CN106282582A - A kind of recovery non-ferrous metal, rare precious metal and method of iron powder from fume from steel making - Google Patents
A kind of recovery non-ferrous metal, rare precious metal and method of iron powder from fume from steel making Download PDFInfo
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- CN106282582A CN106282582A CN201510285197.2A CN201510285197A CN106282582A CN 106282582 A CN106282582 A CN 106282582A CN 201510285197 A CN201510285197 A CN 201510285197A CN 106282582 A CN106282582 A CN 106282582A
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Abstract
The invention provides a kind of recovery non-ferrous metal, rare precious metal and method of iron powder from fume from steel making, the steps include: to mix fume from steel making with chlorinating agent, reducing agent, add in tunnel cave, reaction point two sections within it is carried out, leading portion is middle temperature chlorination reaction, make non-ferrous metal therein, noble metal be volatized into flue gas, be made for after gathering dust extracting non-ferrous metal, precious metal raw material；Back segment be high temperature reduction reaction so that it is in ferrum be reduced to fe with kiln slag discharge.Kiln slag is cooled, broken, ball milling is made into the slurry less than 60 mesh granularities, and simple substance iron powder and waste residue are isolated in magnetic separation, and this powder iron content is more than 86%, can use as commodity reduced iron powder, waste residue export trade cement plant.Chlorination of the present invention adds reduction metallurgical process segmentation in a tunnel cave and carries out, and simplifies technical process, and easy and simple to handle, the thermal efficiency is high, and production cost is low, and comprehensive utilization ratio is high.It it is the another new way that valuable metal in fume from steel making rationally reclaims, efficiently utilizes resource.
Description
Technical field
The invention belongs to metal metallurgy smelting field, a kind of recovery non-ferrous metal, rare precious metal and method of iron powder from fume from steel making.
Background technology
Steel-making (electric furnace, converter)The quantum of output of flue dust can reach the 1～2 of steel-making batch, it it is the superfine flue dust of a kind of granule, generally granularity accounts for more than the 85% of total amount in 20 μm particles below, chemical composition is the most more complicated, it is both containing a certain amount of ferrum and carbon, also contain outside non-ferrous metals such as a small amount of zinc, lead, stannum, copper, bismuth etc. and the rare precious metal such as indium, germanium, gold, silver, possibly together with the multiple harmful substances such as metal such as lead, cadmium, sexivalent chromium, cyanogen and compound thereof, it is seen that fume from steel making is a kind of extremely harmful solid waste.From recycling economy and protection environment, it is a kind of recyclable non-ferrous metal, rare precious metal and the secondary resource of ferrous metal.Fume from steel making is all to use rotary kiln, retort, shaft furnace, blast furnace to process at present, and its principle is the same, and carbon thermal reduction is volatilized, and purpose reclaims zinc therein, lead, cadmium, germanium etc. exactly.nullAs rotary kiln recycles method，It is that with reducing agent mixing such as substantial amounts of coke powders, (mixing ratio is generally 1:3 by fume from steel making，I.e. 1 ton metallic zinc needs to allocate 3 tons of coke powders into) put into intensification volatilization in rotary kiln afterwards，It is usually at a temperature of rotary kiln is higher and (in the middle part of rotary kiln), controls reducing gases part，Make the zinc in ironmaking dust、Lead、Cadmium、The oxide of germanium etc. is reduced into metal，Owing to their boiling point is relatively low bigger with the vapour pressure of metal under high temperature，The metal being reduced enters gas phase with the form of steam，Dust collecting system is entered with flue gas，Due to leaking out of dust collecting system，After air enters，Metal vapors is oxidized to again oxidation state，Finally with form collecting in dust collecting system of leaded zinc powder，The drawback of this method is stannum、Copper、Bismuth、Indium、Gold、Silver etc. are high boiling has normal complexion rare precious metal to be formed without steam after being reduced and vapour pressure is less，Volatilization of not gasifying also remains in volatilization residue (kiln slag)，Generally as Solid state fermentation or send cement plant to process，Even if sorting into iron ore concentrate to be again introduced into steelmaking system，All it is not recycled.And, UTILIZATION OF VESIDUAL HEAT IN is poor, ferrum in fume from steel making enters in kiln slag of rotary kiln, owing to grade low (iron content 30-40%) can not typically be delivered to slag field store up or cement plant produces cement directly as the raw material (requiring iron content more than 50%) of product steel-making.Also having been reported that after kiln slag shrend, being soaked in water, it is the most oxidized to avoid, and uses ball milling--magnetic separation gravity treatment combined sorting technique, separating ferrum fine powder (ferroso-ferric oxide) and waste residue, the response rate of ferrum is 50%, and the iron ore concentrate after sorting, as the raw material of steel mill, is worth relatively low.In a word, the making a low multiple use of resource.Process relevant method therewith at present as follows:
What Wang Shukai et al. invented relates to from blast furnace ironmaking flue dust producing iron powder and the side (201210179548.8) of recovery non-ferrous metal, blast furnace steel-making flue dust is mixed with reducing agent fuel, add rotary kiln and carry out high temperature reduction reaction, non-ferrous metal therein is made to be volatized into flue gas, being made for after gathering dust extracting non-ferrous metal raw material, iron rule is reduced to fe and discharges with kiln slag；Kiln slag is cooled, broken, ore grinding is made into the ore pulp less than 100 mesh granularities, and magnetic separation is isolated containing Fe more than 65% iron ore concentrate；Iron ore concentrate is through secondary grinding, upper separation by shaking table goes out simple substance iron powder and time iron ore concentrate, and simple substance iron powder drying obtains granularity less than 120 mesh, MFe >=85%, the commodity reduced iron powder of TFe >=92%；Reduced iron powder is the commodity metallurgy iron powder of ore grinding, screening, output MFe >=98% after hydrogen reducing electric furnace reduction is come out of the stove.
