CN118558703A - Method for harmless treatment of lithium slag to remove thallium and beryllium - Google Patents
Method for harmless treatment of lithium slag to remove thallium and beryllium Download PDFInfo
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Abstract
本发明就是要提供一种锂渣无害化处理去除铊、铍的方法，克服上述困难，以锂云母提锂后的废锂渣为主要原料，采用球磨机械与添加化学药剂进行化学处理等工艺相结合的方法，通过将废锂渣进一步研磨破碎，增加废锂渣的表面积使后续稳定化反应更彻底，同时释放被废锂渣包裹的可溶性盐钾、钠、铍、铊，使其在搅洗时能够溶解至水中；同时通过机械球磨能够将一部分不溶锂转化为可溶锂增加金属锂的回收率，并通过水洗与喷淋洗涤等方式，去除废锂渣中的铍、铊等有害元素，使处理后的锂渣铍铊达标，处理后的锂渣中的铍、铊含量如下：Tl<0.01mg/L、Be<0.02mg/L。有利于资源化利用；更环保、更安全；同时实现对废锂渣的再利用。The present invention is to provide a method for harmlessly treating lithium slag to remove thallium and beryllium, overcome the above difficulties, take the waste lithium slag after lithium extraction from lepidolite as the main raw material, adopt a method combining ball milling machinery with chemical treatment by adding chemical agents, further grind and crush the waste lithium slag, increase the surface area of the waste lithium slag, make the subsequent stabilization reaction more thorough, and release the soluble salt potassium, sodium, beryllium and thallium wrapped by the waste lithium slag, so that it can be dissolved in water during stirring and washing; at the same time, a part of insoluble lithium can be converted into soluble lithium by mechanical ball milling to increase the recovery rate of metallic lithium, and remove harmful elements such as beryllium and thallium in the waste lithium slag by water washing and spray washing, so that the beryllium and thallium content of the treated lithium slag meet the standards, and the beryllium and thallium content in the treated lithium slag are as follows: Tl<0.01mg/L, Be<0.02mg/L. It is conducive to resource utilization; more environmentally friendly and safer; and the waste lithium slag can be reused at the same time.
Description
Technical Field
The invention relates to the field of innocent treatment of waste lithium slag, in particular to a method for innocent treatment of waste lithium slag after lithium extraction, namely a method for removing thallium and beryllium by innocent treatment of lithium slag.
Background
With the use of lithium as an important raw material for new energy lithium batteries, the new energy industry of lithium batteries has been developed explosively. Because of the abundant reserves of the lithium ore resources in China, the exploitation and smelting of the lithium ore resources are also unprecedented. However, although the extraction of lithium meets the development requirement of new energy sources of lithium batteries, the development of the lithium batteries has more and more influence on environment and resources with the continuous growth and deep exploitation and smelting. Especially, the influence of the heavy metal elements such as beryllium, thallium and the like on the social environment is not visible in the waste lithium slag generated after the exploitation and smelting of the lithium ores, if the content of the heavy metal elements such as beryllium, thallium and the like in the waste lithium slag is too high after the extraction of lithium by taking lepidolite as a raw material, the waste lithium slag can be converted into dangerous solid waste raw materials to exist, and is not general solid waste, so that the sites, the surrounding environments and the like for piling up the waste lithium slag are greatly damaged. Therefore, the removal of the waste lithium slag after the extraction of lithium or the reduction of the contents of beryllium, thallium and other heavy metal elements is particularly urgent.
The lithium battery industry is also used as a support industry of Yichun, the development and utilization scale of lepidolite is continuously expanded along with the improvement of the output of lithium carbonate in the whole market, the output of lithium carbonate in Yichun is expected to reach 50 ten thousand tons in 2025, and about 1500 ten thousand tons of lithium slag or waste lithium slag are generated at that time. Through detection by related departments, the lithium slag component in the city of China contains various elements such as silicon, rubidium, cesium, sodium, potassium and the like, and is an important material for producing products such as special glass, monocrystalline silicon, phototubes and the like. However, the lithium slag also contains trace beryllium and thallium elements to different degrees due to the inherent components of the lepidolite ore, and often exceeds the standard. And the heavy metals such as beryllium, thallium and the like and the compounds thereof are easy to cause environmental pollution, and have great threat risk to human health. Therefore, the problems of high or low content of beryllium and thallium in the waste lithium slag limit the application of the lithium slag, and harmless treatment of the lithium slag containing beryllium and thallium is needed. However, the prior art has less research on treatment of waste lithium slag containing beryllium and thallium, and is only temporarily stored in a warehouse stacking mode at present, but the temporary storage mode has the problems of large land occupation area, possible secondary pollution and the like. Therefore, the harmless and quantitative reduction treatment is carried out on the beryllium and thallium in the lithium slag containing the beryllium and thallium, so that the environment is not polluted, and the method has important significance for the healthy and benign development of the lepidolite lithium extraction industry.
