CN218146877U - Comprehensive brine utilization system - Google Patents
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- CN218146877U CN218146877U CN202222550855.4U CN202222550855U CN218146877U CN 218146877 U CN218146877 U CN 218146877U CN 202222550855 U CN202222550855 U CN 202222550855U CN 218146877 U CN218146877 U CN 218146877U
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Abstract
The utility model belongs to the technical field of the salt chemical industry, a brine comprehensive utilization system is disclosed. Comprises a filtering unit, a uranium adsorption/desorption unit, a cesium adsorption/desorption unit, a rubidium adsorption/desorption unit, a lithium adsorption/desorption unit and a brine pond; the uranium adsorption/desorption unit comprises a uranium adsorption resin unit, a first membrane concentration unit, a concentration tank and a first solid-liquid separation unit which are sequentially connected; the cesium adsorption/desorption unit comprises a cesium adsorption resin unit, a second concentration and purification unit, a second evaporation and crystallization unit and a second solid-liquid separation unit which are sequentially connected; the rubidium adsorption/desorption unit comprises a rubidium adsorption resin unit, a third concentration and purification unit, a third evaporation and crystallization unit and a third solid-liquid separation unit which are sequentially connected; the lithium adsorption/desorption unit comprises a lithium adsorption resin unit, a fourth membrane concentration unit, an electrodialysis assembly, a lithium precipitation unit and a fourth solid-liquid separation unit which are sequentially connected. All the components of the system are reasonably combined, and the specific components can be orderly extracted step by step.
Description
Technical Field
The utility model belongs to the technical field of the salt chemical industry, more specifically relates to a brine comprehensive utilization system.
Background
The salt lake is a very important open-pit deposit resource in China, and brine of the salt lake is rich in potassium, sodium, magnesium and boron elements and also contains other high-value strategic elements such as lithium, rubidium, cesium, uranium and the like. At present, in the prior art, extraction and utilization of brine are mainly concentrated on elements with high concentration content and elements easy to extract, tail liquid of other elements which are not separated and extracted is often used as waste liquid to be randomly discharged or re-discharged into a salt lake, and thus, the waste of resources is caused by the essential phenomenon. And because the primary enrichment method of each process section is complex and difficult to unify, pretreatment means such as pH adjustment and the like are still required, the continuous operation of large-scale industrialization is not facilitated, and the production efficiency is reduced.
Chinese patent publication No. CN101691239A discloses a method for comprehensive utilization of brine. The method removes H from bittern 2 S, reasonably combining procedures of magnesium precipitation, calcium precipitation and calcium carbonate preparation, first-stage salt preparation, second-stage salt preparation and potassium-sodium mixed salt preparation, potassium chloride flotation extraction, boron extraction by acidification, iodine extraction, bromine extraction, rubidium and cesium extraction, rubidium chloride and cesium chloride preparation, lithium extraction and the like to realize step-by-step and ordered extraction of main components.
Chinese patent publication No. CN114348970A discloses a method for comprehensive utilization of complex underground brine. The method comprises the following steps of 1: removing hydrogen sulfide under negative pressure; and 2, step: first-stage salt preparation; and 3, step 3: precipitating boron and magnesium; returning the separated precipitate to the step 2; and 4, step 4: precipitating calcium; and 5: blowing bromine and iodine; and 6: preparing salt in a second stage; and 7: preparing salt in three stages; adding condensate water into the separated salt slurry for redissolution, and returning to the step 6; and step 8: precipitating lithium; and step 9: precipitating rubidium and cesium; and if the concentration of the rubidium in the brine is not reached, returning to the step 7 to continue concentrating, and completing the circulation.
The technical scheme of the two patents can comprehensively extract a plurality of valuable elements in the brine, thereby avoiding the problems of resource waste and partial environmental pollution. But the flow is long, the process is complicated, and the adopted extraction and enrichment method is still a more traditional chemical precipitation method and an evaporation method; in addition, part of metal elements such as cesium, rubidium and uranium in the process can be precipitated to prepare salt only by evaporation and concentration to a high concentration, the process has high requirements on the quality of brine, and the economic cost is increased.
SUMMERY OF THE UTILITY MODEL
To the problem that exists among the prior art, the utility model aims to provide a brine comprehensive utilization system uses this system can realize extracting lithium, rubidium, cesium, uranium element's high efficiency in brine in coordination, obtains the strategic product of high value of battery level lithium carbonate, rubidium chloride, cesium chloride and ammonium diuranate simultaneously.
