CN107419102A - A kind of method for separating valuable metal in discarded magchrome refractory flotation tailings - Google Patents

A kind of method for separating valuable metal in discarded magchrome refractory flotation tailings Download PDF

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Publication number
CN107419102A
CN107419102A CN201710592062.XA CN201710592062A CN107419102A CN 107419102 A CN107419102 A CN 107419102A CN 201710592062 A CN201710592062 A CN 201710592062A CN 107419102 A CN107419102 A CN 107419102A
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China
Prior art keywords
tailings
discarded
refractory
valuable metal
flotation
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焦芬
刘维
覃文庆
薛凯
徐探
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Central South University
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Central South University
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/001Dry processes
    • C22B7/002Dry processes by treating with halogens, sulfur or compounds thereof; by carburising, by treating with hydrogen (hydriding)
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66Monolithic refractories or refractory mortars, including those whether or not containing clay
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/001Dry processes
    • C22B7/004Dry processes separating two or more metals by melting out (liquation), i.e. heating above the temperature of the lower melting metal component(s); by fractional crystallisation (controlled freezing)
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Structural Engineering (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a kind of method for separating valuable metal in discarded magchrome refractory flotation tailings, including following methods step:Magchrome refractory tailings after flotation is filtered by vacuum, dried, and it is uniform by grinding distribution, obtain tailings powder;Carbonaceous reducing agent is ground;Tailings powder, carbonaceous reducing agent and chlorinating agent are proportionally mixed, it is and uniform by ground and mixed, it is subsequently placed into the tube type resistance furnace under air atmosphere, and the blast pipe of tube furnace is passed through in the Drexel bottle containing sodium hydroxide solution, then it is calcined, the volatile matter of the low-melting-point metal of roasting is reclaimed by Drexel bottle;Remaining tailings takes out cooling, the regenerative raw materials as refractory material.The present invention realizes and waste refractory materials is recycled in the case where ensureing the major premise of metal recovery, economy and obvious environment benefit, while walks sustainable development path for China's metallurgy industry and provide reliable technical support.