The invention provides a method for treating beryllium thallium ions in lithium mine tailings, which is disclosed in Chinese patent publication No. CN118045850A, and comprises the following steps: step a: adding water into the synthesized medicament A, adding the mixture into the crushed and sieved raw slag, uniformly mixing and adsorbing the mixture, and maintaining the mixture for three to six hours; step b: adding a reagent B on the basis of the previous step to complex ore beryllium thallium ions on the surface of the reticular polymer, uniformly mixing and adsorbing the ore beryllium thallium ions with a treated substance, and curing for three to six hours; step c: and (c) after the treatment is finished, performing solid-liquid separation by using a horizontal oscillation method to test the concentration of beryllium thallium ions in the ore, wherein in the step (a), firstly, the raw slag is collected and stored in a container by a worker, and then, the raw slag in the container is put into a pulverizer for pulverization. The method for treating the beryllium thallium ions in the lithium mine tailings has high-efficiency treatment.
According to the technical scheme disclosed above, the method for treating heavy metals in the tailings of the treated lithium ore is firstly to treat beryllium thallium in the tailings of the raw material lepidolite ore flotation lithium concentrate, the content of beryllium thallium in the tailings is relatively low, and the method is not to treat harmless beryllium and thallium removal from lithium waste residues after lithium extraction by the processes of calcining, leaching and the like after lithium extraction by the lithium ore or lepidolite ore. Meanwhile, the treatment process is correspondingly complex, and the treatment cost is high.
Therefore, how to provide a method for removing thallium and beryllium by harmless treatment of lithium slag, which uses waste lithium slag after lithium extraction of lepidolite as a main raw material, adopts a ball milling machine, a chemical agent adding and other technological methods, and further grinds and breaks the waste lithium slag to increase the surface area of the waste lithium slag so as to enable the subsequent stabilizing and mixing reaction to be more thorough, and simultaneously releases soluble salt potassium, sodium, beryllium and thallium wrapped by the waste lithium slag so as to enable the soluble salt potassium, sodium, beryllium and thallium to be dissolved into water during stirring and washing; meanwhile, a part of insoluble lithium can be converted into soluble lithium through mechanical ball milling, so that the recovery rate of metal lithium is increased, and the recycling utilization is facilitated. And adding chemical precipitation reagent to precipitate beryllium and thallium, and filtering to form solid waste residue for dangerous waste treatment. The utilization rate of the waste lithium slag is improved, the production cost of extracting lithium is reduced, and resources are effectively utilized.
Disclosure of Invention
The invention aims to provide a method for removing thallium and beryllium by harmless treatment of lithium slag, which overcomes the above difficulties, and adopts a method of combining ball milling machinery with chemical treatment and other processes by adding chemical agents to the waste lithium slag as a main raw material, and further grinding and crushing the waste lithium slag to increase the surface area of the waste lithium slag so as to enable the subsequent stabilization reaction to be more thorough, and simultaneously release soluble salt potassium, sodium, beryllium and thallium wrapped by the waste lithium slag so as to enable the soluble salt potassium, sodium, beryllium and thallium to be dissolved into water during stirring and washing; meanwhile, a part of insoluble lithium can be converted into soluble lithium through mechanical ball milling, so that the recovery rate of metal lithium is increased, and harmful elements such as beryllium, thallium and the like in waste lithium slag are removed through modes such as water washing, spray washing and the like, so that the recycling utilization is facilitated; the environment is more friendly and safer; and simultaneously, the recycling of the waste lithium slag is realized.
The invention discloses a method for removing thallium and beryllium by harmless treatment of lithium slag, which takes waste lithium slag after lithium extraction as a raw material, and comprises the following steps:
1) Ball milling, namely fully mixing the waste lithium slag with an alkaline medicament to obtain a mixed solution of the waste lithium slag and the alkaline medicament; placing the mixed solution of the waste lithium slag and the alkaline agent into a ball milling device for ball milling treatment to obtain a ball milling mixed material of the waste lithium slag and the alkaline agent;
2) Washing, namely adding a hot water solution into the ball-milling mixture of the waste lithium slag and the alkaline agent in the step 1), controlling the mixture to be fully stirred and washed under alkaline conditions, and filtering to obtain stirring and washing lithium slag and stirring and washing liquid;
3) Performing multi-stage spray filtration, namely performing spray washing on the stirring and washing lithium slag obtained in the step 2) by using spray water by using a spray device, so that the beryllium and thallium contents in the stirring and washing lithium slag are greatly reduced, and spray washing liquid and spray filter residues are obtained;
4) Stabilizing treatment, namely adding a stabilizing agent into the sprayed filter residues in the step 3), and carrying out a mixing reaction on the premise of continuously stirring and mixing; washing with hot water after the mixed reaction is finished, and filtering to obtain filtered residues and filtrate;
5) Innocuous beryllium and thallium removal treatment, namely collecting stirring and spraying washing liquid and filtrate, adding a precipitation reagent X into the stirring and washing liquid, fully stirring and mixing the stirring and washing liquid and the filtrate, performing beryllium and thallium removal treatment, precipitating beryllium thallium enriched in the solution, and performing solid-liquid separation through a filter to obtain beryllium-containing thallium filter residues and filter pressing liquid; the separated beryllium-containing thallium filter residues are collected as hazardous waste in a centralized manner and are treated by a company with hazardous waste treatment qualification, and filter pressing liquid is recovered and enters a normal production procedure of lithium carbonate for use.
