CN112537827A - Bipolar membrane electrodialysis method for preparing sodium hypochlorite and hydrochloric acid from concentrated seawater - Google Patents
Bipolar membrane electrodialysis method for preparing sodium hypochlorite and hydrochloric acid from concentrated seawater Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 120
- 239000013535 sea water Substances 0.000 title claims abstract description 61
- 238000000909 electrodialysis Methods 0.000 title claims abstract description 53
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 28
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000005708 Sodium hypochlorite Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000460 chlorine Substances 0.000 claims abstract description 39
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 39
- 238000011033 desalting Methods 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 8
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011575 calcium Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 239000012141 concentrate Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000003011 anion exchange membrane Substances 0.000 claims description 18
- 238000005341 cation exchange Methods 0.000 claims description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 238000010612 desalination reaction Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000001471 micro-filtration Methods 0.000 claims description 2
- 239000012982 microporous membrane Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- -1 hydrogen ions Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000979 synthetic dye Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- 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
- C02F1/4695—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis electrodeionisation
-
- 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
- B01D61/445—Ion-selective electrodialysis with bipolar membranes; Water splitting
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/04—Hypochlorous acid
- C01B11/06—Hypochlorites
- C01B11/062—Hypochlorites of alkali metals
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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
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/035—Preparation of hydrogen chloride from chlorides
-
- 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
- C02F2103/08—Seawater, e.g. for desalination
-
- 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
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Urology & Nephrology (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- General Chemical & Material Sciences (AREA)
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A bipolar membrane electrodialysis method for preparing sodium hypochlorite and hydrochloric acid from concentrated seawater is carried out in a bipolar membrane electrodialysis device shown in the attached drawing; the bipolar membrane electrodialysis method comprises the following steps: (1) pretreating the concentrated seawater to reduce the concentration of calcium and magnesium ions in the concentrated seawater to below 10 ppm; (2) introducing the concentrated seawater pretreated in the step (1) into a desalting chamber, a chlorine preparation chamber, a cathode chamber and an anode chamber of a bipolar membrane electrodialysis device, and introducing pure water into a concentration chamber; the volumes of the liquids added into the compartments are the same, and the liquid flow rates of the compartments are kept consistent; starting a direct current power supply to carry out electrodialysis treatment, observing that the conductivity of the desalting chamber is not reduced any more, and regarding the conductivity as a reaction end point, or replacing the liquid in the desalting chamber to further concentrate to prepare chlorine; finally, hydrochloric acid is obtained in the concentration chamber, and sodium hypochlorite solution is obtained in the chlorine preparation chamber, the cathode chamber and the anode chamber. The invention avoids the direct discharge of concentrated seawater to affect the environment and obtains obvious economic benefit.
Description
Technical Field
The invention belongs to a technology for application by adopting bipolar membrane electrodialysis in the field of chemical industry, and particularly relates to a bipolar membrane electrodialysis method for preparing sodium hypochlorite and hydrochloric acid from concentrated seawater.
Background
The molecular structural formula of the sodium hypochlorite is NaClO, the molecular weight of the sodium hypochlorite is 74.44, the sodium hypochlorite is soluble in water, the solution is yellowish solution, has the smell similar to chlorine, has strong oxidizing property and the boiling point of 102.2 ℃, is used as a water purifying agent, a bactericide, a disinfectant, a catalyst, a synthetic dye and the like in water treatment at present, and has wide effects in the pharmaceutical industry.
Because the output of the concentrated seawater is large and the salt content thereof is high in the seawater desalination industry, if the concentrated seawater is directly discharged into the sea, great influence is caused on the environment. According to the characteristic of high salt content, the concentrated seawater can be comprehensively utilized to realize the resource utilization. Therefore, in order to reduce the influence of the discharge of the concentrated seawater on the environment, the salt content of the concentrated seawater can be recycled.
In order to achieve the above purpose, a method for recovering salt in the concentrated seawater to reduce the salt content in the concentrated seawater and obtain corresponding acid and sodium hypochlorite which can be put into practical production needs to be found. The method avoids the direct discharge of concentrated seawater to affect the environment and obtains obvious economic benefit.
