System and method for synchronously extracting lithium, bromine and hydrogen from brine and application

Abstract

The invention belongs to the technical field of brine resource utilization, and discloses a system and method for synchronously extracting lithium, bromine and hydrogen from brine and application. According to the system provided by the invention, the catalytic electrolysis device and the adsorption lithium extraction device are connected in series into an organic whole by utilizing the circulation control device; a related pH probe in the detection assembly is used for detecting the pH value of brine in the system; the circulating assembly is controlled based on the pH value of the brine, so that the brine circularly flows between the catalytic electrolysis device and the adsorption lithium extraction device, the brine in the catalytic electrolysis device and the adsorption lithium extraction device is kept in a hydrogen ion dynamic utilization state, and finally the effect of improving the electrolysis efficiency of hydrogen production and bromine production and the lithium adsorption efficiency at the same time is achieved. The system provided by the invention has the advantages of simple structure, high brine comprehensive utilization efficiency, strong applicability and the like, can be well applied to brine resource utilization, and has a good application prospect.

Description

Technical Field

[0001] The present invention belongs to the technical field of brine resource utilization, and in particular relates to a system and method for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine and their application. Background Art

[0002] Lithium, bromine and hydrogen are important resources in modern industry and science and technology, with wide applications and huge economic value. With the rapid development of new energy, battery energy storage technology, industrial chemical industry and environmental protection technology, the importance of these elements is becoming increasingly prominent.

[0003] As a strategic resource, lithium is widely used in many fields such as lithium batteries, new energy vehicles, energy storage systems, aerospace, and high-temperature lubricants. Among them, the rapid development of lithium batteries has driven the rapid growth of global demand for lithium resources. Lithium batteries have become the preferred energy storage device for electric vehicles, power tools, and portable electronic devices due to their high energy density, long life, and light weight. According to global energy demand forecasts, the demand for lithium ions will continue to grow, especially in electric vehicles and energy storage technologies. The shortage of lithium resources has become an important factor affecting the global energy landscape.

[0004] Lithium ore resources can be divided into hard rock type and brine type. The cost of developing brine type lithium ore resources is 30-50% lower than that of hard rock type lithium ore resources. At the same time, lithium extraction from brine also has the advantages of large reserves, low mining cost and small environmental impact, and is an important source of lithium resource development. Therefore, how to efficiently extract lithium from lithium-containing brine has become a problem that experts and scholars at home and abroad are committed to solving.

[0005] Bromine is an important industrial chemical, widely used in flame retardants, medicines, pesticides, photosensitive materials, dyes and water treatment. It can be used as a flame retardant, catalyst for organic synthesis, and raw materials for manufacturing silver bromide photographic materials, medicines and pesticides. The main objects of bromine extraction are seawater, salt lake brine and underground brine. Among them, underground brine is the superior resource with the best quality and the highest bromine yield; however, since underground brine also contains a large amount of other ions, especially chloride ions, the concentration can be as high as 30-200g / L, which brings great technical challenges to the bromine extraction process.

[0006] Brines such as underground brine and seawater are common sources of lithium and bromine, and can be used as raw materials to achieve the purpose of extracting lithium and bromine. For example, a Chinese patent with publication number CN 115321485 A discloses a method for extracting chemical elements from concentrated seawater, wherein concentrated seawater is the solution remaining after fresh water is separated from seawater by desalination treatment, and the method comprises extracting various chemical elements from concentrated seawater through a bromine extraction system, a magnesium extraction system, a calcium extraction system, a liquid salt concentration system, a liquid salt potassium extraction system, a liquid salt lithium extraction system, a liquid salt concentration system, and a carbon dioxide storage system. A Chinese patent with publication number CN117699827A discloses a method for simultaneously extracting lithium and bromine from potassium-extracting brine, comprising the following steps: ultrafiltration of potassium-extracting brine; adjusting the pH value of the ultrafiltered brine to 3.5-4.0 with an acid solution, and then introducing chlorine gas into the obtained water body for oxidation; debrominating the oxidized brine under the action of an aerated membrane; mixing the debrominated brine with water, and then subjecting it to a multi-membrane coupling treatment; the multi-membrane coupling includes nanofiltration, reverse osmosis and electrodialysis to obtain a lithium-containing concentrated solution; treating a portion of the lithium-containing concentrated solution with a bipolar membrane process to obtain lithium hydroxide; and precipitating another portion of the lithium-containing concentrated solution to obtain lithium carbonate.

[0007] However, the above-mentioned method of extracting bromine and lithium from brine is essentially a simple combination of the lithium extraction process and the bromine extraction process. The lithium extraction and bromine extraction are carried out separately and not synchronously. There are problems such as long and complicated extraction process flow and low comprehensive utilization efficiency, which has great limitations. Summary of the invention

[0008] The first purpose of the present invention is to provide a system for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine. The system has a simple structure and has excellent effects of extracting lithium, producing hydrogen and producing bromine, effectively solving the problems of long and complicated extraction process and low extraction efficiency in the prior art, and has good application prospects in realizing the resource utilization of brine.

