CN113620491B - High-salt deacidification wastewater recycling system and method - Google Patents
High-salt deacidification wastewater recycling system and method Download PDFInfo
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Abstract
The invention discloses a high-salt deacidification wastewater recycling system and a method, wherein the system comprises a homogenizing tank, a first reaction tank, a second reaction tank, a sedimentation tank, a concentration tank, an ultrafiltration device, an ultrafiltration water producing tank, a nanofiltration device, a nanofiltration water producing tank, a reverse osmosis device, a triple-effect evaporation unit, a nanofiltration concentrated liquid tank and a freezing crystallization device which are sequentially connected with the nanofiltration device; caCl is arranged above the first reaction tank 2 The dosing device is provided with Na above the second reaction tank 2 CO 3 And a hydrochloric acid dosing device is arranged above the ultrafiltration water producing tank. The invention can deacidify SO in wastewater by matching the medicament reaction with the membrane treatment devices with different precision at each level 4 2‑ And Cl ‑ Effectively separating to obtain Na with higher purity 2 SO 4 And NaCl, so that the effective recovery and resource utilization of salts in deacidification wastewater can be realized, the solid waste production is reduced, and the energy conservation and emission reduction degree is improved.
Description
Technical Field
The invention relates to the technical field of deacidification wastewater resource utilization, in particular to a high-salt deacidification wastewater resource utilization system and a high-salt deacidification wastewater resource utilization method.
Background
The incineration technology is one of effective treatment technologies of urban household garbage and hazardous waste, and along with the increasing severity of flue gas emission indexes, the wet deacidification technology is an effective guarantee means for up-to-standard emission of incineration flue gas at present, but the wet technology can generate acidic wastewater with complex composition and high salt content, and the effective treatment of deacidification wastewater becomes one of the key points and the difficult points of zero emission of wastewater in garbage incineration plants.
At present, the deacidification wastewater treatment method mainly adopts a physical and chemical treatment process to remove impurities and salts in the deacidification wastewater, so that the treated effluent meets the discharge standard. For example, a "method and system for treating wet deacidification wastewater" disclosed in chinese patent literature, publication No. CN108439651a, the method for treating includes: s1, preprocessing wet deacidification wastewater, and oxidizing reducing substances in the wet deacidification wastewater; s2, performing primary flocculation precipitation treatment on the pretreated wet deacidification wastewater to remove calcium, magnesium and silicate; s3, performing secondary flocculation precipitation treatment on the supernatant obtained by the primary flocculation precipitation treatment to remove heavy metal ions; s4, regulating the pH value of the supernatant obtained by the secondary flocculation precipitation treatment; s5, performing primary filtration on the supernatant with the pH value adjusted to perform interception and separation; s6, performing secondary filtration on the filtrate obtained after the primary filtration.
However, after the deacidification wastewater is treated by the method in the prior art, the salt recovered from the deacidification wastewater is mixed salt of various components, the recycling treatment cannot be performed, the deacidification wastewater can only be used as solid waste for outward transportation treatment, the comprehensive treatment cost of the waste salt is high, and the energy conservation and emission reduction requirements are not met.
Disclosure of Invention
The invention aims to overcome the defects that after deacidification wastewater is treated by adopting a method in the prior art, salt recovered from the deacidification wastewater is mixed salt of various components, recycling and reusing treatment cannot be carried out, the salt can only be used as solid waste for outward transportation treatment, and the comprehensive treatment cost of the waste salt is very highProvides a system and a method for recycling high-salt deacidification wastewater, which can be used for recycling SO in deacidification wastewater by matching medicament reaction with membrane treatment devices with different levels of precision 4 2- And Cl - Effective separation is carried out, and finally Na with higher purity and capability of directly recycling is obtained 2 SO 4 And NaCl, so that the effective recovery and resource utilization of salts in deacidification wastewater can be realized, the solid waste production is reduced, and the energy conservation and emission reduction degree is improved.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a high-salt deacidification wastewater recycling system comprises a homogenizing pool, a first reaction pool, a second reaction pool, a sedimentation pool, a concentration pool, an ultrafiltration device, an ultrafiltration water producing pool, a nanofiltration device, a nanofiltration water producing pool, a reverse osmosis device, a triple effect evaporation unit, a nanofiltration concentrated pool and a freezing crystallization device which are sequentially connected with the nanofiltration device; caCl is arranged above the first reaction tank 2 The dosing device is provided with Na above the second reaction tank 2 CO 3 And a hydrochloric acid dosing device is arranged above the ultrafiltration water producing tank.
The invention also provides a method for recycling the high-salt deacidification wastewater by using the system, which comprises the following steps:
(1) Homogenizing deacidification wastewater in a homogenizing tank, then entering a first reaction tank, and adding CaCl 2 Carrying out reaction;
(2) The effluent of the first reaction tank enters a second reaction tank, and Na is added 2 CO 3 Carrying out reaction;
(3) The effluent of the second reaction tank sequentially passes through a sedimentation tank and a concentration tank to be precipitated, and then supernatant enters an ultrafiltration system to be ultrafiltered;
(4) Allowing the ultrafiltered permeate to enter an ultrafiltration water producing tank, and adding hydrochloric acid for reaction;
(5) The effluent of the ultrafiltration water producing pool enters a nanofiltration device for nanofiltration, concentrated solution after nanofiltration enters a freezing crystallization device, and Na is recovered after freezing crystallization 2 SO 4 ；
(6) The permeate after nanofiltration enters a reverse osmosis device through a nanofiltration water producing pool to perform reverse osmosis;
(7) And (3) allowing the concentrated solution after reverse osmosis to enter a triple-effect evaporation unit, and recovering NaCl after evaporation.
In deacidification wastewater generated by waste incineration, the main component is mainly sodium chloride and is mixed with fluoride ions, sulfate radicals, carbonate radicals, bicarbonate radicals and other ions, suspended matters such as calcium sulfate and the like in the deacidification wastewater are removed by a homogenizing pool, and the unnecessary influence of the suspended matters on subsequent devices is avoided; then pass through a first reaction tank, and then pass through CaCl 2 The dosing device doses CaCl into the wastewater 2 Make most of F in water - And CO 3 2- With Ca 2+ The reaction generates calcium fluoride and calcium carbonate sediment to remove F - And CO 3 2- The purpose of (2); the effluent water enters a second reaction tank again and passes through Na 2 CO 3 The dosing device adds Na into the wastewater 2 CO 3 So that most of metal ions (such as calcium, magnesium, barium, strontium, iron, manganese and the like) and CO in the wastewater 3 2- Generating carbonate precipitate by reaction, and achieving the purpose of primarily removing metal ions; because a large amount of suspended matters are formed in the first reaction tank and the second reaction tank, the effluent of the second reaction tank firstly enters a sedimentation tank, the large-particle suspended matters in the water are removed in a gravity sedimentation mode, and the supernatant fluid enters a concentration tank to further remove the suspended matters in the wastewater; the supernatant of the concentration tank enters an ultrafiltration device, and suspended matters which cannot be precipitated in the wastewater are finally removed through an ultrafiltration membrane; introducing the ultrafiltered permeate into an ultrafiltration water producing tank, adding hydrochloric acid into the ultrafiltration water producing tank by a hydrochloric acid adding device, adjusting the pH of the wastewater, and removing HCO in the wastewater 3 - The method comprises the steps of carrying out a first treatment on the surface of the The wastewater after pH callback enters a nanofiltration device, and SO is carried out under the action of a nanofiltration membrane 4 2- With Cl - Separation, rich in SO 4 2- The nanofiltration concentrated solution of (2) enters a nanofiltration concentrated solution tank, and then is subjected to freezing crystallization by a freezing crystallization device, and then Na can be recovered 2 SO 4 The method comprises the steps of carrying out a first treatment on the surface of the Is rich in Cl - The nanofiltration permeate of (2) enters a nanofiltration water producing tank and then continuously enters reverse osmosis equipmentAnd (3) performing reverse osmosis treatment in a centering way, separating NaCl from water, recycling or directly discharging the separated effluent, and enabling the separated NaCl-rich concentrated solution to enter a triple-effect evaporation unit, wherein NaCl with higher purity can be recovered after evaporation.
