CN111500877A - Process method for recovering and regenerating refined tin from tin foil ash of tin foil sacrificial offerings - Google Patents
Process method for recovering and regenerating refined tin from tin foil ash of tin foil sacrificial offerings Download PDFInfo
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- CN111500877A CN111500877A CN202010521069.4A CN202010521069A CN111500877A CN 111500877 A CN111500877 A CN 111500877A CN 202010521069 A CN202010521069 A CN 202010521069A CN 111500877 A CN111500877 A CN 111500877A
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 238000000034 method Methods 0.000 title claims abstract description 51
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 13
- 239000002893 slag Substances 0.000 claims abstract description 55
- 238000003723 Smelting Methods 0.000 claims abstract description 26
- 238000007670 refining Methods 0.000 claims abstract description 24
- 238000005469 granulation Methods 0.000 claims abstract description 10
- 230000003179 granulation Effects 0.000 claims abstract description 10
- 238000005453 pelletization Methods 0.000 claims abstract description 8
- 239000000779 smoke Substances 0.000 claims description 74
- 239000000428 dust Substances 0.000 claims description 69
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 41
- 239000002994 raw material Substances 0.000 claims description 32
- 239000008188 pellet Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 17
- 238000003860 storage Methods 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 239000003245 coal Substances 0.000 claims description 12
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 7
- 235000019738 Limestone Nutrition 0.000 claims description 6
- 239000006028 limestone Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 5
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052683 pyrite Inorganic materials 0.000 claims description 5
- 239000011028 pyrite Substances 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000002910 solid waste Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000002912 waste gas Substances 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract 2
- 229910052718 tin Inorganic materials 0.000 description 87
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000004568 cement Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 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
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
-
- 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
- C22B25/00—Obtaining tin
- C22B25/02—Obtaining tin by dry processes
-
- 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
- C22B25/00—Obtaining tin
- C22B25/08—Refining
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
-
- 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
- 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
- C22B7/02—Working-up flue dust
-
- 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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a process method for recovering and regenerating refined tin from tin foil ash of tin foil sacrificial offerings, which comprises the steps of pelletizing granulation, rotary kiln roasting, electric furnace reduction smelting, crude tin refining, crystallizer purification, slag fuming furnace treatment and the like, so that tin is scientifically and effectively recovered from the tin foil ash to the maximum extent, other solid waste resources in the tin foil ash are scientifically and environmentally treated, the environmental pollution problem of the tin foil ash and the recovery problem of tin in the tin foil ash are comprehensively and effectively solved, the cyclic recycling of the solid waste resources is fully and effectively solved, waste water, waste gas and waste residues are not generated, the environmental protection problem is effectively solved, the environment-friendly cyclic economy is developed, and the aims and effects of energy conservation, consumption reduction, high efficiency and environmental protection are really achieved.
Description
Technical Field
The invention relates to the technical field of tin metal recycling, in particular to a process method for recycling and regenerating refined tin from tin foil ash of a tin foil sacrificial offering.
Background
The Chaoshan region of Guangdong province adopts high tin alloy containing more than 95.5% of Sn, and the metal foil is formed by soft mechanical rolling, and is generally called as 'Guangshi foil' for distinction. In order to ensure that the tinfoil does not break during further processing, and to improve the strength of the foil after rolling, the tinfoil is called as a backed tinfoil formed by adding white paper as a backing, and the thickness is generally less than 0.020 mm. The tin foil with or without paper backing can be used in different aspects or made into tin foil products for different purposes.
In the burning process of the memorial ceremony, the back lining is firstly burnt, then tin foil is burnt and melted, the temperature is above 320 ℃, and finally the back lining is changed into ash, the ash is the mixture of paper ash and tin foil ash, and is called as tin foil ash.
