CN113860385A - Recycling method of ferro-manganese desulfurizer solid waste - Google Patents
Recycling method of ferro-manganese desulfurizer solid waste Download PDFInfo
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- CN113860385A CN113860385A CN202111173947.9A CN202111173947A CN113860385A CN 113860385 A CN113860385 A CN 113860385A CN 202111173947 A CN202111173947 A CN 202111173947A CN 113860385 A CN113860385 A CN 113860385A
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 229910000616 Ferromanganese Inorganic materials 0.000 title claims abstract description 12
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000002910 solid waste Substances 0.000 title claims abstract description 12
- 238000004064 recycling Methods 0.000 title claims description 6
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 239000007789 gas Substances 0.000 claims abstract description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 239000012495 reaction gas Substances 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000005587 bubbling Effects 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 4
- 239000002699 waste material Substances 0.000 claims description 30
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 17
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003546 flue gas Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000002485 combustion reaction Methods 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims 2
- 239000003054 catalyst Substances 0.000 claims 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims 2
- WQHONKDTTOGZPR-UHFFFAOYSA-N [O-2].[O-2].[Mn+2].[Fe+2] Chemical compound [O-2].[O-2].[Mn+2].[Fe+2] WQHONKDTTOGZPR-UHFFFAOYSA-N 0.000 claims 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims 1
- 239000003570 air Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 229910001935 vanadium oxide Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000006477 desulfuration reaction Methods 0.000 abstract description 10
- 230000023556 desulfurization Effects 0.000 abstract description 10
- 239000011259 mixed solution Substances 0.000 abstract description 8
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 abstract description 8
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- 239000003345 natural gas Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 101100289061 Drosophila melanogaster lili gene Proteins 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention relates to a resource method of solid waste of a ferro-manganese oxide desulfurizer, which is characterized by comprising the following steps: the desulfurization solid waste components are FeS and MnS, the powder is ground and then put into a reactor 1 containing a mixed solution of 1-10% of dilute sulfuric acid and 0.01-1% of vitriol, and high-temperature reaction gas and air (or oxygen) are introduced into the reactor 1 for circular bubbling, wherein the molar ratio of solid to liquid is 0.01-0.1: 1, the molar ratio of gas to liquid is 0.01-0.1: 1, and the reaction retention time is 2 hours. Solid, liquid, gas obtained in the separation reactor 1: dehydrating the solid, heating to above 480 ℃, separating to obtain silicon dioxide powder as a product 1, and sending sulfur vapor into a circulating gas catalytic reactor 2; the liquid is crystallized step by step to obtain Fe2(SO4)3、MnSO4The circulating liquid is returned to the reactor 1; the gas and the added oxygen enter a circulating gas catalytic reactor 2 together, and the circulating gas catalytic reactor 2 mixes sulfur vapor and H2S、SO2All converted into sulfur trioxide and then are introduced into the reactor 1 to be absorbed by the aqueous solution.
Description
Technical Field
The invention relates to the fields of chemical industry, energy conservation and environmental protection, and discloses a method for realizing sulfur resource circulation, pollution-free and consumption-free by natural gas desulfurization waste.
Background
For a long time, dry desulfurization is widely applied because of the advantages of simple process, no problem of sewage and waste acid treatment, low energy consumption and the like, and natural gas is treated by dry desulfurization and simultaneously generates a great amount of waste desulfurizer, which gradually becomes a new solid pollution source and needs to be subjected to harmless treatment.
The waste desulfurizing agent contains a large amount of sulfide which is usually treated by a moistening method, a burning burying method, an acid washing method, a chemical inhibition method, an oxidizing agent method and the like. H is treated by burning method and acid washing method2S，SO2The generation of the fire-resistant coating has great harm to human bodies and the environment, and can cause potential safety hazards and cause accidents such as fire, explosion and the like while polluting the environment; the chemical inhibition method using sodium hydroxide is high in cost, and the use of other reducing agents to form solution or precipitate is another worthless waste; the neutralization process also uses lime to convert it to stable, harmless calcium sulfide for landfilling and is of no economic value. In summary, there is an urgent need in our country for a technical method for harmless treatment of desulfurizer solid waste while producing products with added value.
CN108796215B Zhudeqing and other announcements use a waste desulfurizer treatment method, and waste desulfurizer, iron ore powder, solid fuel, flux and return ore are mixed to obtain sintering mixture; adding water into the sintering mixture, mixing and granulating to obtain a granulating material; sintering the granulated material to obtain sintered ore and sintered flue gas; and discharging the sintering flue gas into the atmosphere after desulfurization and denitrification. The technology produces sinter from the waste desulfurizer and other raw materials for ironmaking, the mode of discharging sintering flue gas after desulfurization and denitrification has low economic value, and the conversion of sulfur in the waste desulfurizer into sulfur oxide is to transfer desulfurization treatment to a rear working section without solving the problem.