For realizing the purpose of the utility model, the concrete technical proposal is as follows:
a comprehensive brine utilization system comprises a filtering unit, a uranium adsorption/desorption unit, a cesium adsorption/desorption unit, a rubidium adsorption/desorption unit, a lithium adsorption/desorption unit and a brine pool;
the uranium adsorption/desorption unit comprises a first desorption liquid tank, a uranium adsorption resin unit, a first membrane concentration unit, a concentration tank and a first solid-liquid separation unit which are sequentially connected;
the cesium adsorption/desorption unit comprises a second desorption liquid tank, a cesium adsorption resin unit, a second concentration and purification unit, a second evaporation and crystallization unit and a second solid-liquid separation unit which are sequentially connected;
the rubidium adsorption/desorption unit comprises a third desorption liquid tank, a rubidium adsorption resin unit, a third concentration and purification unit, a third evaporation and crystallization unit and a third solid-liquid separation unit which are sequentially connected;
the lithium adsorption/desorption unit comprises a fourth desorption liquid tank, a lithium adsorption resin unit, a fourth membrane concentration unit, a lithium precipitation unit and a fourth solid-liquid separation unit which are sequentially connected;
the uranium adsorption resin unit, the cesium adsorption resin unit and the rubidium adsorption resin unit can be arranged in any order.
Preferably, the filtration unit consists of a multi-media filter; the medium in the filter is quartz sand.
Preferably, an iron removal resin unit is arranged between the uranium adsorption resin unit and the first membrane concentration unit, and the iron removal resin unit consists of an iron removal resin column.
Preferably, the first membrane concentration unit is formed by connecting a first primary nanofiltration membrane and a first primary reverse osmosis membrane in series; the fourth membrane concentration unit is formed by connecting a fourth primary nanofiltration membrane, a fourth primary reverse osmosis membrane, a fourth secondary nanofiltration membrane and an electrodialysis assembly in series.
Further preferably, the water production end of the first primary nanofiltration membrane and the water inlet end of the first primary reverse osmosis membrane are communicated with the uranium adsorption resin unit; the concentrated water end of the fourth-stage nanofiltration membrane is communicated with a brine tank; the concentrated water end of the fourth primary reverse osmosis membrane is communicated with the water inlet end of the fourth secondary nanofiltration membrane; the water production end of the fourth secondary nanofiltration membrane is connected with the water inlet end of the electrodialysis assembly; the water production end of the fourth stage reverse osmosis membrane is communicated with the water inlet end of the lithium adsorption resin unit.
Further preferably, the concentrated water end of the electrodialysis assembly is communicated with the water inlet end of the lithium precipitation unit, and the clear water end of the lithium precipitation unit and the water production end of the electrodialysis assembly are both communicated with the water inlet end of the fourth desorption liquid tank; the clear water end of the second evaporative crystallization unit is communicated with the water inlet end of the second concentration and purification unit, and the clear water end of the third evaporative crystallization unit is communicated with the water inlet end of the third concentration and purification unit.
Preferably, the first solid-liquid separation unit comprises a first plate-and-frame filter press and a first conveyor; the second solid-liquid separation unit comprises a second plate-and-frame filter press and a second dryer; the third solid-liquid separation unit comprises a third plate-frame filter press and a third dryer; the fourth solid-liquid separation unit comprises a fourth plate-and-frame filter press and a fourth dryer.
Further preferably, the filter water end of the first plate-and-frame filter press is communicated with a second desorption liquid tank and a third desorption liquid tank; the water filtering end of the second plate-and-frame filter press is communicated with the water inlet end of the second evaporative crystallization unit; the water filtering end of the third plate frame filter press is communicated with the water inlet end of the third evaporation crystallization unit; and the water filtering end of the fourth plate-and-frame filter press is communicated with a fourth desorption liquid tank.
Preferably, the third concentration and purification unit and the second concentration and purification unit comprise at least one of an extraction unit, a high selectivity ion exchange unit and an electric adsorption and desorption unit; the high-selectivity ion exchange unit consists of an adsorption and desorption column bed consisting of inorganic nano-fillers; the electric adsorption and desorption unit consists of a direct-current power supply, a cathode and an anode which have high selectivity cesium and rubidium ions for electric adsorption and electric desorption.
Preferably, a primary pulp washing unit, a demagnetizing unit and a secondary pulp washing unit are sequentially arranged between the lithium precipitation unit and the fourth solid-liquid separation unit; the primary pulp washing unit and the secondary pulp washing unit are communicated with the brine tank through the middle water tank.
