CN109650413B - Method and system for enriching lithium from sodium aluminate solution in alumina plant - Google Patents
Method and system for enriching lithium from sodium aluminate solution in alumina plant Download PDFInfo
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Abstract
The invention discloses a method and a system for enriching lithium from a sodium aluminate solution in an alumina plant, the method comprises the steps of carrying out heat exchange and temperature reduction on the lithium-containing sodium aluminate solution, then reacting the lithium-containing sodium aluminate solution with an aluminum hydroxide adsorbent to deposit lithium, collecting filter cakes after filtration, heating the filter cakes for redissolution, filtering slurry after redissolution, pulping the obtained second filter cake, then carrying out filtration, and carrying out multiple countercurrent washing, wherein the obtained third filter cake is the lithium-enriched adsorbent; the system comprises an adsorption component, an adsorbent preparation tank, a first centrifugal pump, a first-stage heat exchanger, a second-stage heat exchanger, a first filtering component, a re-dissolving component, a second filtering component, a second centrifugal pump, a third filtering component and a third centrifugal pump. The invention firstly provides and applies the aluminum hydroxide crystal seed to prepare the adsorbent to adsorb lithium in a lithium-rich sodium aluminate solution system, thereby realizing the high-efficiency separation of lithium; the rapid and efficient separation is realized by utilizing cooling adsorption and rapid heating filtration; further enrichment of lithium in the adsorbent by re-dissolution of the adsorbent creates favorable conditions for subsequent extraction of lithium salts.
Description
Technical Field
The invention belongs to the technical field of inorganic chemical industry, and relates to a method for extracting lithium salt with high added value from refined solution in alumina production by a Bayer process or a sintering process, in particular to a method and a system for enriching lithium from sodium aluminate solution in an alumina plant.
Background
Lithium carbonate, an inorganic compound of the formula Li2CO3The crystal is colorless monoclinic crystal or white powder. Density 2.11g/cm3Melting point 618 ℃, soluble in dilute acid, slightly soluble in water, more soluble in cold water than in hot water, insoluble in alcohol and acetone. The method is widely applied to industries such as batteries, ceramic glass, lubricants, pharmacy and the like.
Lithium carbonate is a basic material for producing secondary lithium salts and lithium metal products, so that the lithium carbonate becomes a lithium product with the largest usage amount in the lithium industry, and other lithium products are downstream products of lithium carbonate. The production process of lithium carbonate can be divided into salt lake brine extraction and ore extraction according to different raw material sources. At present, the lithium carbonate is mainly produced by a salt lake brine extraction process abroad, and the solid ore extraction process is mainly adopted in China. Although China is also actively exploiting the lithium resources in the salt lake, the development speed is relatively slow due to the limitation of factors such as technology, resources and the like.
The process for extracting lithium from ore comprises the following steps: the extraction of lithium from the ore is mainly to produce lithium carbonate and other lithium products by using solid lithium ores such as spodumene, lepidolite and the like. The history of extracting lithium resources from ores is long, the technology is mature, and the main production processes include a lime sintering method and a sulfuric acid method, wherein the sulfuric acid method is the main method used at present, and a process flow chart is shown in fig. 1.
The process for extracting lithium from salt lake brine comprises the following steps: the process for extracting lithium from salt lake brine refers to extracting lithium carbonate and other lithium salt products from the salt lake brine containing lithium. At present, salt lake brine extraction technologies adopted in the world mainly comprise a precipitation method (a carbonate precipitation method, an aluminate precipitation method, a boron-magnesium and boron-lithium coprecipitation method), a calcination leaching method, a carbonization method, a solvent extraction method, an ion exchange method and the like, wherein the solvent extraction method and the ion exchange method are not applied to large-scale industrialization. Typical process flow diagrams of the precipitation method, the calcination leaching method and the ion exchange method are respectively shown in FIG. 2, FIG. 3 and FIG. 4.
In recent years, with the rapid development and popularization of new energy technology in China, the production scale of lithium ion batteries is rapidly increased, so that the lithium carbonate market is in a short supply and demand situation for a long time, high-quality spodumene ore in China is deficient, high-magnesium brine magnesium and lithium in salt lake in China are difficult to separate, and the huge capacity increase of lithium industry in China is limited, so that the supply is insufficient.