Description

A kind of method for separating valuable metal in discarded magchrome refractory flotation tailings
Technical field
The invention belongs to the refractory material comprehensive reutilization field in non-ferrous metal metallurgy, and in particular to one kind separation is useless The method for abandoning valuable metal in magchrome refractory flotation tailings.
Background technology
The raw material of non-ferrous metal metallurgy industry is sulphide ore, and impurity content is more in raw material, is mainly produced in its smelting process Raw sulfur dioxide gas, stove is interior to be in acid atmosphere, although the metal bath temperature at smelting furnace bottom is relatively low compared with steel fusant temperature, But its mobility is preferable, corrosive power is strong, it is easy to is chemically reacted with refractory material, in addition because ore grade It is relatively low, it is therefore desirable to which that a large amount of slag making, the quantity of slag is larger, and slag is with alkaline in the majority, alkali resistance and anti-erosion intensity to refractory material It is it is required that higher.Since half a century, magnesia chrome spinel structure is because its slag resistance is good, structural stability is strong and the spies such as calorific intensity is high Point, have been widely used in metallurgical and other pyroprocess industry.Smeltery can all produce largely discarded magnesite-chrome brick every year, according to Statistics, China discard magchrome refractory more than 3,000,000 tons every year.This part in the waste refractory materials of furnace lining as permeating Substantial amounts of valuable metal, such as Ag, Pb, Bi, Cu, Zn, Ni, potential age deduction are huge.In addition, if this part tailings is not added with With processing, environmental pressure will certainly be also caused.In addition, with the reduction of high-grade magnesium resource and high-quality chrome ore resource, resource Deficient getting worse, the anxiety of resource can effectively be alleviated by recycling secondary resource.
These discarded magchrome refractories for containing various heavy are difficult processing at present, and smeltery is typically in order to reclaim gold Category, smelted after being crushed on a small quantity containing the more refractory brick picking of metal as the auxiliary material of metallurgical raw material, although this method can To solve the problems, such as that a part of refractory brick heap is abandoned, but a large amount of high-melting-point materials add in melting system and greatly destroy melting The stability of journey, so as to be unfavorable for the recovery of non-ferrous metal.Industrial most of refractory material is dumped due to that can not recycle Concentration landfill disposal is deposited, although so simple processing mode cost is smaller, but makes the wasting of resources, it is often more important that to ring Border causes great destruction.
Publication No. is that " a kind of flotation reclaims copper metallurgy and discards fire resisting disclosed in CN106179769A Chinese invention patent application " one kind passes through weight disclosed in the method for metallic copper in material " and the Chinese invention patent application that publication No. is CN106269170A The method of valuable metal in choosing-kerosene aggregative flotation process integration recovery waste refractory materials ", it is all the side by ore dressing Method, particularly floatation reclaim to valuable metal in refractory material, and this method advantage is targetedly to reclaim Certain several valuable metal, and relative inexpensiveness, can reclaim part valuable metal to a certain extent.But these fire proofed woods After sorting, still having about 75% ore dressing tailings can not effectively utilize material.If still being handled in a manner of landfill, because weight The presence of metallic element chromium, the pollution of soil and water resource can be caused.
The content of the invention
The present invention is directed in current waste refractory materials and only carries out metal recovery and ignore what is recycled to sorting rear tailings Problem, there is provided a kind of method for separating valuable metal in discarded magchrome refractory flotation tailings, can high efficiente callback it is wherein remaining Valuable metal simultaneously realizes that flotation tailings recycles.
