CN113860385B - Recycling method of solid waste of ferro-manganese desulfurizing agent - Google Patents
Recycling method of solid waste of ferro-manganese desulfurizing agent Download PDFInfo
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- CN113860385B CN113860385B CN202111173947.9A CN202111173947A CN113860385B CN 113860385 B CN113860385 B CN 113860385B CN 202111173947 A CN202111173947 A CN 202111173947A CN 113860385 B CN113860385 B CN 113860385B
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- 238000000034 method Methods 0.000 title claims abstract description 31
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000002910 solid waste Substances 0.000 title claims abstract description 12
- 238000004064 recycling Methods 0.000 title claims abstract description 10
- 229910000616 Ferromanganese Inorganic materials 0.000 title claims abstract description 7
- 230000003009 desulfurizing effect Effects 0.000 title claims description 27
- 239000003795 chemical substances by application Substances 0.000 title claims description 25
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 239000007789 gas Substances 0.000 claims abstract description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 239000012495 reaction gas Substances 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000002699 waste material Substances 0.000 claims description 29
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 239000011593 sulfur Substances 0.000 claims description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003546 flue gas Substances 0.000 claims description 8
- 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
- 229910000360 iron(III) sulfate Inorganic materials 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
- 239000000843 powder Substances 0.000 claims description 3
- 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
- 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
- 239000002131 composite material Substances 0.000 claims 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims 1
- 229910001935 vanadium oxide Inorganic materials 0.000 claims 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000011259 mixed solution Substances 0.000 abstract description 8
- 238000006477 desulfuration reaction Methods 0.000 abstract description 7
- 230000023556 desulfurization Effects 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 238000001640 fractional crystallisation Methods 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000003345 natural gas Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 229910052742 iron Inorganic materials 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
- 239000000203 mixture Substances 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 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 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 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
- 230000004907 flux Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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
Landscapes
- 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 recycling method of solid waste of a ferro-manganese oxide desulfurizer, which is characterized by comprising the following steps of: the desulfurization solid waste comprises FeS and MnS, the FeS and the MnS are ground, the ground FeS and the MnS are placed into a reactor 1 containing a mixed solution of 1-10% of dilute sulfuric acid and 0.01-1% of vitriol, and then high-temperature reaction gas and air (or oxygen) are introduced into the reactor 1 for circulation bubbling, wherein the solid-liquid molar ratio is 0.01-0.1:1, the gas-liquid molar ratio is 0.01-0.1:1, and the reaction residence time is 2 hours. Separation of the solid, liquid, gas obtained in reactor 1: the solid is dehydrated and heated to above 480 ℃ to be separated to obtain silicon dioxide powder which is used as a product 1, and sulfur vapor is sent into a circulating gas catalytic reactor 2; the liquid is subjected to fractional crystallization to obtain Fe 2 (SO 4 ) 3 、MnSO 4 Circulating liquid back into the reactor 1; the gas and the added oxygen enter a circulating gas catalytic reactor 2 together, and the circulating gas catalytic reactor 2 carries out sulfur vapor and H 2 S、SO 2 Are all converted into sulfur trioxide and then 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, in particular to a method for realizing sulfur resource circulation by using natural gas desulfurization waste, which has no pollution and no consumption.
Background
For a long time, the dry desulfurization has been widely used because of its simple process, no sewage and acid treatment problems, low energy consumption, and the like, and the natural gas adopts the dry desulfurization treatment and simultaneously causes a great increase of the generated waste desulfurizing agent, which gradually becomes a new solid pollution source, and the harmless treatment must be performed on the waste desulfurizing agent.
The waste desulfurizing agent contains a large amount of sulfides which are usually treated by a wetting method, an incineration burying method, an acid washing method, a chemical inhibition method, an oxidizing agent method and the like. Incineration method and acid washing method are difficult to avoid H 2 S，SO 2 Is harmful to human body and environment, and can cause safety when polluting the environmentHidden danger, fire, explosion and other accidents are caused; the chemical inhibition method has high cost due to the use of sodium hydroxide, and the use of other reducing agents to form a solution or a precipitate is another waste without value; the neutralization method uses lime to convert the calcium sulfide into stable and harmless calcium sulfide for landfill, so that the economic value is not high. In summary, there is an urgent need in China for a technical method for harmlessly treating solid waste of desulfurizing agents while producing products with added value.