[0009] The second object of the present invention is to provide a method for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine.

[0010] The third object of the present invention is to provide the application of the above-mentioned system for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine in the resource utilization of brine.

[0011] Specifically, the system for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine provided by the present invention specifically includes: a catalytic electrolysis device, which includes an anode chamber and a cathode chamber, and the anode chamber and the cathode chamber are separated by a diaphragm; an adsorption lithium extraction device, which includes a lithium ion adsorption component, and an ion sieve type lithium ion adsorption column is provided on the lithium ion adsorption component; the water inlet of the lithium ion adsorption component is connected with the water outlet of the catalytic electrolysis device, and the water outlet of the lithium ion adsorption component is connected with the water inlet of the cathode chamber; a circulation control device, which includes a detection component and a circulation component; the detection component includes an adsorption column pH probe and a cathode chamber pH probe, the adsorption column pH probe is used to detect the pH value of the lithium ion adsorption component, and the cathode chamber pH probe is used to detect the pH value of the cathode chamber; the circulation component includes a first control water pump and a second control water pump; the first control water pump is arranged between the lithium ion adsorption component and the catalytic electrolysis device, and the first control water pump is in communication with the cathode chamber pH probe; the second control water pump is arranged between the lithium ion adsorption component and the cathode chamber, and the second control water pump is in communication with the adsorption column pH probe.

[0012] Furthermore, the diaphragm is a non-ion exchange membrane or an anion exchange membrane, the water inlet of the first control water pump is connected to the water outlet of the anode chamber and the water outlet of the cathode chamber, and the water outlet of the first control water pump is connected to the water inlet of the lithium ion adsorption component.

[0013] Furthermore, the diaphragm is a cation exchange membrane, the water inlet of the first control water pump is connected to the water outlet of the cathode chamber, and the water outlet of the first control water pump is connected to the water inlet of the lithium ion adsorption component.

[0014] Furthermore, the membrane is a monovalent cation exchange membrane.

[0015] Furthermore, an ion sieve type lithium ion adsorbent is arranged on the ion sieve type lithium ion adsorption column, and the ion sieve type lithium ion adsorbent includes a manganese-based adsorbent and / or a titanium-based adsorbent.

[0016] Furthermore, the manganese-based adsorbent is selected from one or more of λ-MnO2, MnO2·0.3H2O and MnO2·0.5H2O.

[0017] Furthermore, the titanium-based adsorbent is Li2TiO3 and / or Li4Ti5O 12 .

[0018] Furthermore, the packing density of the ion sieve type lithium ion adsorbent on the ion sieve type lithium ion adsorption column is 0.3 to 0.9 g / mL.

[0019] Furthermore, the adsorption and lithium extraction device includes a water washing component, a desorption component and an acid washing component. The water washing component is used to elute impurity ions on the ion sieve type lithium ion adsorption column, the desorption component is used to elute lithium ions on the ion sieve type lithium ion adsorption column, and the acid washing component is used to acid wash and regenerate the ion sieve type lithium ion adsorption column.

[0020] Furthermore, the system includes a gas collecting device, which includes a bromine gas collecting component and a hydrogen gas collecting component.

[0021] The method for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine provided by the present invention adopts the above-mentioned system for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine to treat the brine, and specifically comprises the following steps: obtaining the pH value of the brine; using an adsorption lithium extraction device to perform adsorption treatment on the brine with a pH value ≥7 to obtain brine with a pH value of 3-4; using a catalytic electrolysis device to perform electro-oxidation-reduction treatment on the brine with a pH value <7 to obtain brine with a pH value of 8-9; the brine circulates between the adsorption lithium extraction device and the catalytic electrolysis device through the circulation control device to realize repeated cycles of the adsorption treatment and the electro-oxidation-reduction treatment; collecting lithium ions from the adsorption lithium extraction device, and collecting hydrogen and bromine gases from the catalytic electrolysis device.

[0022] Furthermore, the temperature of the adsorption treatment is 20-40° C., and the time is 100-1000 min.

[0023] Furthermore, in the electrical oxidation-reduction treatment, the potential of the anode chamber is 1 to 1.5V, and the potential of the cathode chamber is 1.25 to 1.45V.

[0024] The present invention also provides the application of the system for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine in the resource utilization of brine.

[0025] Beneficial effects:

[0026] In the system provided by the present invention, a process combining an electrolytic catalytic method with an adsorption method is adopted, a catalytic electrolysis device and an adsorption lithium extraction device are connected in series into an organic whole by a circulation control device, the pH value of the brine in the catalytic electrolysis device and the adsorption lithium extraction device is detected by a detection component, and the circulation component is controlled based on the pH value of the brine to circulate the brine between the catalytic electrolysis device and the adsorption lithium extraction device, so as to keep the brine in the catalytic electrolysis device and the adsorption lithium extraction device in a state of dynamic utilization of hydrogen ions, and finally achieve the effect of simultaneously improving the electrolysis efficiency of hydrogen and bromine production and the lithium adsorption efficiency. The system has the advantages of excellent comprehensive utilization efficiency of brine, simple structure, strong applicability to different brines, etc., and has good application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1This is a schematic diagram of the structure of a system for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine provided in the first embodiment of the present invention.