Therefore, the invention can deacidify SO in the wastewater by matching the medicament reaction with the membrane treatment devices with different precision at each stage 4 2- And Cl - The purity of the finally recovered NaCl can reach 96.9 to 98.2 percent, which meets the physicochemical index requirement of industrial salt standard, na 2 SO 4 The purity can reach 92.8-94.6%, and the physicochemical index requirement of anhydrous sodium sulfate standard is met; therefore, the effective recovery and resource utilization of the salts in the deacidification wastewater can be realized, the solid waste production is reduced, and the energy conservation and emission reduction degree is improved.
Preferably, a fluorine removal reactor is arranged between the ultrafiltration water producing tank and the nanofiltration device, and fluorine removal resin is arranged in the fluorine removal reactor. A defluorination reactor is arranged in front of the nanofiltration device, F in the wastewater can be treated by defluorination resin - Further adsorption removal is carried out, thereby improving the finally obtained Na 2 SO 4 And the concentration of NaCl.
Preferably, a sludge tank and a filter press which are connected are also arranged in the system; the sludge tank is provided with a sludge inlet, a sludge outlet and a wastewater outlet; sludge hoppers are arranged at the bottoms of the sedimentation tank and the concentration tank; the sludge inlet of the sludge tank is respectively connected with sludge hoppers of the sedimentation tank and the concentration tank, the sludge outlet of the sludge tank is connected with the filter press, and the wastewater outlet of the sludge tank is connected with the water inlet of the first reaction tank. The sludge tank and the filter press are arranged in the system, so that the sludge generated in the sedimentation tank and the concentration tank can be recovered and dehydrated, and the subsequent transportation and disposal of the sludge are facilitated; the supernatant of the sludge tank can flow back to the first reaction tank for reprocessing.
Preferably, a tubular ultrafiltration membrane component is arranged in the ultrafiltration device; the ultrafiltration device is provided with an ultrafiltration device water inlet, an ultrafiltration device permeate outlet and an ultrafiltration device concentrate outlet, wherein the ultrafiltration device water inlet is connected with a water outlet of the concentration tank, the ultrafiltration device permeate outlet is connected with an ultrafiltration water producing tank, and the ultrafiltration device concentrate outlet is connected with a water inlet of the concentration tank. And allowing the permeate liquid of the wastewater after passing through the ultrafiltration device to enter a subsequent treatment device for subsequent treatment, and allowing the concentrated liquid to flow back to a concentration tank for re-precipitation treatment.
Preferably, the nanofiltration device comprises a primary nanofiltration device and a secondary nanofiltration device, nanofiltration membrane components are arranged in the primary nanofiltration device and the secondary nanofiltration device, and a water inlet, a permeate outlet and a concentrate outlet are respectively arranged on the primary nanofiltration device and the secondary nanofiltration device; the water inlet of the primary nanofiltration device is connected with the defluorination reactor, the permeate outlet of the primary nanofiltration device is connected with the water inlet of the secondary nanofiltration device, and the concentrate outlet of the primary nanofiltration device is connected with the nanofiltration concentrate pool; and a permeate outlet of the secondary nanofiltration device is connected with a nanofiltration water production pool, and a concentrate outlet of the secondary nanofiltration device is connected with a water inlet of the primary nanofiltration device. The application sets up two-stage nanofiltration device in the system, fully guarantees SO 4 2- With Cl - The separation effect of the catalyst is improved, so that the purity of NaCl crystalline salt obtained after triple effect evaporation is improved, and the subsequent recycling of NaCl is facilitated.
Preferably, the preparation method of the nanofiltration membrane used in the nanofiltration membrane component comprises the following steps:
a) ZrCl with the mol ratio of 1:1-2 4 Dissolving 2-amino terephthalic acid in DMF, adding hydrochloric acid, performing ultrasonic dispersion for 20-30 min, heating to 120-140 ℃ for hydrothermal reaction for 24-36 h, cooling to room temperature, filtering, cleaning and drying the product to obtain a metal organic framework material; wherein the mass concentration of the added hydrochloric acid is 35-37%, and the volume ratio of the added hydrochloric acid to DMF is 1:50-60; first through step A) with ZrCl 4 2-amino terephthalic acid is used as an organic ligand to prepare a metal organic framework material with amino;
b) Adding a metal organic frame material and N-methylimidazole into ethanol, and stirring for 12-18 h under the protection of nitrogen; adding 3-bromopropylamine hydrobromide, and carrying out reflux reaction for 24-36 h under the protection of nitrogen; wherein the mass ratio of the metal organic framework material to the N-methylimidazole to the 3-bromopropylamine hydrobromide is 2-2.5:1:2.9-2.95; filtering the product, washing with ethanol, and vacuum drying to obtain an ionic liquid modified metal organic frame material; in the step B), firstly, N-methylimidazole is adsorbed and diffused into a frame structure of a metal organic frame material, then 3-bromopropylamine hydrobromide is adsorbed and diffused into the frame structure to react with the N-methylimidazole, so that ionic liquid 1- (3-aminopropyl) -3-methylimidazole bromine is generated, and the ionic liquid is loaded into the frame structure of the metal organic frame material, so that the ionic liquid modified metal organic frame material is obtained;
c) Dissolving piperazine in deionized water, adding an ionic liquid modified metal organic framework material, uniformly dispersing, and then adjusting the pH value of the solution to 5-7 to obtain an aqueous phase solution, wherein the mass concentration of the piperazine in the aqueous phase solution is 0.2-0.4%, and the mass ratio of the piperazine to the metal organic framework material is 2-4:1;
D) Adding trimesic acid chloride into ethyl cyclohexane, stirring and dissolving to obtain an oil phase solution with the mass concentration of the trimesic acid chloride of 0.1-0.2%;
e) Immersing the porous polysulfone base membrane in the aqueous phase solution for 5-10 min, taking out, and purging the superfluous aqueous phase solution on the base membrane until no water drops exist on the surface of the base membrane; immersing the base film into the oil phase solution for contact reaction for 2-5 min; taking out, pre-drying the base film at 50-70 ℃ for 1-2 min, cleaning with hot water at 70-90 ℃ for 4-6 min, soaking in glycerol with the mass concentration of 7-9% for 1-3 min, taking out, and drying at 50-70 ℃ to obtain the nanofiltration film. In the steps D) to E), piperazine and trimesoyl chloride are subjected to interfacial polymerization reaction on the surface of the porous polysulfone membrane to generate a polypiperazine amide functional layer, so that the nanofiltration membrane has good selective permeability, and divalent ions and monovalent ions can be separated. In the interfacial polymerization process, amino groups in the metal organic frame material can also participate in the reaction, so that the metal organic frame material can be firmly loaded in the polypiperazine amide functional layer and is not easy to fall off from the surface of the nanofiltration membrane.
