CN116949291A - Comprehensive recovery method for high-arsenic multi-metal hazardous waste - Google Patents
Comprehensive recovery method for high-arsenic multi-metal hazardous waste Download PDFInfo
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- CN116949291A CN116949291A CN202310690450.7A CN202310690450A CN116949291A CN 116949291 A CN116949291 A CN 116949291A CN 202310690450 A CN202310690450 A CN 202310690450A CN 116949291 A CN116949291 A CN 116949291A
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 74
- 239000002184 metal Substances 0.000 title claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 46
- 239000002920 hazardous waste Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000011084 recovery Methods 0.000 title claims abstract description 17
- 239000002893 slag Substances 0.000 claims abstract description 84
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000000463 material Substances 0.000 claims abstract description 71
- 239000011133 lead Substances 0.000 claims abstract description 65
- 238000007664 blowing Methods 0.000 claims abstract description 62
- 239000010949 copper Substances 0.000 claims abstract description 52
- 229910052802 copper Inorganic materials 0.000 claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000001301 oxygen Substances 0.000 claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 45
- 239000002912 waste gas Substances 0.000 claims abstract description 37
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000003723 Smelting Methods 0.000 claims abstract description 32
- 230000009467 reduction Effects 0.000 claims abstract description 32
- 238000006722 reduction reaction Methods 0.000 claims abstract description 28
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 238000004073 vulcanization Methods 0.000 claims abstract description 16
- 238000007599 discharging Methods 0.000 claims abstract description 15
- 239000002699 waste material Substances 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 238000004064 recycling Methods 0.000 claims abstract description 8
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 claims abstract 5
- 239000007921 spray Substances 0.000 claims description 40
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 27
- 239000003546 flue gas Substances 0.000 claims description 27
- 239000003245 coal Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 16
- 239000010453 quartz Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000006477 desulfuration reaction Methods 0.000 claims description 12
- 230000023556 desulfurization Effects 0.000 claims description 12
- 239000008187 granular material Substances 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 238000010791 quenching Methods 0.000 claims description 12
- 230000000171 quenching effect Effects 0.000 claims description 12
- 239000004575 stone Substances 0.000 claims description 12
- 239000002918 waste heat Substances 0.000 claims description 12
- 239000003345 natural gas Substances 0.000 claims description 6
- 150000004763 sulfides Chemical class 0.000 claims description 6
- 239000000571 coke Substances 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 3
- 229910052602 gypsum Inorganic materials 0.000 claims description 3
- 239000010440 gypsum Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011028 pyrite Substances 0.000 claims description 3
- 229910052683 pyrite Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000007769 metal material Substances 0.000 abstract description 4
- 230000000737 periodic effect Effects 0.000 abstract description 4
- 239000002440 industrial waste Substances 0.000 abstract description 3
- 150000003568 thioethers Chemical class 0.000 abstract 1
- 239000000428 dust Substances 0.000 description 24
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 16
- 229960002594 arsenic trioxide Drugs 0.000 description 16
- 239000000779 smoke Substances 0.000 description 16
- 239000002994 raw material Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000005453 pelletization Methods 0.000 description 5
- 229910000640 Fe alloy Inorganic materials 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- VETKVGYBAMGARK-UHFFFAOYSA-N arsanylidyneiron Chemical compound [As]#[Fe] VETKVGYBAMGARK-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000011946 reduction process Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000005486 sulfidation Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- WIKSRXFQIZQFEH-UHFFFAOYSA-N [Cu].[Pb] Chemical compound [Cu].[Pb] WIKSRXFQIZQFEH-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- -1 containing oxides Chemical compound 0.000 description 1
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 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
- 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
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G28/00—Compounds of arsenic
- C01G28/005—Oxides; Hydroxides; Oxyacids
-
- 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
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0054—Slag, slime, speiss, or dross treating
-
- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a comprehensive recovery method of high-arsenic multi-metal hazardous waste, which comprises the steps of preparing materials of the high-arsenic multi-metal hazardous waste, a reducing agent and a vulcanizing agent according to a preset proportion to obtain a mixed material; adding the mixed material into a top-blowing furnace for reduction, vulcanization and smelting to obtain first slag, mixed copper matte, crude lead and first waste gas, wherein the mixed copper matte comprises sulfides of arsenic, lead, copper and iron; discharging first slag and crude lead, and treating the first waste gas and discharging the treated first waste gas; oxygen-enriched blowing is carried out on the mixed copper matte in a top blowing furnace to obtain second slag, blister copper and second waste gas; and recycling the arsenic trioxide in the second waste gas, and treating the second waste gas and discharging the treated second waste gas. The method is suitable for treating the multi-metal material containing arsenic, and can be matched with the treatment of the industrial waste without arsenic; the top-blown furnace adopts periodic operation, is very suitable for a dangerous waste disposal production system with smaller scale, saves investment and reduces cost.
