CN112723320A - Method and device for recovering sulfuric acid by electroheat dialysis - Google Patents
Method and device for recovering sulfuric acid by electroheat dialysis Download PDFInfo
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 198
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000000502 dialysis Methods 0.000 title claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 65
- 239000012528 membrane Substances 0.000 claims abstract description 42
- 239000002253 acid Substances 0.000 claims abstract description 24
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 24
- 239000002699 waste material Substances 0.000 claims abstract description 22
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 229920000767 polyaniline Polymers 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- 238000011084 recovery Methods 0.000 claims description 9
- 238000005485 electric heating Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 abstract description 13
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000006477 desulfuration reaction Methods 0.000 abstract description 6
- 230000023556 desulfurization Effects 0.000 abstract description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 229910000342 sodium bisulfate Inorganic materials 0.000 abstract description 4
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 abstract description 3
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000000909 electrodialysis Methods 0.000 description 10
- 230000009471 action Effects 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 230000005684 electric field Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- ZACYQVZHFIYKMW-UHFFFAOYSA-N iridium titanium Chemical compound [Ti].[Ir] ZACYQVZHFIYKMW-UHFFFAOYSA-N 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 210000003040 circulating cell Anatomy 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/901—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids
- C01B17/904—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids by ion-exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
- B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
- B01D61/485—Specific features relating to the ion-exchange material
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Urology & Nephrology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a method for recycling sulfuric acid by electroheat dialysis, which utilizes a hydrophobic acid-resistant anion exchange membrane to divide an electroheat dialysis tank into an anode chamber and a cathode chamber, liquid to be treated and dilute sulfuric acid respectively circulate through the cathode chamber and the anode chamber, a potential difference and a steam pressure difference are provided at two sides of the membrane, and the sulfuric acid is separated and purified from the liquid to be treated and concentrated; the method has simple, green and economic process, can realize rapid and low-cost concentration while separating and purifying the sulfuric acid from the waste sulfuric acid, and improves the added value of the sulfuric acid product; meanwhile, the high-concentration sulfuric acid is prepared by taking the solution containing sulfate radicals and sulfite ions, such as dilute sulfuric acid, sodium sulfate, sodium bisulfate and the like which are liquid-phase desulfurization products, as a raw material, so that the economic benefit of the novel desulfurization technology is improved.
Description
Technical Field
The invention relates to a method and a device for recovering sulfuric acid by electric heating dialysis, belonging to the field of waste recycling.
Background
H2SO4As a functional reagent, the sulfuric acid is commonly used in the processes of wet leaching, papermaking, chemical bath pickling, chemical production, PCB etching and the like, and a large amount of waste sulfuric acid is generated. With H2SO4For the production of titanium dioxide, for example, 6-8 t of titanium dioxide containing 18-22% of H is produced per 1t of titanium dioxide2SO4The amount of the generated waste acid is up to 1570-2054 ten thousand t/year; the metal smelting industry produces about 3.05% H annually2SO4About 24.78 million tons of spent acid; in the steel pickling industry, the H content is 8-15% per year2SO4The waste acid is about 334-506 hundred million t. In addition, a large amount of waste sulfuric acid or salt solution containing sulfate radicals and sulfite radicals is generated in the air pollution control process, such as removal of SO by SNOX process, WSA process, electrochemical liquid phase oxidation and the like2All generate a large amount of H2SO4Waste liquor; absorption by NaOH, Na2SO4Liquid phase absorption methods such as absorption produce large amounts of sulfate and sulfite containing salt solutions. The waste liquid has huge separation, enrichment and recycling potential, but the waste liquid has complex components, low concentration and strong corrosivity and also contains a plurality of toxic and harmful heavy metals, the existing waste acid treatment technology has various problems, and a new economic and efficient waste acid recycling technology is urgently needed.