According to the research results of Li Chunhao et al (Li Chunhao, Huangjia, the existence behavior of lithium in the process of producing alumina, Li Chunhao, light metals, No. 6 in 2005, P17-19), lithium entering into the sodium aluminate solution is separated out along with aluminum hydroxide in the subsequent seed precipitation or carbon precipitation and enters into aluminum hydroxide crystals, and the mother liquor has no residue basically, so the lithium cannot be accumulated. The new process separates a small amount of lithium in the sodium aluminate fine solution from the sodium aluminate solution through a precipitator before seed precipitation, and further purifies the lithium into a qualified lithium carbonate product, so that the lithium extracting raw material is developed for China and even the world, and the significance of improving the economic benefit of the alumina industry is particularly great.
In the middle area of China, general bauxite has high lithium content, taking a depressed mountain mining area in Xinan county in Henan province as an example, the average content of lithium oxide is about 0.085%, lithium is dispersed and exists in minerals such as bauxite, kaolinite, illite and the like (Jiqinghai, Jiguo and the like, research on geological characteristics and associated elements of bauxite in Xinan county, Yushan in No. 3 of 2014, P10-14), about 80% of lithium enters into a solution in the process of dissolving out by a Bayer process, 20% of lithium is discharged along with red mud, and lithium entering into a sodium aluminate solution finally enters into finished alumina, wherein Table 1 is the determination of the content of lithium oxide in alumina products of several main alumina enterprises in the middle area of China, and the data source is a detection center of Zhengzhou light metal research institute.
TABLE 1 lithium content in partial alumina plant finished product alumina in the middle part of China
| Factory | Li2O，％ |
| A plant | 0.094 |
| B plant | 0.11 |
| C plant | 0.13 |
| D plant | 0.12 |
| E plant | 0.13 |
As can be seen from Table 1, Li in alumina plant products in the middle of China2O is generally higher and is usually imported into alumina Li2O is only 0.006%, if estimated at 0.1%, alumina production is estimated at 1200 million tons/year, Li taken over per year by metallurgical grade alumina2O is as high as 12000 tons, these lithium resources are not reasonably utilized, and what is more, lithium enrichment in the electrolyte of the electrolytic plant using lithium-rich alumina as a raw material for a long time exceeds a reasonable interval, which leads to deterioration of the working condition of the electrolytic cell, and in turn, lithium-rich alumina has to be used in a limited amount.
The examination and reading of relevant documents at home and abroad does not report that lithium is enriched in a sodium aluminate solution in an alumina factory.
Therefore, the invention provides the method for enriching lithium from the middle part of lithium-rich aluminum oxide plant concentrate, which not only reasonably utilizes resources, but also improves the quality of aluminum oxide and solves the worries of an electrolysis plant.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method and a system for enriching lithium from a sodium aluminate solution in an alumina plant.
According to one aspect of the present invention there is provided a process for the enrichment of lithium from sodium aluminate liquors of an alumina plant, comprising:
s1, cooling the lithium-containing sodium aluminate solution in an alumina plant to 60-85 ℃, then shunting 2-5% of the cooled sodium aluminate solution, adding aluminum hydroxide seed crystals to prepare an aluminum hydroxide adsorbent, reacting the rest of the cooled lithium-containing sodium aluminate solution with the aluminum hydroxide adsorbent to precipitate lithium, controlling the addition amount of the aluminum hydroxide adsorbent to be 1-10g/l, heating the adsorbent-containing slurry to 95-105 ℃ after full reaction, then filtering the adsorbent-containing slurry, returning the obtained first filtrate to the alumina plant for seed precipitation, and collecting a first filter cake for later use;
s2, adding the circulating mother liquor of the alumina plant into the first filter cake, heating to boiling for redissolving, controlling partial alumina to be dissolved, and further enriching lithium in the residual aluminum hydroxide adsorbent;
and S3, filtering the re-dissolved slurry, returning the obtained second filtrate, converging the second filtrate with a lithium-containing sodium aluminate solution from an alumina plant for reaction and lithium precipitation, pulping the second filter cake, filtering and carrying out multiple times of countercurrent washing, and obtaining a third filter cake which is the lithium-rich adsorbent.
In the above technical scheme, in step S1, the adsorption reaction temperature of the aluminum hydroxide adsorbent is 60-85 ℃, and the reaction time is 1-6 h.
Further, in the above technical solution, in step S1, after the lithium-containing sodium aluminate solution in the alumina plant is subjected to primary heat exchange with the fully reacted adsorbent-containing slurry, the temperature is reduced to 60-85 ℃, and then the adsorbent-containing slurry is subjected to secondary heat exchange with low-pressure steam, and the temperature is increased to 95-105 ℃.
