CN214051178U - Bipolar membrane electrodialysis device for preparing alkali concentrated solution by seawater carbon sequestration - Google Patents
Bipolar membrane electrodialysis device for preparing alkali concentrated solution by seawater carbon sequestration Download PDFInfo
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- CN214051178U CN214051178U CN202022934425.3U CN202022934425U CN214051178U CN 214051178 U CN214051178 U CN 214051178U CN 202022934425 U CN202022934425 U CN 202022934425U CN 214051178 U CN214051178 U CN 214051178U
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Abstract
The utility model provides a bipolar membrane electrodialysis device for sea water carbon fixation system alkali strong solution, let in pipeline, alkali lye memory cell, salt solution memory cell, hydrochloric acid liquid memory cell, sulfuric acid liquid memory cell, utmost point liquid memory cell and bipolar membrane electrodialysis membrane pile including carbon dioxide. The utility model provides a bipolar membrane electrodialysis device for solid carbon system alkali strong solution of sea water has used multipurposely the sodium resource in the sea water and greenhouse gas carbon dioxide, has reduced manufacturing cost simultaneously, accords with green requirement.
Description
Technical Field
The utility model belongs to the technical field of sea water resource utilization and mineralize solid carbon, a device that is used for sea water solid carbon system alkali strong solution is related to, especially relate to a bipolar membrane electrodialysis device that is used for sea water solid carbon system alkali strong solution.
Background
At present, the emission of greenhouse gas carbon dioxide is continuously increased, which causes a series of environmental problems such as global warming, glacier melting and the like, so that a plurality of scholars at home and abroad are dedicated to research and exploration of novel carbon dioxide capture and utilization technology. In addition, the ocean is used as a huge global resource treasury, the development and the utilization of chemical resources in the seawater are highly valued by people, and particularly, the development potential of an emerging technology related to the high-value utilization of sodium resources is extremely high.
The method for preparing alkali by utilizing the sodium resource in the seawater and the greenhouse gas carbon dioxide is a good idea. The traditional alkali preparation process such as the Sovier alkali preparation method and the Hough alkali preparation method faces the problems of high cost, harsh reaction conditions, generation of waste gas and waste liquid and the like; and in recent years, the energy consumption for preparing alkali by an emerging electrolytic method is high, so that the method is not beneficial to large-scale production.
CN 108117092A discloses a process for producing alkali by directly pressurizing kiln gas with low carbon dioxide concentration in a gas burning kiln, which comprises the following steps: the lime kiln for calcining limestone takes natural gas as fuel, the generated high-temperature carbon dioxide gas is not subjected to additional concentration treatment, is directly sent into a carbon dioxide compressor unit only after being subjected to dust removal and temperature reduction, and the pressurized carbon dioxide gas is directly sent into a carbonization tower to carry out chemical reaction to produce soda. The method takes natural gas as the fuel of the lime kiln, utilizes kiln gas with low carbon dioxide concentration to directly pressurize for soda production, reduces the production cost, simultaneously the quality of soda products is equal to or higher than the technical index of the lime kiln taking coke or white coal as the fuel, enhances the enterprise competitiveness and improves the economic benefit. However, the invention is easy to generate waste gas and liquid, does not meet the requirement of environmental protection, and can not realize the development and utilization of sodium resources in seawater.
CN 108218072a discloses a high-salt water alkali-making process and a device thereof, wherein the process comprises the following steps: (1) adding alkali into high-salinity water to form calcium carbonate and magnesium hydroxide, removing precipitates, filtering by a first-stage ceramic membrane device, adding acid into produced water, and then desalting; (2) adding alkali into the concentrated water of the membrane desalting device again, treating the concentrated water by using a second-stage ceramic membrane device, adding acid into the produced water to adjust the pH value, and then feeding the water into a nanofiltration device; (3) the water produced by the nanofiltration device is mainly a sodium chloride solution, the sodium chloride solution is treated by a membrane concentration device, a weak acid anode bed and a decarbonization device, the produced water enters bipolar membrane electrodialysis, and the sodium chloride solution is prepared into sodium hydroxide and hydrochloric acid through the bipolar membrane electrodialysis; (4) the main component of the concentrated water of the nanofiltration device is sodium sulfate solution, and the sodium sulfate solution is crystallized into mirabilite after being frozen. The invention enables the produced water of high-salt water to be completely recycled, and the salt in the water can be recycled. However, the device is not suitable for preparing alkali from seawater, and cannot realize resource utilization of greenhouse gas carbon dioxide.
CN 102198952a discloses a combined soda production large circulation process, which comprises: a. obtaining an alkali-making raw material by adopting a leaching alkali-collecting method; b. obtaining hydrogen sulfide and methane by using microbial resources in the alkali brine; c. the evaporation and concentration of the light alkali liquor are realized by utilizing natural energy; d. combining a natural alkali method with a chemical combination method to prepare various products; e. combining deep processing in coal chemical industry with alkali making process to prepare an auxiliary product; f. the series products are prepared by combining an electrolysis method and a chemical combination method. The invention excavates natural alkali waste resources and hidden resources, develops the potential of coal chemical deep processing, applies the activated carbon purification technology to low-carbon economy, enables the technologies in various fields to be tightly combined with the alkali making process, and realizes the large circulation of combined alkali making. However, the invention has complex flow, relates to a plurality of devices, has high production cost and is difficult to popularize and apply.
Therefore, how to provide an alkali making device, comprehensively utilize sodium resources in seawater and greenhouse gas carbon dioxide, reduce production cost, meet the requirements of environmental protection and become a problem to be solved urgently by technical personnel in the field at present.
SUMMERY OF THE UTILITY MODEL
Not enough to prior art exists, the utility model aims to provide a bipolar membrane electrodialysis device for solid carbon system alkali thick solution of sea water, bipolar membrane electrodialysis device has used multipurposely the sodium resource in the sea water and greenhouse gas carbon dioxide, has reduced manufacturing cost simultaneously, accords with green requirement.
