GB2601212A - System and method for efficient recovery of valuable metals from tin secondary raw materials - Google Patents
System and method for efficient recovery of valuable metals from tin secondary raw materials Download PDFInfo
- Publication number
- GB2601212A GB2601212A GB2108783.8A GB202108783A GB2601212A GB 2601212 A GB2601212 A GB 2601212A GB 202108783 A GB202108783 A GB 202108783A GB 2601212 A GB2601212 A GB 2601212A
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- United Kingdom
- Prior art keywords
- furnace
- flue gas
- tin
- rotary
- smelting furnace
- Prior art date
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000002994 raw material Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000002184 metal Substances 0.000 title claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 35
- 150000002739 metals Chemical class 0.000 title claims abstract description 32
- 238000011084 recovery Methods 0.000 title abstract 3
- 238000003723 Smelting Methods 0.000 claims abstract description 111
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000003546 flue gas Substances 0.000 claims abstract description 59
- 239000002893 slag Substances 0.000 claims abstract description 46
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 38
- 239000000956 alloy Substances 0.000 claims abstract description 38
- 230000008569 process Effects 0.000 claims abstract description 31
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 15
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052738 indium Inorganic materials 0.000 claims abstract description 13
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052709 silver Inorganic materials 0.000 claims abstract description 13
- 239000004332 silver Substances 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- 230000007246 mechanism Effects 0.000 claims abstract description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000779 smoke Substances 0.000 claims abstract description 7
- 238000009835 boiling Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 11
- 241001062472 Stokellia anisodon Species 0.000 claims description 9
- 238000006477 desulfuration reaction Methods 0.000 claims description 8
- 230000023556 desulfurization Effects 0.000 claims description 8
- 239000003500 flue dust Substances 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 7
- -1 speiss Substances 0.000 claims description 7
- 239000006256 anode slurry Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000002485 combustion reaction Methods 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000012141 concentrate Substances 0.000 description 7
- 229910020836 Sn-Ag Inorganic materials 0.000 description 4
- 229910020988 Sn—Ag Inorganic materials 0.000 description 4
- 238000007664 blowing Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- DZXKSFDSPBRJPS-UHFFFAOYSA-N tin(2+);sulfide Chemical compound [S-2].[Sn+2] DZXKSFDSPBRJPS-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals 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
- 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
-
- 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
- C22B15/0056—Scrap treating
-
- 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
- C22B25/06—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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/06—Obtaining bismuth
-
- 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
- C22B58/00—Obtaining gallium or indium
-
- 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
- C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
-
- 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
- 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)
- Physics & Mathematics (AREA)
- Acoustics & Sound (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A system and method for efficient recovery of valuable metals from tin secondary raw materials. The system comprises a batching system (1), a rotary smelting furnace (4), a vacuum furnace (5), a fuming furnace (6) and a flue gas processing system (7) which are arranged in a unified site. A material mixing hopper (3) of the batching system (1) is connected to the rotary smelting furnace (4) by means of a feeding mechanism (12). The rotary smelting furnace (4) is directly or indirectly connected to the vacuum furnace (5), the fuming furnace (6) and the flue gas processing system (7), respectively. The rotary smelting furnace (4) is connected to the vacuum furnace (5) by means of an alloy ingot transferring device (14). The rotary smelting furnace (4) is connected to the fuming furnace (6) by means of a slag transferring device (15). Smoke vents of the rotary smelting furnace (4) and the fuming furnace (6) are connected to the flue gas processing system (7). According to the system and method, the tin secondary raw materials with complex components can be efficiently recovered, the valuable metals such as tin, lead, bismuth, indium, silver, and copper contained in the tin secondary raw materials are fully recovered and utilized, the process is short, the operation is simple, the operation cost is low, the valuable metal recovery rate is high, and the energy saving and environmental protection effects are good.
Description
Descriptions
A System Applied to Efficiently Recycle Valuable Metals from Secondary Raw Materials of Tin and Its Method
Technical Field
The present invention relates to the technical field of the system applied to efficiently recycle valuable metals from secondary raw materials of tin and its smelting processes.
