CN113698025B - System and method for recycling acid and alkali from high-salt deacidification wastewater - Google Patents
System and method for recycling acid and alkali from high-salt deacidification wastewater Download PDFInfo
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- 239000003513 alkali Substances 0.000 title claims abstract description 27
- 238000004064 recycling Methods 0.000 title claims abstract description 16
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- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
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- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 12
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- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 7
- 229910007926 ZrCl Inorganic materials 0.000 claims description 7
- 229920002492 poly(sulfone) Polymers 0.000 claims description 7
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 29
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
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- 230000016615 flocculation Effects 0.000 description 4
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- AISVWMPCZVTUTK-UHFFFAOYSA-N CN1C=CN(CCCN)C1.Br Chemical compound CN1C=CN(CCCN)C1.Br AISVWMPCZVTUTK-UHFFFAOYSA-N 0.000 description 2
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 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
- 230000002349 favourable effect Effects 0.000 description 2
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- 229910052749 magnesium Inorganic materials 0.000 description 2
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- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
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- 238000004065 wastewater treatment Methods 0.000 description 2
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
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- IVXQBCUBSIPQGU-UHFFFAOYSA-N piperazine-1-carboxamide Chemical compound NC(=O)N1CCNCC1 IVXQBCUBSIPQGU-UHFFFAOYSA-N 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
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- 238000012958 reprocessing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- 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
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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Abstract
The invention discloses a system for recycling acid and alkali from high-salt deacidification wastewater, which is characterized by comprising 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 reverse osmosis concentrated tank and a bipolar membrane electrodialysis device which are connected in sequence; 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. According to the invention, naCl in the deacidification wastewater can be effectively separated through the cooperation of the medicament reaction and the membrane treatment devices with different precision at each level, and NaOH and HCl are prepared through electrodialysis, so that acid and alkali can be recovered from the deacidification wastewater, the resource utilization of the deacidification wastewater is 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 system and a method for recycling acid and alkali from high-salt deacidification wastewater.
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 removed from the deacidification wastewater is mixed salt of various components, the resource 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 solve the problems that after deacidification wastewater is treated by adopting a method in the prior art, salt removed from the deacidification wastewater is mixed salt of various components, recycling treatment cannot be performed, the deacidification wastewater can only be treated as solid waste for outward transportation, and the comprehensive treatment cost of waste salt is very high.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the system for recycling acid and alkali from high-salt deacidification wastewater is characterized by comprising 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 reverse osmosis concentrated tank and a bipolar membrane electrodialysis device which are connected in sequence; 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 acid and alkali from 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;
(6) The permeate after nanofiltration enters a reverse osmosis device through a nanofiltration water producing pool to perform reverse osmosis;
(7) And (3) enabling the concentrated solution after reverse osmosis to enter a bipolar membrane electrodialysis device, and obtaining NaOH solution and hydrochloric acid after electrodialysis.
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 achieve the primary removal of 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- Interception of divalent ions, organics, bacteria, viruses, etc.; while Na is + With Cl - The water can permeate the nanofiltration membrane, and then enters a nanofiltration water producing pond along with nanofiltration permeate liquid, and then continuously enters a reverse osmosis device for reverse osmosis treatment, naCl and water are separated, the separated effluent can be recycled or directly discharged, the separated concentrated solution rich in NaCl enters a bipolar membrane electrodialysis device, and NaOH solution and hydrochloric acid are obtained after electrodialysis, so that deacidification waste can be realizedAcid and alkali are recovered from water, so that the resource utilization of deacidification wastewater is 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 and removal are carried out, so that the purity of NaCl in the nanofiltration permeate is improved, and subsequent electrodialysis for NaCl is facilitated to recover acid and alkali.
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 first-stage nanofiltration device is connected with the defluorination reactor, and the permeate outlet of the first-stage nanofiltration device is connected with the water inlet of the second-stage nanofiltration device; 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 invention arranges the two-stage nanofiltration device in the system to fully ensure SO 4 2- Plasma of divalent ion and Cl - The separation effect of the nano-filtration membrane improves the purity of NaCl in the nano-filtration permeate, and is favorable for subsequent electrodialysis recovery of acid and alkali for NaCl.
