CN117448592A - Low-energy-consumption spodumene roasting transformation method - Google Patents
Low-energy-consumption spodumene roasting transformation method Download PDFInfo
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- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910052642 spodumene Inorganic materials 0.000 title claims abstract description 72
- 238000005265 energy consumption Methods 0.000 title claims abstract description 14
- 238000011426 transformation method Methods 0.000 title abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011593 sulfur Substances 0.000 claims abstract description 50
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 39
- 229910052644 β-spodumene Inorganic materials 0.000 claims abstract description 28
- 230000009466 transformation Effects 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012141 concentrate Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052643 α-spodumene Inorganic materials 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 54
- 238000002386 leaching Methods 0.000 claims description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 22
- 239000003546 flue gas Substances 0.000 claims description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 19
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- 239000000428 dust Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002918 waste heat Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- 230000001180 sulfating effect Effects 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 5
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 4
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 2
- 238000005188 flotation Methods 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 14
- 239000003345 natural gas Substances 0.000 abstract description 7
- 239000003245 coal Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 230000005611 electricity Effects 0.000 abstract description 2
- 239000000446 fuel Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052629 lepidolite Inorganic materials 0.000 description 2
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a low-energy-consumption spodumene roasting transformation method, which comprises the steps of adding spodumene or spodumene concentrate materials into a transformation roasting furnace for roasting, and adding sulfur into the transformation roasting furnace; in the roasting process, air, oxygen-enriched air or pure oxygen is blown into a transformation roasting furnace to enable sulfur and oxygen to undergo oxidation reaction, heat is released, the temperature in the furnace is kept at 950-1150 ℃, and alpha spodumene is transformed into beta spodumene; the dosage of the sulfur is 2% -90% of the weight of spodumene or spodumene concentrate. According to the invention, a certain amount of sulfur is added into the spodumene material, and a large amount of heat is released by the reaction of the sulfur and oxygen in the roasting process, so that the temperature in the transformation roasting furnace is increased or maintained, the spodumene material is heated, the transformation of alpha-type spodumene into beta-type spodumene is promoted, and the consumption of energy sources such as natural gas, coal, electricity and the like can be reduced.
Description
Technical Field
The invention relates to the technical field of spodumene extraction, in particular to a low-energy-consumption spodumene roasting transformation method.
Background
Lithium is an indispensable raw material for the development of modern industry as a novel energy source and strategic resource, and is widely used in the fields of power batteries of new energy automobiles, aerospace, nuclear industry and the like. With the increasing demand for lithium, the development and utilization of lithium resources has become the focus of current technological and industrial attention.
The lithium is mainly extracted from spodumene, lepidolite and salt lakes, but compared with spodumene, the lepidolite has lower grade and higher extraction cost, and the factors such as high magnesium-lithium ratio, close magnesium-lithium ion radius, difficult separation and the like in salt lakes in China lead to the main extraction of the lithium from the spodumene in China.
