CN114262794B - Method for comprehensively extracting valuable components such as rare elements, organic matters and the like from lignite - Google Patents
Method for comprehensively extracting valuable components such as rare elements, organic matters and the like from lignite Download PDFInfo
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Abstract
The invention discloses a method for comprehensively extracting valuable components such as rare elements, organic matters and the like from brown coal, which mainly comprises the following steps: (1) crushing raw coal; (2) Oxidizing pretreatment, namely preliminarily releasing rare metals such as germanium, gallium, rare earth and the like contained in the lignite; (3) Heating alkali treatment, namely deeply releasing rare metals in the lignite and dissolving alkali-soluble organic matters in the lignite; (4) Carrying out potential control acid treatment, precipitating acid insoluble organic matters from the alkali treatment liquid, and promoting the analysis of rare metals complexed by the organic matters; (5) Waste water treatment and circulation, wherein the neutralization and circulation of residual acid liquor and residual alkali liquor in the alkali treatment process are carried out after rare metals are extracted in the treatment process; according to the invention, on the premise of considering production cost, the production of residual organic matters in the lignite is realized while the extraction of rare metals in the lignite is carried out, the amount of residual solids is small, the construction is easy, most of residual acid-base solution in the treatment process can be processed in the process and recycled, and the process flow has the advantages of less environmental pollution, high economic benefit and high comprehensive utilization rate of valuable components.
Description
Technical Field
The invention discloses a method for comprehensively extracting valuable components such as rare elements and organic matters from lignite, and relates to the technical field of comprehensive recovery treatment of solid materials.
Background
Lignite is brown-black low-grade coal with the coal formation degree between peat and asphalt coal, is humic coal formed by the peat through diagenetic effect, and has the lowest coal formation degree. Lignite has the advantages of cleanliness, low volatility and low sulfur, but has the disadvantages of high humidity, low ignition point and high carbon dioxide emission. The lignite resource reserve in China is rich and about 2118 hundred million tons, and accounts for 13% of the national coal reserve, but the lignite resource reserve is regarded as inferior fuel due to the defects of high moisture, low heat value, easy spontaneous combustion and the like, so that the development of a non-fuel utilization technology of the lignite is very necessary, and the high value-added utilization of the lignite is realized.
Meanwhile, the lignite is rich in organic matter resources, and oxygen-containing chemicals can be obtained from the lignite. The humic acid in the organic matters can be used as a drilling mud regulator, an industrial water stabilizer, a cement water reducing agent, a boiler scale remover, an ore flotation agent, a waste gas and waste water treatment agent, a compound fertilizer and the like, can be widely applied to various fields of agriculture, forestry, pasture, petroleum, chemical industry, building materials, medicine sanitation, environmental protection and the like, shows strong vitality and has very broad prospect. In addition, organic matters in lignite are easy to adsorb rare metals such as germanium, gallium and rare earth. Taking germanium as an example, when the germanium content in the lignite is more than 20ppm, the reserve can be calculated to have a certain extraction value, the germanium-containing lignite in the inner Mongolia region is large in reserve, the germanium grade can reach 100-200 ppm, the estimated germanium reserve exceeds 4000 tons, and the estimated germanium reserve in the lignite in the Yunnan Shang, the Shandong, the Mang Hui and the like is 2177 tons in total. Therefore, the comprehensive utilization of the lignite is enhanced, the comprehensive recycling of valuable resources such as rare elements, organic matters, minerals and the like in the lignite is enhanced, the utilization value of coal is improved, and the method has important practical significance.
However, the comprehensive utilization rate of valuable components in the lignite is low at present, researches on extraction of rare elements in raw lignite are few, most of the researches are carried out around extraction of germanium in ash and gallium in fly ash, the acid content is high and the cost is high in the current wet extraction process, and the problems of low volatilization rate, long volatilization time and difficult guarantee of atmosphere exist in the pyrogenic extraction process. Research on extraction of rare earth from lignite is still in a starting stage, so that research and development of a method for comprehensively extracting valuable components such as rare elements and organic matters from lignite with high economic benefit and less environmental pollution is urgently needed.