CN108796215B Zhu Deqing, et al announced that a treatment method of waste desulfurizing agent is used, waste desulfurizing agent, iron ore powder, solid fuel, flux and return ore are mixed to obtain a sintered mixture; adding water into the sintering mixture, mixing and granulating to obtain granules; sintering the granulated material to obtain sintered ore and sintering flue gas; and (3) desulfurizing and denitrating the sintering flue gas, and then discharging the sintering flue gas into the atmosphere. The technology uses the waste desulfurizing agent and the rest raw materials to produce the sintering mine for iron making, and the mode of desulfurization, denitrification and emission of sintering flue gas has low economic value, and the sulfur in the waste desulfurizing agent is converted into sulfur oxide, so that the sulfur oxide is transferred to a rear working section of desulfurization treatment, and the problem is not solved.
CN111607704a Li Li, et al, discloses a treatment process for a waste desulfurizing agent, wherein a mixed solid is obtained by mixing the waste desulfurizing agent with pyrolusite, a leaching solution is obtained by leaching the mixed solid with sulfuric acid, a carbonization agent is added into the leaching solution for carbonization and crystallization, and after the carbonization and crystallization are completed, manganese carbonate is obtained by filtration, and the treatment process for the manganese-based waste desulfurizing agent is completed. The technology adopts the method of leaching carbonized crystals by sulfuric acid to obtain manganese carbonate only and completely neglects leaching H 2 S gas pollution and technical economy.
CN103771346a Liu Shuhe, et al announces a method for recovering sulfur from waste desulfurizing agent, which comprises drying waste desulfurizing agent, mixing with catalytic cracking diesel oil at 40-250 ℃ for 0.1-10 hours, solid-liquid separating to obtain desulfurizing agent material and desulfurizing liquid, cooling liquid phase to 0-30 ℃, recovering elemental sulfur, and recycling desulfurizing liquid. The technology is to obtain sulfur by solid-liquid separation, but the economic value of sulfur is low.
In summary, it can be seen that the digestion of the spent desulfurizing agent avoids the generation of H 2 S、SO 2 Pollution and new waste, and simultaneously producing products with higher value are technical problems which are not solved at present.
Disclosure of Invention
The invention relates to a recycling method of solid waste of a ferro-manganese oxide desulfurizer, which is characterized by comprising the following steps of: the desulfurization solid waste comprises FeS and MnS, the FeS and the MnS are ground, the ground FeS and the MnS are placed into a reactor 1 containing a mixed solution of 1-10% of dilute sulfuric acid and 0.01-1% of vitriol, and then high-temperature reaction gas and air (or oxygen) are introduced into the reactor 1 for circulation bubbling, wherein the solid-liquid molar ratio is 0.01-0.1:1, the gas-liquid molar ratio is 0.01-0.1:1, and the reaction residence time is 2 hours. Separation of the solid, liquid, gas obtained in reactor 1: the solid is dehydrated and heated to above 480 ℃ to be separated to obtain silicon dioxide powder which is used as a product 1, and sulfur vapor is sent into a circulating gas catalytic reactor 2; the liquid is subjected to fractional crystallization to obtain Fe 2 (SO 4 ) 3 、MnSO 4 Circulating liquid back into the reactor 1; the gas and the added oxygen enter a circulating gas catalytic reactor 2 together, and the circulating gas catalytic reactor 2 carries out sulfur vapor and H 2 S、SO 2 Are all converted into sulfur trioxide and then 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 treatment method of a natural gas iron-manganese waste desulfurizing agent, which has simple and reliable process and not only produces Fe 2 (SO 4 ) 3 、MnSO 4 Valuable products such as solid waste emission is reduced, and new solid, liquid and gas wastes are not generated yet;
(2) The invention provides a treatment method of a natural gas iron-manganese waste desulfurizer, which can treat a great deal of natural gas waste desulfurizer, has low treatment cost, realizes complete conversion of waste into products, and achieves the aim of sustainable development;
(3) The invention provides a treatment method of a natural gas iron-manganese waste desulfurizer, which is characterized in that H generated in the recycling process of the waste desulfurizer 2 S、SO 2 The sulfur trioxide is fully converted into sulfur trioxide and then absorbed by water, so that gas pollution is avoided, and the process of preparing sulfuric acid from the sulfur trioxide and then reacting with a waste desulfurizing agent is simplified;
(4) The invention provides a treatment method of a natural gas iron-manganese waste desulfurizer, sulfur in the waste desulfurizer is treated by MnSO at last 4 And Fe (Fe) 2 (SO 4 ) 3 The form of the sulfur is fully converted into a product, and the full cycle recycling of sulfur is realized.