Spodumene has three crystal forms of alpha, beta and gamma, natural alpha spodumene is converted into beta spodumene when heated to 950-1150 ℃, and beta spodumene is converted into gamma spodumene at higher temperature. The alpha spodumene is monoclinic system, has compact structure and large chemical inertia, hardly reacts with various acids and alkalis except hydrofluoric acid, and is not suitable for directly extracting lithium; beta spodumene is tetragonal crystal form, loose in structure, capable of reacting with acid and alkali, and suitable for lithium extraction. Based on the characteristics of spodumene, el lestad et al propose a sulfuric acid roasting method lithium extraction process, namely, alpha spodumene is subjected to high-temperature roasting transformation at 950-1150 ℃, beta spodumene is mixed with sulfuric acid and then roasted at 250-300 ℃ so as to enable the beta spodumene to undergo a displacement reaction with the sulfuric acid to generate soluble lithium sulfate, calcine is leached by water to obtain a lithium sulfate solution, and the solution is subjected to impurity removal, evaporation concentration and lithium precipitation processes to obtain a lithium carbonate product. The spodumene sulfuric acid process for extracting lithium has the advantages of simple process, high lithium recovery rate and the like, is adopted by a plurality of enterprises, and also faces the problem of high energy consumption.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a spodumene roasting transformation method with low energy consumption, a certain amount of sulfur is added into spodumene materials, and a large amount of heat is released by the reaction of the sulfur and oxygen in the roasting process, so that the temperature in a transformation roasting furnace is increased or maintained, the spodumene materials are heated, the transformation of alpha-spodumene into beta-spodumene is promoted, and the consumption of natural gas, coal, electricity and other energy sources can be reduced.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a low-energy-consumption spodumene transformation roasting method comprises the following specific processes:
adding spodumene or spodumene concentrate materials into a rotary kiln for roasting, and adding sulfur into the rotary kiln; in the roasting process, air, oxygen-enriched air or pure oxygen is blown into a transformation roasting furnace to enable sulfur and oxygen to undergo oxidation reaction, heat is released, the temperature in the furnace is kept at 950-1150 ℃, and alpha spodumene is transformed into beta spodumene; the dosage of the sulfur is 2% -90% of the weight of spodumene or spodumene concentrate.
When the addition amount of sulfur<At 2%, although a certain amount of fuel consumption can be saved, the SO in the flue gas is reduced due to the small addition amount of sulfur 2 The concentration is low, the acid preparation is difficult to recover, and a large amount of medicaments are consumed for flue gas desulfurization; when the addition amount of sulfur>When the temperature is 90%, the temperature in the rotary kiln is still under the condition of no additional fuel>The beta-spodumene can be converted into gamma-spodumene at 1150 ℃, and the service life of the rotary kiln is reduced.
Further, the spodumene or spodumene concentrate has a main component of Li 2 O 1.5-8％、Al 2 O 3 5-30％、SiO 2 30-75%, wherein the spodumene concentrate is a dense medium beneficiation or flotation product.
Further, the sulfur is industrial sulfur, the mass content of the sulfur is larger than or equal to 90%, and the granularity is 0.1-10mm.
Further, the rotary kiln roasting furnace is a rotary kiln, a fluidized bed furnace, a multi-hearth furnace, a tunnel kiln or a suspension roasting furnace.
When the rotary kiln is used as the transformation roasting furnace, spodumene or spodumene concentrate is added to the kiln tail of the rotary kiln, the material moves from the kiln tail to the middle high-temperature section of the rotary kiln along with the rotation of the rotary kiln, and sulfur is sprayed into the kiln for combustion through a spray pipe at the kiln head.
Further, waste heat recovery is carried out on the flue gas generated in the roasting process, then dust collection is carried out, and the flue gas after dust collection is purified, converted and dried to prepare industrial-grade sulfuric acid; the heat generated by the waste heat recovery is used for drying or preheating spodumene or spodumene concentrate materials before roasting.
Further, the beta-spodumene obtained by transformation is finely ground and then is mixed with the prepared industrial grade sulfuric acid according to the beta-spodumene: mixing sulfuric acid at a weight ratio of 1:0.05-0.5, sulfating and roasting at 250-300 deg.C to convert beta spodumene into soluble lithium sulfate, and leaching the roasted product with water to obtain lithium-containing solution.
The invention has the beneficial effects that:
(1) The invention provides a method for mixing spodumene or spodumene concentrate with sulfur for high-temperature roasting transformation for the first time, and the method utilizes the characteristic of sulfur oxidation heat release to effectively reduce the consumption (even no addition) of natural gas, coal and other fuels and reduce carbon emission.
(2) The invention provides a method for mixing and roasting spodumene or spodumene concentrate and sulfur, and the generated SO 2 The flue gas can be used for preparing acid by using a mature acid preparation process, so that the investment and the running cost of a combustion system for preparing acid by sulfur are saved.