Still further, in the above technical solution, in step S3, the countercurrent washing is N times of countercurrent washing, where N is a positive integer greater than 3, where a first washing solution returns to an alumina plant to contain a lithium sodium aluminate solution, a second filtrate is merged and reacts with an aluminum hydroxide adsorbent to precipitate lithium, a second washing solution slurries the second filter cake and then filters the second filter cake, the three-time washing solution to the N-time washing solution are used for filter cake leaching in the countercurrent washing process, and the last washing solution is leached with clean hot water.
In the above technical solution, in step S2, the first filter cake is heated to boiling for redissolution by low-pressure steam after being added to the circulating mother liquor of the alumina plant.
According to another aspect of the present invention, there is provided a system for enriching lithium from a sodium aluminate solution in an alumina plant, comprising:
the adsorption component is used for carrying out lithium deposition reaction on the lithium-containing sodium aluminate solution;
the discharge end of the adsorbent preparation tank is connected with the adsorption component through a first centrifugal pump;
the primary heat exchanger is used for carrying out primary heat exchange on lithium-containing refined liquid in an alumina plant and adsorbent-containing slurry, the feeding end of the adsorption assembly is connected with the feeding end of the adsorbent preparation tank in parallel and is connected with the lithium-containing sodium aluminate solution discharging end of the alumina plant of the primary heat exchanger, and the feeding end of the adsorbent-containing slurry in the primary heat exchanger is connected with the discharging end of the adsorption assembly;
the secondary heat exchanger is used for carrying out secondary heat exchange on the adsorbent-containing slurry and low-pressure steam, and the adsorbent-containing slurry feeding end of the secondary heat exchanger is connected with the adsorbent-containing slurry discharging end of the primary heat exchanger;
the first filter assembly is used for filtering the adsorbent in the adsorbent-containing slurry, and the feed end and the filtrate outlet of the first filter assembly are respectively connected with the discharge end of the adsorbent-containing slurry of the secondary heat exchanger and the branch feed end of the alumina plant;
the re-dissolving component is used for heating re-dissolving reaction, the feed end of the re-dissolving component is connected with the filter cake outlet of the first filtering component, the heat medium inlet of the re-dissolving component is connected with the heat medium inlet of the secondary heat exchanger in parallel, the heat medium adopts low-pressure steam, and the heating mode is indirect heating;
the second filtering component is used for filtering the slurry after re-dissolution, the feed end of the second filtering component is connected with the discharge end of the re-dissolution component through a second centrifugal pump, and the filtrate outlet is connected with the feed end of the adsorption component;
the slurry dissolving tank is used for carrying out slurry dissolving on the second filter cake obtained in the second filtering component, and a first inlet of the slurry dissolving tank is connected with a filter cake outlet of the second filtering component;
and the third filtering component is used for filtering the slurry after the slurry is slurried, and the feed end of the third filtering component is connected with the discharge end of the slurry tank through a third centrifugal pump.
In the technical scheme, the third filtering component comprises a vacuum disc filter, a primary washing liquid tank, a secondary washing liquid tank, a tertiary washing liquid tank and a quartic washing liquid tank, the vacuum disc filter adopts a tertiary countercurrent washing process, filtrate of the vacuum disc filter respectively enters the primary washing liquid tank, the secondary washing liquid tank, the tertiary washing liquid tank and the quartic washing liquid tank, the primary washing liquid tank and the secondary washing liquid tank are respectively communicated with the adsorption component and the slurry dissolving tank, the tertiary washing liquid tank and the quartic washing liquid tank are respectively connected with a primary washing liquid inlet and a secondary washing liquid inlet of the vacuum disc filter, and a last washing liquid inlet of the vacuum disc filter is communicated with clean hot water.
In the above technical solution, the adsorption assembly includes three adsorption tanks connected in series, wherein the first adsorption tank is connected to the discharge end of the adsorbent preparation tank through a first centrifugal pump, and is connected to the discharge end of the lithium-containing sodium aluminate solution in the alumina plant of the primary heat exchanger after being connected in parallel to the feed end of the adsorbent preparation tank, and the discharge end of the third adsorption tank is connected to the feed end of the adsorbent-containing slurry in the primary heat exchanger.