Among the existing techniques for recovering waste sulfuric acid, electrodialysis techniques and membrane distillation techniques have received much attention. The electrodialysis technology can remove most of organic and inorganic components in the waste acid liquor and can separate and enrich the components. But the method has the limitations of the technical method, the concentration rate of the method is low, and the running period is long; more importantly, the concentrated sulfuric acid concentration is lower than 30wt.% due to proton leakage and poor acid resistance of the electrodialysis membrane, and the requirement of industrial application cannot be met. Chinese patent CN 102167293A discloses electrodialysis using bipolar membraneMethod for producing sulfuric acid and sodium hydroxide by using device, and water molecules are dissociated into H by using electric field and bipolar membrane+And OH-Then Na in sodium sulfate is mixed with anion exchange membrane and cation exchange membrane+And SO4 2-Are separated from OH-And H+Sodium hydroxide and sulfuric acid are formed in combination. Compared with the traditional electrodialysis technology, the method has more obvious economic benefit and environmental benefit, but does not solve the problems of low recovery concentration, low concentration rate and the like.
In addition, the membrane distillation technology takes the steam pressure difference on two sides of the membrane as a driving force to complete the evaporation concentration process, can recover sulfuric acid with the concentration of 30-70 wt%, and has the characteristics of greenness, economy, high efficiency and the like compared with the traditional evaporation concentration technology. Compared with electrodialysis technology, membrane distillation technology can obtain sulfuric acid with higher concentration, and has the advantages of high concentration rate and short process period, and unfortunately, the membrane distillation technology cannot realize separation and purification of sulfuric acid. Chinese patent CN 102688706A provides a dilute sulphuric acid membrane distillation concentration device and a concentration method, and the method improves the flux of a system and reduces energy consumption by a hydrophobic PVDF hollow fiber membrane lined with fibers. However, the method also fails to solve the problem that the sulfuric acid cannot be separated and purified in the conventional membrane distillation technology.
Disclosure of Invention
Aiming at the problems, the invention provides a method for recovering sulfuric acid by electroheat dialysis, which is characterized in that an electroheat dialysis tank is divided into an anode chamber and a cathode chamber by a hydrophobic acid-resistant anion exchange membrane, liquid to be treated circulates through the cathode chamber, dilute sulfuric acid is taken as an initial solution in the anode chamber and circulates through a sulfuric acid pump, potential difference and steam pressure difference are provided at two sides of the membrane, sulfuric acid is separated and purified from the liquid to be treated and concentrated, rapid concentration is realized, and the concentration of the sulfuric acid is improved.
The hydrophobic acid-resistant anion exchange membrane is a polyvinylidene fluoride polyaniline (PANI/PVDF) membrane and is prepared by referring to Chinese patent CN 201711061218.8; the key of the membrane distillation process is a hydrophobic membrane, water cannot pass through the hydrophobic membrane, but water vapor is allowed to pass through the hydrophobic membrane, so that the distillation process is realized under the action of the vapor pressure difference; the same ion exchange membrane is also the key of the electrodialysis technology, for the conventional electrodialysis membrane, the migration carrier of ions in the membrane is water molecules, the electrodialysis efficiency is improved, and the conventional electrodialysis membrane has higher water content and better hydrophilicity. In contrast, ion migration in the PANI/PVDF membrane used in the present invention is mainly performed by the molecular chains of PANI, selective ion migration can be achieved with a low water content, and the membrane itself is hydrophobic, so that electric field driving and vapor pressure driving can be simultaneously performed, and separation and concentration of sulfuric acid can be simultaneously achieved.
The PANI/PVDF membrane is prepared by a heat-phase inversion method, and the solvent can be N, N-dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide; the ratio of PANI/PVDF is (1/10-1/5); the heat treatment temperature is 60-100 ℃.
The liquid to be treated is one of dilute sulfuric acid, waste sulfuric acid, and salt solution containing sulfate radical and sulfite radical, such as desulfurization product NaHSO4、Na2SO4、Na2SO3、NaHSO3Etc.; the mass concentration of the dilute sulfuric acid in the anode chamber is 0.1-5%.
