CN108251660A - A kind of method of stanniferous abandoned mine material recycling tin - Google Patents
A kind of method of stanniferous abandoned mine material recycling tin Download PDFInfo
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- CN108251660A CN108251660A CN201810107749.4A CN201810107749A CN108251660A CN 108251660 A CN108251660 A CN 108251660A CN 201810107749 A CN201810107749 A CN 201810107749A CN 108251660 A CN108251660 A CN 108251660A
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
- C22B9/04—Refining by applying a vacuum
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- 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
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Abstract
The present invention relates to a kind of methods of stanniferous abandoned mine material recycling tin, include the following steps：S1 prepares raw material：Raw material is prepared by following parts by weight；S2 smelting processes：S21 material transportations；S22 smelt stages I：Smelting furnace is warming up to 800 1000 DEG C of 120 130min of melting, closes the hump that power supply eliminates liquid level in stove, standing 5 10min makes liquid level steady, removes the slag of liquid level center aggregation in stove；S23 smelt stages II：It is continuously heating to 1,000 1200 DEG C and is passed through 30 45min of oxygen-enriched air melting；S24 smelt stages III：It is warming up to 1,200 1300 DEG C of 90 120min of melting again after adding in reducing agent, closes the hump that power supply eliminates liquid level in stove, standing 5 10min makes liquid level steady, the tin slightly refined；S3 is refined.The present invention has the advantages that purity is high, impurities removing efficiency is high and simple for process.
Description
Technical field
The present invention relates to metal refining techniques fields, and in particular to a kind of method of stanniferous abandoned mine material recycling tin.
Background technology
Tin, metallic element, a kind of low-melting-point metal element of the white gloss of bit bluish, in compound be divalent or
Tetravalence, will not oxidation by air, mainly in the form of dioxide (cassiterite) and various sulfide (such as sulphur cassiterite) exist.Member
Plain symbol Sn.Tin is famous " hardware " -- one of gold, silver, copper, iron, tin.Early in the ancient times, people just have found and make
With tin.In some ancient tombs in China, just often excavate to some tinpots, tin candlestick etc tinware.According to textual criticism, the Zhou Dynasty of China
When, the use of tinware is very universal.In Egyptian ancient tomb, it has been found that have the articles for daily use of tin.
At present all using except tin, detinning method is more, substantially has following several in advance：
1st, fused salt lixiviation process.The advantages of fused salt high temperature detin, directly recycles tin slab, can also take off terne metal.Shortcoming is fused salt
Viscosity is big when fusing point is high, temperature is low, fused salt adhesive tape is more, loss is big, working condition is poor, material high temperature is oxidizable.Raw material is absolute
Dry, when otherwise waste material is put into fused salt immersion, moisture drastically evaporates and splash is hurted sb.'s feelings.
2nd, it is electrolysed stripping method.Electrolyte has two kinds of alkalinity and acidity.Alkaline electrolyte recycles tin for tinplate.Because alkali
Do not corrode steel, matrix steel plate is not any change in detin.But sodium hydroxide is acted on Carbon Dioxide in Air in electrolyte
It is high to generate sodium carbonate, tank voltage height, power consumption.Acidic electrolysis bath good conductivity, performance are stablized, and the solubility of tin is big.So electrolysis
Detin generally uses inexpensive sulfuric acid solution.
3rd, chloridising.Chloridising is volatilized according to tin and chlorine reaction generation low boiling point butter of tin, condensation recycling tetrachloro
Change tin, achieve the purpose that except tin.Tin plating waste cupron is fitted into closed retort, is passed through chlorine, control the flow of chlorine
With temperature, the butter of tin evaporated is condensed into liquid in condenser.Then metallic tin powder is recycled with zinc dust precipitation.Its advantage
It is that productivity is high, bundled material is not required to disassemble.Shortcoming be it is stringent using toxic chlorine, safety measure, it is retort pipe-line system, cold
Condenser leakproofness will be got well, and prevent chlorine from being leaked with butter of tin.It requires in addition that dry materials, moisture cannot be contained, otherwise equipment
Seriously corroded.