Disclosure of Invention
The invention aims to provide a method for comprehensively extracting valuable components such as rare elements, organic matters and the like from lignite. Aiming at the problems of low comprehensive utilization rate of valuable components in lignite, more acid content, higher cost and low volatilization rate, long volatilization time and difficult guarantee of atmosphere in the process of extracting rare elements by a wet method, the invention provides a process for crushing raw coal, oxidizing pretreatment, heating alkali treatment, potential control acid treatment, wastewater treatment and circulation on the premise of considering production cost and provides a promising method for comprehensively extracting the valuable components such as rare elements, organic matters and the like in lignite.
The invention relates to a method for comprehensively extracting valuable components such as rare elements, organic matters and the like from brown coal, which mainly comprises the following steps:
(1) Selection of raw materials
Selecting brown coal with the mesh of-80 as a raw material, wherein the raw material contains rare earth elements and/or rare metal elements; the rare metal element is at least one of germanium, gallium and vanadium;
(2) Oxidative pretreatment
Mixing raw lignite with an oxidation pretreatment agent with the mass concentration of 2% -10% according to the solid-liquid ratio of 1:3-1:8, preferably 1:5-1:8, and reacting for more than or equal to 0.5h after mixing; preliminary release of rare metal elements and/or rare earth elements contained in lignite by mixing; after solid-liquid separation, obtaining a first-stage dissolved solution and a first-stage dissolved residual solid;
(3) Heating alkali treatment
Mixing the residual dissolved solids in the first stage obtained in the step (2) with an alkali solution with the mass concentration of 2% -5%, wherein the solid-liquid ratio is 1:10-1:20, the solution temperature is controlled at 80 ℃ -95 ℃, the treatment time is at least 0.5h, preferably 0.5-3.5 h, more preferably 0.5 h-2 h, rare metal elements and/or rare earth elements in the lignite are deeply released, and alkali-soluble organic matters in the lignite are dissolved; after solid-liquid separation, obtaining second-stage dissolved residual solids and second-stage dissolved liquid;
(4) Controlled potential acid treatment
Adding complexing agent with the mass ratio of 0.1% -1% into the second section of dissolved solution obtained in the step (3), adding acid solution with the mass concentration of 5% -10%, controlling the pH value of the solution to be 1.5-2.0, promoting the analysis of rare metal elements and/or rare earth elements complexed by organic matters, and precipitating acid insoluble organic matters; and after solid-liquid separation, obtaining a third-stage dissolved solution and a third-stage dissolved residual solid.
The invention relates to a method for comprehensively extracting valuable components such as rare elements, organic matters and the like from brown coal, which comprises the steps of adding an oxidation pretreatment agent with the mass concentration of 2% -10% into raw brown coal under the condition of no bubble generation (the mixing mode is suitable for slowly or dropwise adding the pretreatment agent into brown coal in the industrial application), and reacting at 25-75 ℃ for 0.5-16 h, preferably 0.5-10 h. The aim of preliminarily releasing rare metals such as germanium, gallium, rare earth and the like contained in the lignite is fulfilled; after solid-liquid separation, the first-stage dissolved solution is rare metal solution, and can be used for continuously extracting rare metals, and the first-stage dissolved residual solids are continuously treated. When the method is applied in industry, the water content of the lignite is usually 15-35%, and the water content can be reduced to below 13% by airing and other modes before crushing; and then crushing the dried lignite.
Preferably, the granularity of the raw lignite used in the step (2) of the present invention is 80-200 mesh.
The invention relates to a method for comprehensively extracting valuable components such as rare elements, organic matters and the like from lignite, wherein an oxidation pretreatment agent is formed by mixing an oxidant and a wetting defoamer, wherein the wetting defoamer accounts for 0.1-1% of the total mass of the oxidation pretreatment agent, preferably 0.1-0.8%, and further preferably 0.2-0.5%; the oxidant is one or more selected from hydrogen peroxide, perborate, persulfate, perphosphate, nitric acid, chlorate, hypochlorite and chlorine dioxide, the wetting defoamer is one or more selected from tributyl phosphate, methanol and ethanol, the dosage of the wetting defoamer is not excessive, the excessive dosage of tributyl phosphate can cause layering of the solution, and the element content in the aqueous solution is reduced; the excessive amount of methanol and ethanol can affect the detection result of rare elements, and is preferably tributyl phosphate and ethanol.
