CN111733328B - Method for recovering valuable metals in waste lithium ion batteries - Google Patents
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C22B1/02—Roasting processes
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- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
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Abstract
The invention provides a method for recovering valuable metals in waste lithium ion batteries, belonging to the technical field of battery material recovery. The method comprises the steps of carrying out overdischarge, disassembly and NMP dissolution separation on a waste lithium ion battery to obtain a positive electrode material; after ball milling and mixing the positive electrode material, a sulfur-containing reducing agent and chloride, lithium salt which is easy to dissolve in water and a simple substance or oxide of transition metal which is not soluble in water are obtained through reduction roasting; soaking the roasted product in water to obtain a lithium-rich solution and solid filter residue, wherein the lithium-rich solution can be added with sodium carbonate for precipitation to obtain a lithium carbonate product; and carrying out conventional acid leaching or oxidation acid leaching on the solid filter residue to obtain a transition metal mixed solution. The method provided by the invention realizes short-process recovery of valuable metals in the waste lithium ion battery, simplifies the valuable metal recovery process, improves the lithium recovery rate, and realizes efficient recycling of transition metals.
Description
Technical Field
The invention relates to the technical field of recycling of lithium ion batteries, in particular to a method for recycling valuable metals in waste lithium ion batteries.
Background
With the rapid development of the new energy automobile industry and the wide application of ternary power lithium ion batteries in automobiles, the problem of recycling of retired lithium ion batteries becomes more and more serious. The method solves the problem of recycling the retired lithium ion battery, and has important significance on resource recycling and environmental protection.
At present, the traditional recovery method mainly comprises a pyrometallurgical process and a hydrometallurgical process. The pyrometallurgical process is short, can directly recover valuable metals, but is difficult to prepare high-purity products, and has the problems of the need of purifying flue gas and the like. The hydrometallurgical process can obtain high-purity products, but the process is long, the lithium recovery rate is low, and a large amount of industrial wastewater can be generated.
Patent application publication No. CN109935922A discloses a method for recovering valuable metals from waste lithium ion battery materials: the lithium ion battery is roasted by sulfuration, water is soaked after roasting, lithium is selectively recovered, filter residue is subjected to conventional acid leaching, extraction, impurity removal and separation, and nickel, cobalt and manganese products are obtained. The lithium recovery rate (less than 90%) of the method needs to be improved; and the nickel, cobalt and manganese extraction and separation process is complex, and the water treatment pressure is increased.
Patent application publication No. CN106848469A discloses a method for recovering valuable metals from waste lithium ion battery positive electrode materials: the method comprises the steps of discharging and disassembling the waste lithium ion battery, and sorting out a positive pole piece; carrying out pyrolysis degumming on the positive pole piece to separate out a current collector and active substances; mixing the active substance with chloride, and performing chlorination roasting; leaching the chloridized and roasted solid product with water to obtain leaching solution containing valuable metal ions; however, this method cannot separate lithium from the transition metal element, and the recovery rate of cobalt element is low.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art and provide a method for recovering valuable metals in waste lithium ion batteries by respectively recovering lithium and transition metals, wherein the method is safe, environment-friendly, low in cost and high in valuable metal recovery rate.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for recovering valuable metals in waste lithium ion batteries is characterized in that positive active substances in the waste lithium ion batteries are separated, the positive active substances, a sulfur-containing reducing agent and chloride are subjected to reduction roasting in a sectional manner, and roasted products are leached out to obtain lithium-rich filtrate and transition metal filter residues; and respectively treating the lithium-rich filtrate and the transition metal filter residue.
Further, the method for recovering valuable metals in the waste lithium ion batteries is characterized by comprising the following steps:
s1, discharging the waste lithium ion battery, and disassembling to obtain a lithium ion battery positive plate;
s2, soaking the lithium ion battery positive plate obtained in the step S1 in N-methyl pyrrolidone, separating out positive active substances, and drying to obtain positive active substance powder;
s3, mixing the positive active material powder in the step S2 with a sulfur-containing reducing agent and chloride, and ball-milling to obtain mixed powder;
s4, putting the mixed powder obtained in the step S3 into a reaction furnace, and carrying out reduction roasting in sections to obtain reduction roasted powder;
s5, soaking the reduced and roasted powder material S4 in water, filtering to obtain a lithium-rich filtrate and transition metal filter residues, and respectively treating the lithium-rich filtrate and the transition metal filter residues.