Early stage: during the lunar calendar festival, the sacrifice is small in scale and range, the sacrifice is made and incinerated, a small amount of tin foil ash is blown away with wind, and people rarely collect the tin foil ash without paying attention. The increase of demand and consumption promotes the diversification of the variety of the sacrificial offerings, so that the tin foil is artificially rolled by adopting tin alloy in regions such as Guangdong Chaoshan and the like, which gradually becomes an industry. The finished products of the tin foil paper are produced, and the sacrificial offerings are the most important varieties and form a certain market scale. With the increase of the quantity and the demand of the tinfoil paper, the collection and the utilization of tinfoil ash also attract attention, and the collection is accumulated more and more, and the climate is gradually generated. The method is characterized in that an aluminum pot and a ground furnace are heated by coal powder for reduction smelting in an earth method, tin is recovered from tin foil ash, and a finished product is crude tin for sale. The recovery method has small treatment capacity and low recovery rate. And when the crude tin enters the second stage, the crude tin containing 80% of Sn can be produced by adopting vertical tank gas smelting and reducing and recovering the tin in the crude tin. With the increase of the quantity of the tin foil ash raw materials, according to preliminary statistics, more than ten thousand tons of tin foil ash resources exist in China, the requirement cannot be met by adopting a small-scale method for smelting, producing and recovering crude tin by an earth method, a large amount of waste gas and waste residue are generated during the earth method smelting, a large amount of tin is directly discharged without being treated, the environmental pollution is very serious, and the method belongs to the restriction and the banning.
Disclosure of Invention
The invention aims to design a process method for recovering and regenerating refined tin from tin foil ash generated by tin foil worship in Chaoshan region aiming at the defects of the prior art, scientifically and effectively recovers tin from the tin foil ash to the maximum extent, scientifically and environmentally treats other solid waste resources in the tin foil ash, and comprehensively and effectively solves the problems of environmental pollution of the tin foil ash and recovery of tin in the tin foil ash.
In order to achieve the purpose, the invention provides a process method for recovering and regenerating refined tin from tin foil ash of a tin foil sacrificial offering, which comprises the following steps:
step a, pelletizing: adding tin foil ash containing 25-45% of Sn into a disc granulator, adding water accounting for 8-10% of the weight of the tin foil ash, and performing rotary rolling granulation to obtain a pellet granulation raw material with the particle size of 20-30 mm;
step b, roasting in a rotary kiln: b, adding the pellet granulation raw material obtained in the step a into a rotary kiln for roasting, and removing water and combustible substances to obtain roasted tin foil ash pellets containing 26.19-46.87% of Sn and smoke dust containing 2-3% of Sn, wherein the smoke dust is collected and then enters a smoke dust bin for storage, and the yield of the tin foil ash pellets and the yield of the smoke dust are 94-96% and 4-6% respectively;
step c, electric furnace reduction smelting: taking the roasted tin foil ash pellets in the step b as a raw material, adding coal accounting for 12-13% of the weight of the raw material, limestone accounting for 2-3% of the weight of the raw material and iron powder accounting for 2-3% of the weight of the raw material as auxiliary materials, and carrying out reduction smelting in an electric furnace to obtain crude tin containing 92-95% of Sn, 0.5-1.0% of iron, slag containing 2-3% of Sn and smoke dust containing 13-20% of Sn, wherein the smoke dust is collected and then enters a smoke dust bin for storage, and the yield of the crude tin, the slag and the smoke dust is respectively 25-45%, 50-60% and 5-15%;
step d, crude tin refining: adding the crude tin obtained in the step c into a refining pot, refining at the temperature of 250-260 ℃ to remove iron, and obtaining refined tin containing 98.5-99.5% of Sn, refined tin containing 0.04-0.05% of Fe, refined slag containing 70-80% of Sn and refined slag containing 20-26% of Fe, wherein the refined slag returns to the refining pot after being collected, and the yield of the refined tin and the refined slag is 90-95% and 5-10% respectively;
step e, purifying by a crystallizer: d, separating refined tin in the step d in a crystallizer, wherein the crystallizer is divided into 4 sections by temperature control, 1 section is 550 ℃, 2 sections are 450 ℃, 3 sections are 350 ℃ and 4 sections are 190 ℃ to obtain refined tin products containing 99.90-99.95% of Sn, tail tin alloy products containing 75-85% of Sn and smoke dust containing 75-80% of Sn, the smoke dust is collected and then enters a smoke dust bin to be stored, and the yield of the refined tin products, the tail tin alloy products and the smoke dust is 90-92%, 7.92-9.9% and 0.05-0.1% respectively;
step f, treating the slag by a fuming furnace: and c, adding the furnace slag in the step c into a fuming furnace, adding coal powder accounting for 10-12% of the weight of the furnace slag, pyrite auxiliary materials accounting for 5-8% of the weight of the furnace slag, and then carrying out fuming treatment on the furnace slag, and finally generating smoke dust containing Sn 40-45% and fuming furnace water-quenched slag containing Sn0.2-0.3%, wherein the smoke dust is collected and then enters a smoke dust bin for storage, and the yield of the smoke dust and the fuming furnace water-quenched slag is 3-7% and 93-97% respectively.
