CN101781709A - Method for using kiln slag of wet-method zinc-smelting volatilizing kiln - Google Patents
Method for using kiln slag of wet-method zinc-smelting volatilizing kiln Download PDFInfo
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Abstract
The invention relates to a method for using kiln slag of a wet-method zinc-smelting volatilizing kiln, which is characterized by comprising the following steps: dividing crushed kiln slag of the volatilizing kiln into an iron slag part and a carbon-rich part by a magnetic separation method; and replacing pyrite cinder with not less than 30 weight percent of iron slag for lead reduction smelting in a lead blast furnace. The method can greatly reduce the cost of lead smelting.
Description
The application is that application number is 200910169896.5, the applying date is on September 8th, 2009, denomination of invention is divided an application for the Chinese patent application of " recovery of kiln slag of zinc hydrometallurgy volatilizing kiln and utilize method ".
Technical field
The present invention relates to the Metal smelting field, relate in particular to the method that is used to handle and recycle kiln slag of zinc hydrometallurgy volatilizing kiln.
Background technology
Zinc leaching residue is a kind of solid waste that produces in the zinc hydrometallurgy process.Except that containing common metallic elements such as zinc, lead, copper, iron, also contain rare precious metals such as a certain amount of gallium, germanium, indium, silver, have great comprehensive utilization value.Zinc more than 70% is by the hydrometallurgy output in the world, and zinc leaching residue is zinc hydrometallurgy factory first byproduct, so zinc leaching residue is one of very important rare precious metal renewable resource.Valuable element in the zinc leaching residue is comprehensively reclaimed, can obtain very big economic benefit, and can turn waste into wealth, help environment protection.
In order to reclaim, utilize the valuable element in the zinc leaching residue effectively, experts and scholars have carried out comparatively extensive studies both at home and abroad, developed the kinds of processes method, conclusion gets up to have following several: Rotary Kiln fuming process, selecting smelting combination method, hot acid leach-sink iron processes etc.In addition, on the basis of above-mentioned several basic procedures, also derived some other relevant technology.It is to recycle at one or more metals in the zinc leaching residue that some technologies are arranged, as flotation process, thiourea carbon-in-pulp method, synthetic method etc.At present, China zinc hydrometallurgy factory mostly adopts the Rotary Kiln fuming process to handle zinc leaching residue, to reclaim the valuable element in the zinc leaching residue.This method is join a large amount of coke powder of people in zinc leaching residue after, and roasting under 1200～1300 ℃ of temperature condition in Rotary Kiln makes wherein most zinc, lead, indium and the volatilization of small part germanium enter flue dust, and flue dust is handled recyclable part valuable metal.Wherein the evaporation rate of zinc can reach about 90%, and rare precious metal gallium, germanium, silver etc. only have volatilization to a certain degree, all the other most rare precious metals enter in the Rotary Kiln kiln slag, because other elements generate alloy each other or exist with the silicate compound form in these rare precious metals and the slag, tight embedding cloth between each thing phase, be difficult to carry out cost-effective separation, enrichment and recovery with conventional physico-chemical process, cause valuable metal, particularly rare precious metal resource heavy losses.
The Rotary Kiln kiln slag is to allocate a large amount of coke powders at zinc leaching residue, through high temperature reduction, vapors away metals such as zinc, lead, cadmium, indium and forms through shrend from the discharge of kiln tail afterwards in Rotary Kiln.The mixture of zinc leaching residue and coke powder is through the Rotary Kiln high-temperature zone time, slag charge is the semi-molten state, and storeroom has phenomenon adhered to one another, and the ferric oxide major part in the leached mud is reduced into metallic iron, germanium, gallium also major part are reduced into metal, generate alloy with iron.Other metals or formation alloy perhaps form all cpds form.Their mutual embedding cloth is tight.But promptly meet shrend because the high temperature kiln slag is discharged from the kiln tail, granularity is little, carbon residue is high, hardness is big so kiln slag has, contain characteristics such as the many but content of valency metal is low, and essence is iron content, carbon, the higher waste of silicon, and comprehensively recovery difficult is bigger.Discover that main valuable constituent is iron (35～40%) and carbon (15～18%) in the kiln slag.