In the technical scheme, the redissolving assembly comprises two redissolving tanks connected in series, wherein the feed end of the first redissolving tank is connected with the filter cake outlet of the first filtering assembly, the discharge end of the second redissolving tank is connected with the feed end of the second filtering assembly through a second centrifugal pump, the heat medium inlets of the first redissolving tank and the second redissolving tank are connected in parallel with the heat medium inlet of the secondary heat exchanger, the heat medium adopts low-pressure steam, and the heating modes are indirect heating.
Further, in the technical scheme, the adsorption component is a normal-pressure stirring tank made of carbon steel and having a heat preservation function.
Further, in the above technical solution, the primary heat exchanger is one of a double-pipe heat exchanger, a wide-flow-channel plate heat exchanger, and a tube-type heat exchanger.
Further, in the above technical solution, the secondary heat exchanger is one of a double-pipe heat exchanger, a wide-flow-channel plate heat exchanger, and a tube-type heat exchanger.
Further, in the above technical solution, the first filter assembly is a fully automatic vertical leaf filter.
Further, in the above technical scheme, the heating of the re-dissolving component adopts tube bundle heating or external casing pipe circulation heating.
Further, in the above technical solution, the second filtering assembly is a plate and frame filter press.
Further, in the above technical solution, the third filter assembly is one of a vacuum belt filter and a vacuum disc filter.
Compared with the prior art, the invention has the following beneficial effects:
(1) the new process is firstly proposed at home and abroad and applies the special aluminum hydroxide seed crystal prepared adsorbent to adsorb lithium in a lithium-rich sodium aluminate solution system, so that the high-efficiency separation of lithium in the sodium aluminate solution is realized, and the disturbance to the existing alumina production is minimized;
(2) the stability of the sodium aluminate solution is effectively controlled by using a method of temperature reduction adsorption and rapid temperature rise filtration, so that the rapid and efficient separation of the adsorbent is realized;
(3) the lithium in the adsorbent is further enriched by re-dissolving the adsorbent, and favorable conditions are created for subsequent extraction of lithium salt.
Drawings
FIG. 1 is a flow chart of a process for extracting lithium from spodumene by a sulfuric acid roasting method in the prior art;
FIG. 2 is a flow chart of a process for extracting lithium from concentrated brine by precipitation in the prior art;
FIG. 3 is a flow chart of a process for extracting lithium from brine by a calcination leaching method in the prior art;
FIG. 4 is a flow chart of a prior art process for extracting lithium from brine by ion exchange;
FIG. 5 is a flow chart of a process for enriching lithium from a sodium aluminate solution in an alumina plant in an embodiment of the present invention;
FIG. 6 is a schematic diagram showing the system composition for enriching lithium from sodium aluminate solution in alumina plant in accordance with the embodiment of the present invention;
in the figure:
the adsorption component 1 (a first adsorption tank 101, a second adsorption tank 102, a third adsorption tank 103), the adsorbent preparation tank 2, a first centrifugal pump 3, a first-stage heat exchanger 4, a second-stage heat exchanger 5, a first filtering component 6, a redissolution component 7 (a first redissolution tank 71, a second redissolution tank 72), a second filtering component 8, a second centrifugal pump 9, a slurry dissolving tank 10, a third filtering component 11 (a vacuum disc filter 111, a primary washing tank 112, a secondary washing tank 113, a tertiary washing tank 114, a quartic washing tank 115), and a third centrifugal pump 12.
Detailed Description
In order to facilitate an understanding of the present invention, the method and system for enriching lithium from a lithium-rich sodium aluminate liquor of an alumina plant of the present invention will be described in more detail with reference to the accompanying drawings and examples.
The preferred embodiment of the present invention is shown in the drawings; this invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, 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 in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Examples
As shown in fig. 6, the embodiment of the present invention provides a system for enriching lithium from a sodium aluminate solution in an alumina plant, which specifically includes an adsorption component 1, an adsorbent preparation tank 2, a first centrifugal pump 3, a primary heat exchanger 4, a secondary heat exchanger 5, a first filtering component 6, a re-dissolving component 7, a second filtering component 8, a second centrifugal pump 9, a slurrying tank 10, a third filtering group 11, and a third centrifugal pump 12.