Description
Technical Field
The invention relates to the technical field of harmless disposal of arsenic-containing hazardous waste, in particular to a comprehensive recovery method of high-arsenic multi-metal hazardous waste.
Background
The materials such As white smoke dust, kaldo furnace smoke dust, noble lead furnace smoke dust, acid mud, clean liquid residue, lead matte and the like generated by a smelting plant contain various metals such As copper, lead, zinc, gold, silver and the like, and the raw materials contain high arsenic, and the As content is generally 1-10%. In the prior art, a blast furnace reduction smelting process is generally adopted for treating the solid waste of the multi-metal industry containing arsenic mainly containing oxides, and arsenic matte is easy to generate due to arsenic, lead, copper and iron, and a blast furnace spray gun is relatively fixed in position, so that a diaphragm layer cannot be blown through, a furnace knot is easy to form, and the operation is difficult. The raw materials are pretreated, arsenic and copper are removed to a certain degree, and then the raw materials are added into a furnace for treatment. The typical treatment process is that the smoke dust is subjected to operation procedures of primary water leaching, secondary acid leaching, scrap iron copper removal, iron and arsenic removal and the like, and valuable metals in the smoke dust are respectively recycled in the forms of sponge copper, zinc sulfate and the like; and the bottom flow is pumped to a filter press for filter pressing, the filter cake is pulpified and washed, and then pumped to the filter press for filter pressing, and the obtained slag is lead slag with higher lead content. The lead slag has higher lead-bismuth content and contains partial arsenic and copper, and is added into a blast furnace for reduction smelting after being dried and bricked, and crude lead and arsenic-iron alloy are recovered. The process flow is long, the working procedures are more, and the processing cost is higher. The arsenic-iron alloy and copper-lead are mutually dissolved, the recovery rate of valuable metals is low, and the economic benefit is affected.
Currently, a side-blown furnace is also adopted to replace a blast furnace process, but the raw materials also need to be pretreated. The problems are similar to the blast furnace process.
The reduction smelting process of a blast furnace (or a side blowing furnace) is adopted to treat high-arsenic polymetallic hazardous waste, and the following problems exist: the arsenic matte is easy to form by directly treating the materials; the position of the side blowing spray gun is relatively fixed, and the diaphragm layer cannot be blown through, so that the heat transfer and fluidity of a molten pool are poor, and the separation of metals is affected; raw materials need pretreatment for copper removal and arsenic removal, and the waste acid and wastewater generated are complex to treat; the arsenic-iron alloy is mutually soluble with copper and lead, is not easy to separate, and has low metal recovery rate; the process flow is long, the investment is large, and the processing cost is high; the product of the arsenic-iron alloy has no industry standard and has low market sales value.
Disclosure of Invention
The invention aims to provide a comprehensive recovery method of high-arsenic multi-metal hazardous waste. In order to achieve the above purpose, the present invention provides the following technical solutions:
the invention provides a comprehensive recovery method of high-arsenic multi-metal hazardous waste, which comprises the following steps of,
mixing the high-arsenic multi-metal hazardous waste, the reducing agent and the vulcanizing agent according to a preset proportion to obtain a mixed material;
adding the mixed material into a top-blowing furnace for reduction, vulcanization and smelting to obtain first slag, mixed copper matte, crude lead and first waste gas, wherein the mixed copper matte comprises sulfides of arsenic, lead, copper and iron;
discharging first slag and crude lead, and treating the first waste gas and discharging the treated first waste gas;
oxygen-enriched blowing is carried out on the mixed copper matte in a top blowing furnace to obtain second slag, blister copper and second waste gas;
and recycling the arsenic trioxide in the second waste gas, and treating the second waste gas and discharging the treated second waste gas.
Optionally, after the high-arsenic multi-metal hazardous waste, the reducing agent and the vulcanizing agent are proportioned according to a preset proportion, a mixed material is obtained, and the method comprises the following steps:
after the high-arsenic multi-metal hazardous waste, the first reducing agent and the vulcanizing agent are subjected to primary batching, humidifying and granulating are carried out to obtain a granular material;
carrying out secondary batching on the granular materials, a second reducing agent and other hazardous waste materials to obtain a mixed material;
wherein, the proportion of the high-arsenic multi-metal hazardous waste to the first reducing agent and the vulcanizing agent is 100 (1-5) in (1-5).
The other hazardous waste materials comprise blowing slag, and the proportion of the granular materials to the second reducing agent to other hazardous waste materials is 100 (10-20) (1-5).