Compared with the prior art, the beneficial effects of the utility model reside in that:
the utility model discloses reasonable combination between each constitutional unit of system can realize its peculiar composition substep and draw in order.
The utility model discloses the system passes through the series connection adsorption element of uranium, cesium, rubidium, lithium with brine, realizes the high-efficient continuous operation of whole absorption technology that synthesizes and draws, and each element draws each other noninterference, each other not influencing between the technology, forms one set of salt lake brine resource comprehensive utilization integrated technology package, the extensive industrial application of being convenient for promotes.
All filtrate and clear liquid in each unit of the system realize all internal recycling; the primary enrichment and concentration process of the adsorption and desorption method can ensure that other ions and organic pollutants are not introduced into the adsorption tail liquid of each process section, only uranium, cesium, rubidium and lithium are selectively removed, the adsorption tail liquid can finally return to a brine pool safely and pollution-free, and the green cycle of comprehensive extraction of high-value strategic elements of brine is really realized.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention, and together with the description serve to explain the invention and not to limit the invention.
In the drawings:
FIG. 1 is a process flow diagram of the comprehensive brine utilization method of the present invention;
fig. 2 is a schematic structural diagram of the comprehensive brine utilization system of the present invention.
Detailed Description
To facilitate understanding of the present invention, the present invention will be described more fully and specifically with reference to the accompanying drawings and preferred embodiments, but the scope of the present invention is not limited to the specific embodiments described below.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by an existing method.
Example 1
Referring to fig. 1 and 2, the present embodiment provides a comprehensive utilization method of brine and a comprehensive utilization system adapted to the same.
The embodiment provides a comprehensive utilization method of brine, which comprises the following steps:
(1) Filtering the brine in the brine pond by using a filtering unit;
(2) Sequentially carrying out uranium adsorption/desorption, cesium adsorption/desorption and rubidium adsorption/desorption on the filtered brine;
uranium adsorption/desorption: selectively adsorbing uranyl ions through a uranium adsorption column; desorbing the uranium adsorption column with saturated adsorption by using a hydrochloric acid solution to obtain a first desorbed liquid containing uranyl ions, concentrating the first desorbed liquid by using a membrane concentration unit to obtain a first concentrated liquid, and adding ammonia water into the first concentrated liquid to generate ammonium diuranate precipitate; filtering and drying to obtain yellow cake;
cesium adsorption/desorption: selectively adsorbing cesium ions through a cesium adsorption column; desorbing the cesium adsorption column with saturated adsorption by using an ammonium chloride solution to obtain a second desorbed solution containing cesium ions, concentrating the second desorbed solution by using a concentration passivation unit to obtain a second concentrated solution, and carrying out evaporative crystallization, filtration and drying on the second concentrated solution to obtain cesium chloride;
rubidium adsorption/desorption: selectively adsorbing rubidium ions through a rubidium adsorption column; desorbing the saturated rubidium adsorption column by using an ammonium chloride solution to obtain a third desorbed solution containing rubidium ions, concentrating the third desorbed solution by using a concentration passivation unit to obtain a third concentrated solution, and evaporating, crystallizing, filtering and drying the third concentrated solution to obtain rubidium chloride;
(3) Lithium adsorption/desorption: selectively adsorbing lithium ions by tail solution brine after uranium, cesium and rubidium adsorption through a lithium adsorption column, desorbing the lithium adsorption column subjected to adsorption saturation by using dilute hydrochloric acid to obtain a fourth desorbed solution containing lithium, concentrating the fourth desorbed solution through a membrane concentration unit to obtain a fourth concentrated solution, then adjusting the temperature and the pH of the fourth concentrated solution, adding soda and sodium hydroxide to respectively convert calcium and magnesium into calcium carbonate and magnesium hydroxide precipitates, filtering, adding soda into the solution to perform a precipitation reaction to generate crude lithium carbonate, and performing solid-liquid separation to obtain a crude lithium carbonate filter cake;
conveying the crude lithium carbonate filter cake to a primary slurry washing unit, and finishing primary slurry washing by using pure water to obtain crude lithium carbonate slurry after impurity removal;
crushing the coarse lithium carbonate slurry subjected to impurity removal in a crushing unit;
feeding the crushed coarse lithium carbonate slurry into a demagnetizing unit for demagnetizing;
the demagnetized crude lithium carbonate slurry enters a secondary slurry washing unit, and secondary slurry washing is completed by using pure water;
and carrying out solid-liquid separation to obtain a battery-grade lithium carbonate product.