At present, the commercialized nanofiltration membrane mainly comprises a polypiperazine-amide composite nanofiltration membrane, the existing nanofiltration membrane is low in general water flux, and the water flux is attenuated tightly along with the extension of the service time Heavy, influence Cl - And SO 4 2- Is a separation effect of (a). Therefore, when the nanofiltration membrane is prepared, the metal organic frame material is added in the polypiperazine amide functional layer, and the water flux of the nanofiltration membrane can be effectively improved by utilizing the hollow porous structure of the metal organic frame material; however, the addition of the metal organic framework material also causes the density of the polypiperazine amide functional layer generated in the interfacial polymerization process to be reduced, thereby affecting the SO of the nanofiltration membrane 4 2- Therefore, the invention modifies the ionic liquid in the porous structure of the metal organic framework material, and the SO is subjected to the ionic liquid 4 2- Is improved on SO by the nanofiltration membrane 4 2- The retention rate of the nano-filtration membrane is high, SO that the prepared nano-filtration membrane has high SO 4 2- The retention rate and the water flux can effectively treat Cl - And SO 4 2- And (5) separating.
Preferably, a reverse osmosis membrane component is arranged in the reverse osmosis device, and a water inlet of the reverse osmosis device, a permeate outlet of the reverse osmosis device and a concentrate outlet of the reverse osmosis device are arranged on the reverse osmosis device; the water inlet of the reverse osmosis device is connected with the nanofiltration water producing pool, and the concentrated solution outlet of the reverse osmosis device is connected with the triple-effect evaporation unit; the system is also internally provided with a recycling water tank connected with a permeate outlet of the reverse osmosis device.
Preferably, the three-effect evaporation unit comprises a first-effect evaporator, a second-effect evaporator and a third-effect evaporator which are sequentially connected, wherein the top parts of the first-effect evaporator, the second-effect evaporator and the third-effect evaporator are respectively provided with a steam outlet, the middle part of the first-effect evaporator, the second-effect evaporator and the third-effect evaporator are respectively provided with a feed inlet and a steam inlet, and the bottom part of the first-effect evaporator is respectively provided with a condensed water outlet and a discharge outlet; the feed inlet of the first effect evaporator is connected with the concentrate outlet of the reverse osmosis device, and the discharge outlet and the steam outlet of the first effect evaporator are respectively connected with the feed inlet and the steam inlet of the second effect evaporator; and the discharge port and the steam outlet of the second effect evaporator are respectively connected with the feed port and the steam inlet of the third effect evaporator. The invention carries out evaporation treatment on the concentrated solution rich in NaCl after reverse osmosis treatment by a triple effect evaporation unit to obtain NaCl crystalline salt for recycling. In the triple-effect evaporation unit, the reverse osmosis concentrated solution sequentially passes through a first evaporator, a second evaporator and a third evaporator, the concentrated solution is heated by steam, the water in the concentrated solution is continuously evaporated, and NaCl is continuously separated out to realize brine separation; the steam after the concentrated solution in the first effect evaporator is evaporated can enter the second effect evaporator to be used as a heating source, and the secondary steam in the second effect evaporator can be used as a heating source of the third effect evaporator, so that the energy-saving effect is good.
Preferably, a security filter is arranged between the nanofiltration water producing pool and the reverse osmosis device, and a folding filter element with the filtering precision of 4-6 mu m is arranged in the security filter. The invention sets up the security filter before reverse osmosis unit, make the waste water pass the security filter to further remove the particulate matter before entering the reverse osmosis unit, avoid because the concentration of particulate matter is too high causes the reverse osmosis membrane to block up; and the phenomena of salt leakage and the like caused by overlarge particle size of particles to break down a reverse osmosis membrane component are avoided, and the recovery effect of NaCl is influenced.
Preferably, high-pressure pumps are respectively arranged in front of the ultrafiltration device, the nanofiltration device and the reverse osmosis device. The high-pressure pump is used for pressurizing the water inflow of the ultrafiltration device, the nanofiltration device and the reverse osmosis device, and providing enough water inflow and water inflow pressure for each membrane treatment device, so that the water inflow of the membrane treatment device has a certain driving force to overcome the resistances such as osmotic pressure and the like, thereby ensuring the designed water yield and effectively realizing the brine separation.
Preferably, the residence time in the first reaction tank in the step (1) is 20 to 40min, caCl 2 The addition amount of the catalyst is 8-20 kg/m 3 Deacidifying the wastewater.
Preferably, in the step (2), the residence time in the second reaction tank is 20-40 min, and Na with mass fraction of 20-40% is added 2 CO 3 Solution, na 2 CO 3 The adding amount of the solution is 5-15L/m 3 Deacidifying the wastewater.
Preferably, the ultrafiltration device in step (3) is operated at a pressure of 2 to 3MPa.
Preferably, the mass fraction of the hydrochloric acid added in the step (4) is 10-30%, and the addition amount of the hydrochloric acid is 5-15L/m 3 Deacidifying wasteAnd (3) water.
Preferably, the operation pressure of the first-stage nanofiltration device in the step (5) is 2.5-3.5 MPa, and the operation pressure of the second-stage nanofiltration device is 1.5-2.0 MPa.
Preferably, the reverse osmosis unit in step (6) is operated at a pressure of 7.5 to 8MPa.
Therefore, the invention has the beneficial effects that: SO in deacidified wastewater can be treated by the cooperation of the membrane treatment devices with different precision at each level and the reagent reaction 4 2- And Cl - Effective separation is carried out, and finally Na with higher purity and capability of directly recycling is obtained 2 SO 4 And NaCl, so that the effective recovery and resource utilization of salts in deacidification wastewater can be realized, the solid waste production is reduced, and the energy conservation and emission reduction degree is improved.
Drawings
Fig. 1 is a schematic view of a connection structure according to the present invention.