The method (201310490196.2) producing Second-rate zinc oxide powder with blast furnace dust for raw material rotary kiln of Yang Zhengwu et al. invention, a kind of method producing oxide powder and zinc for raw material rotary kiln with blast furnace dust, the step of Second-rate zinc oxide powder is produced including rotary kiln high temperature fuming process feed stock for blast furnace, it is characterized in that feed stock for blast furnace prepares through the following step: by the raw material of following masses proportioning: blast furnace dust 50～60%, sedimentation powder 20～40%, back powder 8～15%, Calx 5～8%, mixing, controlling mixture moisture content is 16～22% mass ratio；Make pelletizing routinely, stove pellet feed must be entered.Make blast furnace dust become regenerated resources, reclaim and have valency zinc element, and properly settle blast furnace dust because of outer row, store up and the problem that causes environmental pollution.
Summary of the invention
Present invention aims to the problems referred to above, there is provided a kind of from fume from steel making, reclaim non-ferrous metal, rare precious metal and the method for iron powder, the method can make the non-ferrous metal in fume from steel making and rare precious metal selective chlorination vaporization at high temperature, reaching ferrum and non-ferrous metal and rare precious metal efficiently separates, ferrum is reduced to iron powder and reclaims, and non-ferrous metal and rare precious metal after chlorination vaporization at high temperature can purify recovery the most again, present invention process is simple, the thermal efficiency is high, and production cost is low, and comprehensive utilization ratio is high.
The technical solution used in the present invention is: a kind of recovery non-ferrous metal, rare precious metal and method of iron powder from fume from steel making, it is characterised in that mainly include that step is carried out in detail below:
(1) by same for fume from steel making chlorinating agent, reducing agent is sufficiently humidified so as to, mixing, make mixture moisture content at 3-8%, the material mixed loading kiln car is inserted in tunnel cave, material in kiln car divides two sections during advancing in tunnel cave and reacts successively, leading portion is middle temperature chlorination reaction, temperature controls at 1000-1050 DEG C, 60-120 minute time, chlorinating agent and the non-ferrous metal in fume from steel making, rare precious metal Zn, Pb, Bi, Sn, In, Ge, Ag, there is chlorination reaction in Au etc., it is converted into volatilizable chloride-sublimation and enters flue gas, non-ferrous metal, the chloridizing volatilization rate of rare precious metal is more than 90%, and the oxide of ferrum is more stable compared with chloride, non-volatile and stay in solid residue.Flue gas containing non-ferrous metal, rare precious metal Zn, Pb, Bi, Sn, In, Ge, Ag, Au etc. enters sack cleaner after extracting out after expansion chamber, high-temperature anticorrosion pipeline, surface-cooler, the chloride that flue dust is non-ferrous metal, rare precious metal Zn, Pb, Bi, Sn, In, Ge, Ag, Au etc. collected, separates and recovers to obtain various non-ferrous metals, rare precious metal product through conventional method.(2) back segment is high temperature reduction reaction, kiln car equipped with iron content residue continues to advance forward in tunnel cave, at this moment the reducing agent needed for reaction is added from the top of tunnel cave, the thermal material making full use of leading portion chlorination reaction proceeds the heating reduction of ferrum, temperature controls at 1200-1250 DEG C, time is 60-120 minute, and the ferrum in iron content residue is reduced to fe and discharges with kiln slag, has the iron oxides of more than 95% to be reduced to metallic iron.Kiln slag is cooled, broken, ball milling is made into the slurry less than 60 mesh granularities, and simple substance iron powder is isolated in magnetic separation, and simple substance iron powder iron content is more than 86%.