The invention relates to a method for comprehensively extracting valuable components such as rare elements, organic matters and the like from brown coal.
The invention relates to a method for comprehensively extracting valuable components such as rare elements, organic matters and the like from brown coal, wherein alkali used in heating alkali treatment in step (3) is one or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
The invention relates to a method for comprehensively extracting valuable components such as rare elements, organic matters and the like from brown coal, wherein at least one of tripolyphosphate, polyphosphate and pyrophosphate with the mass percent of 10-30% is added into alkali solution.
The invention relates to a method for comprehensively extracting valuable components such as rare elements, organic matters and the like from brown coal, which is characterized in that the residual solids in the second section mainly contain iron, silicon, calcium and aluminum, and can be used for preparing building raw materials, and the second section dissolved liquid is continuously treated.
The invention relates to a method for comprehensively extracting valuable components such as rare elements, organic matters and the like from brown coal, wherein a complexing agent in the step (4) is one or more selected from catechol, N-hydroxyphthalimide, tartaric acid and hydroxamic acid.
The invention relates to a method for comprehensively extracting valuable components such as rare elements, organic matters and the like from brown coal, wherein a third-stage dissolved solution is a solution containing rare metal elements and/or rare earth elements, and can be used for continuously extracting rare metals, and the residual solid after the third-stage dissolved solution can be continuously treated to purify the organic matters to prepare humic acid and the like.
The invention relates to a method for comprehensively extracting valuable components such as rare elements and organic matters from brown coal, which is characterized in that filter cake washing acid liquor or alkali liquor generated in the treatment processes (2) to (4) and residual solution after metal elements are extracted from first-stage dissolved solution and residual solution after metal elements are extracted from third-stage dissolved solution are neutralized to the pH value of the neutralized solution to 5-8 according to the similarity degree of the concentration of acid and alkali in the solution, and clarified neutralized solution is continuously returned to the process flow for recycling, so that on one hand, the cost of a medicament for wastewater treatment is reduced, and on the other hand, the residual low-concentration rare metals in the solution are circularly enriched. By the treatment, on one hand, the cost of the agent for wastewater treatment is reduced, and on the other hand, the residual rare metals with low concentration in the solution are circularly enriched. Thereby realizing the recycling of water and other substances.
The invention relates to a method for comprehensively extracting valuable components such as rare elements, organic matters and the like from brown coal, when the mass content of germanium in raw materials is 100-110 ppm and the mass content of rare earth is 55-60ppm, the temperature is controlled to be 25-30 ℃ during oxidation pretreatment, and the following process is matched; the dissolution rate of germanium is more than 85%, the dissolution rate of rare earth is more than 70%, and the yield of organic matters is 36-37%. The invention realizes the rapid and high-efficient dissolution of rare metals and rare earth metals at room temperature for the first time.
The invention relates to a method for comprehensively extracting valuable components such as rare elements, organic matters and the like from brown coal, wherein the dissolution rate of rare metals is more than or equal to 85%; the rare earth dissolution rate is more than 70 percent.
After optimization, the method for comprehensively extracting valuable components such as rare elements, organic matters and the like from the lignite has the leaching rate of rare metals more than or equal to 89%; the rare earth dissolution rate is more than 75 percent.
After further optimization, the method for comprehensively extracting valuable components such as rare elements, organic matters and the like from the lignite has the leaching rate of rare metals more than or equal to 90 percent; the rare earth dissolution rate is more than 80 percent.
After further optimization, the method for comprehensively extracting valuable components such as rare elements, organic matters and the like from the lignite has the leaching rate of rare metals more than or equal to 93 percent; the rare earth dissolution rate is more than 85 percent.
Principle and advantages
The invention relates to a comprehensive extraction process designed based on the composition characteristics of organic matters and mineral matters in lignite and the occurrence states of rare elements such as germanium, rare earth and the like. Part of germanium, rare earth and the like in the lignite is combined with organic matters, and part of the germanium, the rare earth and the like are adsorbed on clay minerals, so that a small amount of the germanium, the rare earth and the like are combined in the minerals.