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 And 2-amino terephthalic acid is dissolved in DAdding hydrochloric acid into MF, 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 frame 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 seriously attenuated along with the extension of the service time, so that Cl is influenced - 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- Separating to improve NaCl purity in the nanofiltration permeate.
Preferably, a nanofiltration concentrate pond and a freezing crystallization device which are sequentially connected with a concentrate outlet of the primary nanofiltration device are also arranged in the system. The invention arranges a nanofiltration concentrated liquid pool and a freezing crystallization device in the system, and the SO-enriched liquid obtained after passing through the nanofiltration device 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 Crystalline salts of up to purity92.8-94.6%, meets the physical and chemical index requirements of anhydrous sodium sulfate standard, and can be recycled.
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 reverse osmosis concentrated water pool; the system is also internally provided with a recycling water tank connected with a permeate outlet of the reverse osmosis device.
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 concentration effect of NaCl is influenced.
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, 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 the wastewater.
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: through the cooperation of the membrane treatment device with different reagent reaction and each level of precision, naCl in the deacidification wastewater can be effectively separated, and NaOH and HCl are prepared through electrodialysis, so that acid and alkali can be recovered from the deacidification wastewater, the resource utilization of the deacidification wastewater is 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 homogenizing pool, 2 first reaction pool, 3 second reaction pool, 4 sedimentation pool, 4-1 sludge hopper, 5 concentrating pool, 6 ultrafiltration device, 6-1 ultrafiltration device water inlet, 6-2 ultrafiltration device permeate outlet, 6-3 ultrafiltration device concentrate outlet, 7 ultrafiltration water producing pool, 8 defluorination reactor, 9 nanofiltration device, 9-1 first level nanofiltration device, water inlet of 9-1-1 first level nanofiltration device, permeate outlet of 9-1-2 first level nanofiltration device, concentrate outlet of 9-1-3 first level nanofiltration device, 9-2 second level nanofiltration device, water inlet of 9-2-1 second level nanofiltration device, 9-2-2 second level nanofiltration devicePermeate outlet of the stage nanofiltration device, concentrate outlet of the 9-2-3 secondary nanofiltration device, 10 nanofiltration water producing pool, 11 reverse osmosis device, water inlet of the 11-1 reverse osmosis device, permeate outlet of the 11-2 reverse osmosis device, concentrate outlet of the 11-3 reverse osmosis device, 12 reverse osmosis concentrated pool, 13 bipolar membrane electrodialysis device, 14 reuse pool and 15 CaCl 2 Dosing device, 16 Na 2 CO 3 The device comprises a dosing device, a 17 hydrochloric acid dosing device, a 18 sludge pond, a 18-1 sludge inlet, a 18-2 sludge outlet, a 18-3 wastewater outlet, a 19 filter press, a 20 nanofiltration concentrated liquid pond, a 21 freezing crystallization device, a 22 security filter and a 23 high-pressure pump.
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, a system for recovering acid and alkali from high-salt deacidification wastewater 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 22, a reverse osmosis device 11, a reverse osmosis concentrated water tank 12, a bipolar membrane electrodialysis device 13, and a nanofiltration concentrated water tank 20 and a freezing crystallization device 21 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 20 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 reverse osmosis concentrated water pool 12 through a waste water pipeline; the system is also provided with a reuse water tank 14 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, a security filter is provided with a folding filter element with the filtration precision of 5 mu m, and a bipolar membrane stack is arranged in the bipolar membrane electrodialysis device.
Example 1:
a method for recovering acid and alkali from 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, 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) And (3) allowing the permeate after reverse osmosis to enter a reuse water tank, allowing the concentrated solution to enter a bipolar membrane electrodialysis device, and performing electrodialysis at a voltage of 25V to obtain NaOH solution and hydrochloric acid.
