CN114797171A - Production device and production process for extracting lithium from brine by efficient adsorption method - Google Patents
Production device and production process for extracting lithium from brine by efficient adsorption method Download PDFInfo
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Abstract
The invention aims to provide a production device and a production process for extracting lithium from brine by using an efficient adsorption method, wherein the production device comprises: the system comprises a bittern dilution tank, a primary adsorption tower, a primary deep magnesium removal tower, a secondary magnesium removal leacheate storage pool, a reverse osmosis device, an evaporation device, a primary filtering device, a precise filtering device, a lithium precipitation reaction kettle, a centrifugal machine, a concentration airing pool, a countercurrent washing tower, a filter and a dryer. The invention solves the problems that the lithium carbonate production in China depends on a large amount of lithium ores, the brine lithium salt capacity cannot be completely released, and resources are wasted in a large amount. The high-efficiency ion exchange adsorbent adopted by the invention has high selectivity to lithium salt, high recovery rate and high product purity, and the preparation method of the adsorbent is simple, renewable and low in price, and is suitable for large-scale operation and use. And the reaction process is normal pressure and normal temperature, the danger in the production process is small, and the method is a green production process.
Description
Technical Field
The invention relates to a production device and a production process for extracting lithium from brine by an efficient adsorption method, and belongs to the technical field of extracting lithium by an adsorption method.
Background
Lithium (Li) is an "elemental new star" in the twenty-first century, known as "industrial monosodium glutamate" or "energy metal". Lithium metal and its alloys and compounds have been widely used in many fields such as light high specific strength alloys, metallurgy, aluminum production, high-energy batteries, medical glass, ceramics, grease, petroleum, chemical engineering, organic synthesis, light metal welding, surface modification of non-metallic minerals, daily necessities, nuclear power generation, and the like. The largest consumption market of lithium carbonate is additive, fluxing agent and the like used in the lithium battery application, glass manufacturing and ceramic production processes in the new energy technology, the new material market of the lithium battery is steadily grown under the strong drive of the global lithium battery market growth, and the demand of the international market for lithium carbonate is increased by 8% -12% on average each year. With the continuous maturity of the electric automobile market, the market demand of lithium carbonate is expected to be explosively increased, and the market prospect is very wide. In addition, the lithium carbonate is widely applied to industries such as lubricants, rechargeable batteries and air conditioners, and has a wide market prospect.
From the aspect of the reserve of lithium resources, the lithium ion battery mainly exists. The percentage of lithium resources in salt lakes is high, but the current domestic brine resources are difficult to exploit in a large scale, the existing development proportion is very low, the capacity cannot be completely released, and the domestic lithium carbonate yield is caused by the phenomenon that the proportion of lithium ores and brine lithium salts is 75 percent to 25 percent in an inverted manner. In the last decade, because of great attention paid to the foreign extraction research on the development of lithium from salt lake brine, a series of technical problems of lithium extraction from salt lake brine are overcome, and the development trend of lithium extraction from salt lake instead of ore extraction is formed in the world lithium salt production.
Because of the diversity and complexity of salt lake brine systems, the difference of salt lake resource utilization and processing technologies is determined, and the main methods for extracting lithium from salt lake brine can be divided into a precipitation method, an extraction method, an ion exchange adsorption method and a salting-out method. The precipitation method is to add a precipitator to separate lithium from other salts in brine with high lithium content, and the total yield of lithium is about 75%. The solvent extraction method mainly aims at a salt lake system, mainly a high-magnesium chloride salt lake system, and the extraction rate of lithium is 80%. However, the extractant has high solubility in water and high price, and the organic solvent is easy to cause serious environmental pollution to the salt lake region. The ion exchange adsorption method has the greatest advantages of great superiority in economy and environmental protection, simple process, high recovery rate and good selectivity, and has good application prospect for brine with low lithium content. However, no adsorption process for extracting lithium from brine is available.
Therefore, the development of a production device and a production process for extracting lithium from brine by using an efficient adsorption method and the further research and development of an industrialized efficient adsorption lithium extraction process have important strategic significance for the comprehensive utilization of resources in China and the further development of downstream industries.