Preferably, the diameter of the middle rotary kiln in the step b is 1.6 m, the length of the middle rotary kiln is 20m, the rotating speed of the middle rotary kiln is 1 r/min, and the roasting temperature is 500-600 ℃.
Preferably, the power of the electric furnace in the electric furnace reduction smelting in the step c is 1250-1300 KW, and the temperature of the electric furnace is 1200-1500 ℃.
Preferably, the crystallizer in the step e is an inclined horizontal spiral groove body with the length of 6.5m, the width of 0.5m and the height of 0.5m, and the rotating speed is 1 r/3 min.
Preferably, the refined tin product of step e is discharged from the head end of the crystallizer, and the tail tin alloy product is obtained from the tail end of the crystallizer.
Preferably, the treatment temperature of the fuming furnace in the step f is 1200 +/-10 ℃, and the treatment time is 4-4.5 hours.
Preferably, the fuming furnace has an area of 4 square meters, and the slag treatment capacity per batch is 30 tons.
Preferably, the smoke dust is collected by a dust collecting bag and then enters a smoke dust bin for storage and separate treatment.
The invention has the advantages that: the process technology method can effectively aim at tin foil ash after burning Chaoshan tin foil sacrificial offerings, the collected tin foil ash contains 25-45% of tin and a small amount of Fe metal oxides, and the process adopts pelletizing, rotary kiln roasting, electric furnace reduction smelting, crude tin refining, crystallizer purification and slag fuming furnace treatment to form the components: pelletizing, namely performing pretreatment pelletizing on the tin foil ash powder raw material, so that dust flying during rotary kiln treatment can be reduced, air pollution and public nuisance of the surrounding environment of a production area are eliminated, and metal loss of the material in the treatment process is reduced; roasting in a rotary kiln, removing moisture and combustible materials from the pellet raw materials, improving the purity of the raw materials and forming a solidified raw material with certain strength, wherein the treatment capacity of the rotary kiln is 30 tons; reducing and smelting in an electric furnace, namely feeding the pellet raw material after roasting into the electric furnace, adding coal, limestone and iron powder for smelting, and smelting metal oxide (SnO) in the raw material under the reducing condition2) Reducing the raw tin into crude tin containing 97-98% of tin and furnace slag containing 2-3% of tin; meanwhile, other metal oxides in the raw materials are reduced into metal, and the treatment capacity of the smelting furnace is 15 tons; refining the crude tin, wherein the purpose is to remove impurity iron in the crude tin by utilizing metal temperature difference, and the treatment capacity of a refining furnace is 15 tons; purifying by a crystallizer, and treating by the crystallizer to obtain a refined tin product containing 99.90-99.95% of Sns, wherein the treatment capacity of the crystallizer is 10 tons; treating the furnace slag in a fuming furnace, namely treating the furnace slag containing 2-3% of Sn in the furnace slag in the fuming furnace to finally obtain a fuming product containing 40-45% of Sn and a fuming furnace containing 0.2-0.3% of SnThe treatment capacity of the fuming furnace is 30 tons.