In the method for removing thallium and beryllium by harmless treatment of lithium slag, in the step 1), the alkaline agent is a mixture of sodium hydroxide and calcium hydroxide; controlling the adding amount of the alkaline agent to be 0.5-5.5% of the mass of the waste lithium slag; and controlling the pH value of the mixed solution of the waste lithium slag and the alkaline agent to be 10-11.5.
The method for removing thallium and beryllium by harmless treatment of lithium slag is preferably as follows: in the step 1), the liquid-solid ratio during ball milling is controlled to be 0.5:0.8-1, controlling the ball milling time to be 1-2 hours, and controlling the particle size of the solid phase waste lithium slag to be 80-150 meshes.
Further is: step 2) washing, namely controlling the temperature of hot water for washing to be more than 40 ℃, controlling the stirring washing time to be more than 10 minutes/time each time, and repeating the stirring washing operation for a plurality of times; and each stirring and washing is controlled to be carried out under the weak alkaline condition, so that beryllium and thallium in the waste lithium slag enter the stirring and washing liquid as much as possible.
The method for removing thallium and beryllium by harmless treatment of lithium slag comprises the following steps of 3) performing fixed-distance spray washing on stirring lithium slag by using condensed hot water and other recovered water, controlling the temperature of the spray water to be 40-60 ℃, and controlling the spray washing times to be 10-15.
The method for removing thallium and beryllium by harmless treatment of lithium slag comprises the following steps that in the step 4), the stabilizing agent is a mixture of phosphate and silicate; the phosphate is trisodium phosphate and/or disodium phosphate, and the silicate is sodium silicate; controlling the adding amount of the stabilizing agent to be 20-50kg of stabilizing agent per 1000kg of waste lithium slag; the mixing reaction time is controlled to be 1-4 hours.
In the method for removing thallium and beryllium by harmless treatment of lithium slag, in the step 5), the precipitation reagent X is sodium sulfide or hydrogen sulfide solution.
Further is: the stabilizing agent is phosphate and silicate with the mass ratio of 2-5: 95-98.
The invention discloses a method for removing thallium and beryllium by harmless treatment of lithium slag, which comprises the following steps: mixing waste lithium slag with alkaline agent, ball milling the waste lithium slag with alkaline agent, pulping, multi-stage stirring and washing of slurry, filtering and separating, stirring and washing the lithium slag, multi-stage spraying, filtering, stabilizing treatment, stirring and washing liquid and spraying washing liquid, precipitating reagent X, and recycling other filtrate.
The invention discloses a method for removing thallium and beryllium by harmless treatment of lithium slag, provides a new path for harmless treatment of beryllium and thallium by double-tube control of 'washing before stabilizing'. Through repeated detection and verification by a third party, the purpose of removing harmful metal elements such as beryllium, thallium and the like in the waste lithium slag to a large extent in the waste lithium slag after the lithium extraction is achieved, and meanwhile, the effect of further recycling the metal elements such as lithium and the like in the waste lithium slag can be achieved. The technical effects of thallium <0.01mg/L, beryllium <0.02mg/L, fluorine <100mg/L and the like in the detection of the leaching toxicity of the waste lithium slag. The thallium and beryllium contents in the treated waste lithium slag meet the requirements of common solid waste within the above range.
The invention discloses a method for removing thallium and beryllium by harmless treatment of lithium slag, which is characterized in that the basic principle of removing beryllium and thallium from waste lithium slag is mainly that double salt precipitation and lattice transformation mineralization are carried out, and the treated beryllium thallium element exists in a natural mineral phase, has long-term super stability, and accords with common solid waste standards when the treated lithium slag is subjected to toxic leaching. The main reaction formula is as follows:
Tl3++PO4 3-=TlPO4↓
Be2++2SiO2+Al203+CaO = BeAl2Si2O8+Ca2+
BeM+2SiO2+Al203+CaO = BeAl2Si2O8+CaM
Wherein M is one or more anions such as SO 4 2-、OH-、F-、Cl-.
And (3) washing the filtrate with lithium slag to precipitate beryllium thallium removal: the filtrate (brine) after the lithium slag water washing solid-liquid separation is used for precipitating the beryllium-thallium-removal sludge, so that the problem of 'outlet' of the beryllium thallium is solved for the harmless treatment and circulation operation of the lithium slag, and the main reaction formula is as follows:
Be2++S2- = BeS↓
2Tl3++3S2- = Tl2S3↓
According to the method for removing thallium and beryllium by harmless treatment of lithium slag, disclosed by the invention, the lithium slag or waste lithium slag is treated by adopting a water washing and stabilizing treatment process technology, so that the problem of exceeding standard of the beryllium thallium in the lithium slag can be solved under the double guarantee effect. Firstly, washing water to dissolve soluble beryllium thallium in lithium slag into water, and reducing the beryllium thallium in the lithium slag; secondly, undissolved and residual beryllium thallium reacts with excessive stabilizing agent to generate double salt precipitation, lattice transformation and mineralization to natural mineral phase temperature, so that the treated lithium slag beryllium thallium reaches the standard, and the content of beryllium and thallium in the lithium slag treated by the method is as follows when the leaching toxicity is detected: tl <0.01mg/L, be <0.02mg/L.
