodialysis and reverse osmosis integrated conversion method comprises a membrane stack, a polar chamber water tank, a first concentration chamber water tank C1, a second concentration chamber water tank C2, a first fresh chamber water tank D1 and a second fresh chamber water tank D2;
the anode chamber water tank is connected with an anode chamber inlet of the membrane stack, and the electrode liquid in the anode chamber water tank enters the anode chamber from the anode chamber inlet of the membrane stack, flows out from an anode chamber outlet, flows into the cathode chamber from a cathode chamber inlet, and flows back to the anode chamber water tank from a cathode chamber outlet; the first fresh water chamber D1 is connected with the sodium sulfate inlet of the membrane stack, and Na in the first fresh water chamber D12SO4The wastewater enters from the sodium sulfate inlet and flows out from the sodium sulfate outlet to the first fresh water chamber D1; the second fresh water chamber D2 is connected with a potassium chloride inlet of the membrane stack, and KCl solution in the fresh water chamber D2 enters from the potassium chloride inlet and flows out from a potassium chloride outlet to the second fresh water chamber D2; the first concentrate chamber water tank C1 is connected with the potassium sulfate inlet of the membrane stack, K in the first concentrate chamber water tank C12SO4The solution enters from the potassium sulfate inlet and flows out of the potassium sulfate outlet to the water tank C1 of the concentration chamber; the second concentration chamber water tank C2 is connected with a sodium chloride inlet of the membrane stack, and NaCl solution in the second concentration chamber water tank C2 enters from the sodium chloride inlet and flows out from a sodium chloride outlet to return to the second concentration chamber water tank C2;
an overflow hole of the first fresh water chamber water tank D1 is connected with a raw water port of the first reverse osmosis device through a pipeline, and a concentrated water outlet of the first reverse osmosis device is connected with the first fresh water chamber water tank D1; the overflow hole of the second fresh water chamber water tank D2 is connected with the raw water port of the second reverse osmosis device through a pipeline, and the concentrated water outlet of the second reverse osmosis device is connected with the second fresh water chamber water tank D2.
And a pretreatment device is also arranged between an overflow hole of the first fresh water chamber water tank D1 and a raw water port of the first reverse osmosis device.
The pretreatment device is a filter device.
The invention has the substantive characteristics that:
in the device and method for preparing potassium sulfate in the prior art, CN105177619B, the device mainly comprises a membrane stack, a first electrolyte sample injection device, a second electrolyte sample injection device, a first salt solution sample injection device, a second salt solution sample injection device, a third salt solution generation device and a fourth salt solution generation device, but the process of the invention is intermittent operation, namely, the operation is stopped after the solution in a water tank is converted, if the production is continued, the solution needs to be discharged and then the production is restarted, and the invention has two great differences with the method, firstly, the operation raw materials can continuously enter the water tank, overflow and output after the treatment, no machine halt for water change is needed, and the method is complete continuous, so that the invention can more quickly achieve higher conversion effect, and the product is more stable; secondly, CN105177619B does not mention how to treat the low-concentration raw material after the conversion is completed, and if the treatment is not performed, the treatment is very wasteful, but the present invention combines the conversion electrodialysis and the reverse osmosis, and the low-concentration raw material after the conversion electrodialysis is subjected to the reverse osmosis to obtain fresh water which can be used industrially, and then the concentration can be increased to reuse the raw material, so that the conversion rate is increased, and theoretically can reach 100%. Compared with CN105177619B, the invention is not only a matter of difference in the number of components, but also has fundamental difference and change in the process.
The invention has the beneficial effects that:
1. by means of the characteristic that the anion-cation exchange membrane can selectively separate anions and cations, the integration of reaction, separation and concentration in one device is realized through the arrangement and combination of the compartments and the anion-cation exchange membrane, the process is simple, and the parameters are easy to control.
2. The electrodialysis system by the conversion method adopts continuous operation, and is easy to control and industrially apply compared with a batch process.