Aiming at rare elements such as germanium, rare earth and the like which are combined with organic matters and adsorbed on clay minerals, a moderate oxidation and low-acid leaching method is adopted to analyze the rare elements from the organic matters and the clay minerals into a solution, in the process, in order to better wet lignite and reduce the influence of bubble accumulation in the oxidation process, an oxidant and a wetting defoamer are adopted as an oxidation pretreatment agent, so that the contact angle of the lignite and the surface tension of the solution are reduced, the wettability of the lignite is improved, and the generation amount of bubbles is reduced; meanwhile, the pretreatment agent is added into the lignite in a slow or dropwise adding mode, so that on one hand, the extraction rate of rare elements is improved, on the other hand, the sudden generation of bubbles is avoided, and the control of the flow is facilitated. The obtained first-stage dissolved solution is rare metal solution, has low impurity content, and can continuously extract rare metals.
The oxidation pretreatment process plays roles in resolving and releasing rare elements on one hand, and can activate a section of organic matters dissolved out of the residual solids on the other hand. The part of the solid is treated by heating alkali, most alkali-soluble organic matters in the solid can be dissolved out, and rare metal elements which are tightly combined with the organic matters can be released into the second section of dissolved solution; and the second stage of dissolution residual solids mainly contain iron, silicon, calcium and aluminum, and the second stage of dissolution residual solids can be continuously treated to serve as auxiliary raw materials of building materials to prepare building materials, ceramsite, geopolymer and the like.
Organic matters in the second-stage dissolved solution can be precipitated by adding acid to control potential, humic acid and the like can be continuously purified and prepared, but in consideration of the strong adsorption capacity of the organic matters such as humic acid and the like on rare elements such as germanium, rare earth and the like, a selective complexing agent is required to be added to compete and chelate the rare elements from the organic matters, the loss of the rare elements in the organic matter precipitation process is reduced, a third-stage dissolved solution containing the rare metal elements is obtained, and the rare metals are continuously extracted.
In order to give consideration to the production cost of the process, the residual solution after the acid or alkali liquor and the dissolved solution are washed by filter cakes generated in each process step and rare metals are extracted is neutralized according to the similarity degree of the acid concentration and the alkali concentration in the liquid, and the clarified neutralization solution is continuously returned to the process flow for recycling, so that the reagent cost of wastewater treatment can be reduced, and the residual low-concentration rare metals in the solution can be circularly enriched.
The invention has the advantages that aiming at the problems of high cost, heavy pollution and poor economical efficiency in the single extraction and utilization process of valuable components in the lignite, the invention realizes the productization of residual organic matters in the lignite while extracting rare metals in the lignite, has small residual solid content and is easy to be made into building materials, most of residual acid-base solution in the treatment process can be processed in the process and recycled, and the process flow has the advantages of less environmental pollution, high economic benefit and high comprehensive utilization rate of the valuable components.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a process flow for comprehensively extracting valuable components such as rare elements, organic matters and the like from lignite.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
Example 1
Aiming at brown coal with 106ppm germanium and 58ppm rare earth in inner covering, firstly crushing raw coal into small particles below 80 meshes, then slowly dripping an oxidation pretreatment agent with the mass concentration of 10% and formed by mixing hydrogen peroxide and methanol according to the mass ratio of 100:1 into the brown coal, controlling the solid-liquid ratio to be 1:3, controlling the solution temperature to be 25 ℃, stirring for 10 hours, and obtaining a first-stage dissolved solution containing rare elements after solid-liquid separation, wherein the first-stage dissolved solution can be used for continuously extracting rare metals; washing the residual solid in the first stage after solid-liquid separation, adding 5% sodium hydroxide solution (10% of sodium tripolyphosphate) with a solid-liquid ratio of 1:10, controlling the solution temperature at 95 ℃ and the treatment time at 0.5h, and obtaining the residual solid in the second stage after solid-liquid separation, wherein the residual solid can be continuously used for preparing building raw materials; adding tartaric acid and N-hydroxyphthalimide (the mass ratio is 1:1) with the mass ratio of 0.1% as complexing agents into second-stage dissolved solution containing organic matters after solid-liquid separation, and continuously adding hydrochloric acid with the mass concentration of 10%, so as to control the final pH value of the solution to be 1.5; then solid-liquid separation is carried out to obtain the third-stage dissolved residual solid (organic matter solid) and a third-stage dissolved liquid; the separated organic matters can be purified to prepare humic acid after solid-liquid separation and washing, and the third section of dissolved solution can be used for extracting rare elements continuously; and (3) washing acid liquor and alkali liquor of a filter cake in the process of collecting and extracting rare metals, and then neutralizing the residual solution according to the similarity of the acid concentration and the alkali concentration in the liquid, and returning the neutralized solution as additional water to the process for recycling. In this example, the dissolution rate of germanium was 87.38%, the dissolution rate of rare earth was 71.43%, and the yield of organic matter was 37.06%.