To achieve the purpose, the utility model adopts the following technical proposal:
the utility model provides a bipolar membrane electrodialysis device for sea water solid carbon system alkali strong solution, a bipolar membrane electrodialysis device for sea water solid carbon system alkali strong solution includes that carbon dioxide lets in pipeline, alkali lye memory cell, salt solution memory cell, hydrochloric acid liquid memory cell, sulfuric acid liquid memory cell, polar liquid memory cell and bipolar membrane electrodialysis membrane stack.
And the carbon dioxide is introduced into a pipeline and is connected with the alkali liquor storage unit.
And an alkali liquor outlet of the alkali liquor storage unit is connected with an alkali chamber inlet of the bipolar membrane electrodialysis membrane stack, and an alkali chamber outlet of the bipolar membrane electrodialysis membrane stack is connected with an alkali liquor inlet of the alkali liquor storage unit.
And the brine outlet of the brine storage unit is connected with the salt chamber inlet of the bipolar membrane electrodialysis membrane stack, and the salt chamber outlet of the bipolar membrane electrodialysis membrane stack is connected with the brine inlet of the brine storage unit.
The hydrochloric acid liquid outlet of the hydrochloric acid liquid storage unit is connected with the acid chamber inlet of the bipolar membrane electrodialysis membrane stack, and the acid chamber outlet of the bipolar membrane electrodialysis membrane stack is connected with the hydrochloric acid liquid inlet of the hydrochloric acid liquid storage unit.
And a sulfuric acid solution outlet of the sulfuric acid solution storage unit is connected with an anode chamber inlet of the bipolar membrane electrodialysis membrane stack, and an anode chamber outlet of the bipolar membrane electrodialysis membrane stack is connected with a sulfuric acid solution inlet of the sulfuric acid solution storage unit.
And the polar liquid outlet of the polar liquid storage unit is connected with the polar chamber inlet of the bipolar membrane electrodialysis membrane stack, and the polar chamber outlet of the bipolar membrane electrodialysis membrane stack is connected with the polar liquid inlet of the polar liquid storage unit.
The bipolar membrane electrodialysis membrane stack comprises an anode electrode, a cathode electrode and at least one group of four-compartment electrodialysis units arranged between the anode electrode and the cathode electrode, wherein the four-compartment electrodialysis units comprise bipolar membranes, anode membranes, cathode membranes, anode membranes and bipolar membranes.
The utility model discloses a four compartment electrodialysis units in bipolar membrane electrodialysis membrane stack comprise bipolar membrane, positive membrane, negative membrane, positive membrane and bipolar membrane, two adjacent four compartment electrodialysis units bipolar membrane of sharing. When the bipolar membrane electrodialysis membrane stack operates, anions generated by bipolar membrane dissociation water enter the alkali chamber through the anion exchange membrane, and are dissolved and absorbed and balanced with introduced carbon dioxide gas, and bipolar membrane electrodialysis is finished.
The utility model discloses a method that bipolar membrane electrodialysis membrane stack passed through bipolar membrane electrodialysis makes the solid carbon of sea water and prepares sodium bicarbonate concentrated solution, has realized the ionization absorption of greenhouse gas carbon dioxide, need not plus alkali sources, the raw materials is easily obtained, green in the source, has made high-value sodium bicarbonate concentrated solution, has good economic benefits and market perspective.
In the utility model, the concentrated solution is the solution with the concentration of sodium bicarbonate in the alkali liquor being more than or equal to 900 mmol/L.
In the utility model discloses in, including at least a set of four compartment electrodialysis units in the bipolar membrane electrodialysis membrane stack, for example can be 1 group, 2 groups, 3 groups, 4 groups, 5 groups, 6 groups, 7 groups, 8 groups, 9 groups or 10 groups, the technical staff in the art can rationally select according to the concentration of sodium ion in the brine and the volume of letting in of carbon dioxide.
Preferably, the anode electrode of the bipolar membrane electrodialysis membrane stack comprises a titanium electrode or a platinum electrode.
Preferably, the cathode electrode of the bipolar membrane electrodialysis membrane stack comprises a titanium electrode or a stainless steel electrode.
Preferably, a gas refining disc is further connected between the carbon dioxide inlet pipeline and the alkali liquor storage unit.
Preferably, the gas refiner plate has a diameter of 5-10cm, and may be, for example, 5cm, 5.5cm, 6cm, 6.5cm, 7cm, 7.5cm, 8cm, 8.5cm, 9cm, 9.5cm or 10cm, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the alkali liquor storage unit, the brine storage unit, the hydrochloric acid liquor storage unit, the sulfuric acid liquor storage unit and the polar liquor storage unit are respectively and independently liquid storage tanks.
Preferably, the volume of the liquid storage tank is 1-10L, for example, 1L, 2L, 3L, 4L, 5L, 6L, 7L, 8L, 9L or 10L, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, an alkali liquor delivery pump, a control valve and a flow meter are sequentially connected between the alkali liquor outlet of the alkali liquor storage unit and the alkali chamber inlet of the bipolar membrane electrodialysis membrane stack.
Preferably, a saline delivery pump, a control valve and a flow meter are sequentially connected between the saline outlet of the saline storage unit and the saline chamber inlet of the bipolar membrane electrodialysis membrane stack.
Preferably, a hydrochloric acid liquid delivery pump, a control valve and a flow meter are sequentially connected between the hydrochloric acid liquid outlet of the hydrochloric acid liquid storage unit and the hydrochloric acid chamber inlet of the bipolar membrane electrodialysis membrane stack.
Preferably, a sulfuric acid solution delivery pump, a control valve and a flow meter are sequentially connected between a sulfuric acid solution outlet of the sulfuric acid solution storage unit and a sulfuric acid chamber inlet of the bipolar membrane electrodialysis membrane stack.