Wherein:
the adsorption assembly 1 is used for carrying out lithium precipitation reaction on a lithium-containing sodium aluminate solution, and specifically comprises three adsorption tanks which are connected in series, wherein the adsorption tanks are conventional carbon steel normal-pressure stirring tanks with a heat preservation function, a first adsorption tank 101 is connected with a discharge end of an adsorbent preparation tank 2 through a first centrifugal pump 3, and a discharge end of a third adsorption tank 103 is connected with a feed end of adsorbent-containing slurry of a primary heat exchanger 4;
the adsorbent preparation tank 2 is used for preparing an aluminum hydroxide adsorbent, and the feed end of the adsorbent preparation tank 2 is connected in parallel with the first adsorption tank 101 and then connected with the lithium-containing sodium aluminate solution discharge end of the alumina plant of the primary heat exchanger 4;
the primary heat exchanger 4 is used for primary heat exchange between lithium-containing sodium aluminate solution and adsorbent-containing slurry in an alumina plant, the feed end of the adsorbent-containing slurry in the primary heat exchanger 4 is connected with the discharge end of the adsorption component 1, the feed end of the primary heat exchanger 4 is connected with a hot lithium-containing sodium aluminate solution pipeline, the primary heat exchanger 4 is one of a sleeve heat exchanger, a wide-flow-channel plate heat exchanger and a tubular heat exchanger, the primary heat exchanger 4 is preferably a multi-sleeve heat exchanger, a sleeve is designed into multiple passes, usually, the length of a single pass is controlled to be 40-80m, each pass is connected with a 180-degree elbow through a flange, the disassembly and the inspection are convenient, and the pipe diameters of inner and outer pipes of the sleeve are preferably selected to be the flow rate;
the secondary heat exchanger 5 is used for performing secondary heat exchange between adsorbent-containing slurry and low-pressure steam, a feed end of the adsorbent-containing slurry of the secondary heat exchanger 5 is connected with a discharge end of the adsorbent-containing slurry of the primary heat exchanger 4, a heat medium inlet of the secondary heat exchanger 5 is communicated with the low-pressure steam, and the secondary heat exchanger 5 is one of a double-pipe heat exchanger, a wide-flow-channel plate heat exchanger and a tubular heat exchanger;
the first filtering assembly 6 is used for filtering the adsorbent in the adsorbent-containing slurry, a feed end and a filtrate outlet of the first filtering assembly 6 are respectively connected with a discharge end of the adsorbent-containing slurry of the secondary heat exchanger 5 and a branch feed end of an alumina plant, and the first filtering assembly 6 is a fully automatic vertical leaf filter;
the redissolving assembly 7 is used for heating redissolving reaction, the redissolving assembly 7 comprises two redissolving tanks which are connected in series, the redissolving tanks are heated by adopting tube bundle heating or external casing circulation heating, wherein the feed end of a first redissolving tank 71 is connected with the filter cake outlet of the first filtering assembly 6, the discharge end of a second redissolving tank 72 is connected with the feed end of the second filtering assembly 8 through a second centrifugal pump 9, and the heat medium inlet of the first redissolving tank 71 and the heat medium inlet of the second redissolving tank 72 are connected in parallel with the heat medium inlet of the secondary heat exchanger 5 and communicated with low-pressure steam;
the second filtering assembly 8 is used for filtering the slurry after re-dissolution, the feed end of the second filtering assembly 8 is connected with the discharge end of the re-dissolution assembly 7 through a second centrifugal pump 9, the filtrate outlet of the second filtering assembly 8 is connected with the feed end of the first adsorption tank 101, and the second filtering assembly 8 is preferably a plate and frame filter press;
the slurry melting tank 10 is used for melting slurry of a second filter cake obtained in the second filtering component 8, and a first inlet of the slurry melting tank 9 is connected with a filter cake outlet of the second filtering component 8 through a screw conveyer;
the third filtering component 11 is used for filtering slurry after slurrying, a feed end of the third filtering component 11 is connected with a discharge end of the slurrying tank 9 through a third centrifugal pump 12, in detail, the third filtering component 11 comprises a vacuum disc filter 111, a primary washing liquid tank 112, a secondary washing liquid tank 113, a tertiary washing liquid tank 114 and a quaternary washing liquid tank 115, the vacuum disc filter 111 adopts a tertiary countercurrent washing process, filtrate of the vacuum disc filter 111 respectively enters the primary washing liquid tank 112, the secondary washing liquid tank 113, the tertiary washing liquid tank 114 and the quaternary washing liquid tank 115, the primary washing liquid tank 112 and the secondary washing liquid tank 113 are respectively communicated with the first adsorption tank 101 and the slurrying tank 10, the tertiary washing liquid tank 114 and the quaternary washing liquid tank 115 are respectively connected with a primary washing liquid inlet and a secondary washing liquid inlet of the vacuum disc filter 111, and the last washing liquid inlet of the vacuum disc type filter 111 is communicated with clean hot water.