3. Integrating the electrodialysis by the conversion method and a reverse osmosis system, concentrating the low-concentration solution after the electrodialysis by the conversion method through reverse osmosis, and recycling the low-concentration solution to the electrodialysis device to improve Na content2SO4And the utilization rate of KCl, and high-quality fresh water can be obtained for recycling.
4. The conversion method electrodialysis is applied to the treatment of sodium sulfate type industrial wastewater, the utilization rate can reach approximately 100%, water in the solution can be separated, the remaining concentrated water is returned as the raw material, the discharge of the sodium sulfate type wastewater and potassium chloride is basically avoided, and all the concentrated water is returned to the raw material to be used as supplementary material again.
5. The method converts the sodium sulfate into potassium sulfate with higher value while treating the sulfate wastewater, and has higher economic benefit.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a schematic flow diagram of an electrodialysis device in a process for converting and preparing industrial wastewater of sodium sulfate type according to the invention;
wherein, the outlet of the 1-potassium sulfate compartment, the outlet of the 2-sodium sulfate compartment, the outlet of the 3-sodium chloride compartment, the outlet of the 4-potassium chloride compartment, the inlet of the 5-sodium chloride compartment, the inlet of the 6-potassium chloride compartment, the inlet of the 7-potassium sulfate compartment, the inlet of the 8-sodium sulfate compartment, the inlet of the 9-anode chamber, the outlet of the 10-anode chamber, the inlet of the 11-cathode chamber and the outlet of the 12-cathode chamber.
FIG. 2 is a process flow diagram of the present invention as a whole;
FIG. 3 shows two concentrating compartments K according to examples 1 to 3 of the present invention2SO4Graph of the concentration variation of (c).
FIG. 4 is a graph showing changes in NaCl concentration in two concentration chambers according to examples 1 to 3 of the present invention.
FIG. 5 shows two concentrating chambers Na according to examples 1 to 3 of the present invention2SO4Graph of the concentration variation of (c).
FIG. 6 is a graph showing the concentration change of two concentrating compartments KCl according to examples 1 to 3 of the present invention.
Detailed Description
The membrane stack is a known device (such as a device and a membrane stack structure in a method for preparing potassium sulfate in patent CN 105177619B), and is an electrodialysis membrane stack used in a conversion method, and is formed by arranging anion exchange membranes, partition plates, cation exchange membranes and partition plates at intervals. Under the action of an external power supply, KCl and Na are separated from fresh water compartments in the membrane stack2SO4Respectively permeate the anion exchange membrane, respectively permeate the cation exchange membrane, and thus form a higher concentration of K in the adjacent compartment of the concentration chamber2SO4And NaCl.
The device for treating the sodium sulfate type wastewater by the electrodialysis and reverse osmosis integrated conversion method comprises a membrane stack, a polar chamber water tank, a first concentration chamber water tank C1, a second concentration chamber water tank C2, a first fresh chamber water tank D1 and a second fresh chamber water tank D2, wherein the polar chamber water tank is connected with a first concentration chamber water tank C2;
wherein, the polar chamber water tank is connected with an anode chamber inlet 9 of the membrane stack, and polar liquid in the polar chamber water tank enters the anode chamber from the anode chamber inlet 9 of the membrane stack, flows out from an anode chamber outlet 10, flows into the cathode chamber from a cathode chamber inlet 11, and flows out from a cathode chamber outlet 12 to return to the polar chamber water tank; the first dilute chamber water tank D1 is connected with the sodium sulfate inlet 8 of the membrane stack, and Na in the first dilute chamber water tank D12SO4The wastewater enters from a sodium sulfate inlet 8 and flows out of a sodium sulfate outlet 2 to the first fresh water chamber D1; the second fresh water chamber D2 is