Disclosure of Invention
The invention aims to provide a production device and a production process for extracting lithium from brine by an efficient adsorption method, and solves the problems that the domestic lithium carbonate production depends on a large amount of lithium ores, the capacity of lithium salt in brine cannot be completely released, and a large amount of resources are wasted. According to the invention, on the basis of utilizing the adsorption method to complete lithium extraction from brine, the high-efficiency adsorbent is selected, so that the production efficiency is greatly improved, the resources are comprehensively utilized, and the industrial development of the adsorption method for lithium extraction from brine is realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
a production device for extracting lithium from brine by a high-efficiency adsorption method comprises a preliminary adsorption magnesium removal working section, a deep magnesium removal concentration working section and a lithium precipitation reaction working section;
the preliminary magnesium adsorption and removal section comprises: a old brine dilution tank and a primary adsorption tower;
the deep magnesium removal concentration section comprises: a primary deep magnesium removal tower, a secondary magnesium removal leacheate storage pool, a reverse osmosis device, an evaporation device, a primary filtering device and a precise filtering device;
the lithium precipitation reaction section comprises: the device comprises a lithium precipitation reaction kettle, a centrifugal machine, a concentration airing pool, a countercurrent washing tower, a filter and a dryer;
old bittern dilution tank links to each other with preliminary adsorption tower upper portion, the ejection of compact links to each other with the first degree of depth degummed top of the tower at the bottom of the preliminary adsorption tower, the first degree of depth degummed bottom links to each other with the second degree of depth degummed top of the tower, the second degree of depth degummed bottom of the tower is through secondary degummed leacheate reservoir, reverse osmosis unit connection evaporation plant, evaporation plant passes through preliminary filter equipment and links to each other with precision filtration device, precision filtration device links to each other with heavy lithium reation kettle, heavy lithium reation kettle passes through centrifuge's mother liquor discharge gate and concentrated pond of drying in the air and links to each other, centrifuge's solid discharge gate passes through countercurrent washing tower and connects the filter, filter filtrating links to each other with concentrated pond of drying in the air, the filter cake links to each other with drying device, weighing device is connected to drying device.
Preferably, the adsorbent in the preliminary adsorption tower is selected from an ion sieve adsorbent, an aluminum salt adsorbent or a natural mineral modified adsorbent; the adsorbent in the primary deep magnesium removal tower and the secondary deep magnesium removal tower is selected from an organic adsorbent resin adsorbent or an inorganic adsorbent; the adsorbent in the deep magnesium removal tower is cation exchange resin.
Preferably, the ion sieve adsorbent is a metal oxide having a pore structure obtained by ion elution of a composite oxide containing a target ion, and is more preferably a manganese ion sieve (e.g., lambda-MnO) 2 ) Titanium-based lithium ion sieves (e.g. Li) 4 Ti 5 O1 2 Type ion sieve), etc.; the aluminum salt adsorbent is LiX.2Al (OH) which has selective adsorption effect on aluminum chloride 3 ·nH 2 O, wherein X represents an anion, generally Cl, and n is a positive integer of 0 to 10, and the preparation method comprises the following steps: mixing AlCl 3 Mixing the solution with LiCl solution, adding NaOH solution while stirring to generate Li + Embedded in Al (OH) 3 An aluminum salt adsorbent is formed in the precipitated interlayer structure; the natural mineral modified adsorbent is obtained by modifying minerals (kaolin, zeolite and the like) through solid-phase sintering, acid leaching and the like, and has higher cation exchange capacity and specific surface area after modification.
Preferably, the organic adsorbent resin is high molecular polymer such as polystyrene resin and polyacrylate resin, and the inorganic adsorbent is activated carbon.
Preferably, the cation exchange resin is a polymer prepared by polymerizing styrene and divinylbenzene and sulfonating the polymer by sulfuric acid.
Preferably, the preliminary filtering device is a plate-and-frame filter, a vertical filter press or a belt filter.