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:
a method for recovering acid and alkali from 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, 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) And (3) allowing the permeate after reverse osmosis to enter a reuse water tank, allowing the concentrated solution to enter a bipolar membrane electrodialysis device, and performing electrodialysis at a voltage of 25V to obtain NaOH solution and hydrochloric acid.
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 dissolved in DMF, 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:
a method for recovering acid and alkali from 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, caCl 2 The addition amount of (C) is 20kg/m 3 Deacidifying the wastewater for 40min;
(2) The effluent of the first reaction tank enters a second reaction tank, and 20wt% of Na is added 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) And (3) allowing the permeate after reverse osmosis to enter a reuse water tank, allowing the concentrated solution to enter a bipolar membrane electrodialysis device, and performing electrodialysis at a voltage of 25V to obtain NaOH solution and hydrochloric acid.
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 added hydrochloric acid and DMF are mixedThe volume ratio 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, ultrasonic dispersing for 25min, heating to 130deg.C, performing hydrothermal reaction for 30 hr, cooling to room temperature, filtering, cleaning, and drying to obtain goldBelongs to an 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) 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 used in example 1 to effectively reduce the falling-offF in acid 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 is favorable for the subsequent electrodialysis of NaCl solution to recover acid and alkali.
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 interception rate is obviously reduced, which is unfavorable for the recovery of NaCl and the subsequent electrolysis for preparing acid and alkali.
3. And (3) testing the recycling water quality and the recycling effect of NaOH and HCl:
the water quality of the reuse water obtained after reverse osmosis and the purities of NaOH solution and hydrochloric acid obtained by electrodialysis in the above examples and comparative examples were tested and the results are shown in table 5.
Table 5: and (5) recycling the test result of the effect.
As can be seen from Table 5, the recycled water obtained in examples 1 and 2 using the system and method of the present invention has lower TDS and can be directly recycled or discharged; and NaOH solution and hydrochloric acid solution with the concentration of about 8% can be recovered, so that the recycling can be performed.
Claims (10)
1. The system for recycling acid and alkali from high-salt deacidification wastewater 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 reverse osmosis concentrated water tank (12) and a bipolar membrane electrodialysis device (13) which are connected in sequence; 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), and nanofiltration membrane components are arranged in the primary and secondary nanofiltration devices; the preparation method of the nanofiltration membrane used in the nanofiltration membrane component comprises the following steps:
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; 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;
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 system for recovering acid and alkali from high-salt-content deacidification wastewater 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.
3. The system for recovering acid and alkali from high-salt content deacidification wastewater according to claim 1, wherein 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 (9-1-1) of the primary nanofiltration device is connected with the defluorination reactor (8), and 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; 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.
4. A system for recovering acid and alkali from high-salt content deacidification wastewater according to claim 3, wherein a nanofiltration concentrate pool (20) and a freezing crystallization device (21) which are sequentially connected with the concentrate outlet (9-1-3) of the primary nanofiltration device are also arranged in the system.
5. The system for recovering acid and alkali from high-salt-content deacidification wastewater according to claim 1, wherein 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 reverse osmosis concentrated water pool (12); the system is also internally provided with a recycling water tank (14) connected with a permeate outlet of the reverse osmosis device.
6. The system for recycling acid and alkali from high-salt-content deacidification wastewater according to claim 1, wherein a security filter (22) 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 μm is arranged in the security filter.
7. A method for recovering acid and alkali from 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;
(6) The permeate after nanofiltration enters a reverse osmosis device through a nanofiltration water producing pool to perform reverse osmosis;
(7) And (3) enabling the concentrated solution after reverse osmosis to enter a bipolar membrane electrodialysis device, and obtaining NaOH solution and hydrochloric acid after electrodialysis.
8. The method for recovering acid and alkali from 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 recovering acid and alkali from 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% by mass of Na 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. The method for recovering acid and alkali from high-salt-content deacidification wastewater according to claim 7, wherein the mass fraction of hydrochloric acid added in the step (4) is 10-30%, and the addition amount of hydrochloric acid is 5-15L/m 3 Deacidifying the wastewater.
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