connected with a potassium chloride inlet 6 of the membrane stack, and KCl solution in the fresh water chamber D2 enters from the potassium chloride inlet 6 and flows out from a potassium chloride outlet 4 to the second fresh water chamber D2; the first concentrate chamber water tank C1 is connected with the potassium sulfate inlet 7 of the membrane stack, K in the first concentrate chamber water tank C12SO4The solution enters from a potassium sulfate inlet 7 and flows out of a potassium sulfate outlet 1 to the water tank C1 of the concentration chamber; the second concentration chamber water tank C2 is connected with a sodium chloride inlet 5 of the membrane stack, and NaCl solution in the second concentration chamber water tank C2 enters from the sodium chloride inlet 5 and flows out from a sodium chloride outlet 3 to return to the second concentration chamber water tank C2;
an overflow hole of the first fresh water chamber water tank D1 is connected with a raw water port of the first reverse osmosis device through a pipeline, and a concentrated water outlet of the first reverse osmosis device is connected with the first fresh water chamber water tank D1; an overflow hole of the second fresh water chamber water tank D2 is connected with a raw water port of a second reverse osmosis device through a pipeline, and a concentrated water outlet of the second reverse osmosis device is connected with a second fresh water chamber water tank D2;
in the second reverse osmosis concentrated sodium sulfate water, other impurities, especially substances which may cause membrane pollution, are concentrated besides the concentrated sodium sulfate, if the concentrated sodium sulfate water directly returns to the inlet of the electrodialysis like the reverse osmosis of potassium chloride, the membrane pollution is caused by repeated concentration, so that the concentrated sodium sulfate water can also be required to return to the sodium sulfate type industrial wastewater for the pretreatment process by arranging the operation of pretreatment (such as filtration), and is not directly connected to the inlet of the electrodialysis.
The Na is2SO4The concentration range of the wastewater is 10-100g/L, the concentration range of the KCl solution is preferably 10-100g/L, and the concentration of the NaCl of an overflow product is 60-150 g/L. Overflow product K2SO4The concentration of the solution is 80-100 g/L;
the polar solution is NaCl solution and Na2SO4One of the solutions with the mass concentration of 1-3 percent,
the flow rates (inter-membrane flow rates) of the five groups of feed channels are the same.
Each water tank is provided with a circulating pump, and the polar water circulating pump is related to the size of the partition plate, so that the surface flow velocity of the partition plate is ensured to be 1-10 cm/s.
Wherein the electrodialysis system consists of 1 or more electrodialysis membrane stacks, and the total membrane area number is determined by the required Na treatment2SO4The concentration and the flow of the wastewater are determined as follows: na (Na)2SO4Concentration x flow ÷ (200-2)；Na2SO4、KCl、K2SO4And NaCl circulating flow is in direct proportion to the membrane logarithm, and the flow velocity of each pair of membranes is ensured to be 1-10 cm/s. The effective area of a single membrane is 0.02m2
The direct current voltage on the two sides of the membrane stack is in direct proportion to the membrane stack membrane logarithm, and specifically comprises the following steps: the DC voltage is equal to the membrane stack membrane logarithm x (0.1-1) V. In actual industrial application, the logarithm of the membrane stack is calculated most appropriately according to the wastewater treatment capacity required, and specifically, the membrane logarithm of the membrane stack can be calculated by dividing the required total membrane area by the membrane area of a single membrane; the film stack in the embodiment of the invention is 10 groups;
the polar chamber water tank, the first dense chamber water tank C1, the second dense chamber water tank C2, the first fresh chamber water tank D1 and the second fresh chamber water tank D2 are all ordinary open type groove type water tanks, and overflow pipelines are arranged on the side faces of the rest water tanks except the polar chamber water tank to produce products.