The invention also discloses a method for extracting lithium from brine by using the production device through an efficient adsorption method, which comprises the following steps:
s1, conveying the old brine of the salt pan into an old brine diluting tank, adding brackish water or fresh water or a barren solution generated by washing with a saturated adsorbent into the old brine diluting tank, diluting the old brine of the salt pan, conveying the diluted old brine of the salt pan into a primary adsorption tower from the upper part of the primary adsorption tower, selectively adsorbing magnesium and lithium ions by the adsorbent in the tower, directly returning the adsorption tail solution flowing out of the tower kettle to the salt pan without pollution until the adsorbent is saturated, and stopping;
s2, blowing compressed air into the preliminary absorption tower from the top of the tower after the absorbent is saturated, returning the blown residual brine in the preliminary absorption tower to the old brine dilution tank, blowing off the residual brine in the preliminary absorption tower, quickly introducing fresh water or brackish water from the top of the preliminary absorption tower to take away part of magnesium ions absorbed in the absorbent, and returning the magnesium ions to the old brine dilution tank;
s3, dividing the preliminary adsorption tower into an upper section, a middle section and a lower section, leaching the saturated adsorbent which is blown clean and washed away with magnesium ions, introducing fresh water or the fresh water discharged by a reverse osmosis device from the top of the lower section for leaching, obtaining a second barren solution at the bottom of the tower, returning the second barren solution to the upper part of the middle section of the preliminary adsorption tower for continuous leaching, obtaining a barren solution at the bottom of the tower, returning part of the first barren solution to the top of the preliminary adsorption tower for inflow, obtaining lithium-containing qualified solution at the bottom of the tower, and removing the other part of the barren solution from a old brine dilution tank for diluting old brine; the primary adsorption tower adsorbent after desorption can be recycled;
s4, enabling the qualified lithium-containing liquid obtained by leaching in the primary adsorption tower to sequentially enter a primary deep magnesium removal tower and a secondary deep magnesium removal tower, wherein the tops of the towers enter a tower kettle and are discharged out of the tower, further removing the content of magnesium ions in the qualified lithium-containing liquid, and enabling the leacheate subjected to deep magnesium removal to enter a secondary magnesium removal leacheate storage pool;
s5, feeding the secondary magnesium-removing eluent into a reverse osmosis device for concentration, returning the obtained fresh water to the primary adsorption tower to be used as the eluent in the desorption and elution stages, feeding the penetrating fluid into an evaporation device for further concentration of a lithium-containing solution to obtain a high-lithium mother solution, feeding the high-lithium mother solution into a primary filtering device and a precise filtering device in sequence for refining, and obtaining a refined high-lithium solution at the outlet of the precise filtering device;
s6, feeding the refined high-lithium mother liquor into a lithium precipitation reaction kettle for precipitation reaction, adding a saturated sodium carbonate solution into the lithium precipitation reaction kettle, reacting at normal temperature and continuously stirring to obtain lithium carbonate precipitate at the bottom of the reaction kettle;
s7, feeding the lithium carbonate precipitate into a centrifuge for solid-liquid separation, adjusting the pH of the obtained liquid phase, feeding the liquid phase into a concentration airing pool, returning the liquid phase to the lithium precipitation reaction kettle, feeding the residual solid into a countercurrent washing tower, and washing off the residual sodium chloride in the reaction;
s8, adjusting the pH of the washing liquid separated from the solid after the countercurrent washing treatment by the filter, then sending the washing liquid to a concentration airing pool, and adding the rest solid Li 2 CO 3 And drying by a drying device and packaging to form a final product.
Preferably, in the old brine dilution tank, the volume ratio of a barren solution generated by washing the added brackish water or fresh water or saturated adsorbent to the added old brine is 1/5-1/9.
Preferably, the lithium content of the tail liquid at the outlet of the primary adsorption tower is lower than 150 mg/L.
Preferably, the adsorbent in the deep magnesium removal tower can be regenerated by three-stage leaching with sodium chloride-containing washing liquor.
Preferably, the evaporation device consists of a sun-drying pool solar energy concentration device and a boiler forced evaporation concentration device.
Preferably, the reverse osmosis membrane in the reverse osmosis device is mainly made of cellulose acetate and aromatic polyamide materials or a composite membrane consisting of the two materials, the reverse osmosis device operates for 1-2 days, and 1-3% of NaHSO is used 3 The aqueous solution of (a) is maintained and cleaned.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention has simple process, no strict requirement on the magnesium/lithium ratio of the salt lake brine, high selectivity of the lithium salt by adopting the high-efficiency ion exchange adsorbent, high recovery rate and high product purity, can eliminate the interference of a large amount of coexisting alkali metal and alkaline earth metal ions in the brine, has strong process stability, and the preparation method of the adsorbent is simple, renewable and low in price, and is suitable for large-scale operation and use.