[0028] Figure 2 It is a schematic diagram of the structure of the catalytic electrolysis device of the system for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine in the present invention.

[0029] Figure 3 It is a schematic diagram of the structure of the adsorption lithium extraction device of the system for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine in the present invention.

[0030] Figure 4 This is a schematic structural diagram of a catalytic electrolysis device provided in the second embodiment of the present invention.

[0031] Figure 5 This is a schematic structural diagram of a water washing component provided in the first embodiment of the present invention.

[0032] Figure 6 This is a schematic structural diagram of the desorption component provided in the first embodiment of the present invention.

[0033] Figure 7 This is a schematic diagram of the structure of the pickling assembly provided in the first embodiment of the present invention.

[0034] Figure 8 This is a schematic diagram of the structure of a system for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine provided in the fourth embodiment of the present invention. DETAILED DESCRIPTION

[0035] Although the present invention can be easily embodied in different forms of embodiments, only some of the specific embodiments are shown in the drawings and will be described in detail in this specification. It should be understood that this description should be regarded as an exemplary illustration of the principles of the invention and is not intended to limit the invention to that described herein.

[0036] Thus, a feature indicated in this specification will be used to illustrate one of the features of an embodiment of the present invention, rather than implying that each embodiment of the present invention must have the described feature. In addition, it should be noted that this specification describes many features. Although some features can be combined together to illustrate possible system designs, these features can also be used in other combinations that are not explicitly described. Thus, unless otherwise stated, the described combinations are not intended to be limiting.

[0037] In the embodiments shown in the drawings, the indications of directions (such as up, down, left, right, front and back) used to explain the structure and movement of various elements of the present invention are not absolute but relative. These descriptions are appropriate when these elements are in the positions shown in the drawings. If the description of the positions of these elements changes, the indications of these directions also change accordingly.

[0038] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the accompanying drawings in the embodiments of the present invention.

[0039] See also Figures 1 to 3 . Figure 1 It is a schematic diagram of the structure of a system for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine according to the first embodiment of the present invention. Figure 2 yes Figure 1 Schematic diagram of the structure of the catalytic electrolysis device. Figure 3 for Figure 1 The system provided in the first embodiment specifically comprises: a catalytic electrolysis device 1, a lithium extraction device 2 and a circulation control device 3.

[0040] The catalytic electrolysis device 1 specifically comprises an electrolysis chamber, in which a non-ion exchange membrane is installed as a diaphragm 4 to separate the electrolysis chamber into an anode chamber 11 and a cathode chamber 12. An anode is installed in the anode chamber 11 to realize Br - Br2 is prepared by electro-oxidation reaction. The specific electro-oxidation reaction is: 2Br - -2e - →Br2. A cathode is installed in the cathode chamber 12 to realize the H + The electroreduction reaction consumes H + And the purpose of preparing H2, the specific electroreduction reaction is: 2H + +2e - →H2. And the anode and cathode are connected to an external power supply.

[0041] It should be noted that the non-ion exchange membrane, anode, cathode and external power supply in the catalytic electrolysis device 1 are a technical means conventionally used in electrolytic catalytic technology. Those skilled in the art can make adaptive choices according to actual needs, and the present invention does not impose special limitations on them. Among them, specific examples of the non-ion exchange membrane include but are not limited to: one or more of asbestos membrane, ceramic membrane, polyphenylene sulfide membrane, polyetheretherketone membrane, polysulfone membrane and polybenzimidazole membrane. Specific examples of the anode include but are not limited to: one or more of graphite, titanium dioxide electrode, iridium dioxide electrode, ruthenium dioxide electrode, lead-bismuth alloy electrode, nickel-based alloy electrode and titanium-based alloy electrode. Specific examples of the cathode include but are not limited to: one or more of nickel electrode, molybdenum electrode, ruthenium electrode, iridium electrode, titanium electrode, platinum electrode, palladium electrode, nickel-molybdenum alloy electrode, molybdenum-iron alloy electrode, molybdenum sulfide electrode, tungsten sulfide electrode, tantalum nitride electrode and molybdenum nitride electrode.

[0042] In the first embodiment, the non-ion exchange membrane is preferably a PPS membrane (Suzhou Yuemo New Materials); the anode is preferably a graphite electrode; and the cathode is preferably a platinum electrode.