The method for treating the sodium sulfate type wastewater by the electrodialysis and reverse osmosis integrated conversion method comprises the following steps:
(1) adding corresponding solution into each water tank;
wherein, the first concentration chamber water tank C1 is filled with potassium sulfate solution with potassium sulfate concentration of 0.2-0.4mol/L, and the second concentration chamber water tank C2 is filled with sodium chloride solution with sodium chloride concentration of 0.5-1 mol/L; the first fresh water chamber D1 is pretreated (filtered) sodium sulfate type industrial wastewater, Na2SO4The concentration of the wastewater is 10-100g/L, the second fresh water chamber D2 is a potassium chloride solution, and the concentration of the KCl solution is 10-100 g/L; the polar liquid in the polar chamber water tank is NaCl solution and Na2SO4One of the solutions with the mass concentration of 1-3 percent;
(2) opening the magnetic circulating pumps of the water tanks, and adjusting the flow velocity of the membrane surface of each water tank flowing into the membrane stack to be 1-10cm/s, wherein the flow rates of the circulating pumps are consistent; simultaneously, adding solution with the same concentration and components as the initial concentration of the water tank into the first fresh water tank D1 and the second fresh water tank D2 at a constant speed, and keeping the liquid level unchanged;
the added amount of the sodium sulfate type industrial wastewater is the treatment amount of the sodium sulfate type industrial wastewater, and the added amounts of the two fresh water tanks are the same; the first concentration chamber water tank is supplemented with pure water, and the solution concentration of the first concentration chamber water tank is maintained within the range of 80-110 g/L; the second concentrating chamber water tank does not need to be supplemented with solution in the operation process.
(3) Turning on the direct current power supply, adjusting the voltage, wherein the range of the adjusted voltage is as follows: d.c. voltage is membrane stack membrane logarithm x (0.1-1) V;
the sodium chloride solution is continuously overflowed from the second concentration chamber water tank C2 during the operation, the concentration of NaCl of an overflowed product is 60-150 g/L, the potassium sulfate solution is continuously overflowed from the first concentration chamber water tank C1, and an overflowed product K is obtained2SO4The concentration of the solution is 80-100 g/L, and the solution is collected as two product solutions respectively; na overflowing from a first fresh water chamber D12SO4The concentration of the low concentrated water is 5-30 g/L, and the low concentrated water enters a first reverse osmosis device; the concentration of the low-concentration potassium chloride solution overflowing from the second fresh water tank D2 is 5-30 g/L and enters the second reverse osmosis device.
The first reverse osmosis device and the second reverse osmosis device are all known equipment.
Na overflowing from the first fresh water chamber D12SO4The low-concentration water enters a first reverse osmosis device, the operating pressure of the reverse osmosis device is adjusted, so that the sodium sulfate concentrated water produced in the reverse osmosis device is 10-100g/L, the concentration of the initial solution in the first fresh water chamber water tank in the step (1) is met, and the low-concentration water is replenished for continuous use; simultaneously, the produced reverse osmosis desalted water (the salt content is less than 500 mg/L); the low-concentration potassium chloride solution overflowed from the second fresh water chamber D2 enters a second reverse osmosis device, the operating pressure of the reverse osmosis device is adjusted, so that the concentration of potassium chloride concentrated water produced in the reverse osmosis device is 10-100g/L, the concentration of the initial solution in the second fresh water chamber in the step (1) is met, and the low-concentration potassium chloride solution is continuously used by supplementing; meanwhile, reverse osmosis desalted water (the salt content is less than 500mg/L) is produced. The invention returns the concentrated water produced by reverse osmosis to the respective electrodialysis raw material section by the conversion method for continuous reuse, thereby improving the utilization rate; and the reverse osmosis desalted water has better water quality and can be reused.
The concentration operation of the whole circulation of the invention has great flexibility, and the circulation can be ensured. Taking the first fresh water tank as an example, the high-concentration solution enters the membrane stack, becomes the low-concentration solution and is mixed back to the water tank, and meanwhile, a part of the solution overflows; the concentration of the solution entering the film stack in the water tank is reduced certainly, and the concentration of the solution in the water tank is reduced certainly all the time, but another raw material liquid is continuously supplemented from the outside in the water tank, the concentration of the supplemented raw material liquid is consistent with the initial concentration of the solution in the water tank, the concentration in the water tank can be maintained stably only by continuously supplementing the raw material liquid, and the concentration difference between the supplemented raw material liquid and the low-concentration solution in the overflow water outlet tank in a stable state is the component converted away by the film stack.