2. All tail liquid involved in the invention can be returned to a salt field, no harm can be brought to ecological balance and living environment, the flue gas discharged by a hot blast stove and a heat supply boiler is discharged through a chimney 30 meters after dust removal during product drying, no pollution can be caused to the atmospheric environment, the used resin has stable performance, is insoluble in water, is not decomposed, nonvolatile, renewable, and has no solid waste, the production process is a normal-pressure reaction, the reaction temperature is close to normal temperature, and the danger is small in the production process. The process has good environmental benefit, safety guarantee and social benefit, and is a green production process.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a flow chart of a preliminary adsorption magnesium removal working section in the production process for extracting lithium from brine by an efficient adsorption method provided by the invention;
FIG. 2 is a flow chart of a deep magnesium removal concentration working section in the production process for extracting lithium from brine by an efficient adsorption method provided by the invention;
FIG. 3 is a flow chart of a lithium precipitation reaction section in the production process for extracting lithium from brine by using an efficient adsorption method.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: 5 ten thousand t/a lithium carbonate production
As shown in fig. 1-3, a production device for extracting lithium from brine by a high-efficiency adsorption method comprises a preliminary adsorption magnesium removal working section, a deep magnesium removal concentration working section and a lithium precipitation reaction working section;
the preliminary magnesium adsorption and removal section comprises: a old brine dilution tank and a primary adsorption tower;
the deep magnesium removal concentration section comprises: a primary deep magnesium removal tower, a secondary magnesium removal leacheate storage pool, a reverse osmosis device, an evaporation device, a primary filtering device and a precise filtering device;
the lithium precipitation reaction section comprises: the device comprises a lithium precipitation reaction kettle, a centrifugal machine, a concentration airing pool, a countercurrent washing tower, a filter and a dryer;
old bittern dilution tank links to each other with preliminary adsorption tower upper portion, the ejection of compact links to each other with the first degree of depth degummed top of the tower at the bottom of the preliminary adsorption tower, the first degree of depth degummed bottom links to each other with the second degree of depth degummed top of the tower, the second degree of depth degummed bottom of the tower is through secondary degummed leacheate reservoir, reverse osmosis unit connection evaporation plant, evaporation plant passes through preliminary filter equipment and links to each other with precision filtration device, precision filtration device links to each other with heavy lithium reation kettle, heavy lithium reation kettle passes through centrifuge's mother liquor discharge gate and concentrated pond of drying in the air and links to each other, centrifuge's solid discharge gate passes through countercurrent washing tower and connects the filter, filter filtrating links to each other with concentrated pond of drying in the air, the filter cake links to each other with drying device, weighing device is connected to drying device.
Furthermore, the adsorbent in the preliminary adsorption tower can selectively adsorb magnesium ions and lithium ions, and can be selected from ion sieve adsorbents, aluminum salt adsorbents and natural mineral modified adsorbents.
The beneficial effects of the further technical scheme are that: the high-efficiency regenerable adsorbent with high selectivity and low price is adopted to primarily remove magnesium ions in the old brine, so that the overall adsorption efficiency is greatly improved.
Furthermore, an organic adsorption resin adsorbent or an inorganic adsorbent, preferably cation exchange resin, is selected in the primary deep magnesium removal tower and the secondary deep magnesium removal tower.
The beneficial effects of the further technical scheme are that: the deep magnesium removal tower selects cation exchange resin with high selectivity as an adsorbent, so that magnesium ions in the qualified liquid are deeply removed, and the purity and the quality of a final product are improved.
Furthermore, the primary filtering device can select a plate filter, a vertical filter press and a belt filter, and the plate filter is preferred.
The beneficial effects of the further technical scheme are that: most solid particles in the penetrating fluid at the outlet of the reverse osmosis device are removed, the pressure of a next precision filtering device is reduced, and the purity of the refined high-lithium solution is improved.