By utilizing the method for removing thallium and beryllium by harmless treatment of lithium slag, disclosed by the invention, after the harmless thallium removal and beryllium removal treatment of lithium slag or waste lithium slag which takes lepidolite as a raw material are performed, the result is detected by a certain experimental test team in geological bureau of Jiangxi province, namely, hazard specific identification detection is performed, and the results all meet the requirements, namely, all meet the general solid waste standard. The specific results are as follows:
report number: the loop check words 2024-0962,
Sample name: the lithium slag or the waste lithium slag,
Unit of inspection: the inventor's company,
Sample state: solid body
Standard method and number of detection basis: TABLE 1
The test results in the following examples were all carried out according to the above-mentioned standards and methods.
The waste lithium slag after the following treatment is detected according to GB5085.6-2007, dangerous waste identification standard, toxic substance content identification requirement, GB5085.3-2007, dangerous waste identification standard and toxic substance content identification requirement.
Detailed Description
The specific technical scheme of the invention is further described in detail below by referring to examples, wherein the examples relate to the components in parts by mass or mass ratio, the concentrations relate to the components in mass concentration, and the examples of the invention use lithium slag which is obtained by extracting lithium from solid lithium-containing raw materials such as lepidolite or spodumene or waste lithium slag as raw materials. The raw material components in the following examples are all commercially available.
The invention discloses a method for removing thallium and beryllium by harmless treatment of lithium slag, which takes waste lithium slag after lithium extraction as a raw material; ball milling is carried out according to the following method, 1) waste lithium slag and an alkaline agent are fully mixed, and the alkaline agent is the mixture of sodium hydroxide and calcium hydroxide; controlling the adding amount of the alkaline agent to be 0.5-5.5% of the mass of the waste lithium slag; and controlling the pH value of the mixed solution of the waste lithium slag and the alkaline medicament to be 11.48; is a mixed solution of waste lithium slag and alkaline agent; placing the waste lithium slag and alkaline agent mixed solution into a ball milling device for ball milling treatment; meanwhile, the liquid-solid ratio during ball milling is controlled to be 0.5:0.8-1, controlling the ball milling time to be 1-2 hours, and controlling the ball milling until the particle size of the solid waste lithium slag is 80-150 meshes, wherein the solid waste lithium slag and the alkaline agent are ball milling mixture;
2) Washing, namely adding hot water solution into the ball-milling mixture of the waste lithium slag and the alkaline agent in the step 1), and controlling to fully stir and wash under alkaline conditions, wherein the washing is to control the temperature of hot water for washing to be above 40 ℃, control the stirring and washing time to be about 10 minutes/time each time, and repeat the stirring and washing operation for a plurality of times; according to the embodiment, stirring and washing are determined for 10-15 times according to a detection result, each stirring and washing is controlled to be carried out under a weak alkaline condition, beryllium and thallium in waste lithium slag enter a stirring and washing liquid as much as possible, and stirring and washing lithium slag and the stirring and washing liquid are obtained through filtration;
3) Performing multi-stage spray filtration, namely performing spray washing on the stirring and washing lithium slag obtained in the step 2) by using spray water in a spray device, so that the beryllium and thallium contents in the stirring and washing lithium slag are greatly reduced, wherein the spray water is condensed hot water and other recovered water, performing fixed-distance spray washing on the stirring and washing lithium slag, controlling the temperature of the spray water to be 40-60 ℃, and controlling the spray washing times to be 10-15 times; obtaining spray washing liquid and spray filter residues;
4) Stabilizing treatment, namely adding a stabilizing agent into the sprayed filter residues in the step 3), and carrying out a mixing reaction on the premise of continuously stirring and mixing; washing with hot water after the mixed reaction is finished, wherein the stabilizing agent is a mixture of phosphate and silicate; the phosphate is trisodium phosphate and/or disodium phosphate, and the silicate is sodium silicate; controlling the adding amount of the stabilizing agent to be 25kg of stabilizing agent per 1000kg of waste lithium slag; the stabilizing agent is phosphate and silicate with the mass ratio of 2-5: 98-95. Controlling the mixing reaction time to be 1-4 hours; filtering to obtain filtered residue and filtrate;
5) Innocuous beryllium and thallium removal treatment, namely collecting stirring and spraying washing liquid and filtrate, adding a precipitation reagent X into the stirring and washing liquid, fully stirring and mixing the stirring and washing liquid and the filtrate, performing beryllium and thallium removal treatment, precipitating beryllium thallium enriched in the solution, and performing solid-liquid separation through a filter to obtain beryllium-containing thallium filter residues and filter pressing liquid; the precipitation reagent X is sodium sulfide or hydrogen sulfide solution; the addition amount of the precipitation reagent X sodium sulfide or hydrogen sulfide solution is controlled to ensure that thallium and beryllium in the mixed solution of the stirring and spraying liquid and the filtrate completely form sulfide salt, and the sulfide salt is filtered and filtered after precipitation and enters filter residues to be collected and treated as dangerous waste. The filtrate obtained by filtration meets the requirements of thallium and beryllium detection, and is recycled after being recovered; the separated beryllium-containing thallium filter residues are collected as hazardous waste in a centralized way and are treated by a company with hazardous waste treatment qualification, and the filter pressing liquid is recycled and enters a normal production procedure of lithium carbonate for use.