[0043] It should be noted that the number of the diaphragms 4 provided in the first embodiment and the number of the anode chambers and cathode chambers formed by their division are only exemplary. The number of the diaphragms 4 in the catalytic electrolysis device provided by the present invention can be 2 or other integers greater than 2. Those skilled in the art can make adaptive choices according to their needs, and the present invention does not impose any special restrictions on them. Figure 4 , Figure 4 The schematic diagram of the structure of the catalytic electrolysis device 1 according to the second embodiment of the present invention is shown in FIG. In the catalytic electrolysis device 1 provided in the second embodiment, the number of the non-ion exchange membranes is two, so as to separate the electrolysis chamber into two anode chambers and one cathode chamber.

[0044] See also Figure 3 The adsorption and lithium extraction device 2 includes a lithium ion adsorption component 21, a water washing component 22, a desorption component 23 and an acid washing component 24. It should be noted that: Figure 3 The connection lines between the lithium ion adsorption component 21, the water washing component 22, the desorption component 23 and the acid washing component 24 shown in the figure only represent that the above components have a certain connection relationship, and do not represent their specific connection methods.

[0045] An ion sieve type lithium ion adsorption column 5 is installed on the lithium adsorption assembly 21 . The ion sieve type lithium ion adsorption column 5 is filled with an ion sieve type lithium ion adsorbent for adsorbing lithium ions in brine.

[0046] It should be noted that the ion sieve type lithium ion adsorbent in the ion sieve type lithium ion adsorption column 5 is a technical means commonly used in lithium extraction technology. Those skilled in the art can make adaptive choices according to actual needs, and the present invention does not impose special limitations on it. Among them, the ion sieve type lithium ion adsorbent can specifically be a manganese adsorbent and / or a titanium adsorbent. More specifically, specific examples of the manganese adsorbent include but are not limited to: one or more of λ-MnO2, MnO2·0.3H2O and MnO2·0.5H2O. Specific examples of the titanium lithium adsorbent include but are not limited to: Li2TiO3 and / or Li4Ti5O 12 The packing density of the ion sieve type lithium ion adsorbent on the ion sieve type lithium ion adsorption column may be 0.3 to 0.9 g / mL, such as 0.3 g / mL, 0.35 g / mL, 0.4 g / mL, 0.6 g / mL, 0.8 g / mL, 0.9 g / mL or any value therebetween.

[0047] In the first embodiment, the ion sieve type lithium ion adsorbent is preferably Li2TiO3; and the packing density of the ion sieve type lithium ion adsorbent on the ion sieve type lithium ion adsorption column 5 is preferably 0.6 g / mL.

[0048] In the catalytic electrolysis device 1, the water washing component 22 is provided to wash other impurities on the ion sieve type lithium ion adsorption column 5 after the lithium ion adsorption component 21 completes the adsorption of lithium ions in the brine, which is conducive to the recovery of high-purity lithium. It should be noted that the water washing component 22 is a technical means commonly used in lithium extraction technology. Those skilled in the art can make adaptive design of its structure according to actual needs, and the present invention does not impose any special limitation on it.

[0049] See also Figure 5 The washing assembly 22 provided in the first embodiment specifically includes: a washing liquid storage tank 221 and a washing water pump 222. The washing liquid storage tank 221 contains deionized water for eluting the ion sieve type lithium ion adsorption column 5. The water inlet of the washing water pump 222 is connected to the water outlet of the washing liquid storage tank 221 through a pipeline, and the water outlet of the washing water pump 222 is connected to the water inlet of the lithium ion adsorption assembly 21 through a pipeline.

[0050] In the catalytic electrolysis device 1, the desorption component 23 is provided to elute the lithium ions adsorbed on the ion sieve type lithium ion adsorption column 5 after the lithium ion adsorption component 21 completes the adsorption of lithium ions in the brine and washes and cleans them, so as to realize the recovery of lithium ions. It should be noted that the desorption component 23 is a technical means commonly used in lithium extraction technology, and those skilled in the art can make adaptive design of its structure according to actual needs, and the present invention does not impose any special limitation on it.

[0051] See also Figure 6 The desorption assembly 23 provided in the first embodiment specifically includes: a desorption liquid storage tank 231, a first desorption water pump 232, a second desorption water pump 233 and a lithium solution storage tank 224. The desorption liquid storage tank 231 contains Li adsorbed on the ion sieve type lithium ion adsorption column 5. + The water inlet of the first desorption water pump 232 is connected to the water outlet of the desorption liquid storage tank 231 through a pipeline, and the water outlet of the first desorption water pump 232 is connected to the water inlet of the lithium ion adsorption component 21 through a pipeline. The water inlet of the second desorption water pump 233 is connected to the water outlet of the lithium ion adsorption component 21 through a pipeline, and the water outlet of the lithium ion adsorption component 21 is connected to the water inlet of the lithium solution storage tank 224 through a pipeline. The lithium solution storage tank 224 is used to collect lithium-rich + of solution.