Background Technology
As the first resources of stannaries decrease gradually, recycling of the secondary raw materials of tin becomes more and more valued, and the secondary raw materials of tin have gradually become one of the sources of tin and other valuable metals for future. The secondary raw materials of tin refer to all kinds of stanniferous slags, stanniferous wastes, stanniferous flue dust, tin anode slurry, speiss, tin slurry and other materials by which the tin can be regenerated and recycled. Up to now, studies on recycling technologies of the secondary raw materials of tin are less, and generally adopt conventional technologies and configurations to smelt the secondary raw materials of tin with tin concentrate. For this reason, the process of these technologies is long, and the valuable metals contained are easy to disperse, and the recycle rate is low, as well as the effect is poor.
The method for producing crude tin through smelting secondary raw materials of tin with tin concentrate is generally divided into two main processing steps of smelting. The first step is to smelt the tin concentrate and the secondary raw materials into crude tin and slags rich in tin. And the second step is to complete fuming and depletion of slags rich in tin to recycle tin and produce lean slags.
The traditional smelting processes of utilizing secondary raw materials of tin with tin concentrate are utilize blast furnaces, reverberatory furnaces and electric furnaces, etc. to smelt tin concentrate, and thus produce crude tin, as well as produce slags rich in tin. Then, the smelting furnace is utilized to smelt slags rich in tin, and then, uses the side-blowing fuming furnace, etc., to complete fuming, depletion and recycle of stanniferous flue dust. The smelting process utilized the blast furnaces belongs to outdated production capacity, which has been shut down on the whole. And the reverberatory furnaces and electric furnaces are still the smelting equipment to be utilized frequently to smelt secondary raw materials with tin concentrate currently, which are characterized in that the methods utilized are simple and the scale is small, and having high energy consumption and high labor intensity, as well as more production links, and thus, can result in serious environmental pollution, and high safety risks.
In the past 20 years, smelting technologies which strengthen the tin has made a great progress. Utilizing the Ausmelt converting furnace to conduct top-blown smelting and adding oxygen enrichment, has significantly improved the efficiency of smelting. Wherein, the top-blown and submerged smelting method utilized the Ausmelt converting furnace belongs to the field of bath smelting, which has been widely used in copper, tin, lead, steel, and other industries, and has developed rapidly in the past 20 years. The technology of top-blown and submerged smelting method has the advantages of having high smelting concentration, excellent sealing property of furnace body, good environmental conditions in the workshop, and adopting simple structure, and the preparation of materials is simple, as well as is at relatively low cost. However, the disadvantages of such method are that the slags produced after smelting need to be processed separately through a fuming furnace, which requires more production links, and the processes and facilities adopted are complicated, as well as requires intermittent operation, and thus the production efficiency is low, but the energy consumption is high, and recycle rate of tin is low.
At present, smelting slags rich in tin through the method of tin smelting mainly utilizes box-type side-blown fuming furnace sulphation method to complete the fuming, volatilization and depletion as well as the recycle of tin flue dust. Meanwhile, the box-type side-blown fuming furnace is also constantly developing towards the trend of large-scale, which is evolved from mainly utilizing the furnace of 2.6m2-type in the past to mainly utilizing the furnace of 4m2-type. Some manufacturers are already trying to use the box-type side-blown fuming furnace of 8m2-type. The principal advantages of the box-type side-blowing furnace are that the volatilization efficiency of tin is high and the volatilization speed is relatively fast. But the major disadvantages are that it requires intermittent operation, and the slags generated in the smelting furnace need to be added intermittently, as well as there are processes of cooling, transportation, and heating, etc., are required, and thus, the process is long, the operation is complicated, as well as with high safety and environmental risks, and high energy consumption.
The aforesaid equipment and methods not only need complex equipment, large scale of total investment, and complicated processes, but also have common problems, i.e., there are more production links are required, and the process is long, as well as the valuable metals contained in the secondary raw materials of tin are easy to disperse, in addition, the time-consuming is long, and the production efficiency is low, and thus, the recycle rate is low, but the energy consumption is high, and the effect is poor.