Comparative example 1
Other conditions were identical to example 1 except that: methanol is not added into the oxidation pretreatment agent, the dissolution rate of germanium is 84.61 percent, the dissolution rate of rare earth is 65.77 percent, and the yield of organic matters is 35.82 percent.
Comparative example 2
Other conditions were identical to example 1 except that: after the residual solid in the first stage is washed, the temperature is 60 ℃ during heating alkali treatment; finally, the dissolution rate of germanium is 83.03%, the dissolution rate of rare earth is 60.61%, and the yield of organic matters is 31.08%.
Comparative example 3
Other conditions were identical to example 1 except that: adding hydrochloric acid with the mass concentration of 10% into the second-stage dissolved solution containing organic matters after solid-liquid separation, and controlling the final pH value of the solution to be 1.5; finally, the dissolution rate of germanium is 84.40%, the dissolution rate of rare earth is 66.13%, and the yield of organic matters is 34.43%.
Comparative example 4
Other conditions were identical to example 1 except that: adding 0.1% tartaric acid serving as a complexing agent into the second-stage dissolved solution containing organic matters after solid-liquid separation, continuously adding hydrochloric acid with the mass concentration of 10%, controlling the final pH value of the solution to 3.5, and finally controlling the dissolution rate of germanium to 83.58%, the dissolution rate of rare earth to 63.39% and the yield of the organic matters to 32.29%.
Example 2
Aiming at brown coal with 212ppm of inner germanium and 89ppm of rare earth, firstly crushing raw coal into small particles below 200 meshes, then slowly dripping an oxidation pretreatment agent with the mass concentration of 2% and formed by mixing nitric acid and tributyl phosphate according to the mass ratio of 1000:1 into the brown coal, controlling the solid-liquid ratio to be 1:8, controlling the solution temperature to be 75 ℃ and the treatment time to be 0.5h, and obtaining a section of dissolved liquid containing rare elements after solid-liquid separation, wherein the dissolved liquid can be used for continuously extracting rare metals; washing the first stage of residual solid after solid-liquid separation, adding 2% potassium hydroxide solution (30% of which is sodium pyrophosphate) with a solid-liquid ratio of 1:20, controlling the solution temperature at 80 ℃ and the treatment time for 2 hours, and obtaining a second stage of dissolved residual solid after solid-liquid separation, which can be continuously used for preparing building raw materials; adding catechol and hydroxamic acid (the mass ratio is 4:1) with the mass ratio of 1% into the second-stage dissolved solution containing organic matters after solid-liquid separation as complexing agents, continuously adding hydrochloric acid with the mass concentration of 5%, controlling the final pH value of the solution to be 2.0, and continuously purifying the precipitated organic matters after solid-liquid separation and washing to prepare humic acid, wherein rare elements can be continuously extracted from the third-stage dissolved solution; and (3) washing acid liquor and alkali liquor of a filter cake in the process of collecting and extracting rare metals, and then neutralizing the residual solution according to the similarity of the acid concentration and the alkali concentration in the liquid, and returning the neutralized solution as additional water to the process for recycling. In this example, the dissolution rate of germanium was 92.13%, the dissolution rate of rare earth was 81.86%, and the yield of organic matter was 41.25%.