Optionally, the first reductant comprises crushed coal;
the second reductant comprises lump coal or coke;
the vulcanizing agent comprises pyrite, gypsum slag and CaSO 4 Or one of copper concentrates.
Optionally, the water content of the granular material is controlled to be 8-12%.
Optionally, the mixed material is added into a top-blowing furnace for reduction, vulcanization and smelting, comprising,
after the mixed material is added into the furnace, natural gas and oxygen-enriched air are sprayed into the furnace through a top-blowing spray gun, the temperature of a molten pool is controlled to 1250-1550 ℃, the mixed material in the furnace is fully reacted, and slag, crude lead, mixed copper matte and first waste gas are generated.
Optionally, the first slag is sold as waste slag;
the lead bullion is sold as a product;
the mixed matte remains in the top-blown furnace.
Optionally, the first exhaust gas treated exhaust line comprises,
and after the first waste gas is fully combusted, the waste heat is recovered through a waste heat boiler, the quenching tower is cooled, and the waste gas is discharged after desulfurization and denitrification treatment.
Optionally, the oxygen-enriched converting is carried out on the mixed copper matte in a top-blowing furnace, comprising,
oxygen-enriched air is sprayed into the furnace, and the temperature of the molten pool is controlled to be 1200-1250 ℃;
and adding quartz stone and mixed matte in a preset proportion to perform oxygen-enriched converting operation to obtain second slag, blister copper and second waste gas.
Optionally, the blister copper ingot is sold;
and the second slag is added into the top-blown furnace again for reduction, vulcanization and smelting, and then lead is recovered.
Optionally, the second exhaust gas is treated and discharged, including,
the second waste gas is subjected to a dry arsenic trioxide recovery process by flue gas to obtain arsenic trioxide,
and (3) recycling the second waste gas after the arsenic trioxide, and discharging the second waste gas after desulfurization and denitrification treatment reaches the standard.
The invention has the technical effects and advantages that:
(1) The method is suitable for treating the multi-metal material containing arsenic, and can be matched with the treatment of the industrial waste without arsenic;
(2) Raw materials do not need pretreatment, directly enter a top-blowing furnace for pyrometallurgy reduction smelting, and can penetrate a diaphragm layer in the furnace through a lifting gun position so as to fully react the materials in the furnace;
(3) The diameter and the height of the top-blown furnace are related to the smelting scale and are determined according to the treatment scale;
(4) The grade of the mixed copper matte/lead bullion/blister copper and the slag of smelting slag/converting slag can be flexibly adjusted according to different working conditions and requirements;
(5) The top-blown furnace adopts a periodic operation mode, and is very suitable for a hazardous waste disposal production system with smaller scale. Saving investment and reducing cost.
(6) The top blowing furnace adopts the spray gun A and the spray gun B to be respectively used for reduction smelting and oxygen-enriched blowing, and has good production flexibility and strong risk resistance.
(7) And the first and second period flue gas is treated respectively, and the dry quenching arsenic recovery technology is carried out on the flue gas with higher arsenic content in the second period to recover arsenic trioxide, so that the hazardous waste reduction is realized.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a schematic diagram of a main device according to an embodiment of the present invention.
In the figure: 1-top blowing furnace, 2-spray gun A, 3-spray gun B, 4-slag hole and 5-metal discharge hole.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to solve the defects of the prior art, the invention discloses a comprehensive recovery method of high-arsenic multi-metal hazardous waste, as shown in figure 1, which comprises the following steps of,
step 1: preliminary batching is carried out on high-arsenic multi-metal hazardous waste (high-arsenic multi-metal material), a first reducing agent (crushed coal) and a vulcanizing agent, then the mixed material is added into a granulator for humidification and granulation (or pelletization) to obtain a granular material, and the water content of the granular material generated after pelletization is controlled to be 8-12%, wherein the batching ratio of the high-arsenic multi-metal hazardous waste to the first reducing agent to the vulcanizing agent is 100 (1-5), namely (1-5);
step 2: carrying out secondary batching on the granular materials and other hazardous waste materials such as a second reducing agent (lump coal or coke), blowing slag and the like to obtain a mixed material; the proportion of the granular material to the second reducing agent and other dangerous waste materials is 100 (10-20) (1-5);
step 3: and transporting the mixed material to a top-blown furnace factory building through an adhesive tape conveyor, and adding the mixed material into a top-blown furnace from a charging hole at the top of the top-blown furnace. The top-blown furnace is operated in a periodic manner to treat high-arsenic polymetallic materials, and the material is treated in a first period and reduced, vulcanized and smelted; performing oxygen-enriched converting operation in the second period;
step 4: the mixed material is added into a top-blowing furnace to carry out material melting and reduction vulcanization smelting in a first period, and the process is as follows: after the mixed material is added into the furnace, natural gas and oxygen-enriched air are blown into the furnace through a top-blowing spray gun A to melt the material and perform reduction and vulcanization reactions, and the material in the furnace is fully reacted by adjusting the insertion depth of the spray gun to obtain first slag, mixed matte, crude lead and first waste gas, wherein the mixed matte comprises sulfides of arsenic, lead, copper and iron. After the reaction, the top-blowing spray gun A is lifted out, slag and crude lead are discharged, and the mixed copper matte is left in the furnace.