Summary of the Invention
The purpose of the present invention is to address the aforesaid problems related to the recycle system of the secondary raw materials of tin, and provide an environmental and safe system and smelting process which can efficiently recycle valuable metals contained in the secondary raw materials of tin, and adopt simple equipment structure and operation, as well as has high recycle rate and low energy consumption. . The purpose of the present invention can be achieved through following technical scheme: A system applied to efficiently recycle valuable metals from secondary raw materials of tin, which comprises a batching system, a rotary smelting furnace, a vacuum furnace, and a fuming furnace, as well as a flue gas treatment system which are arranged in a unified site; the said batching system comprises a set of batch bins of raw materials which are arranged parallelly, a hopper of mixtures which is arranged below the batch bin of raw materials; wherein, the hopper of mixtures is connected to the rotary smelting furnace through a feed mechanism, and feeds the mixtures to the rotary smelting furnace; in addition, the said the rotary smelting furnace is directly or indirectly connected to the vacuum furnace, the fuming furnace and the flue gas treatment system respectively, wherein, the rotary smelting furnace is connected to the vacuum furnace through the alloy ingot transfer device, and the alloys produced by the rotary smelting furnace will be feed to the vacuum furnace to recycle valuable metals after being cast into ingots, and the rotary smelting furnace is connected to the fuming furnace through the slag transfer device, then, the slags produced by the rotary smelting furnace through smelting will be feed to the fuming furnace to recycle tin by means of sulphation and volatilization, furthermore, the smoke outlet of the rotary smelting furnace is connected to the flue gas treatment system through the flue gas pipeline, meanwhile, the smoke outlet of the fuming furnace is also connected to the flue gas treatment system through the flue gas pipeline, wherein, the said flue gas treatment system comprises a flue gas cooler, a bag collector, a tail gas desulfurization system, and a chimney, which are connected in sequence through pipelines, and the said flue gas pipelines are inserted into the air inlet of the flue gas cooler.
The method for efficiently recycling valuable metals from secondary raw materials of tin by utilizing the said system according to claim 1, which is to feed the secondary raw materials of tin to the rotary smelting furnace to smelt them into alloys and slags firstly, and then feed the alloys to the vacuum furnace to recycle various valuable metals one by one through multiple-stage treatment, as well as feed the slags to the fuming furnace to recycle tin after treatment, after that, feed the flue gas generated by the rotary smelting furnace and the fuming furnace to the flue gas treatment system uniformly, and then discharge the flue gas which has been treated and satisfied emission standards The specific process is: complete batching of tin anode slurry, speiss, tin slurry, fusing agent, and reducing agent through the batching system, and then, put them into the rotary smelting furnace, wherein, the combustion system of the rotary smelting furnace injects the fuel, air, and oxygen that the smelting process required to complete smelting. After each furnace completed smelting, tilt the rotary smelting furnace, and scrabble out slags, and then pour out all alloys; the alloys produced by the smelting will be fed to the vacuum furnace through the alloy ingot transfer device after being cast into ingots, and the vacuum furnace recycles tin, lead, bismuth, indium, silver, and copper successively according to the difference of the boiling points of various valuable metals contained in the alloys; meanwhile, the slags after smelting will be fed to the fuming furnace through the slag transfer device to recycle tin by means of sulphation and volatilization, in addition, the flue gas discharged from the rotary smelting furnace and the fuming furnace enters the flue gas treatment system uniformly, and then to be cooled by the flue gas cooler, after that, the stanniferous flue dust will be recycled by the bag collector and desulfurized low-concentration SO2 through the tail gas desulfurization system, as well as discharged from the chimney (11) if it satisfies emission standards.
Compared with the prior art, the main advantages of the present invention are: (1) The system and process of the present invention adopts pyrometallurgical smelting, which can efficiently recycle tin, lead, bismuth, indium, silver, copper, and other valuable metals contained in the secondary raw materials of tin. And the process is short, the operation is simple, as well as is at a low cost, in addition, the energy consumption is low, and the safety and environmental conditions are perfect.
(2) The system and process of the present invention centrally process the flue gas generated by smelting and fuming, which is at low processing cost and has high efficiency. In addition, after cooling and dust collection process, the low-concentration S02 existed in the tail gas can be desulfurized, and thus, the tail gas can satisfy emission standards The system of the present invention has simple equipment, compact structure, less occupation, low construction investment, high efficiency, and practicality.