Further, the method comprises the following steps:
and washing and acid leaching the transition metal filter residue obtained in the step S5, adding at least one of nickel salt, cobalt salt and manganese salt into the leaching solution, adding a sodium hydroxide solution and ammonia water under the protection of inert gas for codeposition reaction, aging, washing and drying to obtain the nickel-cobalt-manganese ternary precursor material.
Preferably, in step S3, the sulfurous reducing agent is one or more of sulfur, sulfite, and sulfide.
Preferably, in step S3, the mass of the sulfur-containing reducing agent is 10% to 30% of the mass of the positive electrode active material powder.
Preferably, in step S3, the chloride is one or more of sodium chloride, ammonium chloride and calcium chloride.
Preferably, in step S3, the mass of the chloride is 30% to 60% of the mass of the positive electrode active material powder.
Preferably, in step S4, the staged reduction roasting is a two-stage roasting: the roasting temperature of the first section is 200-500 ℃, more preferably 300-400 ℃, and the roasting time is 0.5-3.0h, more preferably 1.0-1.5 h; the roasting temperature of the second section is 600-1000 ℃, and more preferably 800-900 ℃; the roasting time is 0.5-5.0h, more preferably 1.5-2.5 h; the step-by-step reduction roasting is carried out in an inert atmosphere.
Researches show that compared with one-stage roasting, the two-stage roasting can effectively improve the leaching rate of lithium ions in water leaching in the step S5; by adopting the roasting temperature and time, the leaching effect of the lithium ions is very good.
The chloride can be combined with lithium ions at high temperature to destroy the layered crystal structure of the positive active material powder, and the sulfur-containing reducing agent is used for reducing high-price nickel and cobalt elements in the reducing roasting process, and the nickel and cobalt elements act simultaneously to effectively promote the selective leaching of the lithium ions. Research shows that when the mass of the sulfur-containing reducing agent is 10-30% of the mass of the positive active material powder and the mass of the chloride is 30-60% of the mass of the positive active material powder, the water leaching process in the step S5 has a good selective leaching effect on lithium ions.
Preferably, in step S5, the water immersion temperature is 60-95 ℃, more preferably 80-90 ℃; the water immersion time is 0.5-5h, more preferably 1.5-2.5 h.
Preferably, sodium carbonate is added to the lithium-rich solution to obtain a lithium carbonate product.
Preferably, the acid leaching temperature is 50-90 ℃, more preferably 80-85 ℃; the acid leaching time is 0.5-5h, more preferably 2-3 h.
Preferably, an oxidizing agent is added during the acid leaching.
In the invention, the retired lithium ion battery is subjected to overdischarge, disassembly and NMP dissolution and separation to obtain a positive electrode material; after ball milling and mixing the positive electrode material, a sulfur-containing reducing agent and chloride, lithium salt which is easy to dissolve in water and a simple substance or oxide of transition metal which is not soluble in water are obtained through reduction roasting; soaking the roasted product in water to obtain a lithium-rich solution and solid filter residue, wherein the lithium-rich solution can be added with sodium carbonate for precipitation to obtain a lithium carbonate product; the solid filter residue is subjected to conventional acid leaching or oxidation acid leaching to prepare transition metal mixed liquor. Preferentially and selectively extracting lithium, thereby realizing short-process recovery of valuable metals in the waste lithium ion batteries; the transition metal mixed solution is directly synthesized into the nickel-cobalt-manganese ternary precursor material without separation, so that the traditional extraction and separation steps are omitted, and the high-efficiency recycling of valuable metals in the lithium ion battery is realized.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method simplifies the valuable metal recovery process by the aid of chlorine salt assisted vulcanization reduction roasting and selective leaching;
(2) the transition metal is not separated but directly synthesized into a precursor, so that the efficient reutilization of the transition metal is realized;
(3) the invention is safe, environment-friendly, low in cost and high in recovery rate of valuable metals, the once recovery rate of lithium can reach more than 98%, and the recovery rate of cobalt can reach more than 99%;
drawings
FIG. 1 is an XRD pattern of a portion of an intermediate product of an embodiment of the present invention;
fig. 2 is an SEM image of the nickel-cobalt-manganese ternary precursor material obtained in example 1 of the present invention.