The method for enriching lithium from sodium aluminate solution in alumina plant by using the system, as shown in figure 5, comprises the following steps:
s1, after the lithium-containing sodium aluminate solution at 95-105 ℃ in the alumina plant is subjected to primary heat exchange with the fully reacted adsorbent-containing slurry, reducing the temperature to 60-85 ℃, then adding an aluminum hydroxide seed crystal into the lithium-containing sodium aluminate solution with the temperature reduced by 2-5% to prepare an aluminum hydroxide adsorbent, reacting the rest lithium-containing sodium aluminate solution with the aluminum hydroxide adsorbent to deposit lithium, controlling the adsorption reaction temperature to be 60-85 ℃ and the reaction time to be 1-6h, controlling the addition amount of the aluminum hydroxide adsorbent to be 1-10g/l, then performing secondary heat exchange with low-pressure steam on the adsorbent-containing slurry, increasing the temperature to 95-105 ℃, then filtering the adsorbent-containing slurry, returning the obtained first filtrate to the alumina plant for seed separation, and collecting the first filtrate for later use;
s2, adding the circulating mother liquor of the alumina plant into the first filter cake, heating to boiling for redissolution through low-pressure steam, and controlling partial alumina to dissolve to further enrich lithium in the residual aluminum hydroxide adsorbent;
and S3, filtering the re-dissolved slurry, returning the obtained second filtrate, converging the second filtrate with the remaining lithium-containing sodium aluminate solution, reacting with the aluminum hydroxide adsorbent to precipitate lithium, filtering the second filter cake after slurrying, and performing multiple countercurrent washing to obtain a third filter cake, namely the lithium-rich adsorbent.
Specifically, the alumina plant concentrate contains Nk 160g/l, Rp 1.08, and Li+0.050g/l, temperature 102 deg.C, flow rate 150m3H, exchanging heat with the adsorption slurry (80 ℃) in a primary heat exchanger 4, raising the temperature of the adsorption slurry to 97 ℃, and reducing the temperature of the refined liquid to 85 ℃, wherein 145m3The cold sperm enters a first adsorption tank 101 with the specification of
The normal pressure stirring tanks are connected in series by 3 tanks, the retention time is controlled to be 5h and 5m3The cold refined liquid enters an adsorbent preparation tank 2, 10kg/h of special aluminum hydroxide seed crystal is additionally added to prepare the adsorbent, and the specification of the adsorbent preparation tank 2 is
1 stirring tank under normal pressure, and controlling the retention time for 30-50 h; 5m3The slurry of the adsorbent is pumped into the first adsorption tank 101Lithium is adsorbed, the addition amount of the corresponding adsorbent is 2-3g/l, the slurry exchanges heat in a primary heat exchanger 4 and a secondary heat exchanger 5 after the adsorption is finished, and the total heat exchange area of the primary heat exchanger 4 is 300m2And the heat exchange area of the secondary heat exchanger 5 is 20m2The temperature of the adsorption slurry reaches 102 ℃ after heat exchange by the secondary heat exchanger 5, and then the adsorption slurry enters a 226m2Filtering with vertical leaf filter, returning filtrate to alumina plant for seed separation, and filtering to obtain two filter cakes
Redissolving in a redissolving tank with a heating tube bundle, adding a circulating mother liquor in the redissolving tank, heating to boil by using low-pressure steam, and adjusting the adding amount of the circulating mother liquor according to the condition that the redissolving solution RP is 1.05-1.10 and the solid content is 10-30 g/l; the slurry after re-dissolution is subjected to two-stage separation, wherein the first-stage separation uses 120m2The rubber plate-and-frame filter press has rubber filter plate capable of resisting 110 deg.c, filter liquid returning to the first adsorption tank, filter cake entering one filter plate
Adding 2 times of washing liquid into a slurry tank (normal pressure stirring tank), pulping, and feeding the pulp into a two-stage vacuum tilting pan filter with the area of 20m2The two-stage disc-turning filter is used for carrying out primary separation and three-time countercurrent washing, primary separation washing liquor returns to the first adsorption tank, the washing water amount is controlled to be 1.5 times of the weight (dry) of a filter cake, the washing water temperature is 85-95 ℃, the filter cake attached alkali is less than 0.1%, the water content is less than 50%, and the filter cake is sent to the subsequent procedures for treatment.