Examples
The method for removing thallium and beryllium by harmless treatment of lithium slag is disclosed in the embodiment, wherein waste lithium slag after lithium extraction is used as a raw material, and the contents of thallium and beryllium in the raw material are as follows:
The method comprises the following steps: the raw materials used in this example are waste lithium slag after lithium extraction produced by enterprises, and the main chemical components are as follows, with the remainder being other components in table 2.
Table 2 report number of the raw materials of lithium slag waste after lithium extraction: the loop check words 2024-0962;
Description: 1. harmful component mass concentration limit (mg/L) in the leaching solution, be (mg/L) 0.02, fluoride ion: 100 mg/L.
2. The detection method and the detection device are carried out according to the method and the device in the table 1.
The lithium slag raw material described in the above table 2 is subjected to harmless treatment for removing thallium, beryllium and other harmful substances such as fluorine and the like, and is subjected to 1) ball milling, and the waste lithium slag and an alkaline agent are fully mixed to obtain a mixed solution of the waste lithium slag and the alkaline agent; placing the waste lithium slag and alkaline agent mixed solution into a ball milling device for ball milling treatment, wherein the alkaline agent is mixed by 50% of sodium hydroxide and calcium hydroxide in mass ratio; controlling the adding amount of the alkaline agent to be 2.5-3.5% of the mass of the waste lithium slag; and controlling the pH value of the mixed solution of the waste lithium slag and the alkaline agent to be 10-11.5; meanwhile, the liquid-solid ratio during ball milling is controlled to be 0.5:0.8, controlling the ball milling time to be 1-2 hours, and controlling the ball milling until the particle size of the solid-phase waste lithium slag is 80-150 meshes, wherein the solid-phase waste lithium slag and the alkaline agent are ball milling mixture;
2) Washing, namely adding hot water solution into the ball-milling mixture of the waste lithium slag and the alkaline agent in the step 1), and controlling to fully stir and wash under alkaline conditions, wherein the washing is to control the temperature of hot water for washing to be above 40 ℃, control the stirring and washing time to be above 10 minutes/time each time, and repeat the stirring and washing operation for a plurality of times; the washing times are 11 times, each stirring washing is controlled to be carried out under the weak alkaline condition, namely pH is between 10 and 11, beryllium and thallium in the waste lithium slag enter the stirring washing liquid as much as possible, and the stirring washing liquid are obtained through filtration.
3) Performing multi-stage spray filtration, namely performing spray washing on the stirring and washing lithium slag in the step 2) by using spray water in a spray device, so that the beryllium and thallium contents in the stirring and washing lithium slag or the washing lithium slag are greatly reduced, wherein the spray water is condensed hot water and other recovered water, performing fixed-distance spray washing on the stirring and washing lithium slag, controlling the temperature of the spray water to be about 45 ℃, and controlling the spray washing times to be 11 times; obtaining spray washing liquid and spray filter residues;
4) Stabilizing treatment, namely adding a stabilizing agent into the sprayed filter residues in the step 3), and carrying out a mixing reaction on the premise of continuously stirring and mixing; washing with hot water after the mixed reaction is finished, wherein the stabilizing agent is a mixture of phosphate and silicate; the phosphate is trisodium phosphate, and the silicate is sodium silicate; controlling the adding amount of the stabilizing agent to be 25kg of stabilizing agent in every 1000kg of waste lithium slag; the stabilizing agent is phosphate and silicate with the mass ratio of 5: 95. Controlling the mixing reaction time to be 1-4 hours; filtering to obtain filter residue and filtrate.
The contents of thallium and beryllium which are main harmful substances in the mixed liquid, namely stirring washing liquid, spraying washing liquid and filtrate after detection are shown in the following table 3:
6) Innocuous beryllium and thallium removal treatment, namely collecting stirring and spraying washing liquid and filtrate, adding a precipitation reagent X into the stirring and washing liquid, fully stirring and mixing the stirring and washing liquid and the filtrate, performing beryllium and thallium removal treatment, precipitating beryllium thallium enriched in the solution, and performing solid-liquid separation through a filter to obtain beryllium-containing thallium filter residues and filter pressing liquid; the precipitation reagent X is sodium sulfide solution; the adding amount of the precipitation reagent X sodium sulfide solution is controlled to ensure that thallium and beryllium in the mixed solution of the stirring solution, the spraying solution and the filtrate completely form sulfide salts, namely thallium sulfide and beryllium sulfide, and the thallium and the beryllium sulfide enter filter residues through filter pressing after precipitation and are collected and treated as hazardous waste materials. The filtrate obtained by filtration meets the requirements of thallium and beryllium detection, and is recycled after being recovered; the separated beryllium-containing thallium filter residues are collected as hazardous waste in a centralized way and are treated by a company with hazardous waste treatment qualification, and the filter pressing liquid is recycled and enters a normal production procedure of lithium carbonate for use.