[0052] It should be noted that the desorption solution is a technical means commonly used in lithium extraction technology. Those skilled in the art can make adaptive choices according to actual needs, and the present invention does not impose any special restrictions on it. Among them, the desorption solution is preferably an acid solution with a concentration of 0.01 to 0.5 mol / L, and specific examples of the acid solution include but are not limited to: one or more of hydrochloric acid solution, sulfuric acid solution, citric acid solution, potassium persulfate solution and sodium persulfate solution. In the first embodiment, the desorption solution is preferably a hydrochloric acid solution with a concentration of 0.1 mol / L.

[0053] In the catalytic electrolysis device 1, the acid washing component 24 is provided to acid wash and regenerate the ion sieve type lithium ion adsorbent on the ion sieve type lithium ion adsorption column 5 after the lithium ion adsorption component 21 completes the desorption of lithium, so as to realize the recycling of the ion sieve type lithium ion adsorbent. It should be noted that the acid washing component 24 is a technical means commonly used in lithium extraction technology, and those skilled in the art can make adaptive design of its structure according to actual needs, and the present invention does not impose any special limitation on it.

[0054] See also Figure 7 The pickling assembly 24 provided in the first embodiment specifically includes: a pickling liquid storage tank 241 and a pickling water pump 242. The pickling liquid storage tank 241 contains acid liquid for regenerating the ion sieve type lithium ion adsorption column 5. The water inlet of the water washing water pump 242 is connected to the water outlet of the pickling liquid storage tank 241 through a pipeline, and the water outlet of the water washing water pump 242 is connected to the water inlet of the lithium ion adsorption assembly 21 through a pipeline.

[0055] It should be noted that the acid solution is a technical means commonly used in lithium extraction technology. Those skilled in the art can make adaptive choices according to actual needs, and the present invention does not impose any special restrictions on it. Specific examples of the acid solution include but are not limited to: hydrochloric acid solution and / or sulfuric acid solution. In the first embodiment, the desorption solution is preferably a hydrochloric acid solution with a concentration of 0.1 mol / L.

[0056] See also Figures 1 to 3 The circulation control device 3 includes a detection component 31, a circulation component 32 and a control component 33. The detection component 31 includes an adsorption column pH probe 311 and a cathode chamber pH probe 312. The adsorption column pH probe 311 is installed in the lithium ion adsorption component 21 to detect the pH value of the brine in the lithium ion adsorption component 21. The cathode chamber pH probe 312 is installed in the cathode chamber 12 to detect the pH value of the brine in the cathode chamber 12.

[0057] The circulation component 32 includes a first control water pump 321 and a second control water pump 322. The water inlet of the first control water pump 321 is connected to the water outlet of the anode chamber 11 and the water outlet of the cathode chamber 12 through a pipeline, and the water outlet of the first control water pump 321 is connected to the water inlet of the lithium ion adsorption component 21 through a pipeline, so that the brine in the anode chamber 11 and the cathode chamber 12 can be pumped into the lithium ion adsorption component 21 through the first control water pump 321. The water inlet of the second control water pump 322 is connected to the water outlet of the lithium ion adsorption component 21 through a pipeline, and the water outlet of the second control water pump 322 is connected to the water inlet of the cathode chamber 12 through a pipeline, so that the brine in the lithium ion adsorption component 21 can be pumped into the cathode chamber 12 through the second control water pump 322.

[0058] In the circulation control device 3, the control component 33 is set to receive the pH value data measured by the adsorption column pH probe 311 and the cathode chamber pH probe 312 in the detection component 31, and also to control the first control water pump 321 and the second control water pump 322. Among them, the control component 33 controls the opening and closing and flow rate of the second control water pump 322 based on the pH value data measured by the adsorption column pH probe 311, that is, the adsorption column pH probe 311 and the second control water pump 322 are connected to each other through the control component 33. The control component 33 controls the opening and closing and flow rate of the first control water pump 321 based on the pH value data measured by the cathode chamber pH probe 312, that is, the cathode chamber pH probe and the first control water pump 321 are connected to each other through the control component 33.

[0059] In addition, the control component 33 is also set to control the external power supply to control the potential applied to the anode and cathode to achieve excellent hydrogen production and bromine production efficiency. In the first embodiment, the potential applied to the anode chamber 11 is preferably 1-1.5V, such as 1V, 1.05V, 1.1V, 1.3V, 1.4V, 1.5V or any value therebetween; the potential applied to the cathode chamber is preferably 1.25-1.45V, such as 1.25V, 1.28V, 1.33V, 1.38V, 1.4V, 1.45V or any value therebetween.

[0060] It should be noted that the control component 33 is a type of device commonly used in the prior art, and those skilled in the art can make an adaptive choice according to actual needs. The present invention does not impose any special limitation on it, and its specific examples include but are not limited to: a computer. In addition, the signal transmission between the control component 33 and the detection component 31, the circulation component 32 and the external power supply can be achieved through a wired connection or a wireless connection such as Bluetooth.