In the figure: 1 a homogenizing pool, 2 a first reaction pool, 3 a second reaction pool, 4 a sedimentation pool, 4-1 a sludge hopper, 5 a concentration pool, 6 an ultrafiltration device, a water inlet of the 6-1 ultrafiltration device, a permeate outlet of the 6-2 ultrafiltration device, a concentrate outlet of the 6-3 ultrafiltration device, a 7 ultrafiltration water producing pool, an 8 defluorination reactor, a 9 nanofiltration device, a 9-1 level nanofiltration device, a water inlet of the 9-1-1 level nanofiltration device, a permeate outlet of the 9-1-2 level nanofiltration device, a concentrate outlet of the 9-1-3 level nanofiltration device, a 9-2 level nanofiltration device, a water inlet of the 9-2-1 level nanofiltration device the method comprises the steps of a permeate outlet of a 9-2-2 secondary nanofiltration device, a concentrate outlet of a 9-2-3 secondary nanofiltration device, a 10 nanofiltration water producing pond, a 11 reverse osmosis device, a water inlet of the 11-1 reverse osmosis device, a permeate outlet of the 11-2 reverse osmosis device, a concentrate outlet of the 11-3 reverse osmosis device, a 12 three-effect evaporation unit, a 12-1 first-effect evaporator, a 12-1-1 steam outlet, a 12-1-2 feed inlet, a 12-1-3 steam inlet, a 12-1-4 condensate outlet, a 12-1-5 discharge outlet, a 12-2 second-effect evaporator, a 12-3 third-effect evaporator, a 13 nanofiltration concentration pond, a 14 freezing crystallization device and 15CaCl 2 Dosing device, 16Na 2 CO 3 Dosing device, 17 hydrochloric acid dosing device, 18 sludge tank, 18-1 sludge inlet, 18-2 sludge outlet, 18-3 waste water outlet, and 19 filter press20 reuse water tanks, 21 security filters and 22 high-pressure pumps.
Detailed Description
The invention is further described below with reference to the drawings and detailed description.
In the present invention, all the equipment and raw materials are commercially available or commonly used in the industry, and the methods in the following examples are conventional in the art unless otherwise specified.
As shown in fig. 1, the high-salt deacidification wastewater recycling system comprises a homogenizing tank 1, a first reaction tank 2, a second reaction tank 3, a sedimentation tank 4, a concentration tank 5, an ultrafiltration device 6, an ultrafiltration water producing tank 7, a defluorination reactor 8, a nanofiltration device 9, a nanofiltration water producing tank 10, a security filter 21, a reverse osmosis device 11, a triple effect evaporation unit 12, and a nanofiltration concentrated solution tank 13 and a freezing crystallization device 14 which are sequentially connected with the nanofiltration device; caCl is arranged above the first reaction tank 2 The dosing device 15, na is arranged above the second reaction tank 2 CO 3 The dosing device 16 is arranged above the ultrafiltration water producing tank, and the hydrochloric acid dosing device 17 is arranged above the ultrafiltration water producing tank.
A sludge tank 18 and a filter press 19 are also arranged in the system; the sludge tank is provided with a sludge inlet 18-1, a sludge outlet 18-2 and a wastewater outlet 18-3; the bottoms of the sedimentation tank 4 and the concentration tank 5 are provided with sludge hoppers 4-1; the sludge inlet of the sludge tank is connected with sludge hoppers of the sedimentation tank and the concentration tank through sludge pipelines respectively, the sludge outlet of the sludge tank is connected with the filter press through a sludge pipeline, and the wastewater outlet of the sludge tank is connected with the water inlet of the first reaction tank through a return pipeline.
The ultrafiltration device is provided with an ultrafiltration device water inlet 6-1, an ultrafiltration device permeate outlet 6-2 and an ultrafiltration device concentrate outlet 6-3; the water inlet of the ultrafiltration device is connected with the water outlet of the concentration tank, the water inlet of the ultrafiltration device is provided with a high-pressure pump, the permeate outlet of the ultrafiltration device is connected with the ultrafiltration water producing tank, and the concentrate outlet of the ultrafiltration device is connected with the water inlet of the concentration tank.
The nanofiltration device comprises a primary nanofiltration device 9-1 and a secondary nanofiltration device 9-2, wherein the primary nanofiltration device and the secondary nanofiltration device are respectively provided with a water inlet, a permeate outlet and a concentrate outlet; the water inlet 9-1-1 of the first-stage nanofiltration device is connected with the defluorination reactor 8 through a waste water pipeline, the permeate outlet 9-1-2 of the first-stage nanofiltration device is connected with the water inlet 9-2-1 of the second-stage nanofiltration device through a waste water pipeline, and the concentrate outlet 9-1-3 of the first-stage nanofiltration device is connected with the nanofiltration concentrate pool 13 through a waste water pipeline; the permeate outlet 9-2-2 of the secondary nanofiltration device is connected with the nanofiltration water production pool 10 through a waste water pipeline, and the concentrate outlet 9-2-3 of the secondary nanofiltration device is connected with the water inlet of the primary nanofiltration device through a return pipeline; the water inlet of the primary nanofiltration device and the secondary nanofiltration device is provided with a high-pressure pump.
The reverse osmosis device is provided with a reverse osmosis device water inlet 11-1, a reverse osmosis device permeate outlet 11-2 and a reverse osmosis device concentrate outlet 11-3; a high-pressure pump 22 is arranged at the water inlet of the reverse osmosis device, the water inlet of the reverse osmosis device is connected with the nanofiltration water producing pool through a waste water pipeline, and the concentrated solution outlet of the reverse osmosis device is connected with the triple-effect evaporation unit through a waste water pipeline; the system is also provided with a reuse water tank 20 connected with a permeate outlet of the reverse osmosis device.
The ultrafiltration device is provided with a tubular ultrafiltration membrane component, nanofiltration membrane components are arranged in the primary nanofiltration device and the secondary nanofiltration device, a reverse osmosis membrane component is arranged in the reverse osmosis device, a defluorination reactor is provided with defluorination resin, and a folding filter element with the filtration precision of 5 mu m is arranged in the security filter.
The three-effect evaporation unit comprises a first-effect evaporator 12-1, a second-effect evaporator 12-2 and a third-effect evaporator 12-3 which are sequentially connected, wherein the top parts of the first-effect evaporator, the second-effect evaporator and the third-effect evaporator are respectively provided with a steam outlet 12-1-1, the middle part is respectively provided with a feed inlet 12-1-2 and a steam inlet 12-1-3, and the bottom part is respectively provided with a condensed water outlet 12-1-4 and a discharge outlet 12-1-5; the feed inlet of the first effect evaporator is connected with the concentrate outlet of the reverse osmosis device, and the discharge outlet and the steam outlet of the first effect evaporator are respectively connected with the feed inlet and the steam inlet of the second effect evaporator; and the discharge port and the steam outlet of the second effect evaporator are respectively connected with the feed port and the steam inlet of the third effect evaporator.