Chlorinating agent described in step (1) is calcium chloride or sodium chloride or both mixture, and addition ratio is 0.5 ~ 3%；Reducing agent is coke powder or broken coal, and addition is 1 ~ 3%,.Step (2) described reducing agent is coke powder or broken coal, and addition ratio is 15 ~ 30%,.Reducing agent coke powder or broken coal are to be added by the top of tunnel cave or in side spray people's kiln.
Accompanying drawing explanation
Fig. 1 is a kind of recovery non-ferrous metal, rare precious metal and process chart of iron powder from fume from steel making.
Detailed description of the invention
Seeing accompanying drawing 1, use the fume from steel making that Kunming Iron & Steel Co., Ltd.'s converter produces, its chemical composition is (Wt%): Zn 24.52, Pb 4, Fe 26, S 0.5, In 0.02, Ag 0.01, Bi 0.4, Sn 0.5Au 0.00008, processes technique as follows:
Fume from steel making 5000 kg, liquid chlorine agent (calcium chloride and the mixture of sodium chloride 10-12:1) addition ratio is 50kg；Reducing agent is coke powder, addition is 100kg, reducing agent coke powder is sufficiently humidified so as in cylindrical mixer, mixing, make mixture moisture content 4%, insert in tunnel cave, within it chemical reaction divides two sections to carry out, leading portion is middle temperature chlorination reaction, temperature controls at 1000-1050 DEG C, 100 minutes time, non-ferrous metal in fume from steel making, rare precious metal Zn, Pb, Bi, Sn, In, Ge, Ag, there is chlorination reaction in Au etc., produce lower boiling chloride-sublimation and enter flue gas, non-ferrous metal, rare precious metal chloridizing volatilization rate >=90%, it is made for after gathering dust extracting non-ferrous metal, rare precious metal raw material, reducing agent is in addition to oxide effect relevant with material, remainder is allocated as fuel oxidation by air, all generate carbon dioxide；Back segment is high temperature reduction reaction, the reducing agent coke powder needed for reaction is added from the top of tunnel cave, addition is 1000 kg, the thermal material making full use of leading portion chlorination reaction proceeds the heating reduction of ferrum, temperature controls at 1200-1250 DEG C, time is 100 minutes, and the ferrum in fume from steel making is reduced to fe and discharges with kiln slag, has the iron oxides of more than 95% to be reduced to metallic iron.
Tunnel kiln smoke-gas gathers dust: the flue gas that tunnel cave produces enters sack cleaner after expansion chamber, high-temperature anticorrosion pipeline, surface-cooler, the chloride that flue dust is non-ferrous metal, rare precious metal Zn, Pb, Bi, Sn, In, Ge, Ag, Au etc. collected, it is mainly composed of (Wt%): Zn37.5, Pb9.2, Fe1.8, In0.023, Ag0.025, Bi0.78, Sn0.45, Au0.0001, separates and recovers to obtain various metal products through conventional method.
Kiln slag magnetic separation: kiln slag is cooled, broken, ball milling is made into the slurry less than 60 mesh granularities, simple substance iron powder and waste residue are isolated in magnetic separation, and simple substance iron powder iron content is more than 86%, as commodity reduced iron powder export trade, waste residue export trade cement plant.
Claims (3)
- null1. one kind is reclaimed non-ferrous metal from fume from steel making、Rare precious metal and the method for iron powder，It is characterized in that sequentially including the following steps: (1) by same for fume from steel making chlorinating agent、Reducing agent is sufficiently humidified so as to、Mixing，Make mixture moisture content at 3-8%，The material mixed loading kiln car is inserted in tunnel cave，Material in kiln car divides two sections during advancing in tunnel cave and reacts successively，Leading portion is middle temperature chlorination reaction，Temperature controls at 1000-1050 DEG C，60-120 minute time，Chlorinating agent and the non-ferrous metal in fume from steel making、Rare precious metal Zn、Pb、Bi、Sn、In、Ge、Ag、There is chlorination reaction in Au etc.，It is converted into volatilizable chloride-sublimation and enters flue gas，Non-ferrous metal、The chloridizing volatilization rate of rare precious metal is more than 90%，And the oxide of ferrum is more stable compared with chloride，Non-volatile and stay in solid residue，Containing non-ferrous metal、Rare precious metal Zn、Pb、Bi、Sn、In、Ge、Ag、Through expansion chamber after the flue gas extraction of Au etc.、High-temperature anticorrosion pipeline、Sack cleaner is entered after surface-cooler，The flue dust collected is non-ferrous metal、Rare precious metal Zn、Pb、Bi、Sn、In、Ge、Ag、The chloride of Au etc.，Various non-ferrous metals are separated and recovered to obtain through conventional method、Rare precious metal product，(2) back segment is high temperature reduction reaction，Kiln car equipped with iron content residue continues to advance forward in tunnel cave，At this moment the reducing agent needed for reaction is added from the top of tunnel cave，The thermal material making full use of leading portion chlorination reaction proceeds the heating reduction of ferrum，Temperature controls at 1200-1250 DEG C，Time is 60-120 minute，Ferrum in iron content residue is reduced to fe and discharges with kiln slag，The iron oxides having more than 95% is reduced to metallic iron，Kiln slag is cooled、Broken、Ball milling is made into the slurry less than 60 mesh granularities，Simple substance iron powder is isolated in magnetic separation，Simple substance iron powder iron content is more than 86%.