(3) The system of the present invention reasonably combines the prior art and equipment to build a system which can directly and efficiently recycle valuable metals contained in secondary raw materials of tin, and propose a process which can directly and efficiently recycle valuable metals contained in secondary raw materials of tin, and abandon the method adopted in the prior art, which can conduct smelting with secondary raw materials of tin and tin concentrate, and thus effectively solve the problems that need complex equipment, large scale of total investment, and complicated processes, and there are more production links are required, and the process is long, as well as the valuable metals contained in the secondary raw materials of tin are easy to disperse, and thus, the recycle rate is low, and the energy consumption is high.
Brief Description of the Drawings
Figure 1 is a schematic diagram of the system of the present invention.
Detailed Description of the Presently Preferred Embodiments As shown in Figure 1, it is the said system for efficiently recycling valuable metals contained in secondary raw materials of tin of the present invention, which comprises a batching system 1, a rotary smelting furnace 4, a vacuum furnace 5, and a fuming furnace 6, as well as a flue gas treatment system 7 which are arranged in a unified site, the said batching system comprises a set of batch bins of raw materials 2 which are arranged parallelly, a hopper of mixtures 3 which is arranged below the batch bin of raw materials; wherein, the hopper of mixtures is connected to the rotary smelting furnace 4 through a feeding mechanism 12, and feeds the mixtures to the rotary smelting furnace, wherein, the feeding mechanism can be a feed pipeline or a feed wagon, etc, in addition, the said the rotary smelting furnace 4 is directly or indirectly connected to the vacuum furnace 5, the fuming furnace 6 and the flue gas treatment system 7 respectively, wherein, the rotary smelting furnace 4 is connected to the vacuum furnace 5 through the alloy ingot transfer device 14, and the alloys produced by the rotary smelting furnace will be poured in casting mold 13 to form alloy ingots, and then are feed to the vacuum furnace 5 to recycle valuable metals through the alloy ingot transfer device 14, meanwhile, the rotary smelting furnace 4 is connected to the fuming furnace 6 through the slag transfer device 15, then, the slag produced by the rotary smelting furnace through smelting will be feed to the fuming furnace 6 to recycle tin by means of sulphation and volatilization, furthermore, the smoke outlet of the rotary smelting furnace 4 is connected to the flue gas treatment system 7 through the flue gas pipeline, meanwhile, the smoke outlet of the fuming furnace 6 is also connected to the flue gas treatment system 7 through the flue gas pipeline, wherein, the said flue gas treatment system 7 comprises a flue gas cooler 8, a bag collector 9, a tail gas desulfurization system 10, a chimney 11, which are connected in sequence through pipelines, and the said flue gas pipelines are inserted into the air inlet of the flue gas cooler 8.
The said set of batch bins of raw materials 2 respectively store secondary raw materials of tin (including tin anode slurry, speiss, tin slurry, etc.,) fusing agent, reducing agent and other materials in each batch bin. The said batch bin applies the bin with functions of automatic weighing and control existed in the prior art, which can be purchased, to control the batch bin. And there is an automatic weighing mechanism at the outlet of each batch bin, which can automatically weigh and control the discharging. In addition, the hopper of mixtures 3 arranged below the batch bin of raw materials is connected to each batch bin of raw materials through feed pipelines to realize the closed and automatic transportation of the raw materials, which is clean, efficient, and environmentally-friendly. Furthermore, the discharging of each batch bin of raw materials is determined according to the proportion of furnace charge set by the smelting process of the rotary smelting furnace, which will be fed to the rotary smelting furnace 4 through a feeding mechanism after entering the hopper of mixtures 3. The said feeding mechanism is a movable feed hopper with a switch at the bottom which can be swung up, and the said rotary smelting furnace 4 is an equipment utilized in the prior art, such as a rotary smelting furnace with the size of 02800x4200mm. In addition, the rotary smelting furnace is equipped with a combustion system, an exhaust system, a slag scrabbling device, and an alloy pouring device, etc. The said vacuum furnace 5, the fuming furnace 6, the flue gas cooler 8, the bag collector 9, and the tail gas desulfurization system 10 are all equipment utilized in the prior art. Furthermore, the vacuum furnace is equipped with a set of internally heated vacuum furnaces with daily processing of 10 tons, 20 tons, 30 tons, and 50 tons of materials, which are equipped with a feed system, a water supply system, and a negative-pressure system, etc. The said fuming furnace is a box-type fuming furnace with the size of 4m2 utilized in the prior art, and is equipped with a feeding device, an air supply and coal supply device, a flue gas waste-heat utilization device, and a lean slag discharge device.