Disclosure of Invention
The invention aims to provide a method for preparing sodium hypochlorite and hydrochloric acid by bipolar membrane electrodialysis of concentrated seawater.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a bipolar membrane electrodialysis method for preparing sodium hypochlorite and hydrochloric acid from concentrated seawater is carried out in a bipolar membrane electrodialysis device,
the bipolar membrane electrodialysis device comprises an anode plate, a cathode plate and a membrane stack clamped between the anode plate and the cathode plate, wherein the membrane stack is composed of at least one electrodialysis unit, two ends of the membrane stack are bipolar membranes, the electrodialysis unit is a three-compartment structure formed by sequentially arranging the bipolar membranes, an anion exchange membrane, a cation exchange membrane and the bipolar membranes, the three compartments are a concentration compartment formed by the bipolar membranes and the anion exchange membrane, a desalination compartment formed by the anion exchange membrane and the cation exchange membrane and a chlorine preparation compartment formed by the cation exchange membrane and the bipolar membranes, the bipolar membranes at the outermost side of the membrane stack respectively form a cathode compartment and an anode compartment with the cathode plate and the anode plate, and each compartment is provided with an independent circulation pipeline for enabling feed liquid to respectively flow in a circulation mode;
the bipolar membrane electrodialysis method comprises the following steps:
(1) pretreating the concentrated seawater to reduce the concentration of calcium and magnesium ions in the concentrated seawater to below 10 ppm;
(2) introducing the concentrated seawater pretreated in the step (1) into a desalting chamber, a chlorine preparation chamber, a cathode chamber and an anode chamber of a bipolar membrane electrodialysis device, and introducing pure water into a concentration chamber; the volumes of liquid added to each compartment are the same;
connecting a cathode plate of the bipolar membrane electrodialysis device with a cathode of a direct current power supply, connecting an anode plate with an anode of the direct current power supply, wherein liquid in each compartment respectively circularly flows through a circulating pipeline, the flow rate is controlled to be 20-40L/h, and the flow rate of liquid in each compartment is kept consistent so as to avoid permeation caused by pressure difference between the compartments; then starting a direct current power supply of the bipolar membrane electrodialysis device, and controlling the current density to be 5-15A/dm2When the temperature is 20-40 ℃, observing that the conductivity of the desalting chamber is not reduced any more, and regarding the conductivity as a reaction end point, or replacing the liquid in the desalting chamber to further concentrate to prepare chlorine; finally, hydrochloric acid is obtained in the concentration chamber, and sodium hypochlorite solution is obtained in the chlorine preparation chamber, the cathode chamber and the anode chamber.
The principle of the preparation method of the invention is as follows: chloride ions in the desalting chamber are transferred to the concentrating chamber through an anion exchange membrane and combined with hydrogen ions generated by the bipolar membrane to generate a hydrogen chloride solution, and the ion equation is Cl-+H+→ HCl, while the hydroxide ions generated by the bipolar membrane react with the chlorine generated by the anode to generate hypochlorite ions, the ion equation is Cl2+2OH-→2ClO-The hydroxide radical generated by the electrolysis of the cathode plate is combined with chlorine gas to generate hypochlorite ion with the ion equation of Cl2+2OH-→2ClO-. And (3) with the prolonging of the reaction time, the conductivity of the desalting chamber is reduced, and then sodium hypochlorite solution and hydrochloric acid can be collected.
Preferably, the pretreatment method of the concentrated seawater comprises the following steps:
adding sodium carbonate and sodium hydroxide into concentrated seawater to combine calcium and magnesium ions in the concentrated seawater with carbonate and hydroxyl respectively to generate corresponding calcium carbonate and sodium hydroxide precipitates;
filtering the obtained turbid concentrated seawater solution through a microfiltration membrane to obtain a clear concentrated seawater solution; preferably, the pore size of the microporous membrane is not more than 10 μm;
thirdly, the clarified concentrated seawater obtained in the step (2) is introduced into resin with hardness removing function, and the hardness of the clarified concentrated seawater is further removed, so that the clarified concentrated seawater reaches the feeding standard of bipolar membrane electrodialysis.
In the bipolar membrane electrodialysis device, each compartment is provided with an independent circulating pipeline to enable feed liquid to flow in a circulating mode, in a preferred embodiment, the chlorine making chamber, the cathode chamber and the anode chamber are connected in parallel and externally connected with a chlorine making tank, an outlet of the chlorine making tank is connected with inlets of the chlorine making chamber, the cathode chamber and the anode chamber through a circulating pump a and a valve a, and an inlet of the chlorine making tank is communicated with outlets of the chlorine making chamber, the cathode chamber and the anode chamber through pipelines;
the desalting chamber is connected with a desalting tank, an outlet of the desalting tank is connected with an inlet of the desalting chamber through a circulating pump b and a valve b by a pipeline, and an outlet of the desalting chamber is communicated with an inlet of the desalting tank by a pipeline;
the external concentrated jar of concentrating chamber, the export of concentrated jar link to each other through the entry of pipeline through circulating pump c and valve c with the concentrating chamber, the export of concentrating chamber pass through the entry intercommunication of pipeline with the concentrating tank.