In order that those skilled in the art will better understand the technical solutions of the present invention, the technical solutions in the examples of the present invention will be clearly and completely described below, but they should not be construed as limiting the scope of the present invention.
Example 1:
firstly, adding corresponding solution into each water tank, and adding 2L of 3% Na into the water tank of the polar chamber2SO4The solution in the second concentration chamber water tank C2 was filled with 1mol/L NaCl solution, and the first concentration chamber water tank C1 was filled with 0.4mol/L K2SO4The solution is filled in the water tank, the second fresh water chamber D2 is filled with 0.5mol/L potassium chloride, the first fresh water chamber D1 is filled with sodium sulfate type industrial wastewater, then a corresponding pump is started to adjust the corresponding circulating flow rate, and the circulating flow rate of the polar liquid is 1.5L/min. The circulating flow rate of the second concentrate chamber water tank C2 is 2.5cm/s, and the circulating flow rate of the first concentrate chamber water tank C1 is 2.5 cm/s. The circulation flow rate of the second fresh water tank D2 was 2.5cm/s, and the circulation flow rate of the first fresh water tank D1 was 2.5 cm/s. Then starting the feed of two raw material liquids and the feed of a first concentrated chamber water tank C1, feeding 0.5mol/L potassium chloride into a second dilute chamber water tank D2 at a flow rate of 30ml/min, feeding 0.25mol/L sodium sulfate into a first dilute chamber water tank D1 at a flow rate of 30ml/min, feeding pure water into the first concentrated chamber water tank C1 at a constant flow rate of 7ml/min, finally starting a direct current power supply, wherein the applied voltage is 10V, 4 adjacent compartments of a membrane stack adopted in the experiment are combined into one group, the total number of the groups is 10, and the effective area of each membrane is 165mm, 120mm, 1.98dm2During the operation, the second concentration chamber water tank C2 continuously overflows the sodium chloride solution, the first concentration chamber water tank C1 continuously overflows the potassium sulfate solution, and when the concentration rises to be kept unchanged, the concentration of the concentration chamber in the experimental process is analyzed and recorded.
Example 2:
firstly, adding corresponding solution into each water tank, and adding 2L of 3% Na into the water tank of the polar chamber2SO4Solution, second concentrating chamber water tankC2 using 1mol/L NaCl solution full water tank, the first dense chamber water tank C1 using 0.4mol/L K2SO4The solution is filled in a water tank, the second fresh water chamber D2 is filled with 0.5mol/L potassium chloride, the first fresh water chamber D1 is filled with sodium sulfate type industrial wastewater, then a corresponding pump is started to adjust the corresponding circulating flow rate, the circulating flow rate of the polar liquid is 1.5L/min, the circulating flow rate of the second concentrated chamber C2 is 2.5cm/s, and the circulating flow rate of the first concentrated chamber C1 is 2.5 cm/s. The circulation flow rate of the second fresh water tank D2 was 2.5cm/s, and the circulation flow rate of the first fresh water tank D1 was 2.5 cm/s. Then starting the feed of two raw material liquids and the feed of a first concentrated chamber water tank C1, feeding 0.5mol/L potassium chloride into a second dilute chamber water tank D2 at a flow rate of 30ml/min, feeding 0.25mol/L sodium sulfate into a first dilute chamber water tank D1 at a flow rate of 30ml/min, feeding pure water into the first concentrated chamber water tank C1 at a constant flow rate of 7ml/min, finally starting a direct current power supply, wherein the applied voltage is 9V, 4 adjacent compartments of a membrane stack adopted in the experiment are combined into one group, the total number of the groups is 10, and the effective area of each membrane is 165mm, 120mm, 1.98dm2During the operation, the second concentration chamber water tank C2 continuously overflows the sodium chloride solution, the first concentration chamber water tank C1 continuously overflows the potassium sulfate solution, and when the concentration rises to be kept unchanged, the concentration of the concentration chamber in the experimental process is analyzed and recorded.