Preferably, an electrode liquid delivery pump, a control valve and a flow meter are sequentially connected between the electrode liquid outlet of the electrode liquid storage unit and the electrode chamber inlet of the bipolar membrane electrodialysis membrane stack.
Preferably, the alkali liquor delivery pump, the brine delivery pump, the hydrochloric acid liquor delivery pump, the sulfuric acid liquor delivery pump and the polar liquid delivery pump are respectively and independently magnetic force driven pumps.
Preferably, the dimensions of the bipolar membrane, the positive membrane, the negative membrane, the positive membrane and the bipolar membrane are (50-250) mm × 500mm, such as 50mm × 100mm, 100mm × 200mm, 150mm × 300mm, 200mm × 400mm or 250mm × 500mm, but are not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the power supply for connecting the anode electrode and the cathode electrode is a direct current power supply.
Compared with the prior art, the beneficial effects of the utility model are that:
(1) the utility model provides a bipolar membrane electrodialysis device improves traditional bipolar membrane, positive membrane, negative membrane and bipolar membrane three compartment structure into bipolar membrane, positive membrane, negative membrane, positive membrane and bipolar membrane four compartment structure, can produce the higher sodium bicarbonate solution of purity, hydrochloric acid solution and sulfuric acid solution in alkali lye memory cell, hydrochloric acid solution memory cell and sulfuric acid solution memory cell respectively, has improved the efficiency of bipolar membrane electrodialysis, and economic benefits is considerable;
(2) the utility model provides a method that the bipolar membrane electrodialysis device is used for the concentrated solution of the seawater carbon fixation alkali production is simple, the softened seawater is used by the brine storage unit, the raw materials are easy to obtain, and the membrane pollution is effectively avoided; under the conditions of normal temperature and normal pressure and without adding chemical reagents, the preparation of the sodium bicarbonate solution is stably carried out in an alkali liquor storage unit, the reaction condition is mild, and the environment is protected; use the utility model provides a when bipolar membrane electrodialysis device carries out the solid carbon system alkali of sea water, gained sodium bicarbonate solution concentration is more than or equal to 900mmol/L, and the solid carbon rate is more than or equal to 35%.
Drawings
Fig. 1 is a schematic structural diagram of a bipolar membrane electrodialysis device for seawater carbon fixation alkali-making concentrated solution provided by the utility model.
Wherein: 100-carbon dioxide is introduced into the pipeline; 200-an alkali liquor storage unit; 300-brine storage unit; 400-a hydrochloric acid liquid storage unit; 500-sulfuric acid solution storage unit; 600-an electrode liquid storage unit; 700-bipolar membrane electrodialysis membrane stack; 710-an anode electrode; 720-cathode electrode; 730-a four compartment electrodialysis unit; 731-bipolar membrane; 732-sun membrane; 733-negative film.
Detailed Description
It is to be understood that in the description of the present invention, the terms "central," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in the orientation or positional relationship indicated in the drawings for the purpose of convenience and simplicity of description, and are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are not to be construed as limiting the present invention.
It should be noted that, unless explicitly stated or limited otherwise, the terms "disposed," "connected" and "connected" in the description of the present invention are to be construed broadly, and may for example be fixedly connected, detachably connected or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.
The technical solution of the present invention is further explained by the following embodiments with reference to the accompanying drawings.
Example 1
The embodiment provides a bipolar membrane electrodialysis device for preparing an alkali concentrated solution by fixing carbon in seawater, which comprises a carbon dioxide introducing pipeline 100, an alkali liquor storage unit 200, a saline water storage unit 300, a hydrochloric acid liquor storage unit 400, a sulfuric acid liquor storage unit 500, an electrode liquor storage unit 600 and a bipolar membrane electrodialysis membrane stack 700, as shown in fig. 1.
The carbon dioxide inlet pipeline 100 is connected with the alkali liquor storage unit 200, and a gas refining disc with the diameter of 7.5cm is connected between the carbon dioxide inlet pipeline and the alkali liquor storage unit.
An alkali liquor outlet of the alkali liquor storage unit 200 is connected with an alkali chamber inlet of the bipolar membrane electrodialysis membrane stack 700, a magnetic force driving pump, a control valve and a flow meter are sequentially connected between the alkali liquor outlet of the alkali liquor storage unit 200 and the alkali chamber inlet of the bipolar membrane electrodialysis membrane stack 700, and the alkali chamber outlet of the bipolar membrane electrodialysis membrane stack 700 is connected with the alkali liquor inlet of the alkali liquor storage unit 200.
The brine outlet of the brine storage unit 300 is connected with the brine chamber inlet of the bipolar membrane electrodialysis membrane stack 700, a magnetic force driving pump, a control valve and a flow meter are sequentially connected between the brine outlet of the brine storage unit 300 and the brine chamber inlet of the bipolar membrane electrodialysis membrane stack 700, and the brine chamber outlet of the bipolar membrane electrodialysis membrane stack 700 is connected with the brine inlet of the brine storage unit 300.
The hydrochloric acid liquid outlet of the hydrochloric acid liquid storage unit 400 is connected with the hydrochloric acid chamber inlet of the bipolar membrane electrodialysis membrane stack 700, a magnetic force driving pump, a control valve and a flow meter are sequentially connected between the hydrochloric acid liquid outlet of the bipolar membrane electrodialysis membrane stack 700 and the hydrochloric acid chamber inlet of the hydrochloric acid liquid storage unit 400, and the hydrochloric acid chamber outlet of the bipolar membrane electrodialysis membrane stack 700 is connected with the hydrochloric acid liquid inlet of the hydrochloric acid liquid storage unit 400.
The sulfuric acid solution outlet of the sulfuric acid solution storage unit 500 is connected with the sulfuric acid chamber inlet of the bipolar membrane electrodialysis membrane stack 700, a magnetic force driving pump, a control valve and a flow meter are sequentially connected between the sulfuric acid chamber outlet of the bipolar membrane electrodialysis membrane stack 700 and the sulfuric acid chamber inlet of the sulfuric acid solution storage unit 500.