The invention has no special requirements on the cathode plate and the anode plate, and the cathode plate and the anode plate (such as platinum-plated titanium plate, graphite plate and the like) commonly used by a bipolar membrane electrodialysis device are both applicable to the invention.
Preferably, the bipolar membrane electrodialysis membrane stack is formed by arranging 5-10 groups of electrodialysis units in series.
Preferably, the anion exchange membrane and the cation exchange membrane used in the bipolar membrane electrodialysis device are one of homogeneous membranes, semi-homogeneous membranes or heterogeneous membranes. It is further preferred that the bipolar membrane is a BP-1E type bipolar membrane (ASTOM Corporation, Japan), the anion exchange membrane is an AMX type anion exchange membrane (ASTOM Corporation, Japan), and the cation exchange membrane is a CMX type cation exchange membrane (ASTOM Corporation, Japan).
Preferably, the bipolar membrane, the anion exchange membrane and the cation exchange membrane are provided with a reticular clapboard among each other.
Preferably, the NaCl concentration of the concentrated seawater is 35000-40000 ppm.
Compared with the prior art, the invention has the beneficial effects that:
the bipolar membrane electrodialysis method provided by the invention realizes the recovery of high-salt-content concentrated seawater salt to prepare the chlorine acid, and on one hand, the discharge of concentrated seawater can be reduced, thereby reducing the influence of the concentrated seawater on the environment; on the other hand, the hydrochloric acid and the sodium hypochlorite solution are prepared by recovering the chlorine salt in the concentrated seawater to improve the economic benefit, the production cost is greatly reduced, and the method has obvious environmental benefit and economic benefit.
Drawings
FIG. 1 is a production flow diagram of the present invention;
FIG. 2 is a schematic diagram of an electrodialysis device for preparing sodium hypochlorite by bipolar membrane electrodialysis;
FIG. 3 is a diagram showing the working principle of a membrane stack for preparing sodium hypochlorite by bipolar membrane electrodialysis.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples.
The embodiment of the invention adopts a novel bipolar membrane electrodialysis device, which is shown in figures 2 and 3, and comprises an anode plate, a cathode plate and a membrane stack clamped between the anode plate and the cathode plate, wherein the membrane stack consists of 5 groups of electrodialysis units (not completely drawn), two ends of the membrane stack are bipolar membranes, the electrodialysis units are of a three-compartment structure formed by sequentially arranging the bipolar membranes, an anion exchange membrane, a cation exchange membrane and the bipolar membranes, the three compartments are a concentration compartment formed by the bipolar membranes and the anion exchange membrane, a desalination compartment formed by the anion exchange membrane and the cation exchange membrane and a chlorine production compartment formed by the cation exchange membrane and the membranes, and the bipolar membranes at the outermost sides of the membrane stack respectively form a cathode compartment and an anode compartment with the cathode plate and the anode plate;
the chlorine making chamber, the cathode chamber and the anode chamber are externally connected with a chlorine making tank in parallel, an outlet of the chlorine making tank is respectively connected with inlets of the chlorine making chamber, the cathode chamber and the anode chamber through a circulating pump a and a valve a through pipelines, and an inlet of the chlorine making tank is respectively communicated with outlets of the chlorine making chamber, the cathode chamber and the anode chamber through pipelines;
the desalting chamber is connected with a desalting tank, an outlet of the desalting tank is connected with an inlet of the desalting chamber through a circulating pump b and a valve b by a pipeline, and an outlet of the desalting chamber is communicated with an inlet of the desalting tank by a pipeline;
the concentration chamber is externally connected with a concentration tank, an outlet of the concentration tank is connected with an inlet of the concentration chamber through a circulating pump c and a valve c by a pipeline, and an outlet of the concentration chamber is communicated with an inlet of the concentration tank;
the anode plate and the cathode plate are respectively selected from titanium-plated ruthenium and stainless steel plates, the bipolar membrane adopts a BP-1E type bipolar membrane (ASTOM Corporation, Japan), the anion exchange membrane adopts an AMX type anion exchange membrane (ASTOM Corporation, Japan), and the cation exchange membrane adopts a CMX type cation exchange membrane (ASTOM Corporation, Japan);
the effective area of a single membrane is 189cm2The membranes are separated by a partition board, and the partition board is provided with a circulating coil pipe into which circulating chilled water can be introduced.