Example 1:
the method for recycling the high-salt deacidification wastewater by using the system comprises the following steps of:
(1) Homogenizing deacidification wastewater in a homogenizing tank, then entering a first reaction tank, and adding CaCl 2 Carrying out reaction, caCl 2 The dosage of (C) is 14kg/m 3 Deacidifying the wastewater for 25min;
(2) The effluent of the first reaction tank enters a second reaction tank, and 30wt% of Na is added 2 CO 3 The solution reacts, na 2 CO 3 The addition amount of the solution was 7.6L/m 3 Deacidifying the wastewater for 25min;
(3) After the effluent of the second reaction tank sequentially passes through a sedimentation tank and a concentration tank to be precipitated, the supernatant enters an ultrafiltration system to be ultrafiltered, the running pressure of the ultrafiltration device is 2.4MPa, and the inflow water flow is 30m 3 /h；
(4) Introducing the ultrafiltered permeate into an ultrafiltration water producing tank, adding 30wt% hydrochloric acid for reaction, wherein the adding amount of hydrochloric acid is 11.2L/m 3 Deacidifying the wastewater; refluxing the ultrafiltered concentrated solution to a concentrating pool;
(5) F is removed from the effluent of the ultrafiltration water producing pool through a defluorination reactor - Sequentially carrying out two-stage nanofiltration by a first-stage nanofiltration device and a second-stage nanofiltration device; the operation pressure of the first-stage nanofiltration device is 3.0MPa, and the inflow water flow is 1.2m 3 And/h, the operating pressure of the secondary nanofiltration device is 1.8MPa, and the inflow water flow is 1.2m 3 /h; the concentrated solution after two-stage nanofiltration enters a freezing crystallization device, and Na is recovered after freezing crystallization 2 SO 4 ；
(6) The permeate after two-stage nanofiltration enters a nanofiltration water producing pool, then enters a reverse osmosis device for reverse osmosis after passing through a security filter, the operating pressure of the reverse osmosis device is 7.8MPa, and the inflow water flow is 0.15m 3 /h；
(7) The permeate after reverse osmosis enters a recycling water tank, the concentrated solution enters a triple-effect evaporation unit, and NaCl is recovered after evaporation.
Wherein, a tubular ultrafiltration membrane in the ultrafiltration device adopts PEROX treatment capacity of 1m 3 1 inch 10 core tubular ultrafiltration membrane; nanofiltration membranes in the primary and secondary nanofiltration devices adopt DOW NF8040; the reverse osmosis membrane in the reverse osmosis device adopts DOW SW30-400; removal in a defluorination reactorThe fluorine resin adopts Dusheng CH-87.
Example 2:
the nanofiltration membrane preparation method in the primary and secondary nanofiltration devices in example 2 is as follows:
a) ZrCl with the mol ratio of 1:1.5 4 And 2-amino terephthalic acid dissolved in DMF, zrCl 4 And DMF in a mass to volume ratio of 1g to 120mL; adding hydrochloric acid, performing ultrasonic dispersion for 25min, heating to 130 ℃ for hydrothermal reaction for 30h, cooling to room temperature, and filtering, cleaning and drying the product to obtain a metal organic frame material; wherein the mass concentration of the added hydrochloric acid is 36%, and the volume ratio of the added hydrochloric acid to DMF is 1:55;
b) Adding a metal organic frame material and N-methylimidazole into ethanol, and stirring for 14h under the protection of nitrogen; adding 3-bromopropylamine hydrobromide, and carrying out reflux reaction for 30 hours under the protection of nitrogen; wherein the mass ratio of the metal organic framework material to the N-methylimidazole to the 3-bromopropylamine hydrobromide is 2.3:1:2.93; filtering the product, washing with ethanol, and vacuum drying at 80 ℃ to obtain an ionic liquid modified metal organic frame material;
C) Dissolving piperazine in deionized water, adding an ionic liquid modified metal organic framework material, uniformly dispersing, and then adjusting the pH value of the solution to 6 to obtain an aqueous phase solution, wherein the mass concentration of the piperazine in the aqueous phase solution is 0.3%, and the mass ratio of the piperazine to the metal organic framework material is 3:1;
d) Adding trimesic acid chloride into ethyl cyclohexane, and stirring and dissolving to obtain an oil phase solution with the mass concentration of the trimesic acid chloride of 0.15%;
e) Immersing the porous polysulfone base membrane in the aqueous phase solution for 7min, taking out, and purging the superfluous aqueous phase solution on the base membrane until no water drops exist on the surface of the base membrane; immersing the base film into the oil phase solution for contact reaction for 3min; taking out, pre-drying the base membrane at 60 ℃ for 1.5min, washing with 80 ℃ hot water for 5min, soaking in 8% glycerol for 2min, taking out, and drying at 60 ℃ to obtain the nanofiltration membrane.
The remainder was the same as in example 1.
Example 3:
the method for recycling the high-salt deacidification wastewater by using the system comprises the following steps of:
(1) Homogenizing deacidification wastewater in a homogenizing tank, then entering a first reaction tank, and adding CaCl 2 Carrying out reaction, caCl 2 The addition amount of (C) is 8kg/m 3 Deacidifying the wastewater for 20min;
(2) The effluent of the first reaction tank enters a second reaction tank, and 40wt% of Na is added 2 CO 3 The solution reacts, na 2 CO 3 The addition amount of the solution is 5L/m 3 Deacidifying the wastewater for 20min;
(3) After the effluent of the second reaction tank sequentially passes through a sedimentation tank and a concentration tank to be precipitated, the supernatant enters an ultrafiltration system to be ultrafiltered, the running pressure of the ultrafiltration device is 2.0MPa, and the inflow water flow is 30m 3 /h；
(4) Introducing the ultrafiltered permeate into an ultrafiltration water producing tank, adding 30wt% hydrochloric acid for reaction, wherein the adding amount of hydrochloric acid is 5L/m 3 Deacidifying the wastewater; refluxing the ultrafiltered concentrated solution to a concentrating pool;
(5) F is removed from the effluent of the ultrafiltration water producing pool through a defluorination reactor - Sequentially carrying out two-stage nanofiltration by a first-stage nanofiltration device and a second-stage nanofiltration device; the operation pressure of the first-stage nanofiltration device is 2.5MPa, and the inflow water flow is 1.2m 3 And/h, the operating pressure of the secondary nanofiltration device is 1.5MPa, and the inflow water flow is 1.2m 3 /h; the concentrated solution after two-stage nanofiltration enters a freezing crystallization device, and Na is recovered after freezing crystallization 2 SO 4 ；
(6) The permeate after two-stage nanofiltration enters a nanofiltration water producing pool, then enters a reverse osmosis device for reverse osmosis after passing through a security filter, the operating pressure of the reverse osmosis device is 7.5MPa, and the inflow water flow is 0.15m 3 /h；
(7) The permeate after reverse osmosis enters a recycling water tank, the concentrated solution enters a triple-effect evaporation unit, and NaCl is recovered after evaporation.