The majority of the filter residues treated by the method are harmless lithium residues, the minority of the filter residues containing beryllium thallium are treated in a centralized manner as hazardous waste, and the harmful substances thallium and beryllium content in the harmless lithium residues are detected, and the detection results are detected by a detection mechanism in the aspect of third party environmental protection, as shown in the following table 4:
detection result, report number: ring check words 2024-0962, table 4
Description: 1. ND in Table 4 above indicates that the detected value is not detected, i.e., that the detected value is lower than the detection limit value. And thallium is also greatly reduced in the lithium slag after innocent treatment, namely, the thallium meets the current national environmental protection condition requirement value. No environmental impact is caused. The method is characterized in that thallium and beryllium are removed from the waste lithium slag in a harmless way, and the treated filter residue is the thallium and beryllium content in the harmless lithium slag is greatly reduced. The waste lithium slag is prepared according to GB5085.6-2007, dangerous waste identification standard, toxic substance content identification requirement, GB5085.3-2007, dangerous waste identification standard and toxic substance content identification requirement. Detection is performed via a related third party authority.
Examples
The following example 2 is the same as example 1 except for the following description.
The method comprises the following steps: the raw materials used in this example are waste lithium slag after lithium extraction produced by enterprises, and the main chemical components are as follows, the rest is as shown in table 5.
Table 5 report number by taking lithium extracted waste slag as raw material: the loop check words 2024-0962;
Description: 1. harmful component mass concentration limit (mg/L) in the leaching solution, be (mg/L) 0.02, fluoride ion: 100 mg/L.
2. The detection method and the detection device are carried out according to the method and the device in the table 1.
The lithium slag raw material described in the above table 5 is subjected to harmless treatment for removing thallium, beryllium and other harmful substances such as fluorine and the like, and is subjected to 1) ball milling, and the waste lithium slag and an alkaline agent are fully mixed to obtain a mixed solution of the waste lithium slag and the alkaline agent; placing the waste lithium slag and alkaline agent mixed solution into a ball milling device for ball milling treatment, wherein the alkaline agent is mixed with sodium hydroxide and calcium hydroxide according to the mass ratio of 50%; controlling the adding amount of the alkaline agent to be 1.5-2.5% of the mass of the waste lithium slag; and controlling the pH value of the mixed solution of the waste lithium slag and the alkaline agent to be 10-11.5; ball milling the waste lithium slag and the alkaline agent to obtain a mixture; meanwhile, the liquid-solid ratio during ball milling is controlled to be 0.5:1, controlling the ball milling time to be 1-2 hours, controlling the particle size of the solid-phase waste lithium slag to be 80-150 meshes,
2) Washing, namely adding hot water solution into the ball-milling mixture of the waste lithium slag and the alkaline agent in the step 1), and controlling to fully stir and wash under alkaline conditions, wherein the washing is to control the temperature of hot water for washing to be more than 48 ℃, control the stirring and washing time to be more than 10 minutes/time each time, and repeat the stirring and washing operation for a plurality of times; washing times are 13 times, each stirring and washing are controlled to be carried out under the weak alkaline condition, beryllium and thallium in the waste lithium slag enter the stirring and washing liquid as much as possible, and the stirring and washing lithium slag and the stirring and washing liquid are obtained through filtration.
3) Performing multistage spray filtration, namely spraying and washing the stirring and washing lithium slag in the step 2) by using spray water in a spray device, so that the beryllium and thallium contents in the washing lithium slag are greatly reduced, wherein the spray water is condensed hot water and other recovered water, the stirring and washing lithium slag is sprayed and washed at a certain distance, the temperature of the spray water is controlled to be about 48 ℃, and the spraying and washing times are controlled to be 13 times; obtaining spray washing liquid and spray filter residues;
4) Stabilizing treatment, namely adding a stabilizing agent into the sprayed filter residues in the step 3), and carrying out a mixing reaction on the premise of continuously stirring and mixing; washing with hot water after the mixed reaction is finished, wherein the stabilizing agent is a mixture of phosphate and silicate; the phosphate is trisodium phosphate, and the silicate is sodium silicate; controlling the adding amount of the stabilizing agent to be 35kg of stabilizing agent per 1000kg of waste lithium slag; the stabilizing agent is phosphate and silicate with the mass ratio of 2: 98. The mixing reaction time is controlled to be 1-4 hours. Filtering to obtain filter residue and filtrate.
The contents of thallium and beryllium which are main harmful substances in the mixed liquid, namely stirring washing liquid and spraying washing liquid and the filtrate are detected as shown in the following table 6:
7) Innocuous beryllium and thallium removal treatment, namely collecting stirring and spraying washing liquid and filtrate, adding a precipitation reagent X into the stirring and washing liquid, fully stirring and mixing the stirring and washing liquid and the filtrate, performing beryllium and thallium removal treatment, precipitating beryllium thallium enriched in the solution, and performing solid-liquid separation through a filter to obtain beryllium-containing thallium filter residues and filter pressing liquid; the precipitation reagent X is sodium sulfide solution; the adding amount of the precipitation reagent X sodium sulfide solution is controlled to ensure that thallium and beryllium in the mixed solution of the stirring and spraying solution and the filtrate completely form sulfide salt, and the sulfide salt is filtered and filtered after precipitation and enters filter residues to be used as dangerous waste for collection and treatment. The filtrate obtained by filtration meets the requirements of thallium and beryllium detection, and is recycled after being recovered; the separated beryllium-containing thallium filter residues are collected as hazardous waste in a centralized way and are treated by a company with hazardous waste treatment qualification, and the filter pressing liquid is recycled and enters a normal production procedure of lithium carbonate for use.