The operation process of the device is as follows:
s1 old brine of salt field from tank field (flow rate 135.6 m) 3 H) firstly enters an old brine diluting tank, and a barren solution or brackish water or fresh water (with the flow rate of 20.3 m) generated by washing the old brine diluting tank with a saturated adsorbent is added 3 Diluting the salt field old brine, feeding the diluted salt field old brine from the upper part of the primary adsorption tower, selectively adsorbing magnesium and lithium ions by an adsorbent in the tower, wherein the contact time is 6min, the linear speed of an empty tower is 15.8m/h, the adsorption tail liquid flowing out of a tower kettle can directly return to the salt field without pollution, the adsorption is stopped until the adsorbent is saturated, the total adsorption time is 267min, the adsorption condition is normal temperature and normal pressure, and the aluminum salt adsorbent is used;
s2, blowing compressed air (three atmospheric pressures, airspeed of 2 m/S) from the top of the tower after the adsorbent in the primary adsorption tower is saturated, blowing out the residual brine in the primary adsorption tower to return to the old brine dilution tank, wherein the time for use is 7min, and quickly introducing fresh water or brackish water (flow of 594 m) from the top of the primary adsorption tower after blowing off the residual brine in the tower completely 3 The linear speed of the empty tower is 58m/h, the contact time is less than 2min, and the total time is less than 10 min) takes away part of magnesium ions absorbed in the absorbent, and the magnesium ions return to the old brine diluting tank;
s3, dividing the preliminary adsorption tower into three sections, desorbing the saturated adsorbent which is blown clean and washed away with magnesium ions, introducing fresh water from the top of the lower section or the outlet of the reverse osmosis device for leaching (6 BV, contact time 7min, superficial tower linear speed 16.3m/h, flow 174.6 m 3 H, the total time is 75 min), obtaining a second barren solution at the bottom of the tower, and returning the second barren solution to the absorption towerAdding tower, introducing from the upper part of the middle section, continuously leaching (passing the second barren solution for 6BV, contact time of 7min, flow rate of 174.3 m) 3 At an empty column linear speed of 16.3m/h, and 75min in common), a barren solution is obtained at the bottom of the column, and a part of barren solution flows in from the top of the preliminary adsorption column (the barren solution passes through 6BV, the contact time is 14min, and the flow rate is 93.4 m 3 The linear speed of the empty tower is 5.3m/h, and the total time is 150 min), the other part of the waste bittern is removed from a waste bittern diluting tank to dilute the waste bittern, qualified liquid containing lithium ions (containing lithium 370-400 mg/L and magnesium less than 3 g/L) is obtained at the tower bottom, the primary adsorbent of the adsorption tower after desorption can be recycled, leaching is carried out at normal temperature and normal pressure, lithium in the first barren solution is 200-300 mg/L, and lithium in the second barren solution is 350-380 mg/L;
s4, the qualified lithium-containing liquid obtained by leaching in the primary adsorption tower sequentially enters a primary deep magnesium removal tower and a secondary deep magnesium removal tower, the qualified lithium-containing liquid enters a tower kettle from the top of the tower and is discharged from the tower kettle, the primary deep magnesium removal tower passes through 12BV, the contact time is 7min, and the flow rate is 235.6m 3 The linear speed of the empty tower is 17.6m/h, the use time is 150min, the effluent liquid with the lower value of 5-12 BV enters a secondary deep magnesium removal tower, the magnesium ion content in the qualified lithium-containing liquid is further removed by using an adsorbent with higher selectivity and adsorption capacity in the deep magnesium removal tower, the leacheate after deep magnesium removal enters a secondary magnesium removal leacheate storage pool, the temperature and the pressure are normal, the magnesium content after deep magnesium removal is less than 0.1mg/L, and the adsorbent is polystyrene organic adsorption resin;
s5, concentrating the secondary magnesium-removing eluent in a reverse osmosis device to obtain fresh water which is mixed with 1% of NaCl and Li 2 CO 3 Washing the product, returning to a primary adsorption tower for desorption and elution to serve as eluent, enabling the penetrating fluid to enter an evaporation device, further concentrating a lithium-containing solution to obtain a high-lithium mother solution (containing 18.6g/L lithium), enabling the high-lithium mother solution to sequentially enter a primary filtering device and a precise filtering device for refining, and obtaining a refined high-lithium solution at an outlet of the precise filtering device, wherein the filtering precision of the primary filtering device is more than or equal to 5 mu m, the filtering efficiency is 90%, and the filtering precision of the precise filtering device is more than or equal to 0.3 mu m, and the filtering efficiency is 99.9%;