Further, after the reduction smelting is finished, slag is discharged from a slag hole positioned at the upper part of the molten pool and is washed and crushed, and the slag is piled up as waste slag or sold. The lead bullion is discharged from a discharge port located at the bottom of the hearth. The mixed matte melt is kept in the furnace as a raw material for two-period oxygen-enriched converting. And (3) a large amount of CO is generated in the reduction and vulcanization process, secondary air and tertiary air are respectively introduced into the hearth and the boiler inlet for full combustion, and the temperature of flue gas at the boiler inlet is controlled at 1150-1250 ℃. The flue gas is sent to desulfurization and denitrification treatment after waste heat is recovered by a waste heat boiler and the quenching tower is cooled, and the tail gas is discharged after reaching standards.
Step 5: the top blowing furnace is switched into a converting operation mode, and oxygen-enriched converting operation in the second period is carried out, and the specific steps are as follows:
the top blowing spray gun A is pulled out from the furnace, the spray gun B is inserted into the furnace, oxygen-enriched air is sprayed into the furnace through the spray gun B, and quartz stone with a certain proportion is added from a charging hole at the top of the furnace. Controlling the temperature of a molten pool to 1200-1250 ℃, reacting the mixed matte with oxygen-enriched air and quartz stone in a furnace to carry out converting operation, deeply removing impurity elements such as lead, iron, arsenic and the like, and forming a second slag and blister copper two phases from the melt in the furnace. Most of sulfur and arsenic are oxidized in the furnace to form sulfur dioxide and arsenic trioxide, and the sulfur dioxide and the arsenic trioxide enter a gas phase for removal, and enter a subsequent flue gas dust collection treatment system for recycling along with flue gas; lead and iron are oxidized and slag is formed with quartz stone into slag phase. And (3) obtaining a blister copper product after the second period is finished, selling blister copper cast ingots, and returning the second slag which is rich in lead metal as cold charge to the smelting treatment of the first period to recover lead. Arsenic is oxidized into smoke dust, arsenic trioxide can be obtained through a smoke dry method arsenic collecting process, and the purity can reach more than 90%.
In a specific embodiment of the invention, during the oxygen-enriched converting operation of the second period, other high copper materials such as outsourcing matte and lead matte can be mixed for converting together when the matte (arsenic matte) is mixed in the converting furnace.
In one embodiment of the invention, the second cycle boiler inlet flue gas temperature is 900 ℃ to 1100 ℃. The electric dust collection, quenching tower and bag dust collector are arranged behind the boiler, and arsenic trioxide and As are recovered from the flue gas 2 O 3 90-95%. And (5) discharging the furnace gas after the desulfurization treatment reaches the standard.
In one embodiment of the invention, the method is suitable for treating multi-metal materials containing arsenic, and can also be matched for treating industrial waste without arsenic;
in a specific embodiment of the invention, raw materials of the method do not need pretreatment, directly enter a top-blowing furnace for pyrometallurgy reduction smelting, and can penetrate a diaphragm layer in the furnace through lifting a spray gun position;
in one embodiment of the invention, the diameter and height of the top-blown converter of the method of the invention are related to the smelting scale and are determined according to the treatment scale;
in one embodiment of the invention, the raw materials treated by the process can be arsenic-containing hazardous waste, copper-containing hazardous waste and nickel-containing hazardous waste, and can also be copper-free industrial sludge, copper-containing solid waste, solid or semi-solid organic waste, waste activated carbon, waste catalyst and the like. In a specific embodiment of the invention, secondary ingredients can be properly mixed with auxiliary materials such as quartz stone, hematite and the like according to the raw material composition condition to adjust the slag type.
In one embodiment of the invention, the reducing agent may be a carbon-based material such as coke, carbon, particulate coal, waste activated carbon, and the like. The first reducing agent comprises crushed coal; the second reductant comprises lump coal or coke; the vulcanizing agent comprises pyrite, gypsum slag and CaSO 4 Or one of copper concentrates.
In one embodiment of the invention, the organic-based waste minerals may be co-disposed of by being injected as fuel into a top-blown furnace to provide heat to the furnace.