The preparation method of the nanofiltration membrane in the primary and secondary nanofiltration devices comprises the following steps:
a) ZrCl with the mol ratio of 1:1 4 And 2-amino terephthalic acid is dissolved in DIn MF, zrCl 4 And DMF in a mass to volume ratio of 1g to 100mL; adding hydrochloric acid, performing ultrasonic dispersion for 20min, heating to 120 ℃ for hydrothermal reaction for 36h, cooling to room temperature, and filtering, cleaning and drying the product to obtain a metal organic frame material; wherein the mass concentration of the added hydrochloric acid is 35%, and the volume ratio of the added hydrochloric acid to DMF is 1:60;
b) Adding a metal organic frame material and N-methylimidazole into ethanol, and stirring for 12h under the protection of nitrogen; adding 3-bromopropylamine hydrobromide, and carrying out reflux reaction for 36h under the protection of nitrogen; wherein the mass ratio of the metal organic framework material to the N-methylimidazole to the 3-bromopropylamine hydrobromide is 2:1:2.9; filtering the product, washing with ethanol, and vacuum drying at 80 ℃ to obtain an ionic liquid modified metal organic frame material;
c) Dissolving piperazine in deionized water, adding an ionic liquid modified metal organic framework material, uniformly dispersing, and then adjusting the pH value of the solution to 5 to obtain an aqueous phase solution, wherein the mass concentration of the piperazine in the aqueous phase solution is 0.2%, and the mass ratio of the piperazine to the metal organic framework material is 2:1;
D) Adding trimesic acid chloride into ethyl cyclohexane, and stirring and dissolving to obtain an oil phase solution with the mass concentration of the trimesic acid chloride of 0.1%;
e) Immersing the porous polysulfone base membrane in the aqueous phase solution for 5min, taking out, and purging the superfluous aqueous phase solution on the base membrane until no water drops exist on the surface of the base membrane; immersing the base film into the oil phase solution for contact reaction for 2min; taking out, pre-drying the base membrane at 50 ℃ for 2min, washing with hot water at 70 ℃ for 6min, soaking in glycerol with the mass concentration of 7% for 3min, taking out, and drying at 50 ℃ to obtain the nanofiltration membrane.
Example 4:
the method for recycling the high-salt deacidification wastewater by using the system comprises the following steps of:
(1) Homogenizing deacidification wastewater in a homogenizing tank, then entering a first reaction tank, and adding CaCl 2 Carrying out reaction, caCl 2 The addition amount of (C) is 20kg/m 3 Deacidifying the wastewater for 40min;
(2) The water from the first reaction tank entersAdding 20wt% of Na into a second reaction tank 2 CO 3 The solution reacts, na 2 CO 3 The addition amount of the solution is 15L/m 3 Deacidifying the wastewater for 40min;
(3) After the effluent of the second reaction tank sequentially passes through a sedimentation tank and a concentration tank to be precipitated, the supernatant enters an ultrafiltration system to be ultrafiltered, the running pressure of the ultrafiltration device is 3.0MPa, and the inflow water flow is 30m 3 /h；
(4) The ultrafiltered permeate enters an ultrafiltration water producing tank, 10wt% hydrochloric acid is added for reaction, and the adding amount of the hydrochloric acid is 15.0L/m 3 Deacidifying the wastewater; refluxing the ultrafiltered concentrated solution to a concentrating pool;
(5) F is removed from the effluent of the ultrafiltration water producing pool through a defluorination reactor - Sequentially carrying out two-stage nanofiltration by a first-stage nanofiltration device and a second-stage nanofiltration device; the operation pressure of the first-stage nanofiltration device is 3.5MPa, and the inflow water flow is 1.2m 3 And/h, the operating pressure of the secondary nanofiltration device is 2.0MPa, and the inflow water flow is 1.2m 3 /h; the concentrated solution after two-stage nanofiltration enters a freezing crystallization device, and Na is recovered after freezing crystallization 2 SO 4 ；
(6) The permeate after two-stage nanofiltration enters a nanofiltration water producing pool, then enters a reverse osmosis device for reverse osmosis after passing through a security filter, the operating pressure of the reverse osmosis device is 8.0MPa, and the inflow water flow is 0.15m 3 /h；
(7) The permeate after reverse osmosis enters a recycling water tank, the concentrated solution enters a triple-effect evaporation unit, and NaCl is recovered after evaporation.
The preparation method of the nanofiltration membrane in the primary and secondary nanofiltration devices comprises the following steps:
a) ZrCl with the mol ratio of 1:2 4 And 2-amino terephthalic acid dissolved in DMF, zrCl 4 And DMF in a mass to volume ratio of 1g to 150mL; adding hydrochloric acid, performing ultrasonic dispersion for 30min, heating to 140 ℃ for hydrothermal reaction for 24h, cooling to room temperature, and filtering, cleaning and drying the product to obtain a metal organic frame material; wherein the mass concentration of the added hydrochloric acid is 37%, and the volume ratio of the added hydrochloric acid to DMF is 1:50;
B) Adding a metal organic frame material and N-methylimidazole into ethanol, and stirring for 18h under the protection of nitrogen; adding 3-bromopropylamine hydrobromide, and carrying out reflux reaction for 24 hours under the protection of nitrogen; wherein the mass ratio of the metal organic framework material to the N-methylimidazole to the 3-bromopropylamine hydrobromide is 2.5:1:2.95; filtering the product, washing with ethanol, and vacuum drying at 80 ℃ to obtain an ionic liquid modified metal organic frame material;
c) Dissolving piperazine in deionized water, adding an ionic liquid modified metal organic framework material, uniformly dispersing, and then adjusting the pH value of the solution to 7 to obtain an aqueous phase solution, wherein the mass concentration of the piperazine in the aqueous phase solution is 0.4%, and the mass ratio of the piperazine to the metal organic framework material is 4:1;
d) Adding trimesic acid chloride into ethyl cyclohexane, and stirring and dissolving to obtain an oil phase solution with the mass concentration of the trimesic acid chloride of 0.2%;
e) Immersing the porous polysulfone base membrane in the aqueous phase solution for 10min, taking out, and purging the superfluous aqueous phase solution on the base membrane until no water drops exist on the surface of the base membrane; immersing the base film into the oil phase solution for contact reaction for 5min; taking out, pre-drying the base membrane at 70 ℃ for 1min, washing with hot water at 90 ℃ for 4min, soaking in glycerol with the mass concentration of 9% for 1min, taking out, and drying at 70 ℃ to obtain the nanofiltration membrane.
Comparative example 1 (CaCl) 2 Too low dosage):
CaCl in step (1) of comparative example 1 2 The addition amount of (C) is 7kg/m 3 The deacidification wastewater was the same as in example 1.
Comparative example 2 (ionic liquid directly blended with metal organic frameworks):
the nanofiltration membrane preparation method in the primary and secondary nanofiltration devices in comparative example 2 comprises the following steps:
a) ZrCl with the mol ratio of 1:1.5 4 And 2-amino terephthalic acid dissolved in DMF, zrCl 4 And DMF in a mass to volume ratio of 1g to 120mL; adding hydrochloric acid, performing ultrasonic dispersion for 25min, heating to 130 ℃ for hydrothermal reaction for 30h, cooling to room temperature, and filtering, cleaning and drying the product to obtain a metal organic frame material; wherein the mass concentration of the added hydrochloric acid is 36%, and the added saltThe volume ratio of acid to DMF is 1:55;
b) Dissolving piperazine in deionized water, adding a metal organic frame material and ionic liquid 1- (3-aminopropyl) -3-methylimidazole bromide, uniformly dispersing, and then adjusting the pH value of the solution to 6 to obtain an aqueous phase solution, wherein the mass concentration of the piperazine in the aqueous phase solution is 0.3%, and the mass ratio of the piperazine to the metal organic frame material to the 1- (3-aminopropyl) -3-methylimidazole bromide is 3:1:1.7;
c) Adding trimesic acid chloride into ethyl cyclohexane, and stirring and dissolving to obtain an oil phase solution with the mass concentration of the trimesic acid chloride of 0.15%;
D) Immersing the porous polysulfone base membrane in the aqueous phase solution for 7min, taking out, and purging the superfluous aqueous phase solution on the base membrane until no water drops exist on the surface of the base membrane; immersing the base film into the oil phase solution for contact reaction for 3min; taking out, pre-drying the base membrane at 60 ℃ for 1.5min, washing with 80 ℃ hot water for 5min, soaking in 8% glycerol for 2min, taking out, and drying at 60 ℃ to obtain the nanofiltration membrane.