An electrode solution outlet of the electrode solution storage unit 600 is connected with an electrode chamber inlet of the bipolar membrane electrodialysis membrane stack 700, a magnetic force driving pump, a control valve and a flow meter are sequentially connected between the electrode solution outlet and the electrode chamber inlet of the bipolar membrane electrodialysis membrane stack 700, and the electrode chamber outlet of the bipolar membrane electrodialysis membrane stack 700 is connected with the electrode solution inlet of the electrode solution storage unit 600.
The alkali liquor storage unit 200, the saline water storage unit 300, the hydrochloric acid liquor storage unit 400, the sulfuric acid liquor storage unit 500 and the polar liquor storage unit 600 are respectively and independently liquid storage tanks with the volume of 5L.
The bipolar membrane electrodialysis membrane stack 700 is composed of an anode electrode 710, a cathode electrode 720 and six groups of four-compartment electrodialysis units 730 arranged between the anode electrode 710 and the cathode electrode 720, wherein the four-compartment electrodialysis units 730 are composed of bipolar membranes 731, anode membranes 732, cathode membranes 733, anode membranes 732 and the bipolar membranes 731.
The sizes of the bipolar membrane 731, the anode membrane 732, the cathode membrane 733, the anode membrane 732 and the bipolar membrane 731 are respectively 150mm × 300mm, the anode electrode 710 is a platinum electrode, the cathode electrode 720 is a titanium electrode, and the access power supplies of the anode electrode 710 and the cathode electrode 720 are direct current power supplies.
Example 2
The embodiment provides a bipolar membrane electrodialysis device for preparing an alkali concentrated solution by fixing carbon in seawater, which comprises a carbon dioxide introducing pipeline 100, an alkali liquor storage unit 200, a saline water storage unit 300, a hydrochloric acid liquor storage unit 400, a sulfuric acid liquor storage unit 500, an electrode liquor storage unit 600 and a bipolar membrane electrodialysis membrane stack 700, as shown in fig. 1.
The carbon dioxide inlet pipeline 100 is connected with the alkali liquor storage unit 200, and a gas refining disc with the diameter of 5cm is connected between the carbon dioxide inlet pipeline and the alkali liquor storage unit.
An alkali liquor outlet of the alkali liquor storage unit 200 is connected with an alkali chamber inlet of the bipolar membrane electrodialysis membrane stack 700, a magnetic force driving pump, a control valve and a flow meter are sequentially connected between the alkali liquor outlet of the alkali liquor storage unit 200 and the alkali chamber inlet of the bipolar membrane electrodialysis membrane stack 700, and the alkali chamber outlet of the bipolar membrane electrodialysis membrane stack 700 is connected with the alkali liquor inlet of the alkali liquor storage unit 200.
The brine outlet of the brine storage unit 300 is connected with the brine chamber inlet of the bipolar membrane electrodialysis membrane stack 700, a magnetic force driving pump, a control valve and a flow meter are sequentially connected between the brine outlet of the brine storage unit 300 and the brine chamber inlet of the bipolar membrane electrodialysis membrane stack 700, and the brine chamber outlet of the bipolar membrane electrodialysis membrane stack 700 is connected with the brine inlet of the brine storage unit 300.
The hydrochloric acid liquid outlet of the hydrochloric acid liquid storage unit 400 is connected with the hydrochloric acid chamber inlet of the bipolar membrane electrodialysis membrane stack 700, a magnetic force driving pump, a control valve and a flow meter are sequentially connected between the hydrochloric acid liquid outlet of the bipolar membrane electrodialysis membrane stack 700 and the hydrochloric acid chamber inlet of the hydrochloric acid liquid storage unit 400, and the hydrochloric acid chamber outlet of the bipolar membrane electrodialysis membrane stack 700 is connected with the hydrochloric acid liquid inlet of the hydrochloric acid liquid storage unit 400.
The sulfuric acid solution outlet of the sulfuric acid solution storage unit 500 is connected with the sulfuric acid chamber inlet of the bipolar membrane electrodialysis membrane stack 700, a magnetic force driving pump, a control valve and a flow meter are sequentially connected between the sulfuric acid chamber outlet of the bipolar membrane electrodialysis membrane stack 700 and the sulfuric acid chamber inlet of the sulfuric acid solution storage unit 500.
An electrode solution outlet of the electrode solution storage unit 600 is connected with an electrode chamber inlet of the bipolar membrane electrodialysis membrane stack 700, a magnetic force driving pump, a control valve and a flow meter are sequentially connected between the electrode solution outlet and the electrode chamber inlet of the bipolar membrane electrodialysis membrane stack 700, and the electrode chamber outlet of the bipolar membrane electrodialysis membrane stack 700 is connected with the electrode solution inlet of the electrode solution storage unit 600.
The alkali liquor storage unit 200, the saline water storage unit 300, the hydrochloric acid liquor storage unit 400, the sulfuric acid liquor storage unit 500 and the polar liquor storage unit 600 are respectively and independently liquid storage tanks with the volume of 1L.
The bipolar membrane electrodialysis membrane stack 700 is composed of an anode electrode 710, a cathode electrode 720 and a group of four-compartment electrodialysis units 730 arranged between the anode electrode 710 and the cathode electrode 720, wherein the four-compartment electrodialysis units 730 are composed of a bipolar membrane 731, an anode membrane 732, a cathode membrane 733, an anode membrane 732 and the bipolar membrane 731.
The sizes of the bipolar membrane 731, the anode membrane 732, the cathode membrane 733, the anode membrane 732 and the bipolar membrane 731 are respectively 250mm multiplied by 500mm, the anode electrode 710 is a titanium electrode, the cathode electrode 720 is a stainless steel electrode, and the access power supplies of the anode electrode 710 and the cathode electrode 720 are direct current power supplies.