In a specific embodiment of the invention, the mixed copper matte/lead bullion/blister copper grade, smelting slag/converting slag of the method of the invention can be flexibly adjusted according to different working conditions and requirements; the top-blown furnace adopts a periodic operation mode, is very suitable for a dangerous waste disposal production system with smaller scale, saves investment and reduces cost. The top blowing furnace adopts the spray gun A2 and the spray gun B3 to be respectively used for reduction smelting and oxygen-enriched blowing, and has good production flexibility and strong risk resistance. And respectively disposing the first and second period flue gas, and recovering arsenic trioxide by dry quenching and arsenic receiving technology on the flue gas with higher arsenic content in the second period, thereby realizing the reduction of hazardous waste.
The technical scheme and meaning of the present invention will not be described below with reference to specific embodiments.
As shown in fig. 2, the schematic diagram of the main device used in the embodiment of the invention includes a top-blown furnace 1, a spray gun A2, a spray gun B3, a slag hole 4 and a metal discharge hole 5, wherein the spray gun A2 and the spray gun B3 are respectively arranged above the top-blown furnace 1 and are inserted into the top-blown furnace 1 from the upper part of the top-blown furnace 1, and the slag hole 4 and the metal discharge hole 5 are respectively arranged at two sides below the top-blown furnace 1.
In one specific embodiment of the invention, a circle of side-blowing spray gun can be arranged in the circumferential direction of the furnace body reaction zone, oxygen-enriched air is blown into the furnace, and the dynamic reaction of the furnace body is improved;
in one embodiment of the invention, the given melt operating temperature and flue gas temperature may vary from feedstock to feedstock.
In one embodiment of the invention, given copper matte, the composition of the lead bullion and the smelting slag may vary from raw material to raw material.
Example 1
1. Ingredients and pelletization
Primary batching and granulating: white smoke dust, kaldo furnace smoke dust and noble lead furnace smoke dust with water content of 2% are weighed and measured by a weighing screw feeder, and are mixed according to the mass ratio of 3:2:2 to form a high-arsenic multi-metal mixed material, and crushed coal and vulcanizing agent are added. The mixed materials are fed to a rubber belt conveyor and conveyed and added into a disc granulator (or ball press), the mixed materials are sprayed with water and humidified and granulated (or ball press) to form spherical materials, and the water content of the materials is 8-10%. The mass ratio of the high-arsenic multi-metal mixture to the crushed coal to the vulcanizing agent is 100:2:2.5.
And (3) secondary batching: adding lump coal and blowing slag into the top-blowing furnace through a quantitative feeder, and adding the mixture and the spherical materials into the top-blowing furnace through a feeding rubber belt conveyor after secondary batching. The mass ratio of the high-arsenic multi-metal mixture to the lump coal to the blowing slag is 100:15:3.5.
2. Reduction sulfidation smelting (first period)
The top blowing furnace operates in a period mode, the pelletized spherical materials, lump coal and converting slag are added into the furnace from a top blowing furnace charging port, a top blowing spray gun A is inserted into a molten pool for 250mm, and natural gas 450Nm is sprayed into the furnace through the spray gun A when the top blowing spray gun A is in communication 3 /h and oxygen enriched air 1500Nm 3 /h, oxygen-enriched air contains O 2 65%, controlling the temperature of a molten pool to 1420 ℃, and carrying out reduction, vulcanization and smelting on the materials fed into the furnace after the materials are melted in the furnace, wherein the materials are divided into three phases of slag, mixed matte and crude lead, and the mixed matte consists of sulfides of arsenic, lead, copper and iron. After the reduction smelting is finished, slag is discharged from a slag hole positioned at the upper part of a molten pool and is subjected to slag flushing water crushing, and the slag is piled up as waste slag or sold, and the water crushing slag contains 0.7% of Cu. Lead bullion is discharged from a discharge port positioned at the bottom of the hearth, and the lead bullion contains 97.5% of Pb. The mixed matte melt is used As the raw material of two-period oxygen-enriched converting and is kept in the furnace, and the mixed copper matte contains 45% of Cu, 15% of Pb and 16% of As. The reduction and vulcanization process generates a large amount of CO, and secondary air and tertiary air are blown into the hearth and the boiler inlet to make smokeThe CO in the gas is completely combusted, and the O content in the flue gas at the outlet of the boiler is controlled 2 5, controlling the temperature of the flue gas at 1160 ℃. The furnace gas is sent to desulfurization and denitrification treatment after waste heat is recovered by a waste heat boiler and the quenching tower is cooled, and the tail gas is discharged after reaching standards.