Example 3
Aiming at a lignite containing 159ppm of germanium and 160ppm of rare earth in Yunnan, firstly crushing raw coal into small particles below 100 meshes, then slowly dripping an oxidation pretreatment agent with mass concentration of 5% which is formed by mixing sodium perborate, sodium persulfate, sodium perphosphate and ethanol according to a mass ratio of 30:60:15:1 into the lignite, wherein the solid-liquid ratio is 1:5, the solution temperature is controlled at 25 ℃, the treatment time is 3.5 hours, and a section of dissolved solution containing rare elements is obtained after solid-liquid separation and can be used for continuously extracting rare metals; washing the first-stage residual solid after solid-liquid separation, adding 3% sodium carbonate solution (20% of which is sodium polyphosphate), wherein the solid-liquid ratio is 1:15, the solution temperature is controlled at 90 ℃, the treatment time is 1.0h, and obtaining the second-stage dissolved residual solid after solid-liquid separation, which can be continuously used for preparing building raw materials; adding 1% tartaric acid as complexing agent into the second-stage dissolution solution containing organic matters after solid-liquid separation, continuously adding 10% hydrochloric acid, controlling the final pH value of the solution at 1.5, and continuously purifying and preparing humic acid after solid-liquid separation and washing of the precipitated organic matters, wherein the three-stage dissolution solution can continuously extract rare elements; and (3) washing acid liquor and alkali liquor of a filter cake in the process of collecting and extracting rare metals, and then neutralizing the residual solution according to the similarity of the acid concentration and the alkali concentration in the liquid, and returning the neutralized solution as additional water to the process for recycling. In this example, the dissolution rate of germanium was 89.46%, the dissolution rate of rare earth was 75.19%, and the yield of organic matter was 35.12%.
Comparative example 5
Other conditions were identical to example 2 except that: tartaric acid with the mass concentration of 0.5% is not added into the second-stage dissolved solution containing organic matters after solid-liquid separation to serve as a complexing agent, the dissolution rate of germanium is 80.11%, the dissolution rate of rare earth is 62.37%, and the yield of the organic matters is 34.09%.
Example 4
Aiming at a lignite containing 576ppm of germanium, 230ppm of vanadium and 208ppm of rare earth in Yunnan, firstly crushing raw coal into small particles below 200 meshes, then slowly dripping an oxidation pretreatment agent with the mass concentration of 6% and formed by mixing sodium chlorate, sodium hypochlorite, chlorine dioxide and ethanol according to the mass ratio of 20:70:10:1 into the lignite, controlling the solid-liquid ratio to be 1:4, controlling the solution temperature at 55 ℃ and the treatment time to be 3.0h, and obtaining a first-stage dissolved solution containing rare elements after solid-liquid separation, wherein the first-stage dissolved solution can be used for continuously extracting rare metals; washing the first-stage residual solid after solid-liquid separation, adding 2% of potassium carbonate solution (30% of which is sodium triphosphate), wherein the solid-liquid ratio is 1:12, controlling the solution temperature at 85 ℃, and the treatment time is 1.5h, so as to obtain a second-stage dissolved residual solid after solid-liquid separation, and continuously preparing building raw materials; adding N-hydroxyphthalimide with the mass ratio of 0.5% as a complexing agent into a second-stage dissolved solution containing organic matters after solid-liquid separation, continuously adding hydrochloric acid with the mass concentration of 5%, controlling the final pH value of the solution to be 2.0, and continuously purifying and preparing humic acid after solid-liquid separation and washing of the precipitated organic matters, wherein rare elements can be continuously extracted from a third-stage dissolved solution; and (3) washing acid liquor and alkali liquor of a filter cake in the process of collecting and extracting rare metals, and then neutralizing the residual solution according to the similarity of the acid concentration and the alkali concentration in the liquid, and returning the neutralized solution as additional water to the process for recycling. In this example, the dissolution rate of germanium was 93.54%, the dissolution rate of vanadium was 70.13%, the dissolution rate of rare earth was 86.71%, and the yield of organic matter was 36.25%.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and alternative arrangements included within the spirit and scope of the invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (6)
1. A method for comprehensively extracting valuable components such as rare elements, organic matters and the like from lignite is characterized by mainly comprising the following steps:
(1) Selection of raw materials
Selecting brown coal with the mesh of-80 as a raw material, wherein the raw material contains rare earth elements and/or rare metal elements; the rare metal element is at least one of germanium, gallium and vanadium;
(2) Oxidative pretreatment
Under the condition of no bubble generation, adding an oxidation pretreatment agent with the mass concentration of 2% -10% into raw lignite according to the solid-liquid ratio of 1:3-1:8, and carrying out mixing reaction for 0.5-10 h at the temperature of 25 ℃ -75 ℃; preliminary release of rare metal elements and/or rare earth elements contained in lignite by mixing; after solid-liquid separation, obtaining a first-stage dissolved solution and a first-stage dissolved residual solid;
the oxidation pretreatment agent is formed by mixing an oxidant and a wetting defoamer, wherein the wetting defoamer accounts for 0.1% -1% of the total mass of the oxidation pretreatment agent; the oxidant is one or more selected from hydrogen peroxide, perborate, persulfate, perphosphate, nitric acid, chlorate, hypochlorite and chlorine dioxide, and the wetting defoamer is one or more selected from tributyl phosphate, methanol and ethanol;
(3) Heating alkali treatment
Mixing the residual dissolved solids in the first section obtained in the step (2) with an alkali solution with the mass concentration of 2% -5%, wherein the solid-liquid ratio is 1:10-1:20, the solution temperature is controlled to be 80-95 ℃, the treatment time is 0.5-2 h, rare metal elements and/or rare earth elements in the lignite are deeply released, and alkali-soluble organic matters in the lignite are dissolved; after solid-liquid separation, obtaining second-stage dissolved residual solids and second-stage dissolved liquid; adding at least one of tripolyphosphate, polyphosphate and pyrophosphates with the mass percentage of 10-30% into the alkali solution;
(4) Controlled potential acid treatment
Adding complexing agent with the mass ratio of 0.1% -1% into the second section of dissolved solution obtained in the step (3), adding acid solution with the mass concentration of 5% -10%, controlling the pH value of the solution to be 1.5-2.0, promoting the analysis of rare metal elements and/or rare earth elements complexed by organic matters, and precipitating acid-insoluble organic matters; after solid-liquid separation, obtaining a third section of dissolved liquid and a third section of dissolved residual solid;
the complexing agent in the step (4) is selected from one or more of catechol, N-hydroxyphthalimide, tartaric acid and hydroxamic acid.
2. The method for comprehensively extracting valuable components such as rare elements and organic matters from lignite, according to claim 1, is characterized in that: the alkali solution used in the heating alkali treatment in the step (3) is one or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
3. The method for comprehensively extracting valuable components such as rare elements and organic matters from lignite, according to claim 1, is characterized in that:
and (3) washing the filter cake produced in the treatment processes (2) to (4) with acid liquor or alkali liquor, extracting metal elements from the first-stage dissolved liquor, neutralizing the residual solution with the residual solution after extracting metal elements from the third-stage dissolved liquor according to the similarity of the acid concentration and the alkali concentration in the liquor until the pH value of the neutralized liquor is 5-8, and continuously returning the clarified neutralized liquor to the process flow for recycling.
4. The method for comprehensively extracting valuable components such as rare elements and organic matters from lignite, according to claim 1, is characterized in that:
the first-stage dissolved solution is a solution containing rare metal elements and/or rare earth elements and is used for continuously extracting the rare metal elements and/or the rare earth elements, and the residual solid is dissolved in the first stage and is used for continuously processing.
5. The method for comprehensively extracting valuable components such as rare elements and organic matters from lignite according to any one of claims 1-4, which is characterized in that:
the dissolution rate of rare metals is more than or equal to 85%; the rare earth dissolution rate is more than 70 percent.
6. The method for comprehensively extracting valuable components such as rare elements and organic matters from lignite, according to claim 5, which is characterized in that: the dissolution rate of rare metals is more than or equal to 89%; the rare earth dissolution rate is more than 75 percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110534756.4A CN114262794B (en) | 2021-05-17 | 2021-05-17 | Method for comprehensively extracting valuable components such as rare elements, organic matters and the like from lignite |
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