[0061] In the first embodiment, the system for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine further includes a gas collecting component, and the gas collecting device specifically includes a bromine gas collecting component and a hydrogen gas collecting component.

[0062] In the gas collection assembly, the bromine gas collection assembly is provided to collect Br2 generated by electro-oxidation in the anode chamber 11, so as to realize resource utilization of Br2. It should be noted that the bromine gas collection assembly is a technical means commonly used in existing bromine production technology, and those skilled in the art can make adaptive choices according to actual needs, and the present invention does not impose any special limitation on it.

[0063] In the gas collection assembly, the hydrogen collection assembly is provided to collect H2 generated by electroreduction in the cathode chamber 12 to realize resource utilization of H2. It should be noted that the hydrogen collection assembly is a technical means commonly used in existing bromine production technology, and those skilled in the art can make adaptive choices according to actual needs, and the present invention does not impose any special limitation on it.

[0064] It should be noted that the type of the diaphragm 4 provided in the catalytic electrolysis device 1 in the first embodiment is only exemplary. The diaphragm 4 in the catalytic electrolysis device provided by the present invention may also be an anion exchange membrane and / or a cation exchange membrane. Specific examples of the anion exchange membrane include but are not limited to: anion exchange membrane FuMa-Tech FAA3, anion exchange membrane PiperION, A201 anion exchange, Sustainion X37 series anion exchange membrane, Aemion TM One or more of the following: anion exchange membranes of the Orion series and Orion Polymer series. Specific examples of the cation exchange membrane include, but are not limited to, one or more of the Nafion series sulfonic acid membranes.

[0065] In the third embodiment, the diaphragm 4 provided in the catalytic electrolysis device 1 is an anion exchange membrane. In this case, the provision of the anion exchange membrane allows Br - The anions migrate to the anode chamber 11 to achieve Br - The enrichment in the anode chamber and OH - The accumulation in the cathode chamber 12 can be well applied to the treatment of brine with low bromine content to achieve a better bromine production effect.

[0066] In the fourth embodiment, the diaphragm 4 provided in the catalytic electrolysis device 1 is a cation exchange membrane. In this case, the provision of the cation exchange membrane allows Li + , H + The cations migrate to the cathode chamber 12 to achieve Li + and H +The enrichment in the cathode chamber 12 is beneficial to the occurrence of the electroreduction reaction in the cathode chamber 12 and obtaining a lithium-rich solution, so as to realize the lithium ion adsorption component 21 for Li + Better adsorption effect.

[0067] Figure 8 A schematic diagram of the structure of a system for simultaneously extracting lithium, bromine and producing hydrogen from brine provided in the fourth embodiment. Figure 8 and Figure 3 In the fourth embodiment, the water inlet of the first control water pump 321 is connected to the water outlet of the cathode chamber 12 through a pipeline, and the water outlet of the first control water pump 321 is connected to the water inlet of the lithium ion adsorption assembly 21 through a pipeline, so that the brine in the cathode chamber 12 can be pumped into the lithium ion adsorption assembly 21 through the first control water pump 321. The water inlet of the second control water pump 322 is connected to the water outlet of the lithium ion adsorption assembly 21 through a pipeline, and the water outlet of the second control water pump 322 is connected to the water inlet of the cathode chamber 12 through a pipeline, so that the brine in the lithium ion adsorption assembly 21 can be pumped into the cathode chamber 12 through the second control water pump 322.

[0068] In the system for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine provided by the present invention, the catalytic electrolysis device 1 and the adsorption lithium extraction device 2 are connected in series to form an organic whole through the setting of the circulation control device 3, and the pH value of the brine in the lithium ion adsorption component 21 and the cathode chamber 12 is detected by the detection component 31, and the circulation component 32 is controlled by the control component 33 according to the measured pH value to adjust the circulation flow of the brine between the catalytic electrolysis device 1 and the adsorption lithium extraction device 2, so that the brine in the catalytic electrolysis device and the adsorption lithium extraction device is in a state of dynamic utilization of hydrogen ions, which is not only beneficial to improve the adsorption rate and adsorption yield of lithium by the ion sieve type lithium ion adsorbent in the lithium ion adsorption component 21, but also beneficial to improve the electro-oxidation and reduction efficiency in the catalytic electrolysis device 1, so as to simultaneously achieve the effects of "improving the electrolysis efficiency of hydrogen and bromine production" and "improving the adsorption efficiency of lithium ions", and has excellent comprehensive utilization efficiency of brine. The system also has the advantages of simple structure and strong applicability to different brines, which effectively reduces the investment and operation costs of brine treatment.

[0069] Based on this, the present invention also provides a method for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine, which specifically includes: obtaining the pH value of the brine using a detection component 31; using an adsorption lithium extraction device 2 to perform adsorption treatment on brine with a pH value ≥ 7 to obtain brine with a pH value of 3 to 4; using a catalytic electrolysis device 1 to perform electro-oxidation-reduction treatment on brine with a pH value < 7 to obtain brine with a pH value of 8 to 9; the brine circulates between the adsorption lithium extraction device 2 and the catalytic electrolysis device 1 through the circulation control device 3 to achieve repeated cycles of the adsorption treatment and the electro-oxidation-reduction treatment; collecting lithium ions from the adsorption lithium extraction device 2, and collecting hydrogen and bromine from the catalytic electrolysis device 1.