Observe kiln slag material composition with electron probe microanalysis, X light diffracting analysis, microscopically and see Table 1.Respectively form embedding cloth complexity in the kiln slag, the kiln slag matrix mostly is the α-Fe of complex phase, especially some particulate that metallic iron and other compounds combine closely and thin marmatite greatly, and it often is enclosed within the particle of vitreum and coke.Filling FeS at globular α-Fe and marmatite gap, and be embedded with particulate lead-iron, antimony-copper alloy and argent among the FeS, so be difficult to obtain enriched products pure or of high grade with the general physical method.Ferro element in the kiln slag is based on metallic iron, and the most copper element is based on sulfide, and silver element is based on argent and silver sulfide.About the thing phase composite of gallium, germanium in the volatilization kiln slag, do not do research, infer theoretically, because in Rotary Kiln, experienced strong reduction process, as if these two kinds of elements have quite a few to be converted to metallic state, generate alloy with iron, or exist with muriate and salt.Following table 2 is listed gallium, indium, germanium, the distribution of silver in each material of kiln slag, and table 3 is listed the thing phase composite of iron, and table 4 is listed the thing phase composite of copper, and table 5 is listed the thing phase composite of silver.
The material of table 1. kiln slag is formed
Table 2 gallium, indium, germanium, the distribution of silver in each material of kiln slag
The thing phase composite of table 3 iron
The thing phase composite of table 4 copper
The thing phase composite of table 5 silver
Summary of the invention
The invention provides the method that is used to reclaim kiln slag of zinc hydrometallurgy volatilizing kiln, to improve the resource utilization of zinc hydrometallurgy kiln slag.
In a first aspect of the present invention, the method for recycling kiln slag of zinc hydrometallurgy volatilizing kiln may further comprise the steps:
-kiln slag is crushed to the particle size range of about 0.01-2mm, carry out primary election in the magneticstrength of 800-1800 oersted, kiln slag first magnetic part and first nonmagnetic portion;
-described first magnetic part is crushed to 50-60 weight %200 purpose size range, carry out selectedly with 500-1090 oersted magneticstrength, obtain second magnetic part and second nonmagnetic portion.
In a kind of embodiment, described kiln slag contains the iron of 35～40% weight ratios and the carbon of 15～18% weight ratios.
In a kind of embodiment, described primary election and/or selected be wet magnetic separation.
In a kind of embodiment, described selected be to carry out with the magneticstrength of 500-1090 oersted.
In a kind of preferred implementation, comprised that before described primary election one is carried out the step that waterpower is dashed choosing with described kiln slag.
In a kind of preferred implementation, further comprise described second nonmagnetic portion obtaining rich carbonaceous recovery coke powder with the step that shaking table carries out gravity treatment.
In a kind of preferred implementation, also be included in the step of carrying out gravity treatment after the described kiln slag fragmentation, to obtain the step of rich argentiferous silver-colored iron ore.As further preferred, described fragmentation is to use wet-type ball mill, and particle size after cracking is-200 orders, and described gravity treatment is to be undertaken by spiral gravity concentrator.
In a second aspect of the present invention, the method that is used for the recycling kiln slag of zinc hydrometallurgy volatilizing kiln may further comprise the steps:
-will in the flushing cinder pond, carry out waterpower from the kiln slag of Rotary Kiln to dash choosing, to reclaim a part of coke, obtain reuse Jiao;
-the kiln slag that will remove described part of coke is crushed to 2mm or following; With the magneticstrength is the described kiln slag through fragmentation of magnetic separator magnetic separation of 800-1800 oersted, obtains secondary Jiao and scum.
In a kind of preferred implementation, described secondary Jiao is carried out the magnetic separation second time below the 500-1090 oersted, obtain second scum and second coke.
In a kind of embodiment, described reuse Jiao is used for the fuel that part replaces zinc to smelt, and its consumption is no more than 15% of total weight of fuel.
In a kind of preferred implementation, described secondary Jiao is carried out gravity treatment, obtain second reuse Jiao, be used for the fuel that zinc is smelted.Described scum is partly or entirely substituted the slag making that source of iron is used for plumbous dross reverberatory furnace, bismuth reverberatory furnace, copper blast-furnace.