Drawings
FIG. 1 is a process schematic flow diagram of a method for recycling solid waste of iron-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 a waste iron-manganese desulfurizing agent into the mixed solution, wherein the solid-liquid molar ratio is 0.08:1, introducing a mixed gas of high-temperature reaction gas and air (or oxygen) for circulating bubbling, and the gas-liquid molar ratio is 0.1:1; the reaction residence time is 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; the solid is dehydrated and heated to more than 480 ℃ to obtain gaseous sulfur, the gaseous sulfur is sent into a circulating gas catalytic reactor 2, the rest silicon dioxide powder is burned, and sulfur dioxide flue gas generated by combustion is sent back into the reactor 1; and (3) separating manganese sulfate and ferric sulfate by liquid crystallization, 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 a waste iron-manganese desulfurizing agent into the mixed solution, wherein the solid-liquid molar ratio is 0.06:1, introducing a mixed gas of high-temperature reaction gas and air (or oxygen) for circulating bubbling, and the gas-liquid molar ratio is 0.08:1; the reaction residence time is 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 a reactor 1; the solid is dehydrated and heated to more than 480 ℃ to obtain gaseous sulfur, the gaseous sulfur is sent into a circulating gas catalytic reactor 2, the rest silicon dioxide powder is burned, and sulfur dioxide flue gas generated by combustion is sent back into the reactor 1; and (3) separating manganese sulfate and ferric sulfate by liquid crystallization, 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 a waste iron-manganese desulfurizing agent into the mixed solution, wherein the solid-liquid molar ratio is 0.1:1, introducing a mixed gas of high-temperature reaction gas and air (or oxygen) for circulating bubbling, and the gas-liquid molar ratio is 0.08:1; the reaction residence time is 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; the solid is dehydrated and heated to more than 480 ℃ to obtain gaseous sulfur, the gaseous sulfur is sent into a circulating gas catalytic reactor 2, the rest silicon dioxide powder is burned, and sulfur dioxide flue gas generated by combustion is sent back into the reactor 1; and (3) separating manganese sulfate and ferric sulfate by liquid crystallization, and returning the crystallized liquid to the reactor 1.
Claims (2)
1. A recycling method of solid waste of a ferro-manganese desulfurizing agent is characterized in that the waste desulfurizing agent is ground into powder, the powder 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, mixed gas of high-temperature reaction gas and air or mixed gas of high-temperature reaction gas and oxygen is introduced for circulation bubbling, and the gas-liquid molar ratio is 0.01-0.1:1; after 2 hours of residence, separating liquid, solid and gas; delivering the gas into a 360-800 ℃ circulating gas catalytic reactor 2 for staying for 0.1-2 hours, and delivering the reaction gas into a reactor 1; the solid is dehydrated and heated to above 480 ℃ to obtain gaseous sulfur, the gaseous sulfur is sent into a circulating gas catalytic reactor 2, the rest silicon dioxide powder is sold as a product 1, and sulfur dioxide flue gas generated by combustion is sent back into the reactor 1; the liquid is crystallized and separated to obtain manganese sulfate as a product 2, ferric sulfate is sold as a product 3, and the crystallized liquid is returned to the reactor 1, so that solid waste of the ferro-manganese oxide desulfurizer is continuously treated.
2. The recycling method of solid waste of ferro-manganese desulfurizer according to claim 1, wherein the catalyst of the circulating gas catalytic reactor 2 is a composite catalyst of ferric oxide, vanadium oxide and manganese oxide.
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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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| CN113860385B true CN113860385B (en) | 2023-11-17 |
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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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