With the fast development of electronics and information industry, auto industry, wires and cables industry.Tin plating corner is given up in production process
Material and recyclable tin plating waste material are increasing.Annual this waste material up to ten thousand tons of 40-50 according to estimates.Tin plating waste cupron generally contains
Copper 96.0-98.5%, stanniferous 1.5-3.0%.There are considerable economic benefit and significant society to imitate from such waste recovery copper and tin
Benefit.In the past, such tin plating waste cupron does not recycle tin in advance, but as general copper junk, add in copper anode furnace, oxidation also
Former melting is cast into anode plate, and tough cathode is produced through electrorefining.In anode furnace refinement oxide, low boiling point tin voloxidation,
It is collected with flue gas in pulsed jet cloth filter, the main volatile metallic dust such as Zn containing zinc, lead Pb, tin Sn of the flue dust of collection.
Anode furnace oxidation is more difficult than iron removal by oxidation, zinc except slicker solder, and when furnace charge is stanniferous high, the tin in anode plate is removed to being less than
0.2% to meet the needs of electrorefining, and the duration of heat is long, and energy consumption is big.In addition, the gallery ports of anode furnace, skimming gate are unavoidable
There is flue gas to emerge, the rate of recovery of tin is low.
Invention content
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of method of stanniferous abandoned mine material recycling tin, solutions
The problem of recycling tin of having determined removal of impurities is difficult has the advantages that purity is high, impurities removing efficiency is high and simple for process.
The purpose of the present invention is achieved through the following technical solutions：
A kind of method of stanniferous abandoned mine material recycling tin, includes the following steps：
S1 prepares raw material：Raw material is prepared by following parts by weight：Stanniferous 300-400 parts of abandoned mine material, 12-15 parts of lime stone,
10-12 parts of adsorbent, 50-60 parts of reducing agent；
S2 smelting processes：
S21 material transportations：By stanniferous abandoned mine material, lime stone and adsorbent respectively by seal conveyance conduit be transported to it is side-blown
Dispensing in proportion behind stove workshop is added in smelting furnace and is smelted；
S22 smelt stages I：Smelting furnace is warming up to 800-1000 DEG C of melting 120-130min, power supply is closed and eliminates in stove
The hump of liquid level, standing 5-10min makes liquid level steady, removes the slag of liquid level center aggregation in stove；
S23 smelt stages II：It is continuously heating to 1000-1200 DEG C and is passed through oxygen-enriched air melting 30-45min, then be passed through and contain
There is the gas melting 20-30min of oxidant, close the hump that power supply eliminates liquid level in stove, standing 5-10min makes liquid level steady；
S24 smelt stages III：It is warming up to 1200-1300 DEG C of melting 90-120min again after adding in reducing agent, closes power supply
The hump of liquid level in stove is eliminated, standing 5-10min makes liquid level steady, the tin slightly refined；
S3 is refined：The tin slightly refined is carried out to obtain essence except iron, copper removal are transferred in vacuum drying oven later after vacuum distillation removal of impurities
Tin.
Stanniferous abandoned mine material refining recycling tin, raw material sources are extensive, at low cost, and smelting temperature gradually rises in fusion process,
Tin can melt completely, rate of recovery increase, remove clinker after melting once, avoid the content of remaining foreign metal after later stage heating
Raising cleans conducive to the later stage.
Further, oxidant is orange oil in the S1 steps, and reducing agent is coke, and adsorbent is activated carbon, stanniferous
Theil indices >=50% in abandoned mine material.Orange oil can promote to aoxidize, and the reduction effect of coke is good, and impurity is few, clean conducive to the later stage,
The adsorption effect of activated carbon is good, and impurity gold content is few.Orange oil low boiling point is easy to be atomized.
Further, Bi≤0.6%, S≤0.04%, Pb≤0.08%, Fe≤20%, Cu in the stanniferous abandoned mine material≤
20%.The content of foreign metal and poisonous metal is slightly higher in stanniferous abandoned mine material, but smelts and can purify by the later stage.