In a third aspect of the present invention, the method that is used to reclaim kiln slag of zinc hydrometallurgy volatilizing kiln may further comprise the steps:
-will be from the kiln slag ball milling of Rotary Kiln to particle diameter less than 0.074mm;
-will carry out gravity treatment by gravity concentrator through the kiln slag of ball milling, to tell silver-colored iron ore;
-the kiln slag that will be told silver-colored iron ore carries out magnetic separation, with branch tap a blast furnace mud and coal slime.
In a kind of embodiment, described magnetic separation is twice magnetic separation, and the condition of magnetic separation for the first time is that magneticstrength is the 800-1800 oersted, and the condition of magnetic separation for the second time is that magneticstrength is the 500-1090 oersted.
In a fourth aspect of the present invention, the method for the scum of a kind of utilization by handling the kiln slag of zinc hydrometallurgy volatilizing kiln gained is provided, may further comprise the steps:
-by magnetic method the Rotary Kiln kiln slag of pulverizing is divided into scum and rich carbon part;
-described scum is replaced pyrite cinder with the ratio that is not less than 30% weight, be used for plumbous reducing and smelting at lead blast furnace.
In a kind of embodiment, described scum is obtained by following steps:
-with the particle diameter of described Rotary Kiln kiln slag powder essence to 0.1 to 2mm,
-material through pulverizing is carried out magnetic separation under the condition of 800-1800 oersted magneticstrength, obtain described scum and nonmagnetic portion.
In a kind of preferred implementation, described scum also comprises described nonmagnetic portion is carried out the part that further magnetic separation obtained under the condition of 500-1090 oersted magneticstrength.
In a fifth aspect of the present invention, a kind of method of recycling kiln slag of zinc hydrometallurgy volatilizing kiln is provided, may further comprise the steps:
-kiln slag is crushed to the particle size range of about 0.01-2mm, carry out primary election in the magneticstrength of 800-1800 oersted, kiln slag first magnetic part and first nonmagnetic portion;
-described first magnetic part is crushed to 50-60 weight %200 purpose size range, carry out selectedly with 500-1090 oersted magneticstrength, obtain second magnetic part and second nonmagnetic portion;
-described first nonmagnetic portion is partly replaced the fuel of Metal smelting process as the secondary coke powder.
This method may further include: described first magnetic part or described second magnetic part are used as the source of iron in the heavy metal smelting process.
In a kind of preferred implementation, described first magnetic part or described second magnetic part are used for slag making as source of iron in lead blast furnace retailoring.
In a kind of preferred implementation, described first magnetic part or described second magnetic part are substituted pyrite with at least 30% weight ratio.As further preferred, described second magnetic part is substituted pyrite with 100% weight ratio.
In above-mentioned any scheme, as preferably, with described first magnetic part or described second magnetic with after pyrite mixes, on expect that sintered material burns the slag storehouse, carry out batch mixes, granulation with lead ore concentrate and unclassified stores, and then put into sinter machine and carry out roasting, corresponding increase air feed rate when roasting.
Described first magnetic part or described second magnetic part can be used in plumbous dross reverberatory furnace, bismuth reverberatory furnace, copper blast-furnace as source of iron.More specifically, described first magnetic part or the alternative fully iron filings of described second magnetic part are used in plumbous dross reverberatory furnace.
In the method, can replace iron filings in the bismuth reverberatory furnace, to use with 30% to 60% ratio described first magnetic part or described second magnetic part.
In the method, can replace iron filings in copper blast-furnace, to use with 20% to 50% ratio described first magnetic part or the described second magnetic part scum.
In a kind of embodiment,, described first nonmagnetic portion is used for Rotary Kiln zinc metallurgy as the secondary coke powder with the weight ratio substituting disposable coke powder with respect to a coke powder 5% to 25%.
In a kind of embodiment, described selected be to carry out with the magneticstrength of 500-1090 oersted.
In a kind of preferred implementation, comprised that before described preliminary magnetic one is carried out the step that waterpower is dashed choosing with described kiln slag, with a part of coke of direct recovery, is used for the part alternative fuel of Metal smelting.