The potential difference is provided for a direct current constant current applied between the anode and the cathode, and the current range is 50-700 mA. In the electrifying process, sulfate ions or sulfite ions in the solution to be treated selectively enter the anode chamber under the drive of an electric field and the action of an anion exchange membrane, and are subjected to H generation by water electrolysis in the anode chamber+Binding to form H2SO4(ii) a The positive ions are left in the cathode chamber and are electrolyzed to generate OH-And (4) combining. With NaHSO4For example, the following reactions mainly occur in the system:
anode chamber: 2H2O – 4e-→O2(g) + 4H+
H++ HSO4 -→H2SO4
2H++ SO4 2-→H2SO4
A cathode chamber: 2H2O +2e-→H2(g) + 2OH-
OH-+ Na+→ NaOH
When sulfite ions are contained in the treatment, the sulfite ions are oxidized into sulfate by anode:
2SO3 2-+ O2 
2SO4 2-
2HSO3 -+ O2 
2SO4 2-+ 2H+；
the steam pressure difference is provided by the temperature difference of two sides of the membrane, wherein the temperature of dilute sulfuric acid in the anode chamber is 50-80 ℃, and the steam pressure difference is provided by a constant temperature heater, industrial waste heat or tail gas waste heat; the temperature of the liquid to be treated in the cathode chamber is 0-25 ℃, and is controlled by a constant temperature cooler; due to the hydrophobicity of the hydrophobic acid-resistant anion exchange membrane, water molecules are difficult to pass through, but vapor can pass through under the driving of the steam pressure difference, so that the evaporation and concentration of the sulfuric acid are completed.
The invention also provides a device for completing the method, which comprises an electrothermal dialysis tank, a direct current power supply, a hydrophobic acid-resistant anion exchange membrane, a sulfuric acid circulating tank, a constant temperature heater, a liquid circulating tank to be treated and a sulfuric acid pump, wherein the electrothermal dialysis tank is divided into an anode chamber and a cathode chamber by the hydrophobic acid-resistant anion exchange membrane, the anode and the cathode are respectively arranged in the anode chamber and the cathode chamber and are connected with the direct current power supply, a liquid outlet at the top of the cathode chamber is communicated with a liquid inlet of the liquid circulating tank to be treated through a pipeline, a liquid outlet of the liquid circulating tank to be treated is communicated with a liquid inlet at the bottom of the cathode chamber through the pump and a constant temperature cooler, and an exhaust port II for collecting H generated2(ii) a A liquid outlet of the sulfuric acid circulating tank is communicated with a liquid inlet at the bottom of the anode chamber through a sulfuric acid pump, and a liquid outlet at the top of the anode chamber is communicated with a liquid inlet of the sulfuric acid circulating tank; the sulfuric acid circulating tank is provided with an exhaust port I for collecting O generated in the anode chamber2And a constant temperature heater is arranged in the sulfuric acid circulating tank.
The electrode is a plate-shaped electrode, wherein the anode material is a ruthenium/iridium coated electrode, and the cathode material is graphite.
The advantages of the invention are as follows:
(1) the industry is simple, green and economic, and can realize rapid and low-cost concentration and improve the added value of the sulfuric acid product while separating and purifying the sulfuric acid from the waste sulfuric acid;
(2) the high-concentration sulfuric acid is prepared by taking the solution containing sulfate radicals and sulfite ions, such as dilute sulfuric acid, sodium sulfate, sodium bisulfate and the like which are liquid-phase desulfurization products, as raw materials, so that the economic benefit of the novel desulfurization technology is improved;
(3) the preparation of sulfuric acid and the recovery of O2And H2。
Drawings
FIG. 1 is a schematic view of an apparatus of the present invention;
in the figure: 1 is anode chamber, 2 is cathode chamber, 3 is anode, 4 is cathode, 5 is hydrophobic acid-resistant anion exchange membrane, 6 is anode chamber inlet, 7 is anode chamber liquid outlet, 8 is cathode chamber inlet, 9 is cathode chamber liquid outlet.
FIG. 2 is a schematic view of the process of the present invention:
in the figure: 10 electric heating dialysis tank, 11 direct current power supply, 12 sulfuric acid circulating tank, 13 constant temperature heater, 14 exhaust port I, 15 sulfuric acid pump, 16 waste acid circulating tank, 17 exhaust port II, 18 circulating pump, 19 constant temperature cooler.