Example 3:
firstly, adding corresponding solution into each water tank, and adding 2L of 3% Na into the water tank of the polar chamber2SO4The solution in the second concentration chamber water tank C2 was filled with 1mol/L NaCl solution, and the first concentration chamber water tank C1 was filled with 0.4mol/L K2SO4The solution is filled in a water tank, the second fresh water chamber D2 is filled with 0.5mol/L potassium chloride, the first fresh water chamber D1 is filled with sodium sulfate type industrial wastewater, then a corresponding pump is started to adjust the corresponding circulating flow rate, the circulating flow rate of the polar liquid is 1.5L/min, the circulating flow rate of the second concentrated chamber C2 is 2.5cm/s, and the circulating flow rate of the first concentrated chamber C1 is 2.5 cm/s. The circulation flow rate of the second fresh water tank D2 was 2.5cm/s, and the circulation flow rate of the first fresh water tank D1 was 2.5 cm/s. Then, the two raw material liquid feeding and the first dense chamber water tank C1 feeding are started, the second dilute chamber water tank D2 is fed with 0.5mol/L potassium chloride at the flow rate of 30ml/min, and the first dilute chamber water tank D1 is fed with 30 mol/L potassium chloride0.25mol/L sodium sulfate is supplemented at the flow rate of ml/min, pure water is supplemented at the constant speed of 7ml/min in a first concentrated chamber water tank C1, finally a direct-current power supply is started, the applied voltage is 8V, 4 adjacent compartments of a membrane stack adopted in the experiment are grouped into one group, 10 groups are totally adopted, and the effective area of each membrane is 165mm, 120mm and 1.98dm2During the operation, the second concentration chamber water tank C2 continuously overflows the sodium chloride solution, the first concentration chamber water tank C1 continuously overflows the potassium sulfate solution, and when the concentration rises to be kept unchanged, the concentration of the concentration chamber in the experimental process is analyzed and recorded.
As can be seen from the above embodiments,
(1) the invention combines the electrodialysis with reverse osmosis, which is applied to the waste water treatment process, and realizes the treatment of waste water and the production of potash fertilizer with high market price.
(2) In the prior art, other conversion method electrodialysis all are intermittent operation, also need to have exported the product of certain volume, shut down, drain away, reproduction, are unfavorable for large-scale production like this very much. Meanwhile, the continuous change of the parameters of the whole production process in the intermittent process is not beneficial to operation.
(3) The invention sets a flow integrating the conversion method electrodialysis and the reverse osmosis, can concentrate the dilute brine in the conversion method electrodialysis process, and then mix the dilute brine with the raw material for reuse, so that the utilization rate of the raw material is greatly improved, and the theoretical value can reach 100%.
The invention is not the best known technology.