The method for efficiently recycling valuable metals from secondary raw materials of tin by utilizing the system described in Figure 1, which is to feed the secondary raw materials of tin to the rotary smelting furnace to smelt them into alloys and slags firstly, and then feed the alloys to the vacuum furnace to recycle various valuable metals one by one through multiple-stage treatment, as well as feed the slags to the fuming furnace to recycle tin after treatment, after that, feed the flue gas generated by the rotary smelting furnace and the fuming furnace to the flue gas treatment system uniformly, and then discharge the flue gas which has been treated and satisfied emission standards. The specific process is: complete batching of tin anode slurry, speiss, tin slurry, and other secondary raw materials of tin, and fusing agent, as well as reducing agent, which are stored in each batch bin of raw materials 2 respectively after feeding them to the hopper of mixtures 3 according to the set proportion of batching, and then, put them into the rotary smelting furnace 4 automatically through the feed mechanism, wherein, the combustion system of the rotary smelting furnace injects the fuel, air, and oxygen that the smelting process required to complete smelting. After each furnace completed smelting, tilt the rotary smelting furnace, and scrabble out slags to the slag receiving device, and then feed them to the fuming furnace 6 through the slag transfer device to recycle tin by means of sulphation and volatilization, after that, discharged the lean slags outside the furnace after recycling tin. Then, pour out all alloys to the casing mould to cast ingots; and then feed the cast alloy ingots to the vacuum furnace 5 through the alloy ingot transfer device. Wherein, the vacuum furnace recycles tin, lead, bismuth, indium, silver, and copper successively according to the difference of the boiling points of various valuable metals contained in the alloys; The boiling point of the bismuth contained in the alloys is the lowest, which is 1560°C, and the bismuth would be volatilized and recycled firstly after being subjected to one vacuum process to the bismuth; and the boiling point of the lead is 1749°C, and the rank of which is lower, the lead would be volatilized and recycled secondly; and the boiling point of the indium is 2080°C, which ranks the third, the indium would be volatilized and recycled in the third step; furthermore, the boiling point of the silver is 2212°C and the boiling point of the tin is 2260°C, which would be volatilized together and recycled the Sn-Ag alloy in the fourth step, and the Sn-Ag alloy can be used to prepare soldering flux contained silver; and the boiling point of the remaining copper is 2562°C, which would be recycled from the final volatile residues. After that, the flue gas discharged from the top of the rotary smelting furnace 4 and the fuming furnace 6 enters the flue gas treatment system 7 through the discharge pipelines uniformly, then, to be cooled by the flue gas cooler (8), after that, the stanniferous flue dust would be recycled by the bag collector (9) and desulfurized low-concentration 502 through the tail gas desulfurization system 10, as well as discharged from the chimney (11) if it satisfies emission standards. The recycle rates of tin, lead, bismuth, indium, silver, and copper are respectively 98%, 95%, 96%, 90%, 95%, or more than 90%, and the recycle cost is reduced by 20% compared with the existing technologies. The rotary smelting furnace 4, the vacuum furnace 5, the fuming furnace 6, the flue gas cooler 8, the bag collector 9, and the tail gas desulfurization system 10, etc., are controlled in accordance with the operating specifications of each equipment, all of which are existing technologies, and those skilled in the art can operate.
The equipment and devices described in the present invention, such as the batching system 1 which comprises the batch bin of raw materials 2 and the hopper of mixtures 3, the rotary smelting furnace 4, the vacuum furnace 5, the fuming furnace 6, the flue gas treatment system 7, and the feeding mechanism 12, the alloy ingot transfer device 14, and the slag transfer device 15, etc. are all existing equipment and devices utilized in the prior art.