Detailed Description
The technical solutions of the present invention are further described below with reference to the accompanying drawings and specific embodiments, but the scope of the present invention is not limited to the descriptions.
Example 1: the method and the device for recovering the sulfuric acid by the electroheat dialysis are as follows:
as shown in figures 1 and 2, the device of the method for recovering sulfuric acid by electrodialytic dialysis comprises an electrodialytic cell 10, a direct current power supply 11, a hydrophobic acid-resistant anion exchange membrane 5, a sulfuric acid circulating cell 12, a constant temperature heater 13, a liquid to be treated circulating cell 16 and a sulfuric acid pump 15, wherein the electrodialytic cell 10 is divided into an anode chamber 1 and a cathode chamber 2 by the hydrophobic acid-resistant anion exchange membrane 5, an anode and a cathode are respectively arranged in the anode chamber 1 and the cathode chamber 2 and are connected with the direct current power supply 11, and the cathode is respectively arranged in the anodeA liquid outlet at the top of the chamber 2 is communicated with a liquid inlet of a liquid circulation tank 16 to be treated through a pipeline, a liquid outlet of the liquid circulation tank 16 to be treated is communicated with a liquid inlet at the bottom of the cathode chamber 2 through a pump 18 and a constant temperature cooler 19, and the liquid circulation tank 16 to be treated is provided with an air outlet II 17 for collecting H generated in the cathode chamber2(ii) a A liquid outlet of the sulfuric acid circulating tank 12 is communicated with a liquid inlet at the bottom of the anode chamber 1 through a sulfuric acid pump 15, and a liquid outlet at the top of the anode chamber 1 is communicated with a liquid inlet of the sulfuric acid circulating tank 12; the sulfuric acid circulating tank is provided with an exhaust port I14 for collecting O generated in the anode chamber2A constant temperature heater 13 is arranged in the sulfuric acid circulating tank;
an electric heating dialysis tank is divided into an anode chamber and a cathode chamber by utilizing a polyvinylidene fluoride polyaniline (PANI/PVDF) membrane, wherein the initial solution in the anode chamber is dilute sulfuric acid with the mass concentration of 1%, and is communicated with a sulfuric acid circulating tank 12 through a sulfuric acid pump 15 for circulation; the cathode chamber is desulfurization by-product (NaHSO with the concentration of about 0.1 mol/L)4) Communicated with a liquid circulation tank 16 to be treated by a pump 18 and circulated; applying a direct current of 0.1A between an anode and a cathode, wherein the anode is a ruthenium/iridium titanium electrode plate, and the cathode is a graphite plate; under the action of electric field drive and PANI/PVDF film, HSO4 -Selectively enters the anode chamber 1 and is connected with H generated by electrolyzing water in the anode chamber+Binding to form H2SO4. Meanwhile, a temperature difference is provided for the circulating liquid on the two sides of the membrane, wherein the temperature of the sulfuric acid circulating liquid in the anode chamber is 55 ℃, and the temperature of the circulating liquid is provided by a constant temperature heater; the temperature of the liquid to be treated in the cathode chamber is 15 ℃, and the temperature of the circulating liquid is controlled by a constant temperature cooler; under the action of steam pressure difference drive and a hydrophobic membrane, water vapor in the anode chamber enters the cathode chamber through the hydrophobic membrane to be evaporated and concentrated; the sulfuric acid circulating tank is provided with an exhaust port for collecting O generated in the anode chamber2(ii) a The treating liquid circulating tank is provided with an exhaust port for collecting H generated in the cathode chamber2。
After 3 days of concentration, the concentration of sulfuric acid by recovery and concentration reached 35 wt%.