In a kind of preferred implementation, comprise described second nonmagnetic portion obtaining rich carbonaceous recovery coke powder with the step that shaking table carries out gravity treatment, be used for the part alternative fuel of Metal smelting.
In a kind of preferred implementation, also be included in the step of carrying out gravity treatment after the described kiln slag fragmentation, to obtain the step of rich argentiferous silver-colored iron ore, be used for refining silver.
In a kind of embodiment, described fragmentation is to use the wet ball-milling crusher machine, and particle size after cracking is-200 orders (particle diameter is less than 0.074mm), and described gravity treatment is to be undertaken by spiral gravity concentrator.
In a kind of embodiment, with the described selected secondary magnetic separation that comprises, wherein, first step magnetic is to carry out with the magneticstrength of 800-1800 oersted; Second stage magnetic separation is to carry out with the magneticstrength of 500-1090 oersted.
In a kind of preferred implementation, the described selected secondary magnetic separation that comprises, wherein, first step magnetic is to carry out with the magneticstrength of 1050 oersteds; Second stage magnetic separation is to carry out with the magneticstrength of 650 oersteds.
Adopt method of the present invention, obviously improved the rate of recovery of metal ingredient in the kiln slag or carbon component, accomplish farthest effectively to utilize, alleviated environmental stress greatly.
Description of drawings
Fig. 1 is the schema of embodiment 1 and 2;
Fig. 2 is the schema of embodiment 3;
Fig. 3 is the schema of embodiment 4;
Fig. 4 is the device connection diagram of embodiment 4; And
Fig. 5 is the schema of embodiment 5.
Embodiment
Narrate the detailed technology scheme of the inventive method below.
In general, the present invention relates to handle and handling the Rotary Kiln kiln slag (to call kiln slag in the following text) that produces in the zinc leaching residue process with the Rotary Kiln fuming process reclaiming the method for useful resources, and the product that reclaims utilize method.Particularly, method of the present invention comprises that mainly magnetic separation separates the method for kiln slag with enriched in metals and the available carbon of recovery; Magnetic separation is separated the rich metal part (to call iron powder in the following text) obtain make the method for chalybeate with the iron material that replaces adding in the Metal smelting process; This richness metal is partly replaced the iron filings in plumbous dross reverberatory furnace, bismuth reverberatory furnace, the copper blast-furnace batching or the method for pyrite cinder; And the method that the available carbon in the nonmagnetic portion is used for the coke fuel of part replacement refining splicer skill.
In the method for the invention, the employing magnetic selection method separates metal ingredient (being mainly iron) and the nonmetal composition (being mainly carbon) in the kiln slag.This process comprises that optional waterpower is dashed and selects step, and two essential step---primary election (one-level magnetic separation) and selected (secondary magnetic separation).
Waterpower is dashed choosing
As optional, the high temperature kiln slag is after Rotary Kiln kiln tail ejects and pass through shrend, experience a hydrodynamic cleaning step, this operation utilizes the difference of volatilization kiln slag and contained coke powder proportion, selects the coke powder that those density are less, carbon content is higher in Rotary Kiln flushing cinder pond.These coke powders are in directly coke for replacing reuse after super-dry.
Primary election
In the present invention, by primary election kiln slag tentatively is divided into first magnetic part and first nonmagnetic portion.For this reason, kiln slag can be crushed to about 0.01-2mm, then at 800-1800, preferred 1200-1700, more preferably 1300-1600, most preferably the magneticstrength of 1400-1500 oersted is carried out primary election, and this magnetic separation can be a dry type, can be wet type also, is preferably wet type.Used magnetic separator can be permanent magnetic separator or electromagnetic separator; The magnetic field type of magnetic separator can be stationary magnetic field, pulsating magnetic field or alternating magnetic field; These magnetic separators can be belt magnetic separator, drum magnetic separator, roll-type magnetic separator, disk-type magnetic separator, ring type magnetic separator, cage magnetic separator or magnetic-pulley separator.First magnetic part is mainly iron, and first nonmagnetic portion is mainly carbon, metal and gangue content (for example silicon-dioxide).The applicant finds that the valuable metal of 60-70% is enriched in first magnetic part in the kiln slag, and wherein the Armco magnetic iron rate of recovery is near 85%.Table 6 illustrates the resulting result of primary election.