Claims (4)
1. A method for treating sodium sulfate type wastewater by electrodialysis and reverse osmosis integrated conversion is characterized by comprising the following steps:
(1) adding corresponding solution into each water tank;
wherein, the first concentration chamber water tank C1 is filled with potassium sulfate solution, the concentration of potassium sulfate is 0.2-0.4 mol/L; a sodium chloride solution is filled in the second concentration chamber water tank C2, and the concentration of the sodium chloride is 0.5-1 mol/L; sodium sulfate type industrial wastewater, Na, is filled in the first fresh water chamber D12SO4The concentration of the wastewater is 10-100 g/L; the second fresh water chamber D2 is filled with potassium chloride solution and KCl solutionThe concentration of the liquid is 10-100 g/L; the polar liquid in the polar chamber water tank is NaCl solution and Na2SO4One of the solutions with the mass concentration of 1-3 percent;
(2) opening the magnetic circulating pumps of the water tanks, and adjusting the flow velocity of the membrane surface of each water tank flowing into the membrane stack to be 1-10cm/s, wherein the flow rates of the circulating pumps are consistent; simultaneously, adding solution with the same concentration and components as the initial concentration of the water tank into the first fresh water tank D1 and the second fresh water tank D2 at a constant speed, and keeping the liquid level unchanged;
(3) turning on the direct current power supply, adjusting the voltage, wherein the range of the adjusted voltage is as follows: dc voltage = membrane stack membrane pair number x (0.1-1) V;
the second concentrate chamber water tank C2 continuously overflows sodium chloride solution during operation, the concentration of the overflow product NaCl is 60 ~ 150g/L, the first concentrate chamber water tank C1 continuously overflows potassium sulfate solution, and the overflow product K2SO4The concentration of the solution is 80 ~ 100g/L, and the solution is collected as two product solutions respectively, Na overflowed from the first fresh water chamber D12SO4The concentration of the low-concentration water is 5 ~ 30g/L and enters a first reverse osmosis device, and the concentration of the low-concentration water potassium chloride solution overflowed from a second fresh water chamber D2 is 5 ~ 30g/L and enters a second reverse osmosis device;
the flow rates (inter-membrane flow rates) of the five groups of feed channels are the same.
2. The method for treating wastewater in the form of sodium sulfate by electrodialysis and reverse osmosis integrated conversion according to claim 1, wherein the flow velocity on the surface of the partition is 1-10 cm/s.
3. The electrodialysis and reverse osmosis integrated conversion process sodium sulfate type wastewater treatment device as set forth in claim 1, wherein the device comprises a membrane stack, a polar chamber water tank, a first concentrate chamber water tank C1, a second concentrate chamber water tank C2, a first dilute chamber water tank D1 and a second dilute chamber water tank D2;
wherein, the polar chamber water tank is connected with the anode chamber inlet of the membrane stack, polar liquid in the polar chamber water tank enters the anode chamber from the anode chamber inlet of the membrane stack, flows out from the anode chamber outlet, flows into the cathode chamber from the cathode chamber inlet, and flows out from the cathode chamber outletThe water tank is taken out of the return electrode chamber; the first fresh water chamber D1 is connected with the sodium sulfate inlet of the membrane stack, and Na in the first fresh water chamber D12SO4The wastewater enters from the sodium sulfate inlet and flows out from the sodium sulfate outlet to the first fresh water chamber D1; the second fresh water chamber D2 is connected with a potassium chloride inlet of the membrane stack, and KCl solution in the fresh water chamber D2 enters from the potassium chloride inlet and flows out from a potassium chloride outlet to the second fresh water chamber D2; the first concentrate chamber water tank C1 is connected with the potassium sulfate inlet of the membrane stack, K in the first concentrate chamber water tank C12SO4The solution enters from the potassium sulfate inlet and flows out of the potassium sulfate outlet to the water tank C1 of the concentration chamber; the second concentration chamber water tank C2 is connected with a sodium chloride inlet of the membrane stack, and NaCl solution in the second concentration chamber water tank C2 enters from the sodium chloride inlet and flows out from a sodium chloride outlet to return to the second concentration chamber water tank C2;
an overflow hole of the first fresh water chamber water tank D1 is connected with a raw water port of the first reverse osmosis device through a pipeline, and a concentrated water outlet of the first reverse osmosis device is connected with the first fresh water chamber water tank D1; the overflow hole of the second fresh water chamber water tank D2 is connected with the raw water port of the second reverse osmosis device through a pipeline, and the concentrated water outlet of the second reverse osmosis device is connected with the second fresh water chamber water tank D2.
4. The electrodialysis and reverse osmosis integrated conversion sodium sulfate type wastewater treatment device as claimed in claim 3, wherein a pretreatment device is further provided between the overflow hole of the first dilute chamber water tank D1 and the raw water port of the first reverse osmosis device; the pretreatment device is a filter device.
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