Example 3
The embodiment provides a bipolar membrane electrodialysis device for preparing an alkali concentrated solution by fixing carbon in seawater, which comprises a carbon dioxide introducing pipeline 100, an alkali liquor storage unit 200, a saline water storage unit 300, a hydrochloric acid liquor storage unit 400, a sulfuric acid liquor storage unit 500, an electrode liquor storage unit 600 and a bipolar membrane electrodialysis membrane stack 700, as shown in fig. 1.
The carbon dioxide inlet pipeline 100 is connected with the alkali liquor storage unit 200, and a gas refining disc with the diameter of 10cm is connected between the carbon dioxide inlet pipeline and the alkali liquor storage unit.
An alkali liquor outlet of the alkali liquor storage unit 200 is connected with an alkali chamber inlet of the bipolar membrane electrodialysis membrane stack 700, a magnetic force driving pump, a control valve and a flow meter are sequentially connected between the alkali liquor outlet of the alkali liquor storage unit 200 and the alkali chamber inlet of the bipolar membrane electrodialysis membrane stack 700, and the alkali chamber outlet of the bipolar membrane electrodialysis membrane stack 700 is connected with the alkali liquor inlet of the alkali liquor storage unit 200.
The brine outlet of the brine storage unit 300 is connected with the brine chamber inlet of the bipolar membrane electrodialysis membrane stack 700, a magnetic force driving pump, a control valve and a flow meter are sequentially connected between the brine outlet of the brine storage unit 300 and the brine chamber inlet of the bipolar membrane electrodialysis membrane stack 700, and the brine chamber outlet of the bipolar membrane electrodialysis membrane stack 700 is connected with the brine inlet of the brine storage unit 300.
The hydrochloric acid liquid outlet of the hydrochloric acid liquid storage unit 400 is connected with the hydrochloric acid chamber inlet of the bipolar membrane electrodialysis membrane stack 700, a magnetic force driving pump, a control valve and a flow meter are sequentially connected between the hydrochloric acid liquid outlet of the bipolar membrane electrodialysis membrane stack 700 and the hydrochloric acid chamber inlet of the hydrochloric acid liquid storage unit 400, and the hydrochloric acid chamber outlet of the bipolar membrane electrodialysis membrane stack 700 is connected with the hydrochloric acid liquid inlet of the hydrochloric acid liquid storage unit 400.
The sulfuric acid solution outlet of the sulfuric acid solution storage unit 500 is connected with the sulfuric acid chamber inlet of the bipolar membrane electrodialysis membrane stack 700, a magnetic force driving pump, a control valve and a flow meter are sequentially connected between the sulfuric acid chamber outlet of the bipolar membrane electrodialysis membrane stack 700 and the sulfuric acid chamber inlet of the sulfuric acid solution storage unit 500.
An electrode solution outlet of the electrode solution storage unit 600 is connected with an electrode chamber inlet of the bipolar membrane electrodialysis membrane stack 700, a magnetic force driving pump, a control valve and a flow meter are sequentially connected between the electrode solution outlet and the electrode chamber inlet of the bipolar membrane electrodialysis membrane stack 700, and the electrode chamber outlet of the bipolar membrane electrodialysis membrane stack 700 is connected with the electrode solution inlet of the electrode solution storage unit 600.
The alkali liquor storage unit 200, the saline water storage unit 300, the hydrochloric acid liquor storage unit 400, the sulfuric acid liquor storage unit 500 and the polar liquor storage unit 600 are respectively and independently liquid storage tanks with the volume of 10L.
The bipolar membrane electrodialysis membrane stack 700 is composed of an anode electrode 710, a cathode electrode 720 and ten groups of four-compartment electrodialysis units 730 arranged between the anode electrode 710 and the cathode electrode 720, wherein the four-compartment electrodialysis units 730 are composed of bipolar membranes 731, anode membranes 732, cathode membranes 733, anode membranes 732 and the bipolar membranes 731.
The sizes of the bipolar membrane 731, the anode membrane 732, the cathode membrane 733, the anode membrane 732 and the bipolar membrane 731 are respectively 50mm × 100mm independently, the anode electrode 710 is a platinum electrode, the cathode electrode 720 is a stainless steel electrode, and the access power supplies of the anode electrode 710 and the cathode electrode 720 are direct current power supplies.
Comparative example 1
The comparative example provides a bipolar membrane electrodialysis device, which comprises a carbon dioxide introducing pipeline, an alkali liquor storage unit, a brine storage unit, a hydrochloric acid liquor storage unit, an electrode liquor storage unit and a bipolar membrane electrodialysis membrane stack.
The carbon dioxide introducing pipeline is connected with the alkali liquor storage unit, and a gas refining disc with the diameter of 7.5cm is connected between the carbon dioxide introducing pipeline and the alkali liquor storage unit.
The alkali liquor outlet of the alkali liquor storage unit is connected with the alkali chamber inlet of the bipolar membrane electrodialysis membrane stack, a magnetic force driving pump, a control valve and a flow meter are sequentially connected between the alkali liquor outlet of the alkali liquor storage unit and the alkali chamber inlet of the bipolar membrane electrodialysis membrane stack, and the alkali chamber outlet of the bipolar membrane electrodialysis membrane stack is connected with the alkali liquor inlet of the alkali liquor storage unit.
The brine outlet of the brine storage unit is connected with the brine chamber inlet of the bipolar membrane electrodialysis membrane stack, a magnetic force driving pump, a control valve and a flow meter are sequentially connected between the brine outlet of the brine storage unit and the salt chamber inlet of the bipolar membrane electrodialysis membrane stack, and the brine outlet of the bipolar membrane electrodialysis membrane stack is connected with the brine inlet of the brine storage unit.