CN111607704A Lili et al disclose a process for treating waste desulfurizer, which comprises mixing waste desulfurizer with pyrolusite to obtain mixed solid, leaching the mixed solid with sulfuric acid to obtain leachate, adding carbonizing agent into the leachate for carbonization and crystallization, filtering after the carbonization and crystallization to obtain manganese carbonate, and completing manganeseIs a treatment process of waste desulfurizer. The method for leaching carbonized crystals by adopting sulfuric acid in the technology only aims at simply obtaining manganese carbonate and completely omits the leaching of H2Contamination of S gas and technical economy.
CN103771346A Liu Shuhe et al announced a sulfur recovery method in waste desulfurizer, the waste desulfurizer is dried, then mixed with catalytic cracking diesel oil at 40-250 ℃, after 0.1-10 hours, the desulfurizer material and desulfurization liquid are obtained by solid-liquid separation, the liquid phase is cooled to 0-30 ℃, the elemental sulfur is recovered, and the desulfurization liquid can be recycled. The technology is to separate sulfur from solid and liquid to obtain sulfur, but the economic value of the sulfur is low.
In conclusion, it can be seen that the waste desulfurizing agent is digested to avoid the generation of H2S、SO2Pollution and new waste, and simultaneously, the production of products with higher value is a technical problem which is not solved at present.
Disclosure of Invention
The invention relates to a resource method of solid waste of a ferro-manganese oxide desulfurizer, which is characterized by comprising the following steps: the desulfurization solid waste components are FeS and MnS, the powder is ground and then put into a reactor 1 containing a mixed solution of 1-10% of dilute sulfuric acid and 0.01-1% of vitriol, and high-temperature reaction gas and air (or oxygen) are introduced into the reactor 1 for circular bubbling, wherein the molar ratio of solid to liquid is 0.01-0.1: 1, the molar ratio of gas to liquid is 0.01-0.1: 1, and the reaction retention time is 2 hours. Solid, liquid, gas obtained in the separation reactor 1: dehydrating the solid, heating to above 480 ℃, separating to obtain silicon dioxide powder as a product 1, and sending sulfur vapor into a circulating gas catalytic reactor 2; the liquid is crystallized step by step to obtain Fe2(SO4)3、MnSO4The circulating liquid is returned to the reactor 1; the gas and the added oxygen enter a circulating gas catalytic reactor 2 together, and the circulating gas catalytic reactor 2 mixes sulfur vapor and H2S、SO2All converted into sulfur trioxide and then are introduced into the reactor 1 to be absorbed by the aqueous solution.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a method for treating natural gas ferro-manganese waste desulfurizer, which has simple and reliable process and not only produces Fe2(SO4)3、MnSO4Valuable products such as the like reduce solid waste discharge, and new solid, liquid and gas wastes are not generated;
(2) the invention provides a method for treating natural gas waste iron and manganese desulfurizer, which can treat a large amount of natural gas waste desulfurizer, has low treatment cost, realizes complete conversion of waste into products, and achieves the purpose of sustainable development;
(3) the invention provides a method for treating natural gas ferro-manganese waste desulfurizer, which is used for treating H generated in the process of recycling the waste desulfurizer2S、SO2The sulfur trioxide is completely converted and then absorbed by water, thereby not only avoiding gas pollution, but also simplifying the process of preparing sulfuric acid by sulfur trioxide and then reacting with a waste desulfurizer;
(4) the invention provides a method for treating natural gas ferro-manganese waste desulfurizer, wherein the sulfur in the waste desulfurizer is finally MnSO4And Fe2(SO4)3The form of the sulfur is completely converted into a product, and the full-cycle resource utilization of the sulfur is realized.
Drawings
FIG. 1 is a process schematic flow chart of a method for recycling solid waste of a ferro-manganese oxide desulfurizer.
Detailed Description
Example 1: placing a mixed solution of 5% dilute sulfuric acid and 0.2% vanadium sulfate in a reactor 1, adding the waste ferro-manganese desulfurizer into the mixed solution, wherein the solid-liquid molar ratio is 0.08:1, and introducing a mixed gas of high-temperature reaction gas and air (or oxygen) for circular bubbling, and the gas-liquid molar ratio is 0.1: 1; the reaction is kept for 2 hours, and liquid, solid and gas are separated; the gas is sent into a high-temperature catalytic reactor 2, the reaction temperature is 500 ℃, the reaction time is 0.5 hour, and the reaction gas is sent into a reactor 1; dehydrating the solid, heating to over 480 ℃ to obtain gaseous sulfur, sending the gaseous sulfur into a circulating gas catalytic reactor 2, remaining silicon dioxide powder, and sending sulfur dioxide flue gas generated by combustion back to the reactor 1; and (3) crystallizing the liquid to separate manganese sulfate and ferric sulfate, and returning the crystallized liquid to the reactor 1.