Further, the ash content of the coke is 12-15%, and phosphorus content 0.02-0.03%, granularity is granularity in 40-
25mm。
Activated carbon, orange oil, the cost of reducing agent and lime stone are low, and the adsorption effect of activated carbon is good, the reduction of coke
Effect is good, and the content of ashes of coke is low, phosphorus content is few, reduces the usage amount of coke, can reduce industrial cost, improves recycling profit
Profit.
Activated carbon is a kind of porous solid carbonaceous of black, by coal by crush, be molded or with uniform coal grain through charing,
Activation production.Main component is carbon, and containing elements such as a small amount of oxygen, hydrogen, sulphur, nitrogen, chlorine.The specific surface area of normal activated carbon is in 500-
Between 1700m2/g.It is a kind of extremely wide industrial adsorbents of purposes with very strong absorption property.
Coke be bituminous coal under conditions of air is completely cut off, 950-1050 DEG C is heated to, by drying, pyrolysis, melting, viscous
The stages such as knot, curing, contraction are finally made coke, this process is high-temperature coking (high-temperature retorting).It is obtained by high-temperature coking
Coke is used for blast furnace process, casting and gasification.Recovered, the purified coke-stove gas generated in process of coking is both high heating value
Fuel, and be important the organic synthesis raw material of industry.
Further, oxygen concentration is 70-75% in oxygen-enriched air in the S23 steps.
Further, the content of oxidant is 15-20% in the gas containing oxidant in the S23 steps, oxygen concentration
For 30-35%, surplus is nitrogen.The concentration of oxygen-enriched air is high, and early period is used for oxygenation in copper water, can reduce the gas that the later stage is passed through
Middle oxygen concentration, security risk is reduced in industrial smelting process, and the later stage adds in the gas that is mixed with oxidant, can accelerated oxidation into
Journey increases oxidation efficiency.
Further, the orange oil is mixed with oxygen rich gas using atomizer atomization at 65-70 DEG C and is contained
There is the gas of oxidant.
Further, except iron is that condensation method removes iron, copper removal to add sulphur removing in the S3 steps.
Further, the temperature being evaporated in vacuo in the S3 steps is 1200-1400 DEG C, vacuum degree 15-30Pa, distillation
Time is 80-100min.The refined tin purity height that temperature is high, distills is evaporated in vacuo, vacuum distillation can remove foreign metal example
Such as bismuth, lead, the removal step synthesis of early period can remove 99.95% foreign metal.
The beneficial effects of the invention are as follows：
1. stanniferous abandoned mine material refining recycling tin, raw material sources are extensive, at low cost, and smelting temperature gradually rises in fusion process
Height, tin can melt completely, rate of recovery increase removes clinker after melting once, avoid the later stage heat up after remaining foreign metal
Content increases, and cleans conducive to the later stage；
2. orange oil can promote to aoxidize, the reduction effect of coke is good, and impurity is few, cleans conducive to the later stage, the suction of activated carbon
Attached effect is good, and impurity gold content is few, and orange oil low boiling point is easy to be atomized, fast with the mixing of oxygen rich gas, and the uniformity is high；
3. the concentration of oxygen-enriched air is high, early period is used for oxygenation in copper water, can reduce oxygen concentration in the gas that the later stage is passed through,
Security risk is reduced in industrial smelting process, and the later stage adds in the gas that is mixed with oxidant, can accelerated oxidation process, increase oxidation
Efficiency；
4. being evaporated in vacuo, temperature is high, and the refined tin purity distilled is high, and vacuum distillation can remove foreign metal such as bismuth, lead
Deng the removal step synthesis of early period can remove 99.95% foreign metal；
5. activated carbon, orange oil, the cost of reducing agent and lime stone are low, the adsorption effect of activated carbon is good, coke also
Former effect is good, and the content of ashes of coke is low, phosphorus content is few, reduces the usage amount of coke, can reduce industrial cost, improves recycling profit
Profit.