As one of the preferable solutions of the present embodiment:
uranium adsorption/desorption process: the concentration of the hydrochloric acid solution is 0.1-1mol/L, the concentration of uranium in the solution after the first desorption is 100-500mg/L, and the concentration of uranium in the first concentrated solution is 2g-10g/L;
cesium adsorption/desorption process: the concentration of the ammonium chloride solution is 0.1-0.5 mol/L, the concentration of cesium in the solution after the second desorption is 10-20mg/L, and the concentration of cesium in the second concentrated solution is 0.5-1g/L;
rubidium adsorption/desorption process: the concentration of the ammonium chloride solution is 0.5 to 2mol/L, the concentration of rubidium in the solution after the third desorption is 100 to 200mg/L, and the concentration of rubidium in the third concentrated solution is 0.5 to 1g/L;
lithium adsorption/desorption process: the concentration of the hydrochloric acid solution is 0.1-0.5 mol/L, the concentration of lithium in the solution after the fourth desorption is 500-1200 mg/L, and the concentration of lithium in the fourth concentrated solution is 10-20g/L.
As one of the preferable embodiments of the present embodiment:
cesium adsorption/desorption process: the mass ratio of potassium, sodium and cesium in the second desorbed liquid is 5 to 10, and the mass ratio of potassium, sodium and cesium in the second concentrated liquid is 0.01 to 0.1;
rubidium adsorption/desorption process: the mass ratio of potassium, sodium and rubidium in the third desorbed liquid is 5-10, and the mass ratio of potassium, sodium and rubidium in the third concentrated liquid is 0.001-0.01;
as one of the preferable embodiments of the present embodiment:
the filter unit consists of a multi-media filter; the medium in the filter comprises at least one of quartz sand and gravel; and filtering by adopting a solid-liquid separation unit, wherein the solid-liquid separation unit comprises a plate-and-frame filter press and a conveyor.
As one of the preferable solutions of the present embodiment:
in the uranium adsorption/desorption process in the step (2), fe is removed through an iron-removing resin unit before the first desorbed liquid passes through a membrane concentration unit 3+ Impurities; the deironing resin unit comprises a deironing resin column.
As one of the preferable embodiments of the present embodiment:
in the uranium adsorption/desorption process in the step (2), the membrane concentration unit is formed by connecting a primary nanofiltration membrane and a primary reverse osmosis membrane in series; in the uranium adsorption/desorption process in the step (3), the membrane concentration unit is formed by connecting a primary nanofiltration membrane, a primary reverse osmosis membrane and a primary nanofiltration membrane in series.
As one of the preferable embodiments of the present embodiment:
in the cesium and rubidium adsorption/desorption process in the step (2), the concentration and purification unit comprises at least one of an extraction unit, a high-selectivity ion exchange unit and an electric adsorption desorption unit;
further preferably:
the extraction unit takes the sulfonated kerosene mixed solution of t-BAMBP as an extractant and hydrochloric acid as a back extractant;
the high-selectivity ion exchange unit consists of an adsorption and desorption column bed consisting of Prussian blue nano-type packing;
the electric adsorption and desorption unit consists of a direct current power supply and a cathode and an anode which have high selectivity cesium and rubidium ions for electric adsorption and electric desorption.
As one of the preferable solutions of the present embodiment:
in the cesium and rubidium adsorption/desorption process in the step (2), the specific operations of evaporation crystallization, filtration and drying are as follows: the concentrated solution enters an evaporation crystallization unit, is evaporated and heated until cesium chloride or rubidium chloride solution is supersaturated, and is slowly cooled, and cesium chloride or rubidium chloride crystals are separated out, grown and formed; pumping into a filter press for filter pressing to obtain a filter cake, and drying to obtain cesium chloride or rubidium chloride.