(3) According to the invention, the sulfur dosage can be precisely controlled according to market energy, sulfur and sulfuric acid price conditions, the energy consumption is reduced, the sulfuric acid output is regulated, the product structure is optimized, and the maximization of the economic benefit of enterprises is realized.
Detailed Description
The present invention will be further described below, and it should be noted that, while the present embodiment provides a detailed implementation manner and a specific operation process on the premise of the present technical solution, the protection scope of the present invention is not limited to the present embodiment.
Example 1
The embodiment provides a spodumene roasting transformation method with low energy consumption, which comprises the following steps:
(1) Li is mixed with 2 O 1.71％、Al 2 O 3 7.29％、SiO 2 70.83% spodumene is added into the kiln tail of the rotary kiln through a feeder, and the material moves from the kiln tail to the high-temperature section of the middle region of the rotary kiln along with the rotation of the rotary kiln; and simultaneously, 2 percent of sulfur (the sulfur content is 93 percent and the sulfur particle diameter is 0.1 mm) by mass of spodumene is sprayed into the kiln through a spray pipe at the kiln head.
(2) Oxygen is blown in during the roasting process, so that oxidation reaction of sulfur and oxygen occurs, heat is released, the temperature in the furnace is increased, the temperature in the furnace is kept at 950 ℃, the roasting time is 30min, and the alpha spodumene is transformed into beta spodumene. The temperature in the furnace can be maintained by adding fuel such as natural gas in the roasting process.
(3) And (3) carrying out heat exchange on the flue gas of the roasting furnace or cooling the flue gas by a waste heat boiler, collecting dust, and purifying, converting and drying the flue gas after dust collection to prepare the industrial-grade sulfuric acid.
(4) Mixing beta-spodumene obtained in the step (2) with sulfuric acid obtained in the step (3) uniformly according to the mass ratio of the beta-spodumene to the sulfuric acid of 1:0.05, and carrying out sulfating roasting for 30min at the temperature of 250 ℃. The spodumene after roasting is leached by using process water as a leaching agent under the conditions of 2:1 liquid-solid ratio, room temperature leaching temperature and 1h leaching time, and the leaching conditions of lithium are shown in table 1.
Example 2
The embodiment provides a spodumene roasting transformation method with low energy consumption, which comprises the following steps:
(1) Li is mixed with 2 O 2.33％、Al 2 O 3 10.02％、SiO 2 62.77% spodumene is added into the kiln tail of the rotary kiln through a feeder, and materials move to a high-temperature section in the rotary kiln from the kiln tail along with the rotation of the rotary kiln; simultaneously, 23 percent of sulfur (sulfur content is 95 percent and sulfur particle diameter is 4 mm) by mass of spodumene is sprayed into the kiln through a spray pipe at the kiln head.
(2) Oxygen-enriched air is blown in during the roasting process, so that oxidation reaction of sulfur and oxygen occurs, heat is released, the temperature in the furnace is raised, the temperature in the furnace is kept at 1050 ℃, the roasting time is 30min, and the alpha spodumene is transformed into beta spodumene. The temperature in the furnace can be maintained by adding fuel such as natural gas in the roasting process.
(3) And (3) carrying out heat exchange on the flue gas of the roasting furnace or cooling the flue gas by a waste heat boiler, collecting dust, and purifying, converting and drying the flue gas after dust collection to prepare the industrial-grade sulfuric acid.
(4) Mixing beta-spodumene obtained in the step (2) with sulfuric acid obtained in the step (3) uniformly according to the mass ratio of the beta-spodumene to the sulfuric acid of 1:0.25, and carrying out sulfating roasting for 30min at 300 ℃. The spodumene after roasting is leached by using process water as a leaching agent under the conditions of 2:1 liquid-solid ratio, room temperature leaching temperature and 1h leaching time, and the leaching conditions of lithium are shown in table 1.