Detailed Description
In order to better explain the present invention and further understand the technical solution of the present invention, the present invention is further described in detail below with reference to the embodiments and the accompanying drawings. However, the following examples are only a part of the examples of the present invention and should not be construed as limiting the scope of the invention claimed in the present patent application.
Each raw material used in the examples is a common commercially available product.
Example 1
(1) Discharging and disassembling a nickel-cobalt-aluminum (NCA) waste lithium ion battery to obtain a lithium ion battery positive plate;
(2) soaking a lithium ion battery positive plate by using N-methyl pyrrolidone, taking away an aluminum foil after a positive active substance is completely separated from the aluminum foil, and drying the positive active substance to obtain nickel-cobalt lithium aluminate positive active substance powder;
(3) taking 10g of the nickel cobalt lithium aluminate anode active substance powder, adding sulfur which is 30% of the mass of the nickel cobalt lithium aluminate anode active substance powder and sodium chloride which is 60% of the mass of the nickel cobalt lithium aluminate anode active substance powder, and carrying out ball milling and mixing for 2 hours to obtain mixed powder;
(4) putting the mixed powder into a reaction furnace, and carrying out sectional reduction roasting in argon atmosphere, wherein the roasting temperature of the first section is 400 ℃, the roasting time is 2.5 hours, the roasting temperature of the second section is 900 ℃, and the roasting time is 2.5 hours, so as to obtain reduction roasting powder;
(5) soaking the reduction roasting powder in water at 90 ℃ for 2h, and filtering to obtain lithium-rich filtrate and transition metal filter residue; adding sodium carbonate into the lithium-rich filtrate, and precipitating to obtain 3.55 g of a lithium carbonate product;
(6) washing the transition metal filter residue with pure water, adding 4moL/L sulfuric acid, adding until the pH value of the system is 1.5, adding 0.3g of sodium chlorate, supplementing 10mL of 4moL/L sulfuric acid, leaching at 80 ℃ for 2h to obtain a leaching solution, adjusting the pH value to 4.5 to remove iron, copper and aluminum impurity precipitates, and synchronously extracting with a P507 extracting agent to obtain a nickel and cobalt mixed salt solution;
(7) adding corresponding nickel sulfate, cobalt sulfate and manganese sulfate to obtain a mixed solution of nickel, cobalt and manganese with a ratio of 8:1: 1; finally, adding the nickel-cobalt-manganese mixed solution, a sodium hydroxide solution and dilute ammonia water into a stirring reaction kettle under the argon atmosphere to prepare a ternary precursor by adopting a conventional coprecipitation method, and aging, washing and drying to obtain Ni0.8Co0.1Mn0.1(OH)2And (3) ternary precursor.
Respectively detecting the lithium-rich filtrate, the leaching solution and the transition metal filter residue by inductive coupling plasma emission spectroscopy (ICP-OES); the element content in the positive electrode active material is recorded as 100%, the primary recovery rate of lithium is calculated to be 98.2%, the recovery rate of cobalt is up to 99.2%, and the recovery rate of nickel is up to 99.3%.
The metal content in the transition metal filter residue is shown in table 1:
table 1 content of metal in transition metal filter residue obtained in example 1
Fig. 1 is an X-ray diffraction test result, wherein from top to bottom, a first diffraction pattern is a test result of a positive active material sample of an NCA waste lithium ion battery, and a third diffraction pattern is a test result of a transition metal filter residue sample in this example 1.
As can be seen from fig. 1, the positive active material of the NCA waste lithium ion battery is a nickel cobalt lithium aluminate positive electrode material. In the transition metal filter residue obtained in this embodiment 1, the content of nickel is much larger than that of cobalt, nickel mainly exists in a simple substance form, and a diffraction peak of a cobalt-containing substance is not obvious.