Specific embodiment
Technical scheme of the present invention is described in further detail, but protection scope of the present invention is not with reference to specific embodiment
It is confined to as described below.
Embodiment 1
A kind of method of stanniferous abandoned mine material recycling tin, includes the following steps：
S1 prepares raw material：Raw material is prepared by following parts by weight：Stanniferous 300 parts of abandoned mine material, 12 parts of lime stone, adsorbent 10
Part, 50 parts of reducing agent；
S2 smelting processes：
S21 material transportations：By stanniferous abandoned mine material, lime stone and adsorbent respectively by seal conveyance conduit be transported to it is side-blown
Dispensing in proportion behind stove workshop is added in smelting furnace and is smelted；
S22 smelt stages I：Smelting furnace is warming up to 800 DEG C of melting 130min, closes the camel that power supply eliminates liquid level in stove
Peak, standing 5-10min makes liquid level steady, removes the slag of liquid level center aggregation in stove；
S23 smelt stages II：It is continuously heating to 1000 DEG C and is passed through oxygen-enriched air melting 45min, then be passed through containing oxidant
Gas melting 30min, close power supply eliminate stove in liquid level hump, stand 10min make liquid level steady；
S24 smelt stages III：It is warming up to 1200 DEG C of melting 120min again after adding in reducing agent, closes power supply and eliminates in stove
The hump of liquid level, standing 10min makes liquid level steady, the tin slightly refined；
S3 is refined：The tin slightly refined is carried out to obtain essence except iron, copper removal are transferred in vacuum drying oven later after vacuum distillation removal of impurities
Tin.
Specifically, oxidant is orange oil in the S1 steps, and reducing agent is coke, and adsorbent is activated carbon, stanniferous useless
Theil indices >=50% in mineral aggregate.
Specifically, Bi≤0.6%, S≤0.04%, Pb≤0.08%, Fe≤20%, Cu in the stanniferous abandoned mine material≤
20%.
Specifically, the ash content of the coke is 15%, and phosphorus content 0.03%, granularity is granularity in 40-25mm.
Specifically, oxygen concentration is 70-75% in oxygen-enriched air in the S23 steps.
Specifically, the content of oxidant is 15-20% in the gas containing oxidant in the S23 steps, and oxygen concentration is
30-35%, surplus are nitrogen.
Specifically, the orange oil is mixed with to obtain containing oxidation using atomizer atomization at 65 DEG C with oxygen rich gas
The gas of agent.
Specifically, except iron is that condensation method removes iron, copper removal to add sulphur removing in the S3 steps.
Specifically, the temperature being evaporated in vacuo in the S3 steps is 1200 DEG C, vacuum degree 30Pa, and distillation time is
100min。
Embodiment 2
A kind of method of stanniferous abandoned mine material recycling tin, includes the following steps：
S1 prepares raw material：Raw material is prepared by following parts by weight：Stanniferous 400 parts of abandoned mine material, 15 parts of lime stone, adsorbent 12
Part, 60 parts of reducing agent；
S2 smelting processes：
S21 material transportations：By stanniferous abandoned mine material, lime stone and adsorbent respectively by seal conveyance conduit be transported to it is side-blown
Dispensing in proportion behind stove workshop is added in smelting furnace and is smelted；
S22 smelt stages I：Smelting furnace is warming up to 1000 DEG C of melting 120min, closes the camel that power supply eliminates liquid level in stove
Peak, standing 5min makes liquid level steady, removes the slag of liquid level center aggregation in stove；
S23 smelt stages II：It is continuously heating to 1200 DEG C and is passed through oxygen-enriched air melting 30min, then be passed through containing oxidant
Gas melting 20min, close power supply eliminate stove in liquid level hump, stand 5min make liquid level steady；
S24 smelt stages III：It is warming up to 1300 DEG C of melting 90min again after adding in reducing agent, closes power supply and eliminates liquid in stove
The hump in face, standing 5min makes liquid level steady, the tin slightly refined；
S3 is refined：The tin slightly refined is carried out to obtain essence except iron, copper removal are transferred in vacuum drying oven later after vacuum distillation removal of impurities
Tin.