The majority of the filter residues treated by the method are harmless lithium residues, the minority of the filter residues containing beryllium thallium are treated in a centralized manner as hazardous waste, and the harmful substances thallium and beryllium content in the harmless lithium residues are detected, and the detection results are detected by a detection mechanism in the aspect of third party environmental protection, as shown in the following table 7:
Detection result, report number: ring check words 2024-0962, table 7
Description: 1. in table 7, ND indicates that the detection value is not detected, i.e., the detection value is lower than the detection limit value. And thallium is also greatly reduced in the lithium slag after innocent treatment, namely, the thallium meets the current national environmental protection condition requirement value. No environmental impact is caused. The method is characterized in that thallium and beryllium are removed from the waste lithium slag in a harmless way, and the treated filter residue is the thallium and beryllium content in the harmless lithium slag is greatly reduced. The thallium and beryllium content Tl in the harmless lithium slag treated by the method is less than 0.01mg/L, be <0.02mg/L, which is far lower than the requirement of the harmless content.
Examples
The non-illustrated parts of the embodiment are the same as those of the embodiments 1 and 2, but 4) the stabilization treatment is carried out, the stabilization reagent is added into the sprayed filter residue in the step 3), and the mixing reaction is carried out on the premise of continuously stirring and mixing; washing with hot water after the mixed reaction is finished, wherein the stabilizing agent is a mixture of phosphate and silicate; the phosphate is prepared by mixing 70% trisodium phosphate and 30% disodium phosphate according to mass percentage, and the silicate is sodium silicate; controlling the adding amount of the stabilizing agent to be 45kg of stabilizing agent per 1000kg of waste lithium slag; the stabilizing agent is phosphate and silicate with the mass ratio of 3: 97. The mixing reaction time is controlled to be 3-4 hours. Filtering to obtain filter residue and filtrate. Step 5) was the same as in example 2;
most of the filter residues treated by the method are harmless lithium residues, and the small part of the filter residues containing beryllium thallium are treated in a centralized manner as hazardous waste, and the harmful substances thallium and beryllium content in the harmless lithium residues are detected, and the detection results are detected by a detection mechanism in the aspect of third party environmental protection, as shown in the following table 8:
Detection result, report number: ring check 2024-0962, table 8
Description: 1. in table 8, ND indicates that the detection value is not detected, i.e., the detection value is lower than the detection limit value. And thallium is also greatly reduced in the lithium slag after innocent treatment, namely, the thallium meets the current national environmental protection condition requirement value. No environmental impact is caused. The method is characterized in that thallium and beryllium are removed from the waste lithium slag in a harmless way, and the treated filter residue is the thallium and beryllium content in the harmless lithium slag is greatly reduced.
The raw materials used in this comparative example were identical to those used in example 1, but the treatment method used was only a mechanical treatment method such as washing and spraying. The thallium and beryllium content in the treated lithium slag can not meet the requirements of innocent treatment of Tl <0.01mg/L and Be <0.02 mg/L.
The technical features not described in the present invention may be implemented by or using the prior art, and are not described herein.
Claims (8)
1. The method for removing thallium and beryllium by harmless treatment of lithium slag is characterized by taking waste lithium slag after lithium extraction as a raw material and comprising the following steps:
1) Ball milling, namely fully mixing the waste lithium slag with an alkaline medicament to obtain a mixed solution of the waste lithium slag and the alkaline medicament; placing the mixed solution of the waste lithium slag and the alkaline agent into a ball milling device for ball milling treatment to obtain a ball milling mixed material of the waste lithium slag and the alkaline agent;
2) Washing, namely adding a hot water solution into the ball-milling mixture of the waste lithium slag and the alkaline agent in the step 1), controlling the mixture to be fully stirred and washed under alkaline conditions, and filtering to obtain stirring and washing lithium slag and stirring and washing liquid;
3) Performing multi-stage spray filtration, namely performing spray washing on the stirring and washing lithium slag obtained in the step 2) by using spray water by using a spray device, so that the beryllium and thallium contents in the stirring and washing lithium slag are greatly reduced, and spray washing liquid and spray filter residues are obtained;
4) Stabilizing treatment, namely adding a stabilizing agent into the sprayed filter residues in the step 3), and carrying out a mixing reaction on the premise of continuously stirring and mixing; washing with hot water after the mixed reaction is finished, and filtering to obtain filtered residues and filtrate;
5) Harmless beryllium and thallium removal treatment, namely collecting stirring and spraying washing liquid and filtrate, adding a precipitation reagent X into the stirring and spraying washing liquid and filtrate, fully stirring and mixing, performing beryllium and thallium removal treatment, precipitating beryllium thallium enriched in the solution, and performing solid-liquid separation through a filter to obtain beryllium-containing thallium filter residues and filter pressing liquid; and the filter residues are collected intensively as hazardous waste and are treated by a company with hazardous waste treatment qualification, and the filter pressing liquid is recycled and enters a normal production process of lithium carbonate for use.
2. The method for removing thallium and beryllium by harmless treatment of lithium slag according to claim 1, which is characterized in that: in the step 1), the alkaline agent is a mixture of sodium hydroxide and calcium hydroxide; controlling the adding amount of the alkaline agent to be 0.5-5.5% of the mass of the waste lithium slag; and controlling the pH value of the mixed solution of the waste lithium slag and the alkaline agent to be 10-11.5.