Example 2: placing a mixed solution of 8% dilute sulfuric acid and 0.2% vanadium sulfate in a reactor 1, adding the waste ferro-manganese desulfurizer into the mixed solution, wherein the solid-liquid molar ratio is 0.06:1, and introducing a mixed gas of high-temperature reaction gas and air (or oxygen) for circular bubbling, and the gas-liquid molar ratio is 0.08: 1; the reaction is kept for 2 hours, and liquid, solid and gas are separated; the gas is sent into a high-temperature catalytic reactor 2, the reaction temperature is 500 ℃, the reaction time is 1 hour, and the reaction gas is sent into the reactor 1; dehydrating the solid, heating to over 480 ℃ to obtain gaseous sulfur, sending the gaseous sulfur into a circulating gas catalytic reactor 2, remaining silicon dioxide powder, and sending sulfur dioxide flue gas generated by combustion back to the reactor 1; and (3) crystallizing the liquid to separate manganese sulfate and ferric sulfate, and returning the crystallized liquid to the reactor 1.
Example 3: placing a mixed solution of 10% dilute sulfuric acid and 0.1% vanadium sulfate in a reactor 1, adding the waste ferro-manganese desulfurizer into the mixed solution, wherein the solid-liquid molar ratio is 0.1:1, and introducing a mixed gas of high-temperature reaction gas and air (or oxygen) for circular bubbling, and the gas-liquid molar ratio is 0.08: 1; the reaction is kept for 2 hours, and liquid, solid and gas are separated; the gas is sent into a high-temperature catalytic reactor 2, the reaction temperature is 500 ℃, the reaction time is 0.6 hour, and the reaction gas is sent into a reactor 1; dehydrating the solid, heating to over 480 ℃ to obtain gaseous sulfur, sending the gaseous sulfur into a circulating gas catalytic reactor 2, remaining silicon dioxide powder, and sending sulfur dioxide flue gas generated by combustion back to the reactor 1; and (3) crystallizing the liquid to separate manganese sulfate and ferric sulfate, and returning the crystallized liquid to the reactor 1.
Claims (2)
1. A method for recycling solid wastes of a ferro-manganese desulfurizer is characterized in that the waste desulfurizer is ground into powder and is placed into a reactor 1 containing 1-10% of dilute sulfuric acid and 0.01-1% of vanadium sulfate solution, the solid-liquid molar ratio is 0.01-0.1: 1, high-temperature reaction gas and air or oxygen are introduced for circular bubbling, and the gas-liquid molar ratio is 0.01-0.1: 1; after staying for 2 hours, separating liquid, solid and gas; feeding the gas into a circulating gas catalytic reactor 2 at the temperature of 360-800 ℃ for 0.1-2 hours, and feeding the reaction gas into the reactor 1; dehydrating the solid, heating to over 480 ℃ to obtain gaseous sulfur, sending the gaseous sulfur into a circulating gas catalytic reactor 2, taking the rest silicon dioxide powder as a product 1 for sale, and sending sulfur dioxide flue gas generated by combustion back to the reactor 1; and (3) crystallizing and separating the manganese sulfate as a product 2, using the ferric sulfate as a product 3 for sale, and returning the crystallized liquid to the reactor 1, thereby continuously treating the solid waste of the iron-manganese oxide desulfurizer.
2. The method for recycling solid wastes of iron and manganese desulfurizer as claimed in claim 1, wherein the catalyst of the recycle gas catalytic reactor 2 is a composite catalyst of iron oxide, vanadium oxide and manganese oxide.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111173947.9A CN113860385B (en) | 2021-10-09 | 2021-10-09 | Recycling method of solid waste of ferro-manganese desulfurizing agent |
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| CN202111173947.9A CN113860385B (en) | 2021-10-09 | 2021-10-09 | Recycling method of solid waste of ferro-manganese desulfurizing agent |
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|---|---|---|---|---|
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| WO2021075136A1 (en) * | 2019-10-18 | 2021-04-22 | Ｊｆｅスチール株式会社 | Method for recovering manganese from waste dry-cell batteries and recovery equipment |
-
2021
- 2021-10-09 CN CN202111173947.9A patent/CN113860385B/en active Active
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| CN108183207A (en) * | 2017-12-23 | 2018-06-19 | 湖南佳纳能源科技有限公司 | A kind of method that compound manganese ore prepares anode material of lithium battery |
| WO2021075136A1 (en) * | 2019-10-18 | 2021-04-22 | Ｊｆｅスチール株式会社 | Method for recovering manganese from waste dry-cell batteries and recovery equipment |
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