A specific embodiment is as follows: Take 3 tons of anode slurry (containing 41.5% of tin), 4 tons of speiss (containing 41.5% of tin), 3 tons of tin slurry (containing 42.6% of tin), 0.8 tons of fusing agent (which is composed of 0.2 tons of limestone and 0.6 tons of quartz sand), and 0.9 tons of reducing agent (anthracite), then, mix them evenly, and put to a movable feed hopper with a switch at the bottom which can be swung up, after that, lift the mixture to the charging opening of the rotary smelting furnace by hoist, and then add it to the rotary smelting furnace. Make the rotary smelting furnace return to the normal smelting state, and then start the burner to smelt after injecting fuel (pulverized coal) and combustion improver (oxygen-enriched air). During the smelting process, it is required to rotate the smelting furnace regularly to stir the materials. And then, keep the smelting temperature between 1250°C+50°C for about 6 hours. After all materials are melted and completed the reduction smelting and the sedimentation and separation of metals and slags, rotate the smelting furnace to the position of slagging, and then pour out the slags into the slag receiving device (during pouring out the slags, it is required to complete the operation in the form of fast followed by slow, and when the slags approach to the metal layer, use a slagging rake to scrabble out slags slowly so that prevent the metals from being mixed into the slags), after that, feed them to the fuming furnace through the slag transfer device for treatment. After completing slagging, continue to rotate the melting furnace, and pour out the metal alloys into the casting mold to cast ingots, and then feed the alloy ingots to the vacuum furnace system through the alloy ingot transfer device for treatment. In addition, the smelting cycle of each furnace lasts for 8 hours (including feeding, smelting, slagging and metal emission, etc.).
The slags generated in the rotary smelting furnace will be fed to the fuming furnace through the slag transfer device, and then be added to the fuming furnace with the size of 4m2 through the feed system of the fuming furnace, after that, add the sulfurizing reagent (pyrite) to complete sulphation and volatilization, and the stannous sulfide after volatilization will be oxidized into the flue dust of tin oxide at the upper part of the furnace, in the waste heat boiler and the flue, and then to recycle tin The lean slag after completing the fuming and recycle of tin will be discharged out of the furnace otherwise.
The alloys containing tin, lead, bismuth, indium, silver, and copper produced through the smelting process will be recycled tin, lead, bismuth, indium, silver, and copper in the vacuum furnace system successively according to the difference of the boiling points of various valuable metals. Specifically: the boiling point of the bismuth contained in the alloys is the lowest, which is 1560°C, and the bismuth would be volatilized and recycled firstly after being subjected to one vacuum process to the bismuth; and the boiling point of the lead is 1749°C, and the rank of which is lower, and the lead would be volatilized and recycled secondly; and the boiling point of the indium is 2080°C, which ranks the third, and the indium would be volatilized and recycled in the third step; furthermore, the boiling point of the silver is 2212°C and the boiling point of the tin is 2260°C, which would be volatilized together and recycled the Sn-Ag alloy in the fourth step, and the Sn-Ag alloy can be used to prepare soldering flux contained silver; and the boiling point of the remaining copper is 2562°C, which would be recycled from the final volatile residues.
The flue gas discharged from the top of the rotary smelting furnace and the fuming furnace enters the flue gas treatment system uniformly, and then to be cooled by the flue gas cooler, after that, the stanniferous flue dust will be recycled by the bag collector and desulfurized low-concentration S02 through the tail gas desulfurizat on system, as well as discharged from the chimney if it satisfies emission standards.
The system equipment of the present invention is at a low cost, adopts compact structure and short process flow, which can directly and efficiently recycle various valuable metals such as tin, lead, bismuth, indium, silver, and copper, etc., contained in the secondary raw materials of tin, and
S
have a high recycle rate. The system adopts simple operation, and is at a low cost, in addition, the energy consumption is low, and the safety and environmental conditions are perfect.