[0070] In the present invention, before the brine enters the system for simultaneous lithium extraction, bromine extraction and hydrogen production from the brine for treatment, it is preferred to further include: taking the brine for filtering treatment to remove suspended matter and particulate matter in the brine. It should be noted that the filtering treatment is a technical means commonly used in the prior art, and those skilled in the art can make an adaptive choice according to actual needs, and the present invention does not impose any special limitation on it.

[0071] In the present invention, the temperature of the adsorption treatment is preferably 20-40°C, such as 20°C, 23°C, 25°C, 30°C, 35°C, 40°C or any value therebetween; the time is preferably 100-1000min, such as 100min, 150min, 200min, 300min, 500min, 800min, 1000min or any value therebetween.

[0072] In the present invention, in the electro-oxidation-reduction treatment, the anode chamber potential is preferably 1-1.5V, such as 1V, 1.1V, 1.3V, 1.4V, 1.5V or any value therebetween; the cathode chamber potential is 1.25-1.45V, such as 1.25V, 1.28V, 1.33V, 1.38V, 1.4V, 1.45V or any value therebetween.

[0073] The system provided in the first embodiment is used to treat the water produced from underground petroleum production. The pH value of the water produced from underground petroleum production is 8, and the main anion and cation concentrations are: Li + The concentration is 500mg / L, K + The concentration is 17000mg / L, Na + The concentration is 7000mg / L, Ca 2+ The concentration is 120000mg / L, Mg 2+ The concentration is 14000mg / L, Br - The concentration is 8500mg / L, Cl - The concentration is 270000mg / L.

[0074] Based on the pH value of the underground oil production water, it first enters the adsorption and lithium extraction device 2 for treatment, and the following reactions occur:

[0075] H + (Adsorbent)+Li + (Brine) → Li + (Adsorbent)+H + (brine)

[0076] During the adsorption process, the hydrogen ions in the lithium ion adsorption component 21 are replaced with the lithium ions in the brine, and the pH value of the brine decreases, which is recorded in real time by the adsorption column pH probe 311. When the pH value decreases slowly and is less than 7, the second control water pump 322 is turned on to allow the brine to enter the catalytic electrolysis device 1 for treatment, and the following reactions occur:

[0077] Electrooxidation reaction in anode chamber 11: 2Br - -2e - →Br2

[0078] Electroreduction reaction in cathode chamber 12: 2H + +2e - →H2

[0079] In the electro-oxidation reduction process, H in the brine in the cathode chamber 12 + The pH value is consumed, and it is recorded in real time by the cathode chamber pH probe 312. When the pH value rises to close to 9, the first control water pump 321 is turned on to allow the brine to enter the adsorption and lithium extraction device 2 for treatment.

[0080] The pH value of the brine in the lithium ion adsorption assembly 21 and the cathode chamber 12 is continuously detected, and the first control water pump 321 and the second control water pump 322 are controlled to realize the repeated cycle of adsorption treatment and electric redox treatment. The pH value of the brine in the lithium ion adsorption assembly 21 and the cathode chamber 12 and the Li + The concentrations are shown in Table 1.

[0081] Table 1.

[0082]

[0083]

[0084] From the results shown in Table 1, it can be seen that at the 174th minute, the pH value of the brine in the lithium ion adsorption component 21 decreases slowly, that is, the lithium ion adsorption component 21 has a certain effect on the pH value of the brine. + The adsorption rate of lithium ion adsorption component 21 slows down. +The adsorption of Br in the brine is saturated. At this time, the remaining lithium concentration in the brine is 209 mg / L, and the lithium adsorption yield is 58.2%. The brine then enters the catalytic electrolysis device 1, and the electro-oxidation-reduction treatment can consume the Br in the brine. - and the accumulated H + , so that the pH value of the brine in the cathode chamber 12 rises rapidly to 8.81, and enters the lithium ion adsorption assembly 21 again for adsorption treatment, which can also achieve good lithium adsorption effect. At the 774th minute, the remaining lithium concentration in the brine is 121 mg / L, and the lithium adsorption yield is 75.8%. The above adsorption treatment and electro-oxidation-reduction treatment are cycled for the third time. At the 1772th minute, the remaining lithium concentration in the brine is only 23 mg / L, and the lithium adsorption yield reaches 95.4%.

[0085] That is, the system and method for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine provided by the present invention utilizes the organic series connection of adsorption treatment and electro-oxidation-reduction treatment, thereby effectively overcoming the problems of long and complicated extraction process and low comprehensive utilization efficiency in the existing comprehensive resource utilization of brine, and has the advantages of simple treatment device structure and treatment process, high comprehensive utilization efficiency of brine and strong applicability.