Table 6 primary election test-results
Selected
By table 6 as seen, the iron grade in first magnetic part is still not high, also contains the not high silicate of a large amount of utility values.Therefore, be necessary first magnetic part is carried out further meticulous magnetic separation,, obtain second magnetic part,, also improve the content of other metals simultaneously to improve the iron grade to isolate second nonmagnetic portion.In this explanation, in these other metals, although some metal does not have magnetic and since they in kiln slag with very tight close combining, become the form of similar alloy, so also can be come out by magnetic separation with iron.The contriver finds by test, and this is selected to be that 50-60 weight %200 order, magneticstrength are all to be suitable in the scope of 500-1090 oersted in the kiln slag granularity.The contriver finds also that through overtesting this magnetic separation effect under the field intensity of 800-1050 oersted is preferable, and is better at the 900-1050 oersted, in 950-1030 oersted the best.This is selected can be dry type magnetic separation, also can be wet magnetic separation.Generally speaking, wet magnetic separation is better than dry type magnetic separation.This is selected can be only through a procedure, and for example available magnetic separator carries out under the condition of 1000 oersteds; Also can pass through two procedures, for example, earlier under the higher magnetic field intensity in 800-1800 oersted scope, preferred 800-1090 oersted, more preferably magnetic separation is once under the 900-1050 oersted, and then in 500-1090 oersted scope one is than under the low magnetic field intensity, and for example magnetic separation is once under the 550-700 oersted.
In concrete an enforcement of the present invention, carry out once under the condition of 1000 oersteds with magnetic separator earlier, the magnetic pulley with 600 oersted field intensity carries out the secondary magnetic separation again, and table 7 has provided and has adopted this two procedures to carry out selected test result.
The selected proof test result of table 7 magnetic separator (%)
In table 7, Armco magnetic iron concentrate (second magnetic part) is the merging of the selected concentrate of magnetic separator and magnetic pulley.Test-results shows: kiln slag adopts the magnetic separation partition method can effectively separate magnetic product and non-magnetic product.Armco magnetic iron concentrate iron content can be up to 83.67%.It is 69.16% and 50.47% that iron, silver enter the iron ore concentrate rate.
Carbon is selected in gravity treatment
First magnetic part is at the carbon that contains the about 20-30% of weight ratio through second nonmagnetic portion (the magnetic separator mine tailing of table 7 and the combined segment of magnetic pulley mine tailing) that obtains after the meticulous magnetic separation, and the carbon taste is lower.It also contains the iron of the 10-18% that has an appointment, the silicon-dioxide of about 10-15% and a small amount of other metals or metallic compound, can not be directly as the fuel of Rotary Kiln.Adopt table concentration carbon, carbon enters the casting yield of mine tailing can be up to 88.7%, and carbon content rate can be up to 50.55%.In addition, this selects the carbon step also can be applied to first nonmagnetic portion, in some cases, the carbon content of first nonmagnetic portion that obtains in primary election is not high yet, for example in 30 to 50% scope, at this moment, this first nonmagnetic portion is directly fuel reuse as an alternative still, need through selecting carbon, with further enrichment carbon.
The industrial utilization of scum after the magnetic separation
The magnetic part that magneticly elects in the present invention, can be in the heavy metal smelting process as the raw material of slag making.For example, in the plumbous raw ore floatation process of prior art, impurity iron is farthest removed, and in recent years, iron level is more and more lower in the lead ore concentrate.But for satisfying the needs of blast furnace slag type, in lead blast furnace retailoring process, always will mend into extra chalybeate, the purpose of using chalybeate is to obtain certain blast furnace slag type (Fe 21～25%, SiO
220～22%, CaO 16～19%) to obtain ideal lead-in-dreg index, for this reason, plumbous smelting enterprise usually will expend substantial contribution.The original way of applicant is to smelt in the batching at lead to add pyrite cinder