The hydrochloric acid liquid outlet of the hydrochloric acid liquid storage unit is connected with the hydrochloric acid chamber inlet of the bipolar membrane electrodialysis membrane stack, a magnetic force driving pump, a control valve and a flow meter are sequentially connected between the hydrochloric acid liquid outlet of the hydrochloric acid liquid storage unit and the hydrochloric acid chamber inlet of the bipolar membrane electrodialysis membrane stack, and the hydrochloric acid chamber outlet of the bipolar membrane electrodialysis membrane stack is connected with the hydrochloric acid liquid inlet of the hydrochloric acid liquid storage unit.
And the polar liquid outlet of the polar liquid storage unit is connected with the polar chamber inlet of the bipolar membrane electrodialysis membrane stack, a magnetic force driving pump, a control valve and a flowmeter are sequentially connected between the polar liquid outlet of the polar liquid storage unit and the polar chamber inlet of the bipolar membrane electrodialysis membrane stack, and the polar chamber outlet of the bipolar membrane electrodialysis membrane stack is connected with the polar liquid inlet of the polar liquid storage unit.
The alkali liquor storage unit, the brine storage unit, the hydrochloric acid liquor storage unit and the polar liquid storage unit are respectively and independently liquid storage tanks with the volume of 5L.
The bipolar membrane electrodialysis membrane stack comprises an anode electrode, a cathode electrode and six groups of four-compartment electrodialysis units arranged between the anode electrode and the cathode electrode, wherein the four-compartment electrodialysis units comprise bipolar membranes, anode membranes, cathode membranes, anode membranes and the bipolar membranes.
The size of the bipolar membrane, the size of the anode membrane, the size of the cathode membrane, the size of the anode membrane and the size of the bipolar membrane are 150mm multiplied by 300mm respectively and independently, the anode electrode is a platinum electrode, the cathode electrode is a titanium electrode, and the access power supply of the anode electrode and the access power supply of the cathode electrode are direct current power supplies.
Application example 1
The application example provides a method for preparing an alkali concentrated solution by fixing carbon in seawater by using the bipolar membrane electrodialysis device provided in example 1, and the method comprises the following steps:
(1) respectively and independently preparing a sodium bicarbonate solution with a sodium ion concentration of 0.05mol/L, simulated softened seawater with a sodium ion concentration of 1.5mol/L, a hydrochloric acid solution with a hydrogen ion concentration of 0.5mol/L, a sulfuric acid solution with a hydrogen ion concentration of 0.5mol/L and a sodium sulfate solution with a sodium ion concentration of 0.025mol/L in an alkali liquor storage unit 200, a saline water storage unit 300, a hydrochloric acid solution 400, a sulfuric acid solution 500 and a polar liquid storage unit 600;
(2) the sodium bicarbonate solution, the simulated softened seawater, the hydrochloric acid solution, the sulfuric acid solution and the sodium sulfate solution are respectively and independently operated in a circulating way;
(3) and (3) after circulation of the sodium bicarbonate solution, the simulated softened seawater, the hydrochloric acid solution, the sulfuric acid solution and the sodium sulfate solution is started, introducing carbon dioxide with the speed of 520mL/min into the sodium bicarbonate solution, then starting energization in a voltage constant mode, wherein the constant voltage is 21V, the membrane surface flow velocity is 2cm/s, stopping energization when the carbon dioxide in the sodium bicarbonate solution reaches the dissolution and absorption balance, and ending the bipolar membrane electrodialysis process.
In the application example, the simulated softened seawater contains 0.02mol/L of magnesium ions, 0.01mol/L of calcium ions, 1.6mol/L of chloride ions and other trace impurity ions besides sodium ions.
The concentration and carbon fixation rate of the sodium bicarbonate solution obtained in this application example are shown in table 1.
Application example 2
The application example provides a method for preparing an alkali concentrated solution by fixing carbon in seawater by using the bipolar membrane electrodialysis device provided in example 2, and the method comprises the following steps:
(1) respectively and independently preparing a sodium bicarbonate solution with the sodium ion concentration of 0.01mol/L, simulated softened seawater with the sodium ion concentration of 2mol/L, a hydrochloric acid solution with the hydrogen ion concentration of 0.01mol/L, a sulfuric acid solution with the hydrogen ion concentration of 0.01mol/L and a sodium nitrate solution with the sodium ion concentration of 0.01mol/L in an alkali liquor storage unit 200, a saline water storage unit 300, a hydrochloric acid solution 400, a sulfuric acid solution 500 and a polar liquid storage unit 600;
(2) the sodium bicarbonate solution, the simulated softened seawater, the hydrochloric acid solution, the sulfuric acid solution and the sodium nitrate solution are respectively and independently operated in a circulating way;
(3) and (3) after circulation of the sodium bicarbonate solution, the simulated softened seawater, the hydrochloric acid solution, the sulfuric acid solution and the sodium nitrate solution is started, introducing carbon dioxide with the speed of 320mL/min into the sodium bicarbonate solution, then starting energization in a voltage constant mode, wherein the constant voltage is 18V, the membrane surface flow velocity is 1cm/s, stopping energization when the carbon dioxide in the sodium bicarbonate solution reaches the dissolution and absorption balance, and ending the bipolar membrane electrodialysis process.
In the application example, the simulated softened seawater contains 0.02mol/L of magnesium ions, 0.01mol/L of calcium ions, 1.3mol/L of chloride ions and other trace impurity ions besides sodium ions.
The concentration and carbon fixation rate of the sodium bicarbonate solution obtained in this application example are shown in table 1.