Example 1
Adding sodium hydroxide and sodium carbonate reagents into concentrated seawater (wherein the calcium ion concentration is 665ppm, the magnesium ion concentration is 1546ppm, and the Na ion concentration is 15117ppm), and adding 5.1g of sodium hydroxide and 1.4g of sodium carbonate into each liter of concentrated seawater to precipitate most of calcium and magnesium ions and polyvalent metal ions in the concentrated seawater to generate calcium carbonate and magnesium hydroxide. Then filtering the obtained turbid concentrated seawater through a microporous filter (the aperture is less than 10 mu m) to obtain a clear concentrated seawater solution; and then the high-valence metal ions such as calcium, magnesium and the like in the concentrated seawater are further reduced by adsorption through CH-93 ion exchange resin, so that the water inlet requirement of the bipolar membrane is met.
In the pretreated concentrated seawater, the concentration of calcium ions is less than 10 ppm; the concentration of magnesium ions is less than 10 ppm.
Adding 500mL of pretreated concentrated seawater into a desalting tank, starting a circulating pump to pump the pretreated concentrated seawater into a desalting chamber of a bipolar membrane electrodialysis membrane stack, adjusting the flow rate to 20L/h, adding 500mL of pure water into a concentration tank, starting the circulating pump to pump the pure water into the concentration chamber of the membrane stack, adjusting the flow rate to 20L/h, adding 1L of treated concentrated seawater into a chlorine making tank, starting the circulating pump to pump the pure water into the chlorine making chamber, an anode chamber and a cathode chamber of the membrane stack, wherein each compartment operates at the flow rate of 20L/h. Starting a direct current power supply, controlling the temperature of the membrane stack to be about 20 ℃, and controlling the current density to be 5A/dm2And controlling the reaction time to be 60min, obtaining sodium hypochlorite in a chlorine preparation tank, and detecting the content of the sodium hypochlorite to be 4.6 g/l. The hydrogen chloride solution is obtained from the concentration tank, and the energy consumption is 41.2 kWh/kg.
Example 2
The pretreatment of concentrated seawater was performed as in example 1.
Adding 500mL of pretreated concentrated seawater into a desalting tank, starting a circulating pump to pump the pretreated concentrated seawater into a desalting chamber of a bipolar membrane electrodialysis membrane stack, adjusting the flow rate to 20L/h, adding 500mL of pure water into a concentration tank, starting the circulating pump to pump the pure water into the concentration chamber of the membrane stack, adjusting the flow rate to 20L/h, adding 1L of treated concentrated seawater into a chlorine making tank, starting the circulating pump to pump the pure water into the chlorine making chamber, a cathode chamber and an anode chamber of the membrane stack, wherein each compartment operates at the flow rate of 20L/h. Starting a direct current power supply, controlling the temperature of the membrane stack to be about 20 ℃, and controlling the current density to be 13A/dm2Controlling the reaction time to be 13min, and obtaining sodium hypochlorite in a chlorine preparation tankAnd the content thereof was detected to be 4.8 g/l. The concentration tank obtains hydrogen chloride solution with energy consumption of 39.1 kWh/kg.
The above-described embodiments are merely examples for clearly illustrating the present invention and do not limit the embodiments of the present invention. The foregoing examples and description are illustrative only of the principles of the invention, and it will be apparent to those skilled in the art that other variations and modifications may be made on the invention. Not all embodiments are described herein. All obvious variations on the basis of the technical solutions led out by the present invention are within the scope of the present invention.