Example 2: the structure of the device of the embodiment is the same as that of the embodiment 1;
using PANI/PVDF membrane to discharge electricityThe thermal dialysis cell is divided into an anode chamber and a cathode chamber, wherein H with the concentration of 2% is contained in the anode chamber2SO4As initial solution, and is communicated and circulated with a sulfuric acid circulating tank through a sulfuric acid pump; the cathode chamber is waste sulfuric acid (with the concentration of about 0.5mol/L and containing Fe2+And Cu2+) Is communicated and circulated with the waste acid circulating tank through a pump; applying a direct current of 0.5A between an anode and a cathode, wherein the anode is a ruthenium/iridium titanium electrode plate, and the cathode is a graphite plate; under the action of electric field drive and anion membrane, SO4 -2-Selectively enter the anode chamber and electrolyze water in the anode chamber to generate H+Binding to form H2SO4，Fe2+And Cu2+Then the sulfuric acid is trapped in the cathode chamber to realize the separation and purification of the sulfuric acid. Meanwhile, a temperature difference is provided for the circulating liquid on the two sides of the membrane, wherein the temperature of the sulfuric acid circulating liquid in the anode chamber is 80 ℃, and the temperature of the circulating liquid is provided by a constant temperature heater; the temperature of the liquid to be treated in the cathode chamber is 20 ℃, and the temperature of the circulating liquid is controlled by a constant temperature cooler; under the action of steam pressure difference drive and a hydrophobic membrane, water vapor in the anode chamber enters the cathode chamber through the hydrophobic membrane to be evaporated and concentrated; the sulfuric acid circulating tank is provided with an exhaust port for collecting O generated in the anode chamber2(ii) a The waste acid circulating groove is provided with an exhaust port for collecting H generated in the cathode chamber2；
After 2 days of concentration, the concentration of the sulfuric acid recovered and concentrated reaches 65wt%, Fe2+And Cu2+The retention rate of (a) was 99%.
Example 3: the structure of the device of the embodiment is the same as that of the embodiment 1;
the electroheat dialysis cell is divided into an anode chamber and a cathode chamber by using a PANI/PVDF membrane, wherein 3% of H in the anode chamber2SO4As initial solution, and is communicated and circulated with a sulfuric acid circulating tank through a sulfuric acid pump; the cathode chamber is desulfurized by-product (Na with the concentration of about 0.5 mol/L)2SO3) And is communicated and circulated with the waste acid circulating tank through a pump. A constant direct current of 0.1A is applied between the anode and the cathode, the anode is a ruthenium/iridium titanium electrode plate, and the cathode is a graphite plate. Under the action of electric field drive and anion membrane, SO3 2-Selectively enters the anode chamber to be oxidized into SO4 2-H generated by electrolysis of water in the anode compartment+Binding to form H2SO4(ii) a Meanwhile, a temperature difference is provided for the circulating liquid on the two sides of the membrane, wherein the temperature of the sulfuric acid circulating liquid in the anode chamber is 60 ℃, and a constant temperature heater is used for heating the circulating liquid; the temperature of the liquid to be treated in the cathode chamber is 15 ℃, and is controlled by a constant temperature cooler; under the action of steam pressure difference drive and a hydrophobic membrane, water vapor in the anode chamber enters the cathode chamber through the hydrophobic membrane to be evaporated and concentrated; the sulfuric acid circulating tank is provided with an exhaust port for collecting O generated in the anode chamber2(ii) a The waste acid circulating groove is provided with an exhaust port for collecting H generated in the cathode chamber2；
After 3 days of concentration, the concentration of the sulfuric acid recovered and concentrated reaches 40%, wherein the oxidation rate of sulfite ions reaches 98%.
Claims (7)
1. A method for recovering sulfuric acid by electroheat dialysis is characterized by comprising the following steps: an electro-thermal dialysis tank is divided into an anode chamber and a cathode chamber by a hydrophobic acid-resistant anion exchange membrane, liquid to be treated and dilute sulfuric acid respectively circulate through the cathode chamber and the anode chamber, a potential difference and a steam pressure difference are provided at two sides of the membrane, and the sulfuric acid is separated and purified from the liquid to be treated and concentrated.
2. Electrodialytic recovery of sulfuric acid as claimed in claim 1, wherein: the hydrophobic acid-resistant anion exchange membrane is a polyvinylidene fluoride-based polyaniline membrane.
3. Electrodialytic recovery of sulfuric acid as claimed in claim 1, wherein: the liquid to be treated is one of dilute sulfuric acid, waste sulfuric acid and salt solution containing sulfate radical and sulfite radical.