Application example 3
The application example provides a method for preparing an alkali concentrated solution by fixing carbon in seawater by using the bipolar membrane electrodialysis device provided in embodiment 3, and the method comprises the following steps:
(1) respectively and independently preparing a sodium bicarbonate solution with sodium ion concentration of 0.1mol/L, simulated softened seawater with sodium ion concentration of 1mol/L, a hydrochloric acid solution with hydrogen ion concentration of 1mol/L, a sulfuric acid solution with hydrogen ion concentration of 1mol/L and a sodium sulfate solution with sodium ion concentration of 0.05mol/L in an alkali liquor storage unit 200, a brine storage unit 300, a hydrochloric acid solution 400, a sulfuric acid solution 500 and a polar liquid storage unit 600;
(2) the sodium bicarbonate solution, the simulated softened seawater, the hydrochloric acid solution, the sulfuric acid solution and the sodium sulfate solution are respectively and independently operated in a circulating way;
(3) and (3) after circulation of the sodium bicarbonate solution, the simulated softened seawater, the hydrochloric acid solution, the sulfuric acid solution and the sodium sulfate solution is started, introducing carbon dioxide with the speed of 720mL/min into the sodium bicarbonate solution, then starting energization in a voltage constant mode, wherein the constant voltage is 24V, the membrane surface flow velocity is 3cm/s, stopping energization when the carbon dioxide in the sodium bicarbonate solution reaches the dissolution and absorption balance, and ending the bipolar membrane electrodialysis process.
In the application example, the simulated softened seawater contains 0.02mol/L of magnesium ions, 0.01mol/L of calcium ions, 2mol/L of chloride ions and other trace impurity ions besides sodium ions.
The concentration and carbon fixation rate of the sodium bicarbonate solution obtained in this application example are shown in table 1.
Comparative application example 1
The comparative application example provides a method for preparing alkali by fixing carbon in seawater by using the bipolar membrane electrodialysis device provided in comparative example 1, and the method comprises the following steps:
(1) respectively and independently preparing a sodium bicarbonate solution with the sodium ion concentration of 0.05mol/L, simulated softened seawater with the sodium ion concentration of 1.5mol/L, a hydrochloric acid solution with the hydrogen ion concentration of 0.5mol/L and a sodium sulfate solution with the sodium ion concentration of 0.025mol/L in an alkali liquor storage unit, a brine storage unit, a hydrochloric acid solution storage unit and an electrode liquid storage unit;
(2) the sodium bicarbonate solution, the simulated softened seawater, the hydrochloric acid solution and the sodium sulfate solution are respectively and independently operated circularly;
(3) and (3) after circulation of the sodium bicarbonate solution, the simulated softened seawater, the hydrochloric acid solution and the sodium sulfate solution is started, introducing carbon dioxide with the speed of 520mL/min into the sodium bicarbonate solution, then starting energization in a voltage constant mode, wherein the constant voltage is 21V, the membrane surface flow velocity is 2cm/s, stopping energization when the carbon dioxide in the sodium bicarbonate solution reaches the dissolution and absorption balance, and ending the bipolar membrane electrodialysis process.
In the comparative application example, the simulated softened seawater contains 0.02mol/L of magnesium ions, 0.01mol/L of calcium ions, 1.4mol/L of chloride ions and other trace impurity ions besides sodium ions.
The concentration and carbon fixation rate of the sodium bicarbonate solution obtained in this comparative application example are shown in table 1.
TABLE 1
The method for testing the concentration of the sodium bicarbonate solution comprises the following steps: the concentration of carbonate and bicarbonate ions in the solution is determined by applying a double-indicator acid-base neutralization titration method disclosed in GB/T9736-2008, so as to determine the concentration of the sodium bicarbonate.
The carbon fixation rate calculation method comprises the following steps:
wherein L is0(L/h) is the gas flow flowing into the alkali liquor storage unit when the bipolar membrane electrodialysis is in operation;
when the bipolar membrane electrodialysis is in operation, the volume fraction of carbon dioxide in the gas flowing into the alkali liquor storage unit; Δ t (h) is the gas introduction time; 22.4(L/mol) is the gas molar volume;
is the molar increment of bicarbonate radical in the alkali liquor storage unit;
is the molar increment of carbonate in the alkali liquor storage unit.
As can be seen from Table 1, when the bipolar membrane electrodialysis device provided by the utility model is used for preparing alkali concentrated solution by fixing carbon in seawater, the concentration of the obtained sodium bicarbonate solution is not less than 900mmol/L, and the carbon fixing rate is not less than 35%; in comparison with application example 1, comparative application example 1 employs a three-compartment bipolar membrane electrodialysis device, and therefore only a hydrochloric acid solution storage unit or a sulfuric acid solution storage unit can be used. If the sulfuric acid solution storage unit is adopted, chloride ions can enter the sulfuric acid solution storage unit through a negative film, and a mixed solution of hydrochloric acid and sulfuric acid is obtained, so that the application value is reduced; if the hydrochloric acid solution storage unit is adopted, the hydrochloric acid solution storage unit is adjacent to the anode, chloride ions can be oxidized to generate chlorine, on one hand, the concentration of the salt solution is reduced, the application value of the byproduct salt solution is reduced, and on the other hand, the generated chlorine pollutes the environment.
Therefore, the bipolar membrane electrodialysis device provided by the utility model improves the three-compartment structure of the traditional bipolar membrane, positive membrane, negative membrane and bipolar membrane into the four-compartment structure of the bipolar membrane, positive membrane, negative membrane, positive membrane and bipolar membrane, and can respectively produce sodium bicarbonate solution, hydrochloric acid solution and sulfuric acid solution with higher purity in the alkali liquor storage unit, hydrochloric acid solution storage unit and sulfuric acid solution storage unit, thereby improving the efficiency of bipolar membrane electrodialysis and achieving considerable economic benefit; in addition, the bipolar membrane electrodialysis device provided by the utility model has the advantages that the method for preparing alkali concentrated solution by fixing carbon in seawater is simple, the softened seawater is used in the saline water storage unit, the raw materials are easy to obtain, and the membrane pollution is effectively avoided; under the conditions of normal temperature and normal pressure and without adding chemical reagents, the preparation of the sodium bicarbonate solution is stably carried out in an alkali liquor storage unit, the reaction condition is mild, and the environment is protected; use the utility model provides a when bipolar membrane electrodialysis device carries out the solid carbon system alkali of sea water, gained sodium bicarbonate solution concentration is more than or equal to 900mmol/L, and the solid carbon rate is more than or equal to 35%.