3. Oxygen-enriched converting (second period)
The top blowing furnace enters two-cycle operation, a top blowing spray gun A gun is pulled out from the furnace, a spray gun B is inserted into the furnace, oxygen-enriched air is sprayed into the furnace through the spray gun B, and the oxygen-enriched air contains O 2 25% oxygen enriched air sparge 8500Nm 3 And/h. And adding quartz stone with a certain proportion from a charging port at the furnace top, wherein the mass ratio of quartz to mixed copper matte is 2.5:100. Controlling the temperature of a molten pool to 1200 ℃, mixing matte, and reacting with oxygen-enriched air and quartz stone in a furnace to carry out converting operation, wherein a melt in the furnace forms slag and blister copper. After the two periods are finished, a blister copper product is obtained, blister copper cast ingots are sold, the blister copper temperature is 1200 ℃, the blister copper contains 98.5% of copper, 0.15% of As and 0.18% of Pb. The secondary flue gas is provided with an electric dust collection, a quenching tower and a bag dust collector behind the boiler, and the arsenic trioxide is recovered from the flue gas, and the white arsenic contains As 2 O 3 90%. And (5) discharging the furnace gas after the desulfurization treatment reaches the standard. The blown slag contains 7.5% of lead, and is returned to a cycle as cold material to recycle lead.
Example 2
1. Ingredients and pelletization
Primary batching and granulating: white smoke dust, kaldo furnace smoke dust and noble lead furnace smoke dust with water content of 2.5% are weighed and measured by a weighing screw feeder, and are mixed according to the mass ratio of 3:3:1 to form a high-arsenic multi-metal mixed material, and crushed coal and vulcanizing agent are added. The mixed materials are fed to a rubber belt conveyor and conveyed and added into a disc granulator (or ball press), the mixed materials are sprayed with water and humidified and granulated (or ball press) to form spherical materials, and the water content of the materials is 8-12%. The mass ratio of the high-arsenic multi-metal mixture to the crushed coal to the vulcanizing agent is 100:2:2.
And (3) secondary batching: adding lump coal and blowing slag into the top-blowing furnace through a quantitative feeder, and adding the mixture and the spherical materials into the top-blowing furnace through a feeding rubber belt conveyor after secondary batching. The mass ratio of the high-arsenic multi-metal mixture to the lump coal to the blowing slag is 100:12:3.
2. Reduction sulfidation smelting (first period)
The top blowing furnace works in a cycle mode, the pelletized spherical materials, lump coal and converting slag are added into the furnace from a top blowing furnace charging port, a top blowing spray gun A is inserted into a molten pool for 200mm, and natural gas 500Nm is sprayed into the furnace through the spray gun A when the top blowing spray gun A is started 3 1600Nm of oxygen enriched air and/h 3 /h, oxygen-enriched air contains O 2 65%, controlling the temperature of a molten pool at 1400 ℃, and carrying out reduction, vulcanization and smelting on the materials fed into the furnace after melting in the furnace, wherein the materials are divided into three phases of slag, mixed matte and crude lead, and the mixed matte consists of sulfides of arsenic, lead, copper and iron. After the reduction smelting is finished, slag is discharged from a slag hole positioned at the upper part of a molten pool and is subjected to slag flushing water crushing, and the slag is piled up as waste slag or sold, and the water crushing slag contains 0.65% of Cu. Lead bullion is discharged from a discharge port positioned at the bottom of the hearth, and the lead bullion contains 97.6% of Pb. The mixed matte melt is used As the raw material of the two-period oxygen-enriched converting and is kept in the furnace, and the mixed copper matte contains 48% of Cu, 13% of Pb and 18% of As. The reduction and vulcanization process generates a large amount of CO, secondary air and tertiary air are blown into the hearth and the boiler inlet, the CO in the flue gas is completely combusted, and the O content in the flue gas at the boiler outlet is controlled 2 5.5%, and the temperature of the flue gas at the inlet of the boiler is controlled at 1180 ℃. The furnace gas is sent to desulfurization and denitrification treatment after waste heat is recovered by a waste heat boiler and the quenching tower is cooled, and the tail gas is discharged after reaching standards.
3. Oxygen-enriched converting (second period)
The top blowing furnace enters two-cycle operation, a top blowing spray gun A gun is pulled out from the furnace, a spray gun B is inserted into the furnace, oxygen-enriched air is sprayed into the furnace through the spray gun B, and the oxygen-enriched air contains O 2 25% oxygen-enriched air blowing amount 8000Nm 3 And/h. And adding quartz stone with a certain proportion from a charging port at the furnace top, wherein the mass ratio of quartz to mixed copper matte is 2.5:100. Controlling the temperature of a molten pool to 1210 ℃, and reacting the mixed matte with oxygen-enriched air and quartz stone in a furnace to carry out converting operation, wherein a melt in the furnace forms slag and blister copper. After the two periods are finished, a blister copper product is obtained, blister copper cast ingots are sold, the blister copper temperature is 1210 ℃, the blister copper contains 98.6 percent of copper, 0.1 percent of As and 0.12 percent of Pb. The secondary flue gas is provided with an electric dust collection, a quenching tower and a bag dust collector behind the boiler, therebyRecovery of arsenic trioxide from flue gas, white arsenic containing As 2 O 3 90%. And (5) discharging the furnace gas after the desulfurization treatment reaches the standard. The blown slag contains 8% of lead and is used as a cold material to be returned to a cycle for recycling the lead.