The remainder was the same as in example 2.
1. Determination of deacidification wastewater treatment effect:
the water quality during the treatment of example 1 and comparative example 1 was tested and the results are shown in tables 1 and 2.
Table 1: example 1 results of the various stages of water quality testing.
Table 2: example 1 and comparative example 1 results of the test of the quality of effluent from the first reaction tank.
As can be seen from tables 1 and 2, the method of the present invention is adopted in example 1 to effectively reduce F in deacidified wastewater - 、CO 3 2- 、HCO 3 - Content of F is realized - 、CO 3 2- 、HCO 3 - Is removed from the substrate; the secondary nanofiltration concentrated solution has higher SO 4 2- Content of Na can be realized 2 SO 4 Is recovered; the concentration of TDS in reverse osmosis effluent is low, and the reverse osmosis effluent can be directly recycled; the reverse osmosis concentrated solution has higher Cl - The concentration can realize the recovery of NaCl.
While CaCl in the first reaction tank of comparative example 1 2 Is too small in addition amount F - 、CO 3 2- 、HCO 3 - SO and SO 4 2- The removal effect of (c) was significantly reduced as compared with that in example 1.
2. Determination of nanofiltration salt separation effect:
the nanofiltration membranes used in the above examples and comparative examples were subjected to a cross-flow filtration test using a mixed solution of 1000ppm magnesium sulfate and sodium chloride under a test pressure of 0.7MPa and a test condition of 25℃to determine the water flux and SO thereof 4 2- With Cl - The retention rate of (2) is shown in Table 3.
Table 3: nanofiltration membrane performance test results.
| Test item | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 3 |
| Flux of water (L/m) 2 h) | 62 | 88 | 91 | 82 | 110 |
| SO 4 2- Retention (percent) | 99.02 | 99.33 | 98.89 | 99.61 | 95.48 |
| Cl - Retention (percent) | 4.2 | 6.8 | 5.9 | 7.4 | 4.7 |
As can be seen from Table 1, the nanofiltration membranes prepared by the methods of the present invention in examples 2 to 4 have significantly improved water flux compared with the nanofiltration membrane commercially available in example 1, and can be used to produce Cl - Through the simultaneous pair SO 4 2- Has high retention rate. In the preparation process of the nanofiltration membrane in the comparative example 3, the ionic liquid and the metal organic frame are directly blended and added into the aqueous phase solution, the ionic liquid is not loaded in the metal organic frame material, and the water flux of the prepared nanofiltration membrane is obviously improved compared with that in the example 2, but the water flux of the prepared nanofiltration membrane is obviously improved compared with that of SO 4 2- The retention rate of the sodium chloride is reduced, which is not beneficial to the recovery of NaCl; it is possible that the density of the formed polypiperazine amide functional layer is reduced under the influence of steric hindrance and the like of the ionic liquid after the ionic liquid is directly added into the aqueous phase solution, SO that the nanofiltration membrane is opposite to SO 4 2- The retention rate of the polymer is reduced, and the influence of the polymer on the density of the functional layer of the piperazine amide can be reduced after the ionic liquid is loaded in the metal organic framework material.
Water production rate (water production rate/water inflow rate x 100%) and SO for nanofiltration device during operation of the systems in examples and comparative examples 4 2- The retention of (2) was measured and the results are shown in Table 4.
Table 4: nanofiltration device water flow rate and SO 4 2- And (5) testing the interception rate.
As can be seen from Table 4, the nanofiltration membrane produced in the present invention was used in example 2, and the water yield and SO of the nanofiltration device were higher than those of the nanofiltration membrane commercially available in example 1 4 2- The retention rate is improved; in comparative example 2, a nanofiltration membrane prepared by directly blending an ionic liquid with a metal organic framework and adding the blend into an aqueous phase solution was used, and SO was improved although the water yield was improved 4 2- The retention rate is obviously reduced, which is unfavorable for NaCl and Na 2 SO 4 Is recovered.
3. Reuse water quality, naCl and Na 2 SO 4 And (3) recovery effect test:
the water quality of the reuse water obtained after reverse osmosis in the above examples and comparative examples and Na obtained by freeze crystallization were treated 2 SO 4 Purity, naCl purity from triple effect evaporation was tested and the results are shown in table 5.
Table 5: and (5) recycling the test result of the effect.
From Table 5, it can be seen thatThe TDS in the recycled water obtained by using the system and the method is lower, and the recycled water can be directly recycled or discharged; recovering the obtained NaCl and Na 2 SO 4 The purity is higher, the physical and chemical index requirements of industrial salt and anhydrous sodium sulfate standard can be met, and the resource utilization can be carried out.
Claims (10)
1. The high-salt deacidification wastewater recycling system is characterized by comprising a homogenizing tank (1), a first reaction tank (2), a second reaction tank (3), a sedimentation tank (4), a concentration tank (5), an ultrafiltration device (6), an ultrafiltration water producing tank (7), a nanofiltration device (9), a nanofiltration water producing tank (10), a reverse osmosis device (11), a triple effect evaporation unit (12), a nanofiltration concentrated solution tank (13) and a freezing crystallization device (14) which are sequentially connected with the nanofiltration device; caCl is arranged above the first reaction tank 2 The dosing device (15) is provided with Na above the second reaction tank 2 CO 3 A dosing device (16), a hydrochloric acid dosing device (17) is arranged above the ultrafiltration water producing tank;
the nanofiltration device comprises a primary nanofiltration device (9-1) and a secondary nanofiltration device (9-2), nanofiltration membrane components are arranged in the primary nanofiltration device and the secondary nanofiltration device, and the preparation method of nanofiltration membranes used in the nanofiltration membrane components is as follows:
A) ZrCl with the molar ratio of 1:1-2 4 Dissolving 2-amino terephthalic acid in DMF, adding hydrochloric acid, performing ultrasonic dispersion for 20-30 min, heating to 120-140 ℃ for hydrothermal reaction for 24-36 h, cooling to room temperature, and filtering, cleaning and drying the product to obtain a metal organic framework material;
b) Adding a metal organic frame material and N-methylimidazole into ethanol, and stirring for 12-18 h under the protection of nitrogen; adding 3-bromopropylamine hydrobromide, and carrying out reflux reaction for 24-36 h under the protection of nitrogen; wherein the mass ratio of the metal organic framework material to the N-methylimidazole to the 3-bromopropylamine hydrobromide is 2-2.5:1:2.9-2.95; filtering the product, washing with ethanol, and vacuum drying to obtain an ionic liquid modified metal organic frame material;
c) Dissolving piperazine in deionized water, adding an ionic liquid modified metal organic framework material, uniformly dispersing, and then adjusting the pH value of the solution to 5-7 to obtain an aqueous phase solution, wherein the mass concentration of the piperazine in the aqueous phase solution is 0.2-0.4%, and the mass ratio of the piperazine to the metal organic framework material is 2-4:1;
d) Adding trimesic acid chloride into ethyl cyclohexane, and stirring and dissolving to obtain an oil phase solution with the mass concentration of the trimesic acid chloride of 0.1-0.2%;
E) Immersing the porous polysulfone base membrane in the aqueous phase solution for 5-10 min, taking out, and then purging the superfluous aqueous phase solution on the base membrane until no water drops exist on the surface of the base membrane; immersing the base film into the oil phase solution for contact reaction for 2-5 min; and taking out, pre-drying the base film at 50-70 ℃ for 1-2 min, cleaning with hot water at 70-90 ℃ for 4-6 min, soaking in glycerol with the mass concentration of 7-9% for 1-3 min, taking out, and drying at 50-70 ℃ to obtain the nanofiltration film.