The applicant states that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and those skilled in the art should understand that any changes or substitutions easily conceivable by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure scope of the present invention.
Claims (10)
1. The bipolar membrane electrodialysis device for the seawater carbon fixation alkali preparation concentrated solution is characterized by comprising a carbon dioxide introducing pipeline, an alkali liquor storage unit, a saline water storage unit, a hydrochloric acid liquor storage unit, a sulfuric acid liquor storage unit, a polar liquor storage unit and a bipolar membrane electrodialysis membrane stack;
the carbon dioxide inlet pipeline is connected with the alkali liquor storage unit;
an alkali liquor outlet of the alkali liquor storage unit is connected with an alkali chamber inlet of the bipolar membrane electrodialysis membrane stack, and an alkali chamber outlet of the bipolar membrane electrodialysis membrane stack is connected with an alkali liquor inlet of the alkali liquor storage unit;
the brine outlet of the brine storage unit is connected with the salt chamber inlet of the bipolar membrane electrodialysis membrane stack, and the salt chamber outlet of the bipolar membrane electrodialysis membrane stack is connected with the brine inlet of the brine storage unit;
the hydrochloric acid liquid outlet of the hydrochloric acid liquid storage unit is connected with the acid chamber inlet of the bipolar membrane electrodialysis membrane stack, and the acid chamber outlet of the bipolar membrane electrodialysis membrane stack is connected with the hydrochloric acid liquid inlet of the hydrochloric acid liquid storage unit;
a sulfuric acid solution outlet of the sulfuric acid solution storage unit is connected with an anode chamber inlet of the bipolar membrane electrodialysis membrane stack, and an anode chamber outlet of the bipolar membrane electrodialysis membrane stack is connected with a sulfuric acid solution inlet of the sulfuric acid solution storage unit;
an electrode solution outlet of the electrode solution storage unit is connected with an electrode chamber inlet of the bipolar membrane electrodialysis membrane stack, and an electrode chamber outlet of the bipolar membrane electrodialysis membrane stack is connected with an electrode solution inlet of the electrode solution storage unit;
the bipolar membrane electrodialysis membrane stack comprises an anode electrode, a cathode electrode and at least one group of four-compartment electrodialysis units arranged between the anode electrode and the cathode electrode, wherein the four-compartment electrodialysis units comprise bipolar membranes, anode membranes, cathode membranes, anode membranes and bipolar membranes.
2. The bipolar membrane electrodialysis device for seawater carbon sequestration for soda lye concentrated solutions according to claim 1, characterized in that the anode electrode of the bipolar membrane electrodialysis membrane stack comprises a titanium electrode or a platinum electrode.
3. The bipolar membrane electrodialysis device for seawater carbon sequestration for alkaline making concentrated solution according to claim 1 or 2, wherein the cathode electrode of the bipolar membrane electrodialysis membrane stack comprises a titanium electrode or a stainless steel electrode.
4. The bipolar membrane electrodialysis device for seawater carbon sequestration for alkali making concentrated solution according to claim 1, wherein a gas refining disc is further connected between the carbon dioxide inlet pipeline and the alkali liquor storage unit;
the diameter of the gas refining disc is 5-10 cm.
5. The bipolar membrane electrodialysis device for seawater carbon sequestration for alkali making concentrated solution according to claim 1, wherein the alkali solution storage unit, the brine storage unit, the hydrochloric acid solution storage unit, the sulfuric acid solution storage unit and the polar solution storage unit are liquid storage tanks respectively and independently.
6. The bipolar membrane electrodialysis device for seawater carbon fixation alkali preparation concentrated solution according to claim 5, wherein the volume of the liquid storage tank is 1-10L.
7. The bipolar membrane electrodialysis device for seawater carbon sequestration for preparing alkali concentrated solution according to claim 1, wherein a lye delivery pump, a control valve and a flow meter are further connected between the lye outlet of the lye storage unit and the inlet of the alkali chamber of the bipolar membrane electrodialysis membrane stack in sequence;
a saline water delivery pump, a control valve and a flowmeter are sequentially connected between the saline water outlet of the saline water storage unit and the saline chamber inlet of the bipolar membrane electrodialysis membrane stack;
a hydrochloric acid liquid delivery pump, a control valve and a flowmeter are sequentially connected between the hydrochloric acid liquid outlet of the hydrochloric acid liquid storage unit and the hydrochloric acid chamber inlet of the bipolar membrane electrodialysis membrane stack;
a sulfuric acid solution delivery pump, a control valve and a flowmeter are sequentially connected between a sulfuric acid solution outlet of the sulfuric acid solution storage unit and a sulfuric acid chamber inlet of the bipolar membrane electrodialysis membrane stack;
and an electrode liquid delivery pump, a control valve and a flowmeter are sequentially connected between an electrode liquid outlet of the electrode liquid storage unit and an electrode chamber inlet of the bipolar membrane electrodialysis membrane stack.
8. The bipolar membrane electrodialysis device for seawater carbon fixation alkali preparation concentrated solution according to claim 7, wherein the alkali liquor delivery pump, the brine delivery pump, the hydrochloric acid liquor delivery pump, the sulfuric acid liquor delivery pump and the polar liquid delivery pump are respectively and independently magnetic force driven pumps.
9. The bipolar membrane electrodialysis device for seawater carbon sequestration alkali making concentrated solution according to claim 1, wherein the dimensions of the bipolar membrane, the anode membrane, the cathode membrane, the anode membrane and the bipolar membrane are respectively and independently (50-250) mm x (100-500) mm.
10. The bipolar membrane electrodialysis device for seawater carbon sequestration for alkali-making concentrated solution according to claim 1, wherein the power supply for connecting the anode electrode and the cathode electrode is a direct current power supply.
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