Specifically, oxidant is orange oil in the S1 steps, and reducing agent is coke, and adsorbent is activated carbon, stanniferous useless
Theil indices >=50% in mineral aggregate.
Specifically, Bi≤0.6%, S≤0.04%, Pb≤0.08%, Fe≤20%, Cu in the stanniferous abandoned mine material≤
20%.
Specifically, the ash content of the coke is 12%, and phosphorus content 0.02%, granularity is granularity in 40-25mm.
Specifically, oxygen concentration is 70-75% in oxygen-enriched air in the S23 steps.
Specifically, the content of oxidant is 15-20% in the gas containing oxidant in the S23 steps, and oxygen concentration is
30-35%, surplus are nitrogen.
Specifically, the orange oil is mixed with to obtain containing oxidation using atomizer atomization at 70 DEG C with oxygen rich gas
The gas of agent.
Specifically, except iron is that condensation method removes iron, copper removal to add sulphur removing in the S3 steps.
Specifically, the temperature being evaporated in vacuo in the S3 steps is 1400 DEG C, vacuum degree 15Pa, and distillation time is
80min。
Embodiment 3
A kind of method of stanniferous abandoned mine material recycling tin, includes the following steps：
S1 prepares raw material：Raw material is prepared by following parts by weight：Stanniferous 350 parts of abandoned mine material, 13 parts of lime stone, adsorbent 11
Part, 55 parts of reducing agent；
S2 smelting processes：
S21 material transportations：By stanniferous abandoned mine material, lime stone and adsorbent respectively by seal conveyance conduit be transported to it is side-blown
Dispensing in proportion behind stove workshop is added in smelting furnace and is smelted；
S22 smelt stages I：Smelting furnace is warming up to 900 DEG C of melting 125min, closes the camel that power supply eliminates liquid level in stove
Peak, standing 8min makes liquid level steady, removes the slag of liquid level center aggregation in stove；
S23 smelt stages II：It is continuously heating to 1100 DEG C and is passed through oxygen-enriched air melting 40min, then be passed through containing oxidant
Gas melting 25min, close power supply eliminate stove in liquid level hump, stand 8min make liquid level steady；
S24 smelt stages III：It is warming up to 1250 DEG C of melting 100min again after adding in reducing agent, closes power supply and eliminates in stove
The hump of liquid level, standing 8min makes liquid level steady, the tin slightly refined；
S3 is refined：The tin slightly refined is carried out to obtain essence except iron, copper removal are transferred in vacuum drying oven later after vacuum distillation removal of impurities
Tin.
Specifically, oxidant is orange oil in the S1 steps, and reducing agent is coke, and adsorbent is activated carbon, stanniferous useless
Theil indices >=50% in mineral aggregate.
Specifically, Bi≤0.6%, S≤0.04%, Pb≤0.08%, Fe≤20%, Cu in the stanniferous abandoned mine material≤
20%.
Specifically, the ash content of the coke is 13%, and phosphorus content 0.02%, granularity is granularity in 40-25mm.
Specifically, oxygen concentration is 70-75% in oxygen-enriched air in the S23 steps.
Specifically, the content of oxidant is 15-20% in the gas containing oxidant in the S23 steps, and oxygen concentration is
30-35%, surplus are nitrogen.
Specifically, the orange oil is mixed with to obtain containing oxidation using atomizer atomization at 68 DEG C with oxygen rich gas
The gas of agent.
Specifically, except iron is that condensation method removes iron, copper removal to add sulphur removing in the S3 steps.