2. The high-salt-content deacidification wastewater recycling system according to claim 1, wherein a sludge tank (18) and a filter press (19) which are connected are also arranged in the system; the sludge tank is provided with a sludge inlet (18-1), a sludge outlet (18-2) and a wastewater outlet (18-3); sludge hoppers (4-1) are arranged at the bottoms of the sedimentation tank and the concentration tank; the sludge inlet of the sludge tank is respectively connected with sludge hoppers of the sedimentation tank and the concentration tank, the sludge outlet of the sludge tank is connected with the filter press, and the wastewater outlet of the sludge tank is connected with the water inlet of the first reaction tank.
3. The high-salt-content deacidification wastewater recycling system according to claim 1, wherein a tubular ultrafiltration membrane component is arranged in the ultrafiltration device; the ultrafiltration device is provided with an ultrafiltration device water inlet (6-1), an ultrafiltration device permeate outlet (6-2) and an ultrafiltration device concentrate outlet (6-3), wherein the ultrafiltration device water inlet is connected with a water outlet of a concentration tank, the ultrafiltration device permeate outlet is connected with an ultrafiltration water producing tank, and the ultrafiltration device concentrate outlet is connected with a water inlet of the concentration tank.
4. The high-salt-content deacidification wastewater recycling system according to claim 1, wherein the primary nanofiltration device and the secondary nanofiltration device are respectively provided with a water inlet, a permeate outlet and a concentrate outlet; the water inlet (9-1-1) of the primary nanofiltration device is connected with the defluorination reactor (8), the permeate outlet (9-1-2) of the primary nanofiltration device is connected with the water inlet (9-2-1) of the secondary nanofiltration device, and the concentrate outlet (9-1-3) of the primary nanofiltration device is connected with the nanofiltration concentrate pool (13); the permeate outlet (9-2-2) of the secondary nanofiltration device is connected with the nanofiltration water production pool (10), and the concentrate outlet (9-2-3) of the secondary nanofiltration device is connected with the water inlet of the primary nanofiltration device.
5. The recycling system of the high-salt-content deacidification wastewater is characterized in that a reverse osmosis membrane component is arranged in the reverse osmosis device, and a reverse osmosis device water inlet (11-1), a reverse osmosis device permeate outlet (11-2) and a reverse osmosis device concentrate outlet (11-3) are arranged on the reverse osmosis device; the water inlet of the reverse osmosis device is connected with the nanofiltration water producing pool, and the concentrated solution outlet of the reverse osmosis device is connected with the triple-effect evaporation unit; the system is also internally provided with a recycling water tank (20) connected with a permeate outlet of the reverse osmosis device.
6. The recycling system for the high-salt-content deacidification wastewater is characterized in that the three-effect evaporation unit comprises a first-effect evaporator (12-1), a second-effect evaporator (12-2) and a third-effect evaporator (12-3) which are sequentially connected, wherein the tops of the first-effect evaporator, the second-effect evaporator and the third-effect evaporator are respectively provided with a steam outlet (12-1-1), the middle part of the first-effect evaporator, the second-effect evaporator and the third-effect evaporator are respectively provided with a feed inlet (12-1-2) and a steam inlet (12-1-3), and the bottom of the first-effect evaporator is respectively provided with a condensed water outlet (12-1-4) and a discharge outlet (12-1-5); the feed inlet of the first effect evaporator is connected with the concentrate outlet of the reverse osmosis device, and the discharge outlet and the steam outlet of the first effect evaporator are respectively connected with the feed inlet and the steam inlet of the second effect evaporator; and the discharge port and the steam outlet of the second effect evaporator are respectively connected with the feed port and the steam inlet of the third effect evaporator.
7. A method for recycling high-salt deacidification wastewater by using the system as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps:
(1) Homogenizing deacidification wastewater in a homogenizing tank, then entering a first reaction tank, and adding CaCl 2 Carrying out reaction;
(2) The effluent of the first reaction tank enters a second reaction tank, and Na is added 2 CO 3 Carrying out reaction;
(3) The effluent of the second reaction tank sequentially passes through a sedimentation tank and a concentration tank to be precipitated, and then supernatant enters an ultrafiltration system to be ultrafiltered;
(4) Allowing the ultrafiltered permeate to enter an ultrafiltration water producing tank, and adding hydrochloric acid for reaction;
(5) The effluent of the ultrafiltration water producing pool enters a nanofiltration device for nanofiltration, concentrated solution after nanofiltration enters a freezing crystallization device, and Na is recovered after freezing crystallization 2 SO 4 ；
(6) The permeate after nanofiltration enters a reverse osmosis device through a nanofiltration water producing pool to perform reverse osmosis;
(7) And (3) allowing the concentrated solution after reverse osmosis to enter a triple-effect evaporation unit, and recovering NaCl after evaporation.
8. The method for recycling the high-salt-content deacidification wastewater according to claim 7, wherein the residence time in the first reaction tank in the step (1) is 20-40 min, caCl 2 The addition amount of the catalyst is 8-20 kg/m 3 Deacidifying the wastewater.
9. The method for recycling high-salt-content deacidification wastewater according to claim 7, wherein in the step (2), the retention time in the second reaction tank is 20-40 min, and 20-40% of Na by mass is added 2 CO 3 Solution, na 2 CO 3 The adding amount of the solution is 5-15L/m 3 Deacidifying the wastewater.
10. According to claim The method for recycling the high-salt deacidification wastewater is characterized in that the mass fraction of hydrochloric acid added in the step (4) is 10-30%, and the adding amount of the hydrochloric acid is 5-15L/m 3 Deacidifying the wastewater.
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