3. The method for removing thallium and beryllium by harmless treatment of lithium slag according to claim 1, which is characterized in that: in the step 1), the liquid-solid ratio during ball milling is controlled to be 0.5:0.8-1, controlling the ball milling time to be 1-2 hours, and controlling the particle size of the solid phase waste lithium slag to be 80-150 meshes.
4. The method for removing thallium and beryllium by harmless treatment of lithium slag according to claim 1, which is characterized in that: step 2) washing, namely controlling the temperature of hot water for washing to be more than 40 ℃, controlling the stirring washing time to be more than 10 minutes/time each time, and repeating the stirring washing operation for a plurality of times; and each stirring and washing is controlled to be carried out under the weak alkaline condition, so that beryllium and thallium in the waste lithium slag enter the stirring and washing liquid as much as possible.
5. The method for removing thallium and beryllium by harmless treatment of lithium slag according to claim 1, which is characterized in that: and 3) spraying and washing the stirring and washing lithium slag at a fixed distance by using condensed hot water and other recovered water as the spraying water, wherein the temperature of the spraying water is controlled to be 40-60 ℃, and the spraying and washing times are controlled to be 10-15.
6. The method for removing thallium and beryllium by harmless treatment of lithium slag according to claim 1, which is characterized in that: step 4) the stabilizing agent is a mixture of phosphate and silicate; the phosphate is trisodium phosphate and/or disodium phosphate, and the silicate is sodium silicate; controlling the adding amount of the stabilizing agent to be 20-50kg of stabilizing agent per 1000kg of waste lithium slag; the mixing reaction time is controlled to be 1-4 hours.
7. The method for removing thallium and beryllium by harmless treatment of lithium slag according to claim 1, which is characterized in that: the precipitation reagent X in the step 5) is sodium sulfide or hydrogen sulfide solution.
8. The method for removing thallium and beryllium by harmless treatment of lithium slag as claimed in claim 6, which is characterized in that: the stabilizing agent is phosphate and silicate with the mass ratio of 2-5: 95-98.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119076563A (en) * | 2024-11-08 | 2024-12-06 | 中国科学院过程工程研究所 | A method for inhibiting beryllium leaching from lithium smelting slag |
| CN119120954A (en) * | 2024-09-12 | 2024-12-13 | 中国科学院过程工程研究所 | A microbubble oxidation leaching method for low-valent thallium |
| CN119120938A (en) * | 2024-09-12 | 2024-12-13 | 中国科学院过程工程研究所 | A beryllium dissolution curing agent and a method for stabilizing the curing of beryllium in beryllium-containing materials |
| CN119351786A (en) * | 2024-10-24 | 2025-01-24 | 中南大学 | Leaching agent for removing thallium and beryllium from lithium slag and its application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160045841A1 (en) * | 2013-03-15 | 2016-02-18 | Transtar Group, Ltd. | New and improved system for processing various chemicals and materials |
| CN109193064A (en) * | 2018-10-31 | 2019-01-11 | 中南大学 | A kind of method of waste power lithium battery valuable constituent sorting recycling |
| CN115558791A (en) * | 2022-09-08 | 2023-01-03 | 西北矿冶研究院 | A method for enriching and recovering valuable metals such as indium in copper-lead-zinc smelting slag |
| CN117509691A (en) * | 2023-12-26 | 2024-02-06 | 江西协成锂业有限公司 | A method for extracting lithium carbonate from lithium batteries |
| CN117568623A (en) * | 2023-11-17 | 2024-02-20 | 徐浩 | Process for extracting lithium-containing polymetallic brine from lithium ore hydrosmelting without waste tailings |
-
2024
- 2024-06-03 CN CN202410706222.9A patent/CN118558703B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160045841A1 (en) * | 2013-03-15 | 2016-02-18 | Transtar Group, Ltd. | New and improved system for processing various chemicals and materials |
| CN109193064A (en) * | 2018-10-31 | 2019-01-11 | 中南大学 | A kind of method of waste power lithium battery valuable constituent sorting recycling |
| CN115558791A (en) * | 2022-09-08 | 2023-01-03 | 西北矿冶研究院 | A method for enriching and recovering valuable metals such as indium in copper-lead-zinc smelting slag |
| CN117568623A (en) * | 2023-11-17 | 2024-02-20 | 徐浩 | Process for extracting lithium-containing polymetallic brine from lithium ore hydrosmelting without waste tailings |
| CN117509691A (en) * | 2023-12-26 | 2024-02-06 | 江西协成锂业有限公司 | A method for extracting lithium carbonate from lithium batteries |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119120954A (en) * | 2024-09-12 | 2024-12-13 | 中国科学院过程工程研究所 | A microbubble oxidation leaching method for low-valent thallium |
| CN119120938A (en) * | 2024-09-12 | 2024-12-13 | 中国科学院过程工程研究所 | A beryllium dissolution curing agent and a method for stabilizing the curing of beryllium in beryllium-containing materials |
| CN119351786A (en) * | 2024-10-24 | 2025-01-24 | 中南大学 | Leaching agent for removing thallium and beryllium from lithium slag and its application |
| CN119076563A (en) * | 2024-11-08 | 2024-12-06 | 中国科学院过程工程研究所 | A method for inhibiting beryllium leaching from lithium smelting slag |
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