A kind of method for separating valuable metal in discarded magchrome refractory flotation tailings of the present invention, comprises the following steps:
(a) magchrome refractory tailings after flotation is filtered by vacuum, dried, and it is uniform by grinding distribution, obtain tail Ground-slag end;
(b) prepare chlorinating agent and carbonaceous reducing agent, and carbonaceous reducing agent is ground;
(c) carbonaceous reducing agent in tailings powder, step (b) in step (a) and chlorinating agent are mixed, and passes through ground and mixed Uniformly, it is subsequently placed into the tube type resistance furnace under air atmosphere, and the blast pipe of tube furnace is passed through containing sodium hydroxide solution Drexel bottle in, be then calcined at a set temperature, pass through Drexel bottle recovery roasting when low-melting-point metal volatile matter;
(d) the remaining tailings after step (c) is calcined takes out cooling, the regenerative raw materials as refractory material.
In step (a), drying temperature is that tailings powder 85-90% grain diameter is less than 0.074mm no more than 80 DEG C.
In step (b), chlorinating agent is magnesium chloride;Carbonaceous reducing agent is carbon dust, coke blacking, one kind in graphite powder or more Kind;Milling time is 0.5-1min;The particle diameter of carbonaceous reducing agent after grinding should be less than 0.15mm.
In step (c), the percentage by weight of tailings, carbonaceous reducing agent and chlorinating agent is 10:(0.5-1):(1-1.5);Roasting It is 1000-1200 DEG C to burn temperature, roasting time 0.8-1h.
The present invention is main using valuable metal in the discarded magchrome refractory flotation tailings of chloride volatility process separation, its principle It is the generation Cl that can be decomposed under certain condition using chlorinating agent2And HCl, and the simple substance of the metal of low melting point, oxide or Some other compound under certain condition can Cl2Reacted with HCl, generate metal chloride, such as:
2Ag2O(s)+2Cl2(g)=4AgCl (g)+O2(g)
2PbO(s)+2Cl2(g)=2PbCl2(g)+O2(g)
2Bi2O3(s)+6Cl2(g)=4BiCl3(g)+3O2(g)
2Ag(s)+Cl2(g)=2AgCl (g)
Pb(s)+Cl2(g)=PbCl2(g)
2Bi(s)+3Cl2(g)=2BiCl3(g)
Ag2O (s)+2HCl (g)=2AgCl (g)+H2O(g)
PbO (s)+2HCl (g)=PbCl2(g)+H2O(g)
Bi2O3(s)+6HCl (g)=2BiCl3(g)+3H2O(g)
4Ag(s)+4HCl(g)+O2(g)=4AgCl (g)+2H2O(g)
2Pb(s)+4HCl(g)+O2(g)=2PbCl2(g)+2H2O(g)
4Bi(s)+12HCl(g)+3O2(g)=4BiCl3(g)+6H2O(g)
The metal chloride of generation mostly has low melting point, the property of high volatile;Meanwhile chloride generation difficulty or ease and property The difference of matter is again often fairly obvious, therefore during chloridising roasting, can conveniently and effectively realize low-melting-point metal Separation, enrichment, extraction and refining, and the metal chloride of most of generations is all soluble in water, or easily inhaled by liquid mist, drop It is attached, thus wet method can be used to trap.
The technical program inventor study during find, MgO, Cr in flotation tailings2O3、SiO2、CaO、FeO、 Al2O3Deng can meet magchrome refractory production requirement.But the fusing point of the wherein metal such as Ag, Pb, Bi, Cu, Zn, Ni is more resistance to Belong to low melting point for fiery material, during refractory material produces, these low melting points can greatly destroy resistance to The overall structure of fiery material, influence quality and the life-span of reproduction refractory material.These eutectics are separated using the method for the present invention The metal of point, metal fine fodder can be made to reach recovery grade, the content of residual metal in the tailing of roasting by enrichment, separation Also the standard of re-using is down to, gained tailing and refractory material raw materials for production are essentially identical, available for magchrome refractory Reproduction.
The beneficial effects of the invention are as follows:The method of the present invention is simple, and cost is cheap, can not only realize metal recovery, also Waste refractory materials can be recycled, economy and obvious environment benefit.
Brief description of the drawings
Fig. 1 show the process flow diagram of the embodiment of the present invention.
Embodiment
With reference to instantiation, the present invention is further described, but the present invention is not limited to following embodiments.Can basis Technical scheme determines specific embodiment with actual conditions.