As one of the preferable embodiments of the present embodiment:
providing a comprehensive brine utilization system suitable for the system, which comprises a filtering unit, a uranium adsorption/desorption unit, a cesium adsorption/desorption unit, a rubidium adsorption/desorption unit, a lithium adsorption/desorption unit and a brine pool;
the filtering unit is a multi-medium filter 1;
the uranium adsorption/desorption unit comprises a first desorption liquid tank 71, a uranium adsorption resin unit 2, an iron removal resin unit 21, a first primary nanofiltration membrane 22, a first primary reverse osmosis membrane 23, a concentration tank 24, a first plate-and-frame filter press 25 and a first dryer 26 which are connected in sequence;
the cesium adsorption/desorption unit comprises a second desorption liquid tank 72, a cesium adsorption resin unit 3, a second concentration and purification unit 31, a second evaporation and crystallization unit 32, a second plate-and-frame filter press 33 and a second dryer 34 which are sequentially connected;
the rubidium adsorption/desorption unit comprises a third desorption liquid tank 73, a rubidium adsorption resin unit 4, a third concentration and purification unit 41, a third evaporation and crystallization unit 42, a third plate and frame filter press 43 and a third dryer 44 which are connected in sequence;
the lithium adsorption/desorption unit comprises a fourth desorption liquid tank 74, a lithium adsorption resin unit 5, a fourth primary nanofiltration membrane 51, a fourth primary reverse osmosis membrane 52, a fourth secondary nanofiltration membrane 53, an electrodialysis assembly 54, a lithium precipitation unit 55, a primary pulp washing unit 56, a demagnetization unit 57, a secondary pulp washing unit 58, a fourth plate-and-frame filter press 59 and a fourth dryer 510 which are connected in sequence;
the device comprises a brine pool 6, a multi-media filter 1, a uranium adsorption resin unit 2, a cesium adsorption resin unit 3, a rubidium adsorption resin unit 4, a lithium adsorption resin unit 5 and the brine pool 6, wherein the brine pool, the multi-media filter 1, the uranium adsorption resin unit 2, the cesium adsorption resin unit 3, the rubidium adsorption resin unit 4, the lithium adsorption resin unit 5 and the brine pool 6 are sequentially communicated in a circulating mode.
The water production end of the first primary nanofiltration membrane 22 and the water production end of the first primary reverse osmosis membrane 23 are communicated with the water inlet end of the uranium adsorption resin unit 2, and the water filtration end of the first plate-and-frame filter press 25 is communicated with the second desorption liquid tank 72 and the third desorption liquid tank 73;
the clear water end of the second evaporative crystallization unit 32 is communicated with the water inlet end of the second concentration and purification unit 31, and the water filtering end of the second plate-and-frame filter press 33 is communicated with the water inlet end of the second evaporative crystallization unit 32;
the clear water end of the third evaporative crystallization unit 42 is communicated with the water inlet end of the third concentration and purification unit 41, and the water filtering end of the third plate and frame filter press 43 is communicated with the water inlet end of the third evaporative crystallization unit 42;
the concentrated water end of the fourth primary nanofiltration membrane 51 is communicated with the brine tank 6, the primary slurry washing unit 56 and the secondary slurry washing unit 58 are communicated with the brine tank 6 through the middle water tank 511, the water filtering end of the fourth plate-and-frame filter press 59, the clear water end of the lithium precipitation unit 55, the water producing end of the electrodialysis assembly 54 and the water producing end of the fourth primary reverse osmosis membrane 52 are communicated with the fourth desorption liquid tank 74, the concentrated water end of the fourth primary reverse osmosis membrane 52 is communicated with the water inlet end of the fourth secondary nanofiltration membrane 53, and the concentrated water end of the electrodialysis assembly 54 is communicated with the water inlet end of the lithium precipitation unit 55.
Example 2
This example provides a practical example of the comprehensive utilization method of brine and the comprehensive utilization system of brine in example 1.
(1) The salt lake brine with the potassium content of 13760mg/L, the sodium content of 19250mg/L, the iron content of 10mg/L, the uranium content of 139ug/L, the cesium content of 73ug/L, the rubidium content of 4.1mg/L and the lithium content of 149.5mg/L is lifted by a pump and enters a multi-media filter filled with quartz sand to remove suspended matters, so that brine A is obtained;
(2) And (3) sequentially carrying out uranium, cesium and rubidium adsorption/desorption on the brine A.
Uranium adsorption/desorption: carrying out selective adsorption on uranyl radical ions in the brine A through a uranium adsorption column to obtain adsorption tail liquid brine B; desorbing the uranium adsorption column with saturated adsorption by using 1mg/L hydrochloric acid solution to obtain qualified uranium with the uranium concentration of 50mg/LA desorption solution; adsorbing the qualified desorption liquid by an iron-removing resin column to remove Fe 3+ And collecting impurities and iron-containing desorption liquid for recycling iron. Uranium concentration is carried out on the iron-removing resin column effluent through a membrane concentration unit, and the concentration of uranium in the concentrated solution reaches 1g/L; adding concentrated ammonia water into the concentrated solution for reaction to generate ammonium diuranate precipitate; conveying the precipitate into a plate-and-frame filter press by a conveyor for filtering, and then drying in a dryer to obtain a yellow cake product;
cesium adsorption/desorption: selectively adsorbing cesium ions in the brine B through a cesium adsorption column to obtain adsorption tail liquid brine C; desorbing the saturated cesium adsorption column by using 0.2mol/L ammonium chloride solution to obtain cesium with the concentration of 10mg/L, concentrating and purifying qualified desorption solution by using an extraction unit, taking a sulfonated kerosene mixed solution of t-BAMBP as an extractant, hydrochloric acid as a back extractant, and obtaining cesium with the concentration of 100mg/L, potassium with the concentration of 5mg/L and sodium with the concentration of 2mg/L after back extraction; and (3) feeding the concentrated and purified solution into an evaporation crystallization unit, evaporating until supersaturation is achieved, separating out the cesium chloride crystal form, repeating the evaporation crystallization for 8 times to obtain enough formed crystal particles, pumping the crystal particles into a filter press for filter pressing to obtain a filter cake, and drying the filter cake to obtain the high-purity product cesium chloride.