Example 3
1. Ingredients and pelletization
Primary batching and granulating: white smoke dust, kaldo furnace smoke dust and noble lead furnace smoke dust with water content of 3% are weighed and measured by a weighing screw feeder, and are mixed according to the mass ratio of 4:2:1 to form a high-arsenic multi-metal mixed material, and crushed coal and vulcanizing agent are added. The mixed materials are fed to a rubber belt conveyor and conveyed and added into a disc granulator (or ball press), the mixed materials are sprayed with water and humidified and granulated (or ball press) to form spherical materials, and the water content of the materials is 8-10%. The mass ratio of the high-arsenic multi-metal mixture to the crushed coal to the vulcanizing agent is 100:2.5:2.
And (3) secondary batching: adding lump coal and blowing slag into the top-blowing furnace through a quantitative feeder, and adding the mixture and the spherical materials into the top-blowing furnace through a feeding rubber belt conveyor after secondary batching. The mass ratio of the high-arsenic multi-metal mixture to the lump coal to the blowing slag is 100:18:3.
2. Reduction sulfidation smelting (first period)
The top blowing furnace operates in a period mode, the pelletized spherical materials, lump coal and converting slag are added into the furnace from a top blowing furnace charging port, a top blowing spray gun A is inserted into a molten pool for 280mm, and natural gas for 550Nm is sprayed into the furnace through the spray gun A when the top blowing spray gun A is started 3 Per h and oxygen enriched air 1800Nm 3 /h, oxygen-enriched air contains O 2 65%, controlling the temperature of a molten pool to 1500 ℃, and carrying out reduction, vulcanization and smelting on the materials fed into the furnace after melting in the furnace, wherein the materials are divided into three phases of slag, mixed matte and crude lead, and the mixed matte consists of sulfides of arsenic, lead, copper and iron. After the reduction smelting is finished, slag is discharged from a slag hole positioned at the upper part of a molten pool and is subjected to slag flushing water crushing, and the slag is piled up as waste slag or sold out, and the water crushing slag contains 0.75% of Cu. Lead bullion is discharged from a discharge port positioned at the bottom of the hearth, and the lead bullion contains 97.8% of Pb. The mixed matte melt is used As the raw material of two-period oxygen-enriched converting and is kept in the furnace, and the mixed copper matte contains 50% of Cu, 12% of Pb and 20% of As. The reduction and vulcanization process generates a large amount of CO to the hearth and the furnace chamberThe secondary air and the tertiary air are blown into the inlet of the boiler, so that CO in the flue gas is completely combusted, and the O contained in the flue gas at the outlet of the boiler is controlled 2 6, controlling the temperature of the flue gas at 1220 ℃. The furnace gas is sent to desulfurization and denitrification treatment after waste heat is recovered by a waste heat boiler and the quenching tower is cooled, and the tail gas is discharged after reaching standards.
3. Oxygen-enriched converting (second period)
The top blowing furnace enters two-cycle operation, a top blowing spray gun A gun is pulled out from the furnace, a spray gun B is inserted into the furnace, oxygen-enriched air is sprayed into the furnace through the spray gun B, and the oxygen-enriched air contains O 2 25% oxygen enriched air is blown into 7800Nm 3 And/h. And adding quartz stone with a certain proportion from a charging port at the furnace top, wherein the mass ratio of quartz to mixed copper matte is 2.5:100. Controlling the temperature of a molten pool at 1220 ℃, and reacting the mixed matte with oxygen-enriched air and quartz stone in a furnace to carry out converting operation, wherein a melt in the furnace forms slag and blister copper. After the two periods are finished, a blister copper product is obtained, blister copper cast ingots are sold, the blister copper temperature is 1220 ℃, the blister copper contains 98.7% of copper, 0.08% of As and 0.1% of Pb. The secondary flue gas is provided with an electric dust collection, a quenching tower and a bag dust collector behind the boiler, and the arsenic trioxide is recovered from the flue gas, and the white arsenic contains As 2 O 3 92%. And (5) discharging the furnace gas after the desulfurization treatment reaches the standard. The blown slag contains 8.5% of lead, and is returned to a cycle as cold material to recycle lead.