Claims (2)
- Claims I. A system applied to efficiently recycle valuable metals from secondary raw materials of tin, characterized in that comprising a batching system (1), a rotary smelting furnace (4), a vacuum furnace (5), and a fuming furnace (6), as well as a flue gas treatment system (7) which are arranged in a unified site; the said batching system comprises a set of batch bins of raw materials (2) which are arranged parallelly, a hopper of mixtures (3) which is arranged below the batch bin of raw materials; wherein, the hopper of mixtures is connected to the rotary smelting furnace (4) through a feeding mechanism (12), and feeds the mixtures to the rotary smelting furnace; in addition, the said the rotary smelting furnace is directly or indirectly connected to the vacuum furnace (5), the fuming furnace (6) and the flue gas treatment system (7) respectively, wherein, the rotary smelting furnace is connected to the vacuum furnace through the alloy ingot transfer device (14), and the alloys produced by the rotary smelting furnace will be feed to the vacuum furnace (5) to recycle valuable metals after being cast into ingots, and the rotary smelting furnace (4) is connected to the fuming furnace (6) through the slag transfer device (15), then, the slags produced by the rotary smelting furnace through smelting will be feed to the fuming furnace (6) to recycle tin by means of sulphation and volatilization, furthermore, the smoke outlet of the rotary smelting furnace (4) is connected to the flue gas treatment system (7) through the flue gas pipeline, meanwhile, the smoke outlet of the fuming furnace (6) is also connected to the flue gas treatment system (7) through the flue gas pipeline, wherein, the said flue gas treatment system (7) comprises a flue gas cooler (8), a bag collector (9), a tail gas desulfurization system (10), and a chimney (11), which are connected in sequence through pipelines, and the said flue gas pipelines are inserted into the air inlet of the flue gas cooler (8).
- 2. The method for efficiently recycling valuable metals from secondary raw materials of tin by utilizing the said system according to Claim 1, characterized in that the said method is to feed the secondary raw materials of tin to the rotary smelting furnace to smelt them into alloys and slags firstly, and then feed the alloys to the vacuum furnace to recycle various valuable metals one by one through multiple-stage treatment, as well as feed the slags to the fuming furnace to recycle tin after treatment, after that, feed the flue gas generated by the rotary smelting furnace and the fuming furnace to the flue gas treatment system uniformly, and then discharge the flue gas which has been treated and satisfied emission standards. The specific process is: complete batching of tin anode slurry, speiss, tin slurry, fusing agent, and reducing agent through the batching system, and then, put them into the rotary smelting furnace (4), wherein, the combustion system of the rotary smelting furnace injects the fuel, air, and oxygen that the smelting process required to complete smelting After each furnace completed smelting, tilt the rotary smelting furnace, and scrabble out slags, and then pour out all alloys; the alloys produced by the smelting will be fed to the vacuum furnace (5) through the alloy ingot transfer device after being cast into ingots, and the vacuum furnace recycles tin, lead, bismuth, indium, silver, and copper successively according to the difference of the boiling points of various valuable metals contained in the alloys; meanwhile, the slags after smelting will be fed to the fuming furnace (6) through the slag transfer device to recycle tin by means of sulphation and volatilization, in addition, the flue gas discharged from the rotary smelting furnace (4) and the fuming furnace (6) enters the flue gas treatment system (7) uniformly, and then to be cooled by the flue gas cooler (8), after that, the stanniferous flue dust will be recycled by the bag collector (9) and desulfurized low-concentration SO2 through the tail gas desulfurization system (10), as well as discharged from the chimney (11) if it satisfies emission standards.
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| CN202010292882.9A CN111321301A (en) | 2020-04-15 | 2020-04-15 | System and method for efficiently recovering valuable metals in tin secondary raw materials |
| PCT/CN2020/117069 WO2021208357A1 (en) | 2020-04-15 | 2020-09-23 | System and method for efficient recovery of valuable metals from tin secondary raw materials |
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| US20230015594A1 (en) * | 2021-07-16 | 2023-01-19 | Yunnan Tin Co. Ltd. Tin Branch | System for smelting tin-containing materials and method for smelting same |
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| CN113774233A (en) * | 2021-10-09 | 2021-12-10 | 昆明理工大学 | Tin smelting intermediate material processing system and processing method thereof |
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| GB202108783D0 (en) | 2021-08-04 |
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