s6, feeding the refined high-lithium mother liquor into a lithium precipitation reaction kettle for precipitation reaction, and adding a saturated sodium carbonate solution (preferably sodium carbonate NaCO) into the lithium precipitation reaction kettle 3 ) The volume of the added soda ash solution is fine high-lithium solution2-3 times, reacting at normal temperature and continuously stirring to obtain lithium carbonate (Li) at the bottom of the reaction kettle 2 CO 3 ) Precipitating;
s7, precipitating, refining and separating lithium carbonate, then, feeding the lithium carbonate into a centrifuge for solid-liquid separation, adjusting the pH of the obtained liquid phase to 3-8, then, feeding the liquid phase into a concentration airing pool, returning the liquid phase to a lithium precipitation reaction kettle, feeding the residual solid into a countercurrent washing tower, washing out reaction residual sodium chloride (NaCl), washing with fresh water, wherein S: L =1:3, and stirring for 30min at normal temperature;
s8, separating washing liquor from the solid subjected to the countercurrent washing treatment through a centrifugal filter, adjusting the pH value to 4.5-5.5, feeding the washing liquor to a concentration airing pool, and feeding the rest solid Li 2 CO 3 And drying by a drying device and packaging to form a final product.
Furthermore, in the old brine dilution tank, the volume ratio of the barren solution or brackish water or fresh water generated by the saturated adsorption method water washing and the added old brine is 1/5-1/9, and the added dilution solution accounts for 14.97% of the volume of the old brine in the embodiment.
The beneficial effects of the further technical scheme are that: the liquid entering the primary adsorption tower can be ensured to have proper adsorption concentration by selecting proper dilution proportion, and the adsorption efficiency of the adsorbent is improved.
Further, the lithium content of the tail liquid at the outlet of the primary adsorption tower is lower than 150 mg/L.
The beneficial effects of the further technical scheme are as follows: the high-efficiency absorption of the primary absorption tower can reduce the lithium content in the tail liquid, improve the utilization rate of lithium ions in the raw materials and improve the yield.
Furthermore, the adsorbent in the deep magnesium removal tower can be regenerated by three-stage leaching through sodium chloride-containing washing liquor.
The beneficial effects of the further technical scheme are that: cation exchange resin is selected as an adsorbent in the deep magnesium removal tower, so that the cost can be greatly reduced by realizing the regeneration of the adsorbent, the generation of solid waste is prevented, and the cyclic utilization of resources is realized.
Furthermore, the evaporation device consists of a sun-drying pool solar energy concentration and a boiler forced evaporation concentration.
The beneficial effects of the further technical scheme are that: firstly, a solar energy concentration mode is adopted, the inherent advantage of sufficient sunshine near a salt lake is fully utilized, energy is reasonably utilized, the forced evaporation treatment capacity of a boiler is reduced, the energy consumption is greatly reduced, and the green chemical process is realized.
Furthermore, a reverse osmosis membrane in the reverse osmosis device mainly adopts cellulose acetate and aromatic polyamide materials or a composite membrane consisting of the two materials, the reverse osmosis device operates for 1-2 days, and 1-3% of NaHSO is required to be used 3 The aqueous solution of (a) is maintained and cleaned.
The beneficial effects of the further technical scheme are that: the efficient reverse osmosis membrane is selected for use, so that the working efficiency of the reverse osmosis device can be improved, the concentration efficiency is improved, the working stability and the working time of the reverse osmosis membrane can be improved by regularly maintaining the reverse osmosis membrane, and the economic benefit is enlarged.
Furthermore, an imported PLC control system is designed to be used as a computer control system of the processing plant, and energy (water, steam, gas and electricity) metering systems are arranged among all production devices so as to realize energy consumption metering and cost accounting management of all the devices.