FIG. 2 shows Ni obtained in example 10.8Co0.1Mn0.1(OH)2And (3) SEM images of the ternary precursor, wherein the ternary precursor is spherical particles with the particle size of 8-15 microns.
Example 2
(1) Discharging and disassembling the NCA waste lithium ion battery to obtain a lithium ion battery positive plate;
(2) soaking a lithium ion battery positive plate by using N-methyl pyrrolidone, taking away an aluminum foil after a positive active substance is completely separated from the aluminum foil, and drying the positive active substance to obtain nickel-cobalt lithium aluminate positive active substance powder;
(3) taking 10g of the nickel cobalt lithium aluminate anode active substance powder, adding sulfur which is 20% of the mass of the nickel cobalt lithium aluminate anode active substance powder and sodium chloride which is 60% of the mass of the nickel cobalt lithium aluminate anode active substance powder, and carrying out ball milling and mixing for 1.5h to obtain mixed powder;
(4) putting the obtained mixed powder into a muffle furnace, and carrying out sectional reduction roasting at the first stage of roasting temperature of 500 ℃ for 1.5h and at the second stage of roasting temperature of 900 ℃ for 1.5h to obtain reduction roasting powder;
(5) soaking the reduction roasting powder in water at 85 ℃ for 2h, and filtering to obtain lithium-rich filtrate and transition metal filter residue; adding sodium carbonate into the lithium-rich filtrate, and precipitating to obtain 3.48 g of a lithium carbonate product;
(6) washing the transition metal filter residue with pure water, then carrying out conventional acid leaching on the transition metal filter residue at 80 ℃ for 2h, adjusting the pH value to 4.5, removing impurities and precipitates of iron, copper and aluminum, and then using a P507 extractant to carry out synchronous extraction to obtain a nickel-cobalt mixed salt solution;
(7) adding corresponding nickel sulfate, cobalt sulfate and manganese sulfate to obtain a mixed solution of nickel, cobalt and manganese with a ratio of 8:1: 1; finally, adding the nickel-cobalt-manganese mixed solution, a sodium hydroxide solution and dilute ammonia water into a stirring reaction kettle under the nitrogen atmosphere to prepare a ternary precursor by adopting a conventional coprecipitation method, and aging, washing and drying to obtain Ni0.8Co0.1Mn0.1(OH)2And (3) ternary precursor.
Respectively detecting the lithium-rich filtrate, the leaching solution and the transition metal filter residue by inductive coupling plasma emission spectroscopy (ICP-OES); the element content in the positive electrode active material is recorded as 100%, the primary recovery rate of lithium is 97.08%, the primary recovery rate of cobalt is 98.6%, and the recovery rate of nickel is 99.0%.
The metal content of the transition metal filter residue is shown in table 2.
Table 2 content of metals in transition metal filter residue obtained in example 2
Fig. 1 is a diagram showing the results of X-ray diffraction tests, and a second diffraction pattern from top to bottom shows that nickel is mainly present in the transition metal residue in the form of oxide in the transition metal residue obtained from the test results of the transition metal residue sample of example 2.
Example 3
(1) Discharging and disassembling the NCA waste lithium ion battery to obtain a lithium ion battery positive plate;
(2) soaking a lithium ion battery positive plate by using N-methyl pyrrolidone, taking away an aluminum foil after a positive active substance is completely separated from the aluminum foil, and drying the positive active substance to obtain nickel-cobalt lithium aluminate positive active substance powder;
(3) taking 10g of nickel cobalt lithium aluminate anode active substance powder, adding sulfur which is 10% of the mass of the nickel cobalt lithium aluminate anode active substance powder and sodium chloride which is 30% of the mass of the nickel cobalt lithium aluminate anode active substance powder, and carrying out ball milling and mixing for 1h to obtain mixed powder;
(4) putting the mixed powder into a reaction furnace, and carrying out sectional reduction roasting in argon atmosphere, wherein the roasting temperature of the first section is 300 ℃, the roasting time is 1h, the roasting temperature of the second section is 700 ℃, and the roasting time is 1h, so as to obtain reduction roasting powder;
(5) soaking the reduction roasting powder in water at 60 ℃ for 2h, and filtering to obtain lithium-rich filtrate and transition metal filter residue;
(6) washing the transition metal filter residue with pure water; then carrying out conventional acid leaching on the transition metal filter residue at 80 ℃ for 2h, adjusting the pH value to 4.5, removing impurities and precipitates of iron, copper and aluminum, and then using a P507 extractant to synchronously extract to obtain a nickel-cobalt mixed salt solution;
(7) adding corresponding nickel sulfate, cobalt sulfate and manganese sulfate to obtain a mixed solution of nickel, cobalt and manganese with a ratio of 8:1: 1; finally, adding the nickel-cobalt-manganese mixed solution, a sodium hydroxide solution and dilute ammonia water into a stirring reaction kettle under the argon atmosphere to prepare a ternary precursor by adopting a conventional coprecipitation method, and aging, washing and drying to obtain Ni0.8Co0.1Mn0.1(OH)2And (3) ternary precursor.