Specifically, the temperature being evaporated in vacuo in the S3 steps is 1300 DEG C, vacuum degree 25Pa, and distillation time is
90min。
Embodiment 4
A kind of method of stanniferous abandoned mine material recycling tin, includes the following steps：
S1 prepares raw material：Raw material is prepared by following parts by weight：Stanniferous 360 parts of abandoned mine material, 14 parts of lime stone, adsorbent 12
Part, 58 parts of reducing agent；
S2 smelting processes：
S21 material transportations：By stanniferous abandoned mine material, lime stone and adsorbent respectively by seal conveyance conduit be transported to it is side-blown
Dispensing in proportion behind stove workshop is added in smelting furnace and is smelted；
S22 smelt stages I：Smelting furnace is warming up to 1000 DEG C of melting 125min, closes the camel that power supply eliminates liquid level in stove
Peak, standing 7min makes liquid level steady, removes the slag of liquid level center aggregation in stove；
S23 smelt stages II：It is continuously heating to 1200 DEG C and is passed through oxygen-enriched air melting 35min, then be passed through containing oxidant
Gas melting 25min, close power supply eliminate stove in liquid level hump, stand 8min make liquid level steady；
S24 smelt stages III：It is warming up to 1300 DEG C of melting 100min again after adding in reducing agent, closes power supply and eliminates in stove
The hump of liquid level, standing 8min makes liquid level steady, the tin slightly refined；
S3 is refined：The tin slightly refined is carried out to obtain essence except iron, copper removal are transferred in vacuum drying oven later after vacuum distillation removal of impurities
Tin.
Specifically, oxidant is orange oil in the S1 steps, and reducing agent is coke, and adsorbent is activated carbon, stanniferous useless
Theil indices >=50% in mineral aggregate.
Specifically, Bi≤0.6%, S≤0.04%, Pb≤0.08%, Fe≤20%, Cu in the stanniferous abandoned mine material≤
20%.
Specifically, the ash content of the coke is 14%, and phosphorus content 0.02%, granularity is granularity in 40-25mm.
Specifically, oxygen concentration is 70-75% in oxygen-enriched air in the S23 steps.
Specifically, the content of oxidant is 15-20% in the gas containing oxidant in the S23 steps, and oxygen concentration is
30-35%, surplus are nitrogen.
Specifically, the orange oil is mixed with to obtain containing oxidation using atomizer atomization at 70 DEG C with oxygen rich gas
The gas of agent.
Specifically, except iron is that condensation method removes iron, copper removal to add sulphur removing in the S3 steps.
Specifically, the temperature being evaporated in vacuo in the S3 steps is 1400 DEG C, vacuum degree 25Pa, and distillation time is
100min。
The specific performance parameter of embodiment 1- embodiments 4 is as shown in table 1：
| Embodiment | 1 | 2 | 3 | 4 |
| Refined tin purity/% | ≥99.90 | ≥99.90 | ≥99.90 | ≥99.90 |
| The tin rate of recovery/% | 96.5 | 95.9 | 96.5 | 96.8 |
| Lead (Pb) content | ＜ 1000ppm | ＜ 1000ppm | ＜ 1000ppm | ＜ 1000ppm |
| Mercury (Hg) content | ＜ 1000ppm | ＜ 1000ppm | ＜ 1000ppm | ＜ 1000ppm |
Table 1
Poisonous metal content is can be seen that from the data in table 1 to comply with standard, the rate of recovery of tin is high, and refined tin purity is high.
The above is only the preferred embodiment of the present invention, it should be understood that the present invention is not limited to described herein
Form is not to be taken as the exclusion to other embodiment, and available for other combinations, modifications, and environments, and can be at this
In the text contemplated scope, modifications can be made through the above teachings or related fields of technology or knowledge.And those skilled in the art institute into
Capable modifications and changes do not depart from the spirit and scope of the present invention, then all should be in the protection domain of appended claims of the present invention
It is interior.