Rubidium adsorption/desorption: selectively adsorbing rubidium ions in the brine C by virtue of a rubidium adsorption column to obtain adsorption tail solution brine D; desorbing the saturated rubidium adsorption column by using 1mol/L ammonium chloride solution to obtain rubidium with the concentration of 100mg/L, concentrating and purifying the qualified desorption solution by using an adsorption and desorption column bed formed by a high-selectivity ion exchange unit, wherein the rubidium concentration of the concentrated and purified solution is 1g/L, the potassium concentration of the concentrated and purified solution is 23mg/L, and the sodium concentration of the concentrated and purified solution is 14mg/L; and (3) feeding the concentrated and purified solution into an evaporation and crystallization unit, evaporating until supersaturation is achieved, separating out the rubidium chloride crystal form, repeating the evaporation and crystallization for 5 times to obtain enough formed crystal particles, pumping the crystal particles into a filter press for filter pressing to obtain a filter cake, and drying the filter cake to obtain a high-purity product rubidium chloride.
(3) Lithium adsorption/desorption: selectively adsorbing lithium ions by using a lithium adsorption column, desorbing the lithium adsorption column with saturated adsorption by using 0.2mol/L dilute hydrochloric acid to obtain qualified desorption solution with the lithium concentration of 500mg/L, concentrating the lithium of the qualified desorption solution by using a membrane concentration unit until the lithium concentration in the concentrated solution reaches 15g/L, sequentially adding soda ash and sodium hydroxide, adjusting the pH value to 11, respectively converting calcium and magnesium into calcium carbonate and magnesium hydroxide precipitates, raising the temperature to 95 ℃ after filtering, adding soda ash with the lithium content of 1.05 times into the solution, stirring, carrying out precipitation reaction to generate crude lithium carbonate, and carrying out solid-liquid separation to obtain a crude lithium carbonate filter cake; and conveying the coarse lithium carbonate filter cake to a primary slurry washing unit to prepare slurry by using pure water, and further removing impurities through slurry washing. The coarse lithium carbonate slurry enters a grinder with a built-in high-speed shear pump to be completely crushed and sheared into fine particles, the crushed slurry enters a demagnetization unit to be fully contacted with a strong magnetic rod, and magnetic substances are adsorbed on the surface of the magnetic rod to complete demagnetization; the demagnetized crude lithium carbonate slurry enters a secondary slurry washing unit, and secondary slurry washing is completed by using pure water, so that impurities on the surface of the slurry are thoroughly removed; after secondary slurry washing, the lithium carbonate enters a solid-liquid separation unit for solid-liquid separation to obtain solid lithium carbonate, and the filtrate is recycled to a lithium adsorption column and can be used as part of water for leaching; and drying the solid lithium carbonate to obtain a battery-grade lithium carbonate product with the purity of more than 99.5 percent.
Example 3
This example provides a practical example of the comprehensive brine utilization method and the comprehensive brine utilization system in example 1.
(1) The salt lake brine with the potassium content of 9760mg/L, the sodium content of 7890mg/L, the iron content of 3mg/L, the uranium content of 485ug/L, the cesium content of 144ug/L, the rubidium content of 16mg/L and the lithium content of 190mg/L is lifted by a pump to enter a multi-media filter filled with quartz sand and gravel to remove suspended matters, so that brine A is obtained;
(2) And (3) sequentially carrying out uranium, cesium and rubidium adsorption/desorption on the brine A.