Finally, the full utilization and comprehensive recovery of resources are achieved, and finally, the harmless treatment of all raw materials of a factory is achieved. And finally, the water-quenched slag is sold to a cement plant as a raw material, so that resources are completely recycled and utilized, and the resource recycling is promoted.
Compared with the prior art, the method also has the following advantages and effects:
a) the production process of recovering and regenerating refined tin from the tin foil ash after burning the Chaoshan tin foil sacrificial offerings for industrial production has not been reported in literature at home and abroad,
b) the quality of the product produced by the process method completely meets all indexes of the national standard GB/T3131-2006,
c) the process method can ensure high recovery rate of the main metal tin, simultaneously can comprehensively recover nonferrous metals in materials, and can cumulatively recover precious metals such as Au, Ag and the like,
d) the processing method of the tinfoil ash capable of being fully recycled can increase the total supply quantity of domestic tin consumption, ensure the sufficient and stable supply of tin in the market, and reserve the cultural custom of Chaoshan for tinfoil paper on the premise of considering environmental protection.
e) By adopting the process method, the recycling of the solid waste resources of the tinfoil ash is fully and effectively solved, only usable substances are generated in the production process, no waste is generated, no waste water, waste gas or waste residue is generated, the environmental protection problem is well and effectively solved, and the effective recycling of the tin resources of the tinfoil paper is ensured.
f) Other useful metals contained in the tin foil ash can be recovered in the process of recovering the tin in the tin foil ash, so that resources are utilized to the maximum extent and effectively, green recycling economy is developed, and the aims and effects of energy conservation, consumption reduction, high efficiency and environmental protection are really achieved.
Detailed Description
The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1:
adding 30 tons of tin foil ash containing 25% of Sn into a disk granulator, adding 2.4 tons of water, rotating and rolling to granulate into pellet granulation raw materials phi 20mm, adding the pellet granulation raw materials into a rotary kiln phi 1600 mm and 20000mm in length, roasting at the rotating speed of 1 r/min and the temperature of 500 ℃, removing water and combustible substances to obtain 26.47% tin-containing and 28.2 ton roasted tin foil ash pellets and 1.8 tons of smoke dust containing 2% tin, collecting the smoke dust, returning the smoke dust to a smoke dust bin for storage,
taking 15 tons of the roasted tin foil ash pellet raw materials, adding 1.8 tons of coal, 0.3 tons of limestone and 0.3 tons of iron powder as auxiliary materials, reducing and smelting in an electric furnace, wherein the power of the electric furnace is 1250KW, the temperature of the electric furnace is 1200 ℃, the tin foil ash pellet raw materials and 17.4 tons of the auxiliary materials are smelted to obtain 4.35 tons of crude tin containing Sn 92 percent, 1.0 percent of iron, 10.44 tons of slag containing Sn2 percent and 2.61 tons of smoke containing Sn13 percent, collecting the smoke dust, returning the collected smoke dust to a smoke dust storage bin for storage,
adding 15 tons of crude tin prepared by the method into a refining pot, refining at the temperature of 250 ℃ for removing iron to obtain 13.5 tons of refined tin products containing 98.5 percent of Sn0.05 percent of ferrum and 1.5 tons of refined slag containing 70 percent of Sn and 26 percent of ferrum, returning the refined slag to the refining pot,
taking 10 tons of refined tin products prepared by the method, putting the products into a crystallizer for separation, separating the products by the temperature control area of the crystallizer into 4 sections, wherein the temperature control area of the crystallizer is 1 section 550 ℃, 2 section 450 ℃, 3 section 350 ℃, 4 section 190 ℃, the length of the crystallizer is 6500mm, the width of the crystallizer is 500mm, and the height of the inclined horizontal spiral tank body is 500mm, discharging 9.0 tons of refined tin products containing 99.9 percent of Sn at the head end of the crystallizer, obtaining 0.99 tons of tail tin alloy products containing 75 percent of Sn at the tail end and 0.01 tons of smoke dust containing 80 percent of Sn at the tail end of the crystallizer at the rotating speed of 1 r/3 min, returning the collected smoke dust to,
30 tons of slag containing 2 percent of Sn obtained by reduction smelting are added into a fuming furnace with the area of 4 square meters, 3 tons of coal powder are added, 34.5 tons of pyrite auxiliary material and slag with the area of 1.5 tons are subjected to fuming treatment, the time is 4.0 hours at the temperature of 1200 +/-10 ℃, and finally 2.42 tons of smoke dust containing 40 percent of Sn and 32.08 tons of water-quenched slag of the fuming furnace with the content of Sn of 0.2 percent are generated, the smoke dust is collected and returned to a smoke dust storage bin for storage, and the water-quenched slag is sold to a cement plant to be used as a raw material.