Embodiment 1
The raw material of use are discarded furnace lining-magnesium chromium firebricks of Hunan lead smeltery, reclaim and lead by flotation flowsheet Want the flotation tailings after metal, containing Ag be 0.14%, Pb 10.40%, Bi 5.99% in the tailings.
Take the flotation tailings, after vacuum filter filters, be placed in electric drying oven with forced convection and dried at 80 DEG C Dry, obtained drying tailings grinds 20min in agate grinder, it is uniformly dispersed and makes its 85-90% grain diameter Less than 0.074mm.
Coarse grained reducing agent coke powder is ground into 0.5min with vibrating ball-mill, its particle diameter is less than 0.15mm.Will be ready Tailings, coke powder and magnesium chloride press 10:1:1.2 ratio dispensing, is then ground.Material is laid on corundum Noah's ark;And Corundum Noah's ark is put into tube type resistance furnace, air pump is opened and is passed through air, blast pipe is inserted into washing containing sodium hydroxide solution Gas cylinder;Sintering temperature is set as 1200 DEG C, starting switch starts to be calcined, while timing;Stop heating after 1h, be cooled to room Temperature, filter and precipitated in Drexel bottle, reclaimed as metal fine fodder, take out roasting residue, and carry out sampling analysis.
0.02%, 0.06%, 0.10% is down to by chemically examining tri- kinds of impurity contents of Ag, Pb, Bi in residue, meets work For the regenerative raw materials of refractory material.
Embodiment 2
The raw material of use are discarded furnace lining-magnesium chromium firebricks of Hunan lead smeltery, reclaim and lead by flotation flowsheet Want the flotation tailings after metal, containing Cu be 0.33%, Pb 1.04%, Zn 3.52% in the tailings.
Take the flotation tailings, after vacuum filter filters, be placed in electric drying oven with forced convection and dried at 80 DEG C Dry, obtained drying tailings grinds 40min in agate grinder, it is uniformly dispersed and makes its 85-90% grain diameter Less than 0.074mm.
Coarse grained reducing agent coke powder is ground into 0.75min with vibrating ball-mill, its particle diameter is less than 0.15mm.Will be ready Tailings, coke powder and magnesium chloride press 10:0.75:1.5 ratio dispensing, is then ground.Material is laid on corundum Noah's ark; And corundum Noah's ark is put into tube type resistance furnace, open air pump and be passed through air, blast pipe insertion is contained into sodium hydroxide solution Drexel bottle;Sintering temperature is set as 1000 DEG C, starting switch starts to be calcined, while timing;Stop heating after 0.8h, it is to be cooled To room temperature, filter and precipitated in Drexel bottle, reclaimed as metal fine fodder, take out roasting residue, and sampling analysis.
0.04%, 0.02%, 0.56% is down to by chemically examining tri- kinds of impurity contents of Cu, Pb, Zn in regenerative raw materials, symbol Cooperate the regenerative raw materials for refractory material.
Embodiment 3
The raw material of use are discarded furnace lining-magnesium chromium firebricks of Hunan lead smeltery, reclaim and lead by flotation flowsheet Want the flotation tailings after metal, containing Ag be 0.55%, Pb 7.73%, Bi 2.46% in the tailings.
Take the flotation tailings, after vacuum filter filters, be placed in electric drying oven with forced convection and dried at 80 DEG C Dry, obtained drying tailings grinds 20min in agate grinder, it is uniformly dispersed and makes its 85-90% grain diameter Less than 0.074mm.
Coarse grained reducing agent coke powder is ground into 1min with vibrating ball-mill, its particle diameter is less than 0.15mm.By ready tail Slag, coke powder and magnesium chloride press 10:0.5:1 ratio dispensing, is then ground.Material is laid on corundum Noah's ark;And will Corundum Noah's ark is put into tube type resistance furnace, is opened air pump and is passed through air, and blast pipe is inserted into the gas washing containing sodium hydroxide solution Bottle;Sintering temperature is set as 1100 DEG C, starting switch starts to be calcined, while timing;Stop heating after 0.9h, be cooled to room Temperature, filter and precipitated in Drexel bottle, reclaimed as metal fine fodder, take out roasting residue, and sampling analysis.
0.04%, 0.05%, 0.05% is down to by tri- kinds of impurity contents of Ag, Pb, Bi in regenerative raw materials, meets work For the regenerative raw materials of refractory material.