Through three procedures of adsorption, re-dissolution and separation and washing, the lithium adsorption rate in the refined solution from an alumina factory reaches 75-90%, and the produced lithium-rich adsorbent contains Li2The O content reaches 4.0-6%, the purpose of separating and enriching lithium from the lithium-rich sodium aluminate concentrate (or crude) in the alumina plant is realized, the process and equipment have strong operability and low energy consumption, and the influence on the main flow path of alumina is minimum.
Finally, the above is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A system for enriching lithium from a sodium aluminate solution in an alumina plant, comprising:
an adsorption component (1) used for carrying out lithium deposition reaction on the lithium-containing sodium aluminate solution;
the device comprises an adsorbent preparation tank (2) for preparing an aluminum hydroxide adsorbent, wherein the discharge end of the adsorbent preparation tank (2) is connected with an adsorption component (1) through a first centrifugal pump (3);
the primary heat exchanger (4) is used for carrying out primary heat exchange on lithium-containing refined liquid in an alumina plant and adsorbent-containing slurry, the feeding end of the adsorption assembly (1) is connected with the feeding end of the adsorbent preparation tank (2) in parallel and is connected with the lithium-containing sodium aluminate solution discharging end of the alumina plant of the primary heat exchanger (4), and the adsorbent-containing slurry feeding end of the primary heat exchanger (4) is connected with the discharging end of the adsorption assembly (1);
a secondary heat exchanger (5) for performing secondary heat exchange between the adsorbent-containing slurry and low-pressure steam, wherein the adsorbent-containing slurry feeding end of the secondary heat exchanger (5) is connected with the adsorbent-containing slurry discharging end of the primary heat exchanger (4);
a first filter assembly (6) for filtering the adsorbent in the adsorbent-containing slurry, wherein the feed end and the filtrate outlet of the first filter assembly (6) are respectively connected with the discharge end of the adsorbent-containing slurry of the secondary heat exchanger (5) and the branch feed end of the alumina plant;
the redissolution component (7) is used for heating redissolution reaction, the feed end of the redissolution component (7) is connected with the filter cake outlet of the first filtering component (6), the heat medium inlet of the redissolution component (7) is connected with the heat medium inlet of the secondary heat exchanger (5) in parallel, the heat medium adopts low-pressure steam, and the heating mode is indirect heating;
the second filtering component (8) is used for filtering the slurry after re-dissolution, the feeding end of the second filtering component (8) is connected with the discharging end of the re-dissolution component (7) through a second centrifugal pump (9), and the filtrate outlet is connected with the feeding end of the adsorption component (1);
a slurry dissolving tank (10) for dissolving the second filter cake obtained in the second filtering assembly (8), wherein a first inlet of the slurry dissolving tank (10) is connected with a filter cake outlet of the second filtering assembly (8);
and the third filtering assembly (11) is used for filtering the slurried slurry, and the feeding end of the third filtering assembly (11) is connected with the discharging end of the slurrying tank (10) through a third centrifugal pump (12).
2. The system for enriching lithium from sodium aluminate solution in alumina plant according to claim 1, characterized in that the third filtering assembly (11) comprises a vacuum disc filter (111), a primary washing liquid tank (112), a secondary washing liquid tank (113), a tertiary washing liquid tank (114) and a quaternary washing liquid tank (115), the vacuum disc filter (111) adopts a tertiary countercurrent washing process, the filtrate of the vacuum disc filter (111) respectively enters the primary washing liquid tank (112), the secondary washing liquid tank (113), the tertiary washing liquid tank (114) and the quaternary washing liquid tank (115), the primary washing liquid tank (112) and the secondary washing liquid tank (113) are respectively communicated with the adsorption assembly (1) and the chemical pulp tank (10), the tertiary washing liquid tank (114) and the quaternary washing liquid tank (115) are respectively connected with the primary washing liquid inlet and the secondary washing liquid inlet of the vacuum disc filter (111), and the last washing liquid inlet of the vacuum disc type filter (111) is communicated with clean hot water.
3. The system for enriching lithium from alumina plant sodium aluminate solution according to claim 1, characterized in that the adsorption assembly (1) comprises three adsorption tanks connected in series, wherein, the first adsorption tank (101) is connected with the discharge end of the adsorbent preparation tank (2) through a first centrifugal pump (3), and is connected with the discharge end of the adsorbent preparation tank (2) in parallel and then connected with the cooled alumina plant lithium-containing sodium aluminate solution discharge end of the primary heat exchanger (4), and the discharge end of the third adsorption tank (103) is connected with the adsorbent-containing slurry feed end of the primary heat exchanger (4).