Claims (6)
1. A bipolar membrane electrodialysis method for preparing sodium hypochlorite and hydrochloric acid from concentrated seawater is characterized in that: the bipolar membrane electrodialysis method is carried out in a bipolar membrane electrodialysis device,
the bipolar membrane electrodialysis device comprises an anode plate, a cathode plate and a membrane stack clamped between the anode plate and the cathode plate, wherein the membrane stack is composed of at least one electrodialysis unit, two ends of the membrane stack are bipolar membranes, the electrodialysis unit is a three-compartment structure formed by sequentially arranging the bipolar membranes, an anion exchange membrane, a cation exchange membrane and the bipolar membranes, the three compartments are a concentration compartment formed by the bipolar membranes and the anion exchange membrane, a desalination compartment formed by the anion exchange membrane and the cation exchange membrane and a chlorine preparation compartment formed by the cation exchange membrane and the bipolar membranes, the bipolar membranes at the outermost side of the membrane stack respectively form a cathode compartment and an anode compartment with the cathode plate and the anode plate, and each compartment is provided with an independent circulation pipeline for enabling feed liquid to respectively flow in a circulation mode;
the bipolar membrane electrodialysis method comprises the following steps:
(1) pretreating the concentrated seawater to reduce the concentration of calcium and magnesium ions in the concentrated seawater to below 10 ppm;
(2) introducing the concentrated seawater pretreated in the step (1) into a desalting chamber, a chlorine preparation chamber, a cathode chamber and an anode chamber of a bipolar membrane electrodialysis device, and introducing pure water into a concentration chamber; the volumes of liquid added to each compartment are the same;
connecting a cathode plate of the bipolar membrane electrodialysis device with a cathode of a direct current power supply, connecting an anode plate with an anode of the direct current power supply, wherein liquid in each compartment respectively circularly flows through a circulating pipeline, the flow rate is controlled to be 20-40L/h, and the flow rate of liquid in each compartment is kept consistent so as to avoid permeation caused by pressure difference between the compartments; then starting a direct current power supply of the bipolar membrane electrodialysis device, and controlling the current density to be 5-15A/dm2When the temperature is 20-40 ℃, observing that the conductivity of the desalting chamber is not reduced any more, and regarding the conductivity as a reaction end point, or replacing the liquid in the desalting chamber to further concentrate to prepare chlorine; finally, hydrochloric acid is obtained in the concentration chamber, and sodium hypochlorite solution is obtained in the chlorine preparation chamber, the cathode chamber and the anode chamber.
2. The bipolar membrane electrodialysis process according to claim 1, wherein: the pretreatment method of the concentrated seawater comprises the following steps:
adding sodium carbonate and sodium hydroxide into concentrated seawater to combine calcium and magnesium ions in the concentrated seawater with carbonate and hydroxyl respectively to generate corresponding calcium carbonate and sodium hydroxide precipitates;
filtering the obtained turbid concentrated seawater solution through a microfiltration membrane to obtain a clear concentrated seawater solution; preferably, the pore size of the microporous membrane is not more than 10 μm;
thirdly, the clarified concentrated seawater obtained in the step (2) is introduced into resin with hardness removing function, and the hardness of the clarified concentrated seawater is further removed, so that the clarified concentrated seawater reaches the feeding standard of bipolar membrane electrodialysis.
3. The bipolar membrane electrodialysis process according to claim 1 or 2, wherein: the chlorine making chamber, the cathode chamber and the anode chamber are externally connected with a chlorine making tank in parallel, an outlet of the chlorine making tank is respectively connected with inlets of the chlorine making chamber, the cathode chamber and the anode chamber through a circulating pump a and a valve a, and an inlet of the chlorine making tank is respectively communicated with outlets of the chlorine making chamber, the cathode chamber and the anode chamber through pipelines;
the desalting chamber is connected with a desalting tank, an outlet of the desalting tank is connected with an inlet of the desalting chamber through a circulating pump b and a valve b by a pipeline, and an outlet of the desalting chamber is communicated with an inlet of the desalting tank by a pipeline;
the external concentrated jar of concentrating chamber, the export of concentrated jar link to each other through the entry of pipeline through circulating pump c and valve c with the concentrating chamber, the export of concentrating chamber pass through the entry intercommunication of pipeline with the concentrating tank.
4. The bipolar membrane electrodialysis process according to claim 1 or 2, wherein: the bipolar membrane electrodialysis membrane stack is formed by arranging 5-10 groups of electrodialysis units in series.
5. The bipolar membrane electrodialysis process according to claim 1 or 2, wherein: the anion exchange membrane and the cation exchange membrane used by the bipolar membrane electrodialysis device are homogeneous membranes, semi-homogeneous membranes or heterogeneous membranes.
6. The bipolar membrane electrodialysis process according to claim 1 or 2, wherein: reticular clapboards are arranged among the bipolar membrane, the anion exchange membrane and the cation exchange membrane.
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