The smoke dust can be collected and treated independently after the rotary kiln roasting, the reduction smelting, the crude tin refining and the slag fuming furnace treatment.
Example 2
30 tons of tin foil ash containing 35 percent of Sn is added into a disc granulator, 2.7 tons of water is added, the mixture is rotated and rolled to be granulated into pellet granulation raw materials phi of 25mm,
adding the pelletizing material into a phi 1600 mm rotary kiln with a length of 20000mm, roasting at a rotation speed of 1 r/min and a temperature of 550 ℃, removing water and combustible substances to obtain tin foil ash pellets containing 36.71 percent of tin and 28.5 tons of roasted tin and 1.5 tons of smoke dust containing 2.5 percent of tin, collecting the smoke dust, returning the collected smoke dust to a smoke dust bin for storage,
taking 15 tons of the roasted tin foil ash pellets, adding 1.87 tons of coal, 0.375 tons of limestone and 0.375 tons of iron powder as auxiliary materials, reducing and smelting in an electric furnace with the power of 1280KW, the temperature of the electric furnace being 1350 ℃, smelting the tin foil ash pellets and 17.63 tons of the auxiliary materials to obtain 6.17 tons of crude tin containing 93% of Sn, 0.8% of iron, 9.7 tons of slag containing 2.5% of Sn and 1.76 tons of smoke containing 18%, collecting the smoke dust, returning the collected smoke dust to a smoke dust bin for storage,
adding 15 tons of crude tin prepared by the method into a refining pot, refining at 255 ℃ for removing iron to obtain 13.95 tons of refined tin products containing 99.0 percent of Sn0 percent and 0.045 percent of iron and 1.05 tons of refined slag containing 75 percent of Sn and 24 percent of iron, returning the refined slag to the refining pot,
taking 10 tons of refined tin products prepared by the method, putting the products into a crystallizer for separation, separating the products by the temperature control area of the crystallizer into 4 sections, wherein the temperature control area of the crystallizer is 1 section 550 ℃, the temperature control area of the crystallizer is 2 sections 450 ℃, the temperature control area of the crystallizer is 3 sections 350 ℃, the temperature control area of the crystallizer is 4 sections 190 ℃, the length of the crystallizer is 6500mm, the width of the crystallizer is 500mm, the height of the crystallizer is 500mm, when the rotating speed is 1 r/3 min, 9.1 tons of refined tin products containing 99.93 percent of Sn are finally discharged from the head end of the crystallizer, 0.895 ton of tail tin alloy products containing 80 percent of Sn and 0.005 ton of smoke dust containing,
30 tons of slag containing 2.5 percent of Sn obtained by reduction smelting are added into a fuming furnace with the area of 4 square meters, 3.3 tons of coal powder are added, 35.4 tons of pyrite auxiliary material and slag with the weight of 2.1 tons are subjected to fuming treatment, the temperature is 1200 +/-10 ℃, the time is 4.2 hours, 1.77 tons of smoke dust containing 42 percent of Sn and 33.63 tons of water-quenched slag containing 0.2 percent of Sn are finally generated, the water-quenched slag of the fuming furnace is sold to a cement plant to be used as a raw material, and the smoke dust is collected and returned to a smoke dust bin for storage and standby.