Respectively detecting the lithium-rich filtrate, the leaching solution and the transition metal filter residue by inductive coupling plasma emission spectroscopy (ICP-OES); the element content in the positive electrode active material was recorded as 100%, and the primary recovery rate of lithium was calculated to be 93.2%, the recovery rate of cobalt element was 98.3%, and the recovery rate of nickel was calculated to be 98.7%.
The metal content in the transition metal filter residue is shown in table 3:
table 3 content of metal in transition metal filter residue obtained in example 3
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A method for recovering valuable metals in waste lithium ion batteries is characterized in that positive active substances in the waste lithium ion batteries are separated, the positive active substances, a sulfur-containing reducing agent and chloride are subjected to reduction roasting in a sectional manner, and roasted products are leached out to obtain lithium-rich filtrate and transition metal filter residues; respectively treating the lithium-rich filtrate and the transition metal filter residue;
the method specifically comprises the following steps:
s1, discharging the waste lithium ion battery, and disassembling to obtain a lithium ion battery positive plate;
s2, soaking the lithium ion battery positive plate obtained in the step S1 in N-methyl pyrrolidone, separating out positive active substances, and drying to obtain positive active substance powder;
s3, mixing the positive electrode active material powder obtained in the step S2 with a sulfur-containing reducing agent and chloride, and performing ball milling to obtain mixed powder;
s4, putting the mixed powder obtained in the step S3 into a reaction furnace, and carrying out reduction roasting in sections to obtain reduction roasted powder;
s5, soaking the reduced and roasted powder material S4 in water, filtering to obtain a lithium-rich filtrate and transition metal filter residues, and respectively treating the lithium-rich filtrate and the transition metal filter residues;
s6, washing and acid leaching the transition metal filter residue obtained in the step S5, adding at least one of nickel salt, cobalt salt and manganese salt into the leaching solution, adding a sodium hydroxide solution and ammonia water under the protection of inert gas for coprecipitation reaction, aging, washing and drying to obtain a nickel-cobalt-manganese ternary precursor material;
the step-by-step reduction roasting is two-step roasting: the roasting temperature of the first section is 200-500 ℃, and the roasting time is 0.5-3.0 h; the roasting temperature of the second section is 600-; the step-by-step reduction roasting is carried out in an inert atmosphere.
2. The method for recovering valuable metals from waste lithium ion batteries according to claim 1, wherein the sulfur-containing reducing agent is one or more of sulfur, sulfite and sulfide; the chloride is one or more of sodium chloride, ammonium chloride and calcium chloride.
3. The method for recycling valuable metals from waste lithium ion batteries according to claim 1 or 2, wherein in step S3, the mass of the sulfur-containing reducing agent is 10% -30% of the mass of the positive electrode active material powder, and the mass of the chloride is 30% -60% of the mass of the positive electrode active material powder.
4. The method for recycling valuable metals from waste lithium ion batteries according to claim 1, wherein in the step S5, the water immersion temperature is 60-95 ℃, and the water immersion time is 0.5-5 h.
5. The method for recycling valuable metals from used lithium ion batteries according to claim 1, wherein sodium carbonate is added into the lithium-rich solution to obtain a lithium carbonate product.
6. The method for recycling valuable metals from waste lithium ion batteries according to claim 1, wherein the temperature of the transition metal filter residue obtained in the step S5 is 50-90 ℃ and the time is 0.5-5h in the step S6 by leaching with acid.