Claims (10)

  1. A kind of 1. method for separating valuable metal in discarded magchrome refractory flotation tailings, it is characterised in that including with lower section Method step:
    (a) magchrome refractory tailings after flotation is filtered by vacuum, dried, and it is uniform by grinding distribution, obtain ground slag End;
    (b) prepare chlorinating agent and be ground by carbonaceous reducing agent, and by carbonaceous reducing agent;
    (c) carbonaceous reducing agent in tailings powder, step (b) in step (a) and chlorinating agent are mixed, and it is equal by ground and mixed It is even, it is subsequently placed into the tube type resistance furnace under air atmosphere, and the blast pipe of tube furnace is passed through containing sodium hydroxide solution In Drexel bottle, then it is calcined at a temperature of setting, the volatile matter of low-melting-point metal when being calcined is reclaimed by Drexel bottle;
    (d) the remaining tailings after step (c) is calcined takes out cooling, the regenerative raw materials as refractory material.
  2. 2. a kind of method for separating valuable metal in discarded magchrome refractory flotation tailings as claimed in claim 1, it is special Sign is, in the step (a), drying temperature is less than 80 DEG C.
  3. 3. a kind of method for separating valuable metal in discarded magchrome refractory flotation tailings as claimed in claim 1 or 2, its It is characterised by, in the step (a), tailings powder 85-90% grain diameter is less than 0.074mm.
  4. 4. a kind of method for separating valuable metal in discarded magchrome refractory flotation tailings as claimed in claim 1 or 2, its It is characterised by, in the step (b), carbonaceous reducing agent is the one or more in carbon dust, coke blacking, graphite powder.
  5. 5. a kind of method for separating valuable metal in discarded magchrome refractory flotation tailings as claimed in claim 1 or 2, its It is characterised by, in the step (b), milling time 0.5-1min.
  6. 6. a kind of method for separating valuable metal in discarded magchrome refractory flotation tailings as claimed in claim 1 or 2, its It is characterised by, in the step (b), the particle diameter of the carbonaceous reducing agent after grinding should be less than 0.15mm.
  7. 7. a kind of method for separating valuable metal in discarded magchrome refractory flotation tailings as claimed in claim 1 or 2, its It is characterised by, in the step (b), chlorinating agent is magnesium chloride.
  8. 8. a kind of method for separating valuable metal in discarded magchrome refractory flotation tailings as claimed in claim 1 or 2, its It is characterised by, in the step (c), the percentage by weight of tailings, carbonaceous reducing agent and chlorinating agent is 10:(0.5-1):(1- 1.5)。
  9. 9. a kind of method for separating valuable metal in discarded magchrome refractory flotation tailings as claimed in claim 1 or 2, its It is characterised by, in the step (c), sintering temperature is 1000-1200 DEG C.
  10. 10. a kind of method for separating valuable metal in discarded magchrome refractory flotation tailings as claimed in claim 1 or 2, Characterized in that, in the step (c), roasting time 0.8-1h.
CN201710592062.XA 2017-07-19 2017-07-19 A kind of method for separating valuable metal in discarded magchrome refractory flotation tailings Pending CN107419102A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108642288A (en) * 2018-05-23 2018-10-12 中南大学 A kind of method that magnesian-chrome efractoy is discarded in full element recycling

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1106619A (en) * 1977-09-27 1981-08-11 Hans Rausch Waelz process of volatilizing zinc and lead from iron oxide containing materials
JPS6244534A (en) * 1985-08-20 1987-02-26 Tanaka Kikinzoku Kogyo Kk Refining method for noble metal
CN101225468A (en) * 2008-01-30 2008-07-23 张伟晓 Method for recovering gold, silver, iron and lead from acid calcination slag by magnetization chlorination process
CN101792857A (en) * 2010-04-13 2010-08-04 李柏荣 Process for refining metals from minerals
CN106282583A (en) * 2015-05-29 2017-01-04 昆明冶金高等专科学校 A kind of recovery non-ferrous metal, rare precious metal and method of iron powder from ironmaking dust

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1106619A (en) * 1977-09-27 1981-08-11 Hans Rausch Waelz process of volatilizing zinc and lead from iron oxide containing materials
JPS6244534A (en) * 1985-08-20 1987-02-26 Tanaka Kikinzoku Kogyo Kk Refining method for noble metal
CN101225468A (en) * 2008-01-30 2008-07-23 张伟晓 Method for recovering gold, silver, iron and lead from acid calcination slag by magnetization chlorination process
CN101792857A (en) * 2010-04-13 2010-08-04 李柏荣 Process for refining metals from minerals
CN106282583A (en) * 2015-05-29 2017-01-04 昆明冶金高等专科学校 A kind of recovery non-ferrous metal, rare precious metal and method of iron powder from ironmaking dust

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108642288A (en) * 2018-05-23 2018-10-12 中南大学 A kind of method that magnesian-chrome efractoy is discarded in full element recycling

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Application publication date: 20171201