Uranium adsorption/desorption: carrying out selective adsorption on uranyl radical ions in the brine A through a uranium adsorption column to obtain adsorption tail liquid brine B; desorbing the uranium adsorption column with saturated adsorption by using 1.2mg/L hydrochloric acid solution to obtain qualified desorption liquid with the uranium concentration of 100 mg/L; adsorbing the qualified desorption liquid by an iron-removing resin column to remove Fe 3+ And collecting impurities and iron-containing desorption liquid for recycling iron. The iron-removing resin column goes out of the liquid to pass throughThe membrane concentration unit is used for uranium concentration, and the concentration of uranium in the concentrated solution reaches 2g/L; adding concentrated ammonia water into the concentrated solution for reaction to generate ammonium diuranate precipitate; conveying the precipitate into a plate-and-frame filter press by using a conveyor for filtering, and then drying in a dryer to obtain a yellow cake product;
cesium adsorption/desorption: selectively adsorbing cesium ions in the brine B through a cesium adsorption column to obtain adsorption tail liquid brine C; desorbing the adsorption saturated cesium adsorption column by using 0.5mol/L ammonium chloride solution to obtain cesium with the concentration of 10mg/L, concentrating and purifying the qualified desorption solution by using a high-selectivity electric adsorption desorption unit, wherein the concentrated and purified cesium has the concentration of 210mg/L, the potassium concentration of 12mg/L and the sodium concentration of 7mg/L; and (3) allowing the concentrated and purified solution to enter an evaporation and crystallization unit, evaporating until supersaturation is achieved, separating out a cesium chloride crystal form, repeating evaporation and crystallization for 7 times to obtain enough formed crystal particles, pumping the crystal particles into a filter press for filter pressing to obtain a filter cake, and drying the filter cake to finally obtain a high-purity product cesium chloride.
Rubidium adsorption/desorption: selectively adsorbing rubidium ions in the brine C by virtue of a rubidium adsorption column to obtain adsorption tail liquor brine D; desorbing the saturated rubidium adsorption column by using 2mol/L ammonium chloride solution to obtain 100mg/L rubidium concentration, concentrating and purifying the qualified desorption solution by using an adsorption and desorption column bed formed by a high-selectivity ion exchange unit, wherein the rubidium concentration of the concentrated and purified solution is 5g/L, the potassium concentration of the concentrated and purified solution is 31mg/L, and the sodium concentration of the concentrated and purified solution is 19mg/L; and (3) feeding the concentrated and purified solution into an evaporation and crystallization unit, evaporating until supersaturation is achieved, separating out the rubidium chloride crystal form, repeating the evaporation and crystallization for 5 times to obtain enough formed crystal particles, pumping the crystal particles into a filter press for filter pressing to obtain a filter cake, and drying the filter cake to obtain a high-purity product rubidium chloride.
(3) Lithium adsorption/desorption: selectively adsorbing lithium ions by using a lithium adsorption column, desorbing the lithium adsorption column with saturated adsorption by using 0.3mol/L dilute hydrochloric acid to obtain qualified desorption solution with the lithium concentration of 800mg/L, concentrating the lithium of the qualified desorption solution by using a membrane concentration unit until the lithium concentration in the concentrated solution reaches 20g/L, sequentially adding soda ash and sodium hydroxide, adjusting the pH value to 11, respectively converting calcium and magnesium into calcium carbonate and magnesium hydroxide precipitates, raising the temperature to 95 ℃ after filtering, adding soda ash with the lithium content of 1.05 times into the solution, stirring, carrying out precipitation reaction to generate crude lithium carbonate, and carrying out solid-liquid separation to obtain a crude lithium carbonate filter cake; and conveying the coarse lithium carbonate filter cake to a primary slurry washing unit to prepare slurry by using pure water, and further removing impurities through slurry washing. The coarse lithium carbonate slurry enters a grinder internally provided with a high-speed shear pump to be completely crushed and sheared into fine particles, the crushed slurry enters a demagnetizing unit to be fully contacted with a strong magnetic rod, and magnetic substances are adsorbed on the surface of the magnetic rod to complete demagnetization; the demagnetized coarse lithium carbonate slurry enters a secondary slurry washing unit, and secondary slurry washing is completed by pure water, so that impurities on the surface of the slurry are thoroughly removed; after secondary pulp washing, the lithium carbonate enters a solid-liquid separation unit for solid-liquid separation to obtain solid lithium carbonate, and the filtrate is recycled to a lithium adsorption column and can be used as part of water for leaching; and drying the solid lithium carbonate to obtain a battery-grade lithium carbonate product with the purity of more than 99.5 percent.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A comprehensive brine utilization system is characterized by comprising a filtering unit, a uranium adsorption/desorption unit, a cesium adsorption/desorption unit, a rubidium adsorption/desorption unit, a lithium adsorption/desorption unit and a brine pond;
the uranium adsorption/desorption unit comprises a first desorption liquid tank, a uranium adsorption resin unit, a first membrane concentration unit, a concentration tank and a first solid-liquid separation unit which are connected in sequence;
the cesium adsorption/desorption unit comprises a second desorption liquid tank, a cesium adsorption resin unit, a second concentration and purification unit, a second evaporation and crystallization unit and a second solid-liquid separation unit which are sequentially connected;
the rubidium adsorption/desorption unit comprises a third desorption liquid tank, a rubidium adsorption resin unit, a third concentration and purification unit, a third evaporation and crystallization unit and a third solid-liquid separation unit which are sequentially connected;
the lithium adsorption/desorption unit comprises a fourth desorption liquid tank, a lithium adsorption resin unit, a fourth membrane concentration unit, a lithium precipitation unit and a fourth solid-liquid separation unit which are sequentially connected;
the uranium adsorption resin unit, the cesium adsorption resin unit and the rubidium adsorption resin unit can be arranged in any order.