- 2. from fume from steel making, reclaim non-ferrous metal, rare precious metal and the method for iron powder according to a kind of described in claim 1, it is characterised in that chlorinating agent described in step (1) step is calcium chloride or sodium chloride or both mixture, and addition ratio is 0.5 ~ 3%；Reducing agent is coke powder or broken coal, and addition ratio is 1 ~ 3%,.
- 3. according to a kind of recovery non-ferrous metal, rare precious metal and the method for iron powder from fume from steel making described in claim 1, it is characterized in that step (2) described reducing agent is coke powder or broken coal, addition ratio is 15 ~ 30%,, reducing agent coke powder or broken coal are to be added by the top of tunnel cave or in side spray people's kiln.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108486384A (en) * | 2018-03-16 | 2018-09-04 | 湖南腾驰环保科技有限公司 | The recovery process of low-grade stanniferous bismuth tungsten slag |
| CN110229965A (en) * | 2019-06-05 | 2019-09-13 | 王俊英 | A kind of flue gas magnetization separation method |
| CN110904328A (en) * | 2019-12-10 | 2020-03-24 | 扬州泰富特种材料有限公司 | Method for improving comprehensive utilization rate of dust in pellet mill |
| CN112939572A (en) * | 2019-12-11 | 2021-06-11 | 桂阳县皓钰新材料有限公司 | Process for treating iron slag of steel plant by tunnel kiln |
| CN113073198A (en) * | 2021-03-26 | 2021-07-06 | 江苏竣业过程机械设备有限公司 | Method for efficiently treating zinc-containing dust and mud |
| WO2021134385A1 (en) * | 2019-12-31 | 2021-07-08 | 耒阳市焱鑫有色金属有限公司 | Oxygen-enriched side blowing furnace smelting method for secondary resource having arsenic and dispersed elements by adding ion and chlorinating agent respectively |
| CN113462902A (en) * | 2021-07-07 | 2021-10-01 | 广东金宇环境科技股份有限公司 | Method for recovering nonferrous metal from smelting waste residue |
| CN115747511A (en) * | 2022-10-19 | 2023-03-07 | 中国恩菲工程技术有限公司 | Method and system for processing zinc-containing ash in iron and steel plant by adopting chlorination smelting process |
| WO2023116074A1 (en) * | 2021-12-20 | 2023-06-29 | 昆明理工大学 | Method for treating titanium-containing slag and enriching rutile |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108486384A (en) * | 2018-03-16 | 2018-09-04 | 湖南腾驰环保科技有限公司 | The recovery process of low-grade stanniferous bismuth tungsten slag |
| CN110229965A (en) * | 2019-06-05 | 2019-09-13 | 王俊英 | A kind of flue gas magnetization separation method |
| CN110904328A (en) * | 2019-12-10 | 2020-03-24 | 扬州泰富特种材料有限公司 | Method for improving comprehensive utilization rate of dust in pellet mill |
| CN112939572A (en) * | 2019-12-11 | 2021-06-11 | 桂阳县皓钰新材料有限公司 | Process for treating iron slag of steel plant by tunnel kiln |
| WO2021134385A1 (en) * | 2019-12-31 | 2021-07-08 | 耒阳市焱鑫有色金属有限公司 | Oxygen-enriched side blowing furnace smelting method for secondary resource having arsenic and dispersed elements by adding ion and chlorinating agent respectively |
| CN113073198A (en) * | 2021-03-26 | 2021-07-06 | 江苏竣业过程机械设备有限公司 | Method for efficiently treating zinc-containing dust and mud |
| CN113462902A (en) * | 2021-07-07 | 2021-10-01 | 广东金宇环境科技股份有限公司 | Method for recovering nonferrous metal from smelting waste residue |
| WO2023116074A1 (en) * | 2021-12-20 | 2023-06-29 | 昆明理工大学 | Method for treating titanium-containing slag and enriching rutile |
| CN115747511A (en) * | 2022-10-19 | 2023-03-07 | 中国恩菲工程技术有限公司 | Method and system for processing zinc-containing ash in iron and steel plant by adopting chlorination smelting process |
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