[0086] Based on this, the present invention also provides the application of the above-mentioned system for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine in the resource utilization of brine.

[0087] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention without departing from the principles and intent of the present invention.

Claims

1. A system for simultaneously extracting lithium, bromine and producing hydrogen from brine, characterized in that: The system includes: A catalytic electrolysis device comprising an anode chamber and a cathode chamber, wherein the anode chamber and the cathode chamber are separated by a diaphragm; The lithium extraction device comprises a lithium ion adsorption component, on which an ion sieve type lithium ion adsorption column is arranged; the water inlet of the lithium ion adsorption component is connected to the water outlet of the catalytic electrolysis device, and the water outlet of the lithium ion adsorption component is connected to the water inlet of the cathode chamber; A circulation control device, comprising a detection component and a circulation component; the detection component comprises an adsorption column pH probe and a cathode chamber pH probe, the adsorption column pH probe is used to detect the pH value of the lithium ion adsorption component, and the cathode chamber pH probe is used to detect the pH value of the cathode chamber; the circulation component comprises a first control water pump and a second control water pump; the first control water pump is connected and arranged between the lithium ion adsorption component and the catalytic electrolysis device, and the first control water pump is in communication with the cathode chamber pH probe; the second control water pump is connected and arranged between the lithium ion adsorption component and the cathode chamber, and the second control water pump is in communication with the adsorption column pH probe.

2. The system for simultaneously extracting lithium, bromine and producing hydrogen from brine according to claim 1, characterized in that: The diaphragm is a non-ion exchange membrane or an anion exchange membrane, the water inlet of the first control water pump is connected to the water outlet of the anode chamber and the water outlet of the cathode chamber, and the water outlet of the first control water pump is connected to the water inlet of the lithium ion adsorption component.

3. The system for simultaneously extracting lithium, bromine and producing hydrogen from brine according to claim 1, characterized in that: The diaphragm is a cation exchange membrane, the water inlet of the first control water pump is connected to the water outlet of the cathode chamber, and the water outlet of the first control water pump is connected to the water inlet of the lithium ion adsorption component; Optionally, the membrane is a monovalent cation exchange membrane.

4. The system for simultaneously extracting lithium, bromine and producing hydrogen from brine according to claim 1, characterized in that: The ion sieve type lithium ion adsorption column is provided with an ion sieve type lithium ion adsorbent, and the ion sieve type lithium ion adsorbent includes a manganese adsorbent and / or a titanium adsorbent; Optionally, the manganese-based adsorbent is selected from one or more of λ-MnO2, MnO2·0.3H2O and MnO2·0.5H2O; Optionally, the titanium-based adsorbent is Li2TiO3 and / or Li4Ti5O 12 ; Optionally, the packing density of the ion sieve type lithium ion adsorbent on the ion sieve type lithium ion adsorption column is 0.3 to 0.9 g / mL.

5. The system for simultaneously extracting lithium, bromine and producing hydrogen from brine according to claim 1, characterized in that: The adsorption and lithium extraction device includes a water washing component, a desorption component and an acid washing component. The water washing component is used to elute impurity ions on the ion sieve type lithium ion adsorption column, the desorption component is used to elute lithium ions on the ion sieve type lithium ion adsorption column, and the acid washing component is used to acid wash and regenerate the ion sieve type lithium ion adsorption column.

6. The system for simultaneously extracting lithium, bromine and producing hydrogen from brine according to claim 1, characterized in that: The system includes a gas collection device, which includes a bromine gas collection component and a hydrogen gas collection component.

7. A method for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine, characterized in that: The method uses the system for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine as described in any one of claims 1 to 5 to treat brine, comprising the following steps: Obtaining the pH value of the brine; using an adsorption lithium extraction device to perform adsorption treatment on the brine with a pH value ≥ 7 to obtain brine with a pH value of 3 to 4; using a catalytic electrolysis device to perform electro-oxidation-reduction treatment on the brine with a pH value < 7 to obtain brine with a pH value of 8 to 9; the brine circulates between the adsorption lithium extraction device and the catalytic electrolysis device through the circulation control device to achieve repeated cycles of the adsorption treatment and the electro-oxidation-reduction treatment; Lithium ions are collected from the lithium adsorption and extraction device, and hydrogen and bromine gases are collected from the catalytic electrolysis device.

8. The method for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine according to claim 7, characterized in that: The temperature of the adsorption treatment is 20-40° C., and the time is 100-1000 min.

9. The method for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine according to claim 7, characterized in that: In the electro-oxidation-reduction treatment, the potential of the anode chamber is 1 to 1.5V, and the potential of the cathode chamber is 1.25 to 1.45V.

10. Use of the system for simultaneously extracting lithium, extracting bromine and producing hydrogen from brine as described in any one of claims 1 to 5 in the resource utilization of brine.

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