4. Electrodialytic recovery of sulfuric acid as claimed in claim 1, wherein: the mass concentration of the dilute sulfuric acid in the anode chamber is 0.1-5%.
5. Electrodialytic recovery of sulfuric acid as claimed in claim 1, wherein: the potential difference is provided for a direct current constant current applied between the anode and the cathode, and the current range is 50-700 mA.
6. Electrodialytic recovery of sulfuric acid as claimed in claim 1, wherein: the steam pressure difference is provided by the temperature difference of two sides of the membrane, wherein the temperature of dilute sulfuric acid in the anode chamber is 50-80 ℃, and the temperature of liquid to be treated in the cathode chamber is 0-25 ℃.
7. Apparatus for carrying out a process for the recovery of sulfuric acid by electrodialytic dialysis as claimed in any one of claims 1 to 6, wherein: comprises an electric heating dialysis tank (10), a direct current power supply (11), a hydrophobic acid-resistant anion exchange membrane (5), a sulfuric acid circulating tank (12), a constant temperature heater (13), a liquid circulating tank to be treated (16) and a sulfuric acid pump (15), an electric heating dialysis tank (10) is divided into an anode chamber (1) and a cathode chamber (2) by a hydrophobic acid-resistant anion exchange membrane (5), an anode and a cathode are respectively arranged in the anode chamber (1) and the cathode chamber (2) and are connected with a direct current power supply (11), a liquid outlet at the top of the cathode chamber (2) is communicated with a liquid inlet of a liquid circulation tank (16) to be treated through a pipeline, a liquid outlet of the liquid circulation tank (16) to be treated is communicated with a liquid inlet at the bottom of the cathode chamber (2) through a pump (18) and a constant temperature cooler (19), and an exhaust port II (17) for collecting H generated in the cathode chamber is formed in the liquid circulation tank (16) to be treated.2(ii) a A liquid outlet of the sulfuric acid circulating tank (12) is communicated with a liquid inlet at the bottom of the anode chamber (1) through a sulfuric acid pump (15), and a liquid outlet at the top of the anode chamber (1) is communicated with a liquid inlet of the sulfuric acid circulating tank (12); the sulfuric acid circulating tank is provided with an exhaust port I (14) for collecting O generated in the anode chamber2And a constant temperature heater (13) is arranged in the sulfuric acid circulating tank.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045568A (en) * | 2007-04-29 | 2007-10-03 | 哈尔滨工业大学 | Recoverying method for sulfate in high concentration acid-containg waste liquid of battery factory |
| WO2010017563A1 (en) * | 2008-08-08 | 2010-02-11 | University Of Toledo | Polymeric ionic liquids, methods of making and methods of use thereof |
| CN107930420A (en) * | 2017-11-02 | 2018-04-20 | 昆明理工大学 | A kind of acidproof high conductivity anion-exchange membrane of hydrophobicity and preparation method thereof |
| CN111924807A (en) * | 2020-05-26 | 2020-11-13 | 萍乡市华星环保工程技术有限公司 | Method and device for trapping carbon dioxide and simultaneously producing sulfuric acid by sodium bisulfate |
-
2020
- 2020-12-25 CN CN202011565106.8A patent/CN112723320A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045568A (en) * | 2007-04-29 | 2007-10-03 | 哈尔滨工业大学 | Recoverying method for sulfate in high concentration acid-containg waste liquid of battery factory |
| WO2010017563A1 (en) * | 2008-08-08 | 2010-02-11 | University Of Toledo | Polymeric ionic liquids, methods of making and methods of use thereof |
| CN107930420A (en) * | 2017-11-02 | 2018-04-20 | 昆明理工大学 | A kind of acidproof high conductivity anion-exchange membrane of hydrophobicity and preparation method thereof |
| CN111924807A (en) * | 2020-05-26 | 2020-11-13 | 萍乡市华星环保工程技术有限公司 | Method and device for trapping carbon dioxide and simultaneously producing sulfuric acid by sodium bisulfate |
Non-Patent Citations (1)
| Title |
|---|
| 中国材料研究学会, 中国铁道出版社 * |
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