7. The method for recycling valuable metals from waste lithium ion batteries according to claim 1 or 6, wherein an oxidizing agent is added during the step of leaching the transition metal filter residue of the step S5 with acid in the step S6.
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| CN112062143A (en) * | 2020-09-17 | 2020-12-11 | 南昌航空大学 | Acid-free lithium carbonate preparation method using waste lithium ion battery as raw material |
| CN112779421B (en) * | 2020-12-09 | 2023-01-13 | 广东微电新能源有限公司 | Method for recycling anode material of waste lithium ion battery |
| CN112652807A (en) * | 2020-12-18 | 2021-04-13 | 中北大学 | Method for selectively recovering lithium in anode material of waste lithium ion battery by using Lewis acid |
| CN112877548B (en) * | 2021-01-12 | 2022-11-25 | 中国科学院过程工程研究所 | Method for recovering valuable metals from waste lithium ion battery anode powder |
| CN112366381B (en) * | 2021-01-14 | 2021-04-02 | 矿冶科技集团有限公司 | Method for recovering lithium from waste lithium battery anode material and application |
| CN113684374B (en) * | 2021-07-22 | 2022-11-15 | 广东邦普循环科技有限公司 | Method for selectively extracting lithium from retired battery and application thereof |
| CN113964407B (en) * | 2021-08-31 | 2024-08-30 | 江西天奇金泰阁钴业有限公司 | Method for recycling lithium from waste lithium ion battery |
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| CN113999967A (en) * | 2021-11-02 | 2022-02-01 | 赣州有色冶金研究所有限公司 | Method for recovering lithium in lithium ion battery anode material |
| CN114291854A (en) * | 2021-12-30 | 2022-04-08 | 中南大学 | Treatment method for recycling waste battery anode material |
| CN114717422B (en) * | 2022-04-27 | 2024-04-09 | 江西格润新材料有限公司 | Method for recovering valuable metals in retired lithium battery by mechanochemical method |
| CN115287470A (en) * | 2022-08-05 | 2022-11-04 | 中南大学 | Reduction alkaline leaching recovery process for constructing galvanic cell effect |
| CN115354161B (en) * | 2022-08-29 | 2024-02-02 | 通化建新科技有限公司 | Method for recycling lithium in waste power battery by rotary hearth furnace |
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| JP5360135B2 (en) * | 2011-06-03 | 2013-12-04 | 住友金属鉱山株式会社 | Valuable metal recovery method |
| RU2564806C2 (en) * | 2013-08-28 | 2015-10-10 | Общество с ограниченной ответственностью "Экостар-Наутех" (ООО"Экостар-Наутех") | Method of producing ultrapure lithium carbonate from technical-grade lithium carbonate and apparatus therefor |
| CN106129511B (en) * | 2016-06-27 | 2018-12-07 | 北京科技大学 | A method of the comprehensively recovering valuable metal from waste and old lithium ion battery material |
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| CN109755539A (en) * | 2019-02-21 | 2019-05-14 | 湖南邦普循环科技有限公司 | Utilize the method for lithium ion cell anode waste production aluminium doping ternary precursor |
| CN110643816A (en) * | 2019-09-16 | 2020-01-03 | 浙江省冶金研究院有限公司 | Method for recovering lithium from waste ternary lithium battery |
| CN110938743B (en) * | 2019-10-29 | 2022-01-28 | 北京矿冶科技集团有限公司 | Method for extracting lithium and nickel and cobalt from waste lithium ion battery step by step |
| CN110817905B (en) * | 2019-12-11 | 2022-06-10 | 赣州有色冶金研究所有限公司 | Method for recovering lithium in ternary cathode material by microwave roasting |
| CN111082178B (en) * | 2019-12-16 | 2021-12-31 | 中南大学 | Method for regenerating lithium-rich manganese-based positive electrode material by using waste lithium batteries |
| AU2020100054A4 (en) * | 2020-01-10 | 2020-02-20 | Zhao, Tianyi Mr | A combined process for the recovery of valuable metals from waste ternary cathode materials based on chlorination roasting at medium temperature and water leaching |
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