Example 3
The embodiment provides a spodumene roasting transformation method with low energy consumption, which comprises the following steps:
(1) Li is mixed with 2 O 5.28％、Al 2 O 3 18.22％、SiO 2 56.83% spodumene is added into the kiln tail of the rotary kiln through a feeder, and the material moves from the kiln tail to the high-temperature section of the middle region of the rotary kiln along with the rotation of the rotary kiln; simultaneously, 30 percent of sulfur (sulfur content is 99 percent and sulfur particle diameter is 10 mm) by mass of spodumene is sprayed into the kiln through a spray pipe at the kiln head.
(2) Air is blown in the roasting process, so that oxidation reaction of sulfur and oxygen is carried out, heat is released, the temperature in the furnace is increased, the temperature in the furnace is kept at 1100 ℃, the roasting time is 30min, and the alpha spodumene is transformed into beta spodumene. The temperature in the furnace can be maintained by adding fuel such as natural gas in the roasting process.
(3) And (3) carrying out heat exchange on the flue gas of the roasting furnace or cooling the flue gas by a waste heat boiler, collecting dust, and purifying, converting and drying the flue gas after dust collection to prepare the industrial-grade sulfuric acid.
(4) Mixing beta spodumene obtained in the step (2) with sulfuric acid obtained in the step (3) uniformly according to the mass ratio of calcine to sulfuric acid of 1:0.5, and carrying out sulfating roasting for 30min at 270 ℃. The spodumene after roasting is leached by using process water as a leaching agent under the conditions of 2:1 liquid-solid ratio, room temperature leaching temperature and 1h leaching time, and the leaching conditions of lithium are shown in table 1.
Example 4
The embodiment provides a spodumene roasting transformation method with low energy consumption, which comprises the following steps:
(1) Li is mixed with 2 O 6.46％、Al 2 O 3 21.57％、SiO 2 51.92% spodumene is added into the kiln tail of the rotary kiln through a feeder, and materials move to a high-temperature section in the rotary kiln from the kiln tail along with the rotation of the rotary kiln; and simultaneously, 50% of sulfur (sulfur content is 95%, and sulfur particle diameter is 7.4 mm) by mass of spodumene is sprayed into the kiln through a spray pipe at the kiln head.
(2) Oxygen-enriched air is blown in during the roasting process, so that oxidation reaction of sulfur and oxygen occurs, heat is released, the temperature in the furnace is raised, the temperature in the furnace is kept at 1150 ℃, the roasting time is 30min, and the alpha spodumene is transformed into beta spodumene. The temperature in the furnace can be maintained by adding fuel such as natural gas in the roasting process.
(3) And (3) carrying out heat exchange on the flue gas of the roasting furnace or cooling the flue gas by a waste heat boiler, collecting dust, and purifying, converting and drying the flue gas after dust collection to prepare the industrial-grade sulfuric acid.
(4) Mixing beta spodumene obtained in the step (2) with sulfuric acid obtained in the step (3) uniformly according to the mass ratio of calcine to sulfuric acid of 1:0.35, and carrying out sulfating roasting for 30min at 250 ℃. The spodumene after roasting is leached by using process water as a leaching agent under the conditions of 2:1 liquid-solid ratio, room temperature leaching temperature and 1h leaching time, and the leaching conditions of lithium are shown in table 1.
Example 5
The embodiment provides a spodumene roasting transformation method with low energy consumption, which comprises the following steps:
(1) Li is mixed with 2 O 6.13％、Al 2 O 3 21.14％、SiO 2 53.51% spodumene is added into the kiln tail of the rotary kiln through a feeder, and materials move to a high-temperature section in the rotary kiln from the kiln tail along with the rotation of the rotary kiln; and simultaneously, 90 percent of sulfur (sulfur content is 99 percent and sulfur particle diameter is 3.7 mm) by mass of spodumene is sprayed into the kiln through a spray pipe at the kiln head.