The beneficial effects of the further technical scheme are that: the comprehensive detection and control of all parameters of all sections of the whole process by adopting an advanced computer control system are an important part of modern factory production, so that the production efficiency is greatly improved, the accurate determination of control is improved, and the method is safer and more efficient.
According to the production device and the production process of the production device for extracting lithium from brine by using the efficient adsorption method, the composition of the final lithium carbonate product obtained after implementation is detailed in table 1.
TABLE 1 lithium carbonate product composition
| Serial number | Substance(s) | Content (mass fraction%) |
| 1 | Li 2 CO 3 | ≥99.0 |
| 2 | Na 2 O | ≤0.2 |
| 3 | Fe 2 O 3 | ≤0.008 |
| 4 | CaO | ≤0.040 |
| 5 | SO 4 2- | ≤0.2 |
| 6 | Cl - | ≤0.005 |
| 7 | H 2 O | ≤0.5 |
| 8 | Hydrochloric acid insoluble substance | ≤0.01 |
| 9 | MgO | ≤0.037 |
According to the detection results in table 1, the lithium carbonate production process disclosed by the invention can completely meet the content requirements on particulate matters and metal ion impurities, and the high-efficiency adsorbent is adopted, so that the lithium carbonate production process has the advantages of high selectivity, high recovery rate and high product purity, and is suitable for large-scale industrial production. The lithium carbonate belongs to a high-end product, and the process has good environmental benefit, social benefit and economic benefit.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A production device for extracting lithium from brine by a high-efficiency adsorption method is characterized by comprising a preliminary adsorption magnesium removal working section, a deep magnesium removal concentration working section and a lithium precipitation reaction working section;
the preliminary magnesium adsorption and removal section comprises: a old brine dilution tank and a primary adsorption tower;
the deep magnesium removal concentration section comprises: a primary deep magnesium removal tower, a secondary magnesium removal leacheate storage pool, a reverse osmosis device, an evaporation device, a primary filtering device and a precise filtering device;
the lithium precipitation reaction section comprises: the device comprises a lithium precipitation reaction kettle, a centrifugal machine, a concentration airing pool, a countercurrent washing tower, a filter and a dryer;
old bittern dilution tank links to each other with preliminary adsorption tower upper portion, the ejection of compact links to each other with the first degree of depth degummed top of the tower at the bottom of the preliminary adsorption tower, the first degree of depth degummed bottom links to each other with the second degree of depth degummed top of the tower, the second degree of depth degummed bottom of the tower is through secondary degummed leacheate reservoir, reverse osmosis unit connection evaporation plant, evaporation plant passes through preliminary filter equipment and links to each other with precision filtration device, precision filtration device links to each other with heavy lithium reation kettle, heavy lithium reation kettle passes through centrifuge's mother liquor discharge gate and concentrated pond of drying in the air and links to each other, centrifuge's solid discharge gate passes through countercurrent washing tower and connects the filter, filter filtrating links to each other with concentrated pond of drying in the air, the filter cake links to each other with drying device, weighing device is connected to drying device.
2. The production device according to claim 1, wherein the adsorbent in the preliminary adsorption tower is selected from an ion sieve adsorbent, an aluminum salt adsorbent or a natural mineral modified adsorbent; the adsorbent in the primary deep magnesium removal tower and the secondary deep magnesium removal tower is selected from an organic adsorbent resin adsorbent or an inorganic adsorbent; the adsorbent in the deep magnesium removal tower is cation exchange resin.
3. The production device according to claim 1, wherein the preliminary filtering device is a plate and frame filter, a vertical filter press or a belt filter.