2. The brine integrated utilization system of claim 1, wherein said filtration unit is comprised of a multi-media filter; the medium in the filter is quartz sand.
3. The comprehensive utilization system of brine as claimed in claim 1, wherein an deironing resin unit is arranged between the uranium adsorption resin unit and the first membrane concentration unit, and the deironing resin unit is composed of a deironing resin column.
4. The brine comprehensive utilization system of claim 1, wherein the first membrane concentration unit consists of a first primary nanofiltration membrane and a first primary reverse osmosis membrane connected in series; the fourth membrane concentration unit is formed by connecting a fourth primary nanofiltration membrane, a fourth primary reverse osmosis membrane, a fourth secondary nanofiltration membrane and an electrodialysis assembly in series.
5. The comprehensive brine utilization system of claim 4, wherein the water production end of the first primary nanofiltration membrane and the water production end of the first primary reverse osmosis membrane are communicated with the water inlet end of the uranium adsorption resin unit; the concentrated water end of the fourth-stage nanofiltration membrane is communicated with a brine tank; the concentrated water end of the fourth primary reverse osmosis membrane is communicated with the water inlet end of the fourth secondary nanofiltration membrane; the water production end of the fourth stage reverse osmosis membrane is communicated with the water inlet end of the lithium adsorption resin unit.
6. The comprehensive brine utilization system of claim 4, wherein the concentrate end of the electrodialysis assembly is communicated with the water inlet end of the lithium precipitation unit, and the clear water end of the lithium precipitation unit and the water production end of the electrodialysis assembly are both communicated with the water inlet end of the fourth desorption liquid tank; the clear water end of the second evaporative crystallization unit is communicated with the water inlet end of the second concentration and purification unit, and the clear water end of the third evaporative crystallization unit is communicated with the water inlet end of the third concentration and purification unit.
7. The brine integrated utilization system of claim 1, wherein the first solid-liquid separation unit comprises a first plate-and-frame filter press and a first conveyor; the second solid-liquid separation unit comprises a second plate-and-frame filter press and a second dryer; the third solid-liquid separation unit comprises a third plate-frame filter press and a third dryer; the fourth solid-liquid separation unit comprises a fourth plate-and-frame filter press and a fourth dryer.
8. The comprehensive brine utilization system of claim 7, wherein the filtrate end of the first plate-and-frame filter press is in communication with a second desorption liquid tank and a third desorption liquid tank; the water filtering end of the second plate-and-frame filter press is communicated with the water inlet end of the second evaporation crystallization unit; the water filtering end of the third plate frame filter press is communicated with the water inlet end of the third evaporation crystallization unit; and the water filtering end of the fourth plate-and-frame filter press is communicated with a fourth desorption liquid tank.
9. The brine integrated utilization system of claim 1, wherein the second and third concentration and purification units comprise at least one of an extraction unit, a highly selective ion exchange unit, and an electro-adsorption desorption unit; the high-selectivity ion exchange unit consists of an adsorption and desorption column bed consisting of inorganic nano-fillers; the electric adsorption and desorption unit consists of a direct-current power supply, a cathode and an anode which have high selectivity cesium and rubidium ions for electric adsorption and electric desorption.
10. The comprehensive brine utilization system of claim 1, wherein a primary slurry washing unit, a demagnetizing unit and a secondary slurry washing unit are sequentially arranged between the lithium precipitation unit and the fourth solid-liquid separation unit; the primary pulp washing unit and the secondary pulp washing unit are communicated with a brine tank through an intermediate water tank.
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