(2) Air is blown in during the roasting process, so that oxidation reaction of sulfur and oxygen occurs, heat is released, and the temperature in the furnace is increased. At this time, the temperature in the transformation roasting furnace is still kept at about 1138 ℃ without adding any additional fuel, the roasting time is 30min, and the alpha spodumene is transformed into beta spodumene.
(3) And (3) carrying out heat exchange on the flue gas of the roasting furnace or cooling the flue gas by a waste heat boiler, collecting dust, and purifying, converting and drying the flue gas after dust collection to prepare the industrial-grade sulfuric acid.
(4) Mixing beta spodumene obtained in the step (2) with sulfuric acid obtained in the step (3) uniformly according to the mass ratio of calcine to sulfuric acid of 1:0.3, and carrying out sulfating roasting for 30min at 250 ℃. The spodumene after roasting is leached by using process water as a leaching agent under the conditions of 2:1 liquid-solid ratio, room temperature leaching temperature and 1h leaching time, and the leaching conditions of lithium are shown in table 1.
TABLE 1
| Name of the name | Lithium leaching Rate (%) |
| Example 1 | 92.34 |
| Example 2 | 95.28 |
| Example 3 | 97.93 |
| Example 4 | 98.95 |
| Example 5 | 98.16 |
Various modifications and variations of the present invention will be apparent to those skilled in the art in light of the foregoing teachings and are intended to be included within the scope of the following claims.
Claims (7)
1. The low-energy-consumption spodumene transformation roasting method is characterized by comprising the following specific processes:
adding spodumene or spodumene concentrate materials into a rotary kiln for roasting, and adding sulfur into the rotary kiln; in the roasting process, air, oxygen-enriched air or pure oxygen is blown into a transformation roasting furnace to enable sulfur and oxygen to undergo oxidation reaction, heat is released, the temperature in the furnace is kept at 950-1150 ℃, and alpha spodumene is transformed into beta spodumene; the dosage of the sulfur is 2% -90% of the weight of spodumene or spodumene concentrate.
2. The method according to claim 1, wherein the spodumene or spodumene concentrate has a main constituent of Li 2 O 1.5-8％、Al 2 O 3 5-30％、SiO 2 30-75%, wherein the spodumene concentrate is a dense medium beneficiation or flotation product.
3. The method according to claim 1, wherein the sulfur is industrial sulfur, the mass content of the sulfur is larger than or equal to 90%, and the granularity is 0.1-10mm.
4. The method of claim 1, wherein the rotary kiln, fluidized bed furnace, multi-hearth furnace, tunnel kiln, or suspension kiln.
5. The method of claim 4, wherein when the converting roasting furnace is a rotary kiln, spodumene or spodumene concentrate is added to the kiln tail of the rotary kiln, the material moves from the kiln tail to a middle high temperature section of the rotary kiln along with the rotation of the rotary kiln, and sulfur is sprayed into the kiln through a spray pipe at the kiln head for combustion.
6. The method of claim 1, wherein flue gas generated in the roasting process is subjected to waste heat recovery, then dust collection is performed, and the flue gas after dust collection is purified, converted and dried to prepare industrial-grade sulfuric acid; the heat generated by the waste heat recovery is used for drying or preheating spodumene or spodumene concentrate materials before roasting.
7. The process according to claim 6, wherein the beta-spodumene obtained by transformation is finely ground and then mixed with technical grade sulfuric acid obtained, according to the beta-spodumene: mixing sulfuric acid at a weight ratio of 1:0.05-0.5, sulfating and roasting at 250-300 deg.C to convert beta spodumene into soluble lithium sulfate, and leaching the roasted product with water to obtain lithium-containing solution.
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| CN (1) | CN117448592A (en) |
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2023
- 2023-10-27 CN CN202311407456.5A patent/CN117448592A/en active Pending
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