The smoke dust after the roasting, the reduction smelting, the crude tin refining and the slag fuming furnace treatment of the rotary kiln is collected and treated independently.
Example 3
30 tons of tin foil ash containing 45 percent of Sn are added into a disc granulator, 3.0 tons of water are added, the mixture is rotated and rolled to be granulated into a pelletizing raw material phi of 30mm,
adding the pelletized raw material of the precursor pellets into a phi 1600 mm rotary kiln with the length of 20000mm, roasting at the rotation speed of 1 r/min and the temperature of 600 ℃, removing water and combustible substances to obtain tin foil ash pellets which contain 46.75 percent and 28.8 tons of roasted tin and 1.2 tons of roasted smoke dust which contains 3 percent of tin, returning the collected smoke dust to a smoke dust bin for storage,
taking 15 tons of the roasted tin foil ash pellets, adding 3.0 tons of coal, 0.45 tons of limestone and 0.45 tons of iron powder as auxiliary materials, reducing and smelting in an electric furnace with the power of 1300KW and the temperature of 1500 ℃, smelting the tin foil ash pellets and 17.85 tons of the auxiliary materials to obtain 8.03 tons of crude tin containing 95 percent of Sn, 0.5 percent of iron, 8.93 tons of slag containing 3 percent of Sn and 0.89 tons of smoke containing 20 percent of Sn, collecting the smoke dust, returning the collected smoke dust to a smoke dust bin for storage,
adding 15 tons of crude tin prepared by the method into a refining pot, refining at the temperature of 260 ℃ to remove iron, obtaining 14.25 tons of refined tin products containing 99.5 percent of Sn0.04 percent of ferrum and 0.75 tons of refined slag containing 80 percent of Sn and 20 percent of ferrum, returning the refined slag to a refining furnace,
10 tons of refined tin products prepared by the method enter a crystallizer for separation, the temperature control area of the crystallizer is divided into 4 sections, the 1 section is 550 ℃, the 2 section is 450 ℃, the 3 section is 350 ℃, the 4 section is 190 ℃, the length of the crystallizer is 6500mm, the width is 500mm, the height is 500mm, the rotating speed is 1 revolution/3 min, 9.2 tons of refined tin products containing 99.95% of Sn are finally discharged from the head end of the crystallizer, 0.792 ton of tail tin alloy products containing 85% of Sn and 0.008 ton of smoke dust containing 75% of Sn are obtained from the tail end of the crystallizer, the smoke dust is returned to a smoke dust bin for storage after being collected,
30 tons of slag containing 3 percent of Sn obtained by reduction smelting are added into a fuming furnace with the area of 4 square meters, then 3.6 tons of coal powder and 36 tons of pyrite auxiliary material and slag with the area of 2.4 tons are added for fuming treatment, at the temperature of 1200 +/-10 ℃ and the time of 4.5 hours, finally 1.08 tons of smoke dust containing 45 percent of Sn and 34.92 tons of water-quenched slag of the fuming furnace containing 0.2 percent of Sn are generated, the water-quenched slag is sold to a cement plant to be used as a raw material, and the smoke dust is collected and returned to a smoke dust bin for storage and standby.
The smoke dust is collected and treated separately after the roasting, the reduction smelting, the crude tin refining and the treatment of the slag fuming furnace in the rotary kiln.