4. The method for extracting lithium from brine by using the high-efficiency adsorption method by using the production device of any one of claims 1 to 3 is characterized by comprising the following steps of:
s1, conveying the old brine of the salt pan into an old brine diluting tank, adding brackish water or fresh water or a barren solution generated by washing with a saturated adsorbent into the old brine diluting tank, diluting the old brine of the salt pan, conveying the diluted old brine of the salt pan into a primary adsorption tower from the upper part of the primary adsorption tower, selectively adsorbing magnesium and lithium ions by the adsorbent in the tower, directly returning the adsorption tail solution flowing out of the tower kettle to the salt pan without pollution until the adsorbent is saturated, and stopping;
s2, blowing compressed air into the preliminary absorption tower from the top of the tower after the absorbent is saturated, returning the blown residual brine in the preliminary absorption tower to the old brine dilution tank, blowing off the residual brine in the preliminary absorption tower, quickly introducing fresh water or brackish water from the top of the preliminary absorption tower to take away part of magnesium ions absorbed in the absorbent, and returning the magnesium ions to the old brine dilution tank;
s3, dividing a saturated adsorption tower into an upper section, a middle section and a lower section, leaching the saturated adsorbent which is blown clean and washed away with magnesium ions, introducing fresh water or the fresh water discharged by a reverse osmosis device from the top of the lower section for leaching, obtaining a second barren solution at the bottom of the tower, returning the second barren solution to the upper part of the middle section of the primary adsorption tower for continuous leaching, obtaining a barren solution at the tower kettle, returning part of the first barren solution to the top of the primary adsorption tower for inflow, obtaining lithium-containing qualified solution at the tower kettle, and removing the other part of the barren solution from a old brine dilution tank to dilute old brine; the primary adsorption tower adsorbent after desorption can be recycled;
s4, enabling the qualified lithium-containing liquid obtained by leaching in the primary adsorption tower to sequentially enter a primary deep magnesium removal tower and a secondary deep magnesium removal tower, wherein the tops of the towers enter a tower kettle and are discharged out of the tower, further removing the content of magnesium ions in the qualified lithium-containing liquid, and enabling the leacheate subjected to deep magnesium removal to enter a secondary magnesium removal leacheate storage pool;
s5, feeding the secondary magnesium-removing eluent into a reverse osmosis device for concentration, returning the obtained fresh water to the primary adsorption tower to be used as the eluent in the desorption and elution stages, feeding the penetrating fluid into an evaporation device for further concentration of a lithium-containing solution to obtain a high-lithium mother solution, feeding the high-lithium mother solution into a primary filtering device and a precise filtering device in sequence for refining, and obtaining a refined high-lithium solution at the outlet of the precise filtering device;
s6, allowing the refined high-lithium mother liquor to enter a lithium precipitation reaction kettle for precipitation reaction, adding a saturated sodium carbonate solution into the lithium precipitation reaction kettle, reacting at normal temperature and continuously stirring to obtain lithium carbonate precipitate at the bottom of the reaction kettle;
s7, feeding the lithium carbonate precipitate into a centrifuge for solid-liquid separation, adjusting the pH of the obtained liquid phase, feeding the liquid phase into a concentration airing pool, returning the liquid phase to the lithium precipitation reaction kettle, feeding the residual solid into a countercurrent washing tower, and washing off the residual sodium chloride in the reaction;
s8, adjusting the pH of the washing liquid separated from the solid after the countercurrent washing treatment by the filter, then sending the washing liquid to a concentration airing pool, and adding the rest solid Li 2 CO 3 And drying by a drying device and packaging to form a final product.
5. The method for extracting lithium from brine by using the high-efficiency adsorption method according to claim 4, wherein the volume ratio of a barren solution generated by water washing of brackish water or fresh water or a saturated adsorbent added into the old brine dilution tank to the old brine added is 1/5-1/9.
6. The method for extracting lithium from brine by using a high efficiency adsorption method according to claim 4, wherein the lithium content of the tail liquid at the outlet of the primary adsorption tower is lower than 150 mg/L.
7. The method for extracting lithium from brine by using a high-efficiency adsorption method according to claim 4, wherein the adsorbent in the deep magnesium removal tower can be regenerated by three-stage leaching with a sodium chloride-containing washing solution.
8. The method for extracting lithium from brine by using a high efficiency adsorption method according to claim 4, wherein the evaporation device consists of a solar concentration in a sunning pond and a boiler forced evaporation concentration.
9. The method for extracting lithium from brine through high-efficiency adsorption method according to claim 4, wherein reverse osmosis membrane in the reverse osmosis device is mainly made of cellulose acetate, aromatic polyamide material or composite membrane made of two materials, the reverse osmosis device is operated for 1-2 days, and 1-3% of NaHSO is used 3 The aqueous solution of (a) is maintained and cleaned.
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