Finally, it should be noted that: the foregoing description is only illustrative of the preferred embodiments of the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described, or equivalents may be substituted for elements thereof, and any modifications, equivalents, improvements or changes may be made without departing from the spirit and principles of the present invention.
Claims (10)
1. A comprehensive recovery method of high-arsenic multi-metal hazardous waste is characterized by comprising the following steps of,
mixing the high-arsenic multi-metal hazardous waste, the reducing agent and the vulcanizing agent according to a preset proportion to obtain a mixed material;
adding the mixed material into a top-blowing furnace for reduction, vulcanization and smelting to obtain first slag, mixed copper matte, crude lead and first waste gas, wherein the mixed copper matte comprises sulfides of arsenic, lead, copper and iron;
discharging first slag and crude lead, and treating the first waste gas and discharging the treated first waste gas;
oxygen-enriched blowing is carried out on the mixed copper matte in a top blowing furnace to obtain second slag, blister copper and second waste gas;
and recycling the arsenic trioxide in the second waste gas, and treating the second waste gas and discharging the treated second waste gas.
2. The comprehensive recycling method of high-arsenic multi-metal hazardous waste according to claim 1, wherein the high-arsenic multi-metal hazardous waste, the reducing agent and the vulcanizing agent are proportioned according to a preset proportion to obtain a mixed material, and the method comprises the following steps:
after the high-arsenic multi-metal hazardous waste, the first reducing agent and the vulcanizing agent are subjected to primary batching, humidifying and granulating are carried out to obtain a granular material;
carrying out secondary batching on the granular materials, a second reducing agent and other hazardous waste materials to obtain a mixed material;
wherein, the proportion of the high-arsenic multi-metal hazardous waste to the first reducing agent and the vulcanizing agent is 100 (1-5) in (1-5).
The other hazardous waste materials comprise blowing slag, and the proportion of the granular materials to the second reducing agent to other hazardous waste materials is 100 (10-20) (1-5).
3. The comprehensive recovery method of high-arsenic multi-metal hazardous waste according to claim 2, which is characterized in that,
the first reducing agent comprises crushed coal;
the second reductant comprises lump coal or coke;
the vulcanizing agent comprises pyrite, gypsum slag and CaSO 4 Or one of copper concentrates.
4. The comprehensive recovery method of high-arsenic multi-metal hazardous waste according to any one of claims 2 or 3, wherein the water content of the granular material is controlled to be 8% -12%.
5. The method for comprehensively recovering high-arsenic multi-metal hazardous waste according to claim 1, wherein the mixed material is added into a top-blown furnace for reduction, vulcanization and smelting, comprising,
after the mixed material is added into the furnace, natural gas and oxygen-enriched air are sprayed into the furnace through a top-blowing spray gun, the temperature of a molten pool is controlled to 1250-1550 ℃, the mixed material in the furnace is fully reacted, and slag, crude lead, mixed copper matte and first waste gas are generated.
6. The method for comprehensively recovering high-arsenic multi-metal hazardous waste according to any one of claims 1 to 3 or 5, which is characterized in that,
the first furnace slag is sold as waste slag;
the lead bullion is sold as a product;
the mixed matte remains in the top-blown furnace.
7. The method for comprehensively recovering high-arsenic multi-metal hazardous waste according to any one of claims 1 to 3 or 5, wherein the first exhaust gas is discharged after being treated, comprising,
and after the first waste gas is fully combusted, the waste heat is recovered through a waste heat boiler, the quenching tower is cooled, and the waste gas is discharged after desulfurization and denitrification treatment.
8. The method for comprehensively recovering high-arsenic multi-metal hazardous waste according to claim 1, wherein the oxygen-enriched converting is carried out on the mixed copper matte in a top-blown furnace, comprising,
oxygen-enriched air is sprayed into the furnace, and the temperature of the molten pool is controlled to be 1200-1250 ℃;
and adding quartz stone and mixed matte in a preset proportion to perform oxygen-enriched converting operation to obtain second slag, blister copper and second waste gas.
9. The comprehensive recovery method of high-arsenic multi-metal hazardous waste according to claim 8, wherein,
the blister copper ingot is sold;
and the second slag is added into the top-blown furnace again for reduction, vulcanization and smelting, and then lead is recovered.
10. The method for the integrated recovery of high-arsenic multi-metal hazardous waste according to claim 9, wherein the second waste gas is treated and discharged, comprising,
the second waste gas is subjected to a dry arsenic trioxide recovery process by flue gas to obtain arsenic trioxide,
and (3) recycling the second waste gas after the arsenic trioxide, and discharging the second waste gas after desulfurization and denitrification treatment reaches the standard.
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