4. The system for enriching lithium from sodium aluminate solution in alumina plant according to claim 1, characterized in that the redissolution unit (7) comprises two redissolution tanks connected in series, wherein the feeding end of the first redissolution tank (71) is connected with the filter cake outlet of the first filter unit (6), the discharging end of the second redissolution tank (72) is connected with the feeding end of the second filter unit (8) through a second centrifugal pump (9), the heat medium inlets of the first redissolution tank (71) and the second redissolution tank (72) are connected with the heat medium inlet of the secondary heat exchanger (5) in parallel, the heat medium adopts low-pressure steam, and the heating modes are indirect heating.
5. System for the enrichment of lithium from sodium aluminate solutions of alumina plants according to any of claims 1 to 4, characterized in that,
the adsorption component (1) is a normal-pressure stirring tank made of conventional carbon steel and having a heat preservation function;
and/or the primary heat exchanger (4) is one of a double-pipe heat exchanger, a wide-runner plate heat exchanger and a shell-and-tube heat exchanger;
and/or the secondary heat exchanger (5) is one of a double-pipe heat exchanger, a wide-runner plate heat exchanger and a shell-and-tube heat exchanger;
and/or the first filtering component (6) is a full-automatic vertical leaf filter;
and/or the heating of the re-dissolving component (7) adopts tube bundle heating or external sleeve circulating heating;
and/or the second filtering component (8) is a plate-and-frame filter press;
and/or the third filter assembly (11) is one of a vacuum belt filter and a vacuum disc filter.
6. A method for enriching lithium from alumina plant sodium aluminate solution by using the system for enriching lithium from alumina plant sodium aluminate solution of any one of claims 1 to 5, which is characterized by comprising the following steps:
s1, cooling the lithium-containing sodium aluminate solution in an alumina plant to 60-85 ℃, then shunting 2-5% of the cooled sodium aluminate solution, adding aluminum hydroxide seed crystals to prepare an aluminum hydroxide adsorbent, reacting the rest of the cooled lithium-containing sodium aluminate solution with the aluminum hydroxide adsorbent to precipitate lithium, controlling the addition amount of the aluminum hydroxide adsorbent to be 1-10g/l, heating the adsorbent-containing slurry to 95-105 ℃ after full reaction, then filtering the adsorbent-containing slurry, returning the obtained first filtrate to the alumina plant for seed precipitation, and collecting a first filter cake for later use;
s2, adding the circulating mother liquor of the alumina plant into the first filter cake, heating to boiling for redissolving, controlling partial alumina to be dissolved, and further enriching lithium in the residual aluminum hydroxide adsorbent;
and S3, filtering the re-dissolved slurry, returning the obtained second filtrate, converging the second filtrate with a lithium-containing sodium aluminate solution from an alumina plant for reaction and lithium precipitation, pulping the second filter cake, filtering and carrying out multiple times of countercurrent washing, and obtaining a third filter cake which is the lithium-rich adsorbent.
7. The method of claim 6, wherein in step S1, the adsorption reaction temperature of the aluminum hydroxide adsorbent is 60-85 ℃ and the reaction time is 1-6 h.
8. The method according to claim 6, wherein in step S1, the temperature of the lithium-containing sodium aluminate solution in the alumina plant is reduced to 60-85 ℃ after the first heat exchange with the fully reacted sorbent-containing slurry, and then the sorbent-containing slurry is increased to 95-105 ℃ by the second heat exchange with low-pressure steam.
9. The method according to any one of claims 6 to 8, wherein in step S3, the countercurrent washing is N times of countercurrent washing, N is a positive integer greater than 3, wherein the first washing liquid returns to an alumina plant to contain the lithium sodium aluminate solution, the second filtrate is merged and reacts with the aluminum hydroxide adsorbent to precipitate lithium, the second washing liquid is used for pulping the second filter cake and then filtering, the three-time washing liquid to the N-time washing liquid are used for washing the filter cake in the countercurrent washing process, and the last washing liquid is used for washing with clean hot water.
10. The method of claim 6, wherein in step S2, the first filter cake is heated to boiling redissolution by low pressure steam after being added to the alumina plant recycle mother liquor.
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| CN111825152B (en) * | 2020-07-07 | 2022-11-01 | 西宁永正锂业有限公司 | Belt filter and application thereof in adsorption method brine lithium extraction |
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