Claims (9)
- A kind of 1. method of stanniferous abandoned mine material recycling tin, which is characterized in that include the following steps：S1 prepares raw material：Raw material is prepared by following parts by weight：Stanniferous 300-400 parts of abandoned mine material, 12-15 parts of lime stone, absorption 10-12 parts of agent, 50-60 parts of reducing agent；S2 smelting processes：S21 material transportations：Stanniferous abandoned mine material, lime stone and adsorbent are transported to side-blown converter vehicle by sealing conveyance conduit respectively Between after dispensing in proportion, add in smelting furnace and smelted；S22 smelt stages I：Smelting furnace is warming up to 800-1000 DEG C of melting 120-130min, power supply is closed and eliminates liquid level in stove Hump, stand 5-10min make liquid level steady, remove stove in liquid level center aggregation slag；S23 smelt stages II：It is continuously heating to 1000-1200 DEG C and is passed through oxygen-enriched air melting 30-45min, then be passed through containing aerobic The gas melting 20-30min of agent closes the hump that power supply eliminates liquid level in stove, and standing 5-10min makes liquid level steady；S24 smelt stages III：It is warming up to 1200-1300 DEG C of melting 90-120min again after adding in reducing agent, closes power supply and eliminates The hump of liquid level in stove, standing 5-10min makes liquid level steady, the tin slightly refined；S3 is refined：The tin slightly refined is carried out to obtain refined tin except iron, copper removal are transferred in vacuum drying oven later after vacuum distillation removal of impurities.
- A kind of 2. method of stanniferous abandoned mine material recycling tin according to claim 1, which is characterized in that oxygen in the S1 steps Agent is orange oil, and reducing agent is coke, and adsorbent is activated carbon, Theil indices >=50% in stanniferous abandoned mine material.
- 3. the method for a kind of stanniferous abandoned mine material recycling tin according to claim 1 or 2, which is characterized in that described stanniferous useless Bi≤0.6%, S≤0.04%, Pb≤0.08%, Fe≤20%, Cu≤20% in mineral aggregate.
- 4. the method for a kind of stanniferous abandoned mine material recycling tin according to claim 1 or 2, which is characterized in that the coke Ash content is 12-15%, and phosphorus content 0.02-0.03%, granularity is granularity in 40-25mm.
- 5. the method for a kind of stanniferous abandoned mine material recycling tin according to claim 1, which is characterized in that in the S23 steps Oxygen concentration is 70-75% in oxygen-enriched air.
- 6. the method for a kind of stanniferous abandoned mine material recycling tin according to claim 1, which is characterized in that in the S23 steps The content of oxidant is 15-20% in gas containing oxidant, and oxygen concentration 30-35%, surplus is nitrogen.
- 7. the method for a kind of stanniferous abandoned mine material recycling tin according to claim 1, which is characterized in that the orange oil exists It is mixed with to obtain the gas containing oxidant with oxygen rich gas using atomizer atomization at 65-70 DEG C.
- 8. the method for a kind of stanniferous abandoned mine material recycling tin according to claim 1, which is characterized in that removed in the S3 steps Iron is condensation method except iron, copper removal is add sulphur removing.
- 9. the method for a kind of stanniferous abandoned mine material recycling tin according to claim 1, which is characterized in that true in the S3 steps The temperature of sky distillation is 1200-1400 DEG C, vacuum degree 15-30Pa, distillation time 80-100min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021208357A1 (en) * | 2020-04-15 | 2021-10-21 | 云南锡业股份有限公司铜业分公司 | System and method for efficient recovery of valuable metals from tin secondary raw materials |
| GB2601212A (en) * | 2020-04-15 | 2022-05-25 | Copper Branch Company Of Yunnan Tin Company Ltd | System and method for efficient recovery of valuable metals from tin secondary raw materials |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021208357A1 (en) * | 2020-04-15 | 2021-10-21 | 云南锡业股份有限公司铜业分公司 | System and method for efficient recovery of valuable metals from tin secondary raw materials |
| GB2601212A (en) * | 2020-04-15 | 2022-05-25 | Copper Branch Company Of Yunnan Tin Company Ltd | System and method for efficient recovery of valuable metals from tin secondary raw materials |
| GB2601212B (en) * | 2020-04-15 | 2024-03-13 | Copper Branch Company Of Yunnan Tin Company Ltd | A system applied to efficiently recycle valuable metals from secondary raw materials of tin and its method |
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