Finally, it should be noted that: it should be understood that the above examples are only for clearly illustrating the present invention and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (8)
1. A process method for recovering and regenerating refined tin from tin foil ash of tin foil sacrificial offerings is characterized by comprising the following steps:
step a, pelletizing: adding tin foil ash containing 25-45% of Sn into a disc granulator, adding water accounting for 8-10% of the weight of the tin foil ash, and performing rotary rolling granulation to obtain a pellet granulation raw material with the particle size of 20-30 mm;
step b, roasting in a rotary kiln: b, adding the pellet granulation raw material in the step a into a rotary kiln for roasting, removing water and combustible substances to obtain roasted tin foil ash pellets containing 26.19-46.87% of Sn and smoke dust containing 2-3% of Sn, and storing the smoke dust in a smoke dust bin after collecting the smoke dust;
step c, electric furnace reduction smelting: taking the roasted tin foil ash pellets in the step b as a raw material, adding coal accounting for 12-13% of the weight of the raw material, limestone accounting for 2-3% of the weight of the raw material and iron powder accounting for 2-3% of the weight of the raw material as auxiliary materials, carrying out reduction smelting in an electric furnace to obtain crude tin containing 92-95% of Sn, 0.5-1.0% of iron, slag containing 2-3% of Sn and smoke containing 13-20% of Sn, and storing the collected smoke in a smoke bin;
step d, crude tin refining: adding the crude tin obtained in the step c into a refining pot, refining at the temperature of 250-260 ℃ for removing iron to obtain refined tin containing 98.5-99.5% of Sn, 0.04-0.05% of Fe and refined slag containing 70-80% of Sn and 20-26% of Fe, and returning the refined slag into the refining pot after collecting the refined slag;
step e, purifying by a crystallizer: d, separating the refined tin in the step d in a crystallizer, wherein the crystallizer is divided into 4 sections by temperature control, 1 section is 550 ℃, 2 sections are 450 ℃, 3 sections are 350 ℃ and 4 sections are 190 ℃ to obtain refined tin products containing 99.90-99.95% of Sn, tail tin alloy products containing 75-85% of Sn and smoke dust containing 75-80% of Sn, and the smoke dust is collected and then enters a smoke dust bin for storage;
step f, treating the slag by a fuming furnace: and c, adding the furnace slag in the step c into a fuming furnace, adding coal powder accounting for 10-12% of the weight of the furnace slag, pyrite auxiliary materials accounting for 5-8% of the weight of the furnace slag, then carrying out fuming treatment on the furnace slag, finally generating smoke dust containing Sn 40-45% and fuming furnace water-quenched slag containing Sn0.2-0.3%, and storing the collected smoke dust in a smoke dust bin.
2. The process method for recovering and regenerating refined tin from tin foil ash of tin foil sacrificial offerings as claimed in claim 1, wherein the diameter of the middle rotary kiln in step b is 1.6 m, the length is 20m, the rotation speed is 1 r/min, and the roasting temperature is 500-600 ℃; .
3. The process method for recovering and regenerating refined tin from tin foil ash of tin foil sacrificial offerings as claimed in claim 1, wherein in the step c, the electric furnace power is 1250-1300 KW and the electric furnace temperature is 1200-1500 ℃.
4. The process method for recovering and regenerating refined tin from tin foil ash of tin foil sacrificial offerings as claimed in claim 1, wherein the crystallizer in step e is an inclined horizontal spiral groove with a length of 6.5m, a width of 0.5m and a height of 0.5m, and the rotation speed is 1 r/3 min.
5. The process for recovering refined tin from tin foil ash of tin foil sacrificial offerings as claimed in claim 1, wherein step e is carried out by discharging refined tin product from the head end of the crystallizer and collecting the tail tin alloy product from the tail end of the crystallizer.
6. The process method for recovering and regenerating refined tin from tin foil ash of tin foil sacrificial offerings as claimed in claim 1, wherein the treatment temperature of the fuming furnace in step f is 1200 ℃ ± 10 ℃ and the treatment time is 4-4.5 hours.
7. The process of claim 1, wherein the fuming furnace in step f has an area of 4 square meters.
8. The process for recovering and regenerating refined tin from tinfoil ash of tinfoil sacrificial offerings as claimed in claim 1, wherein the smoke is collected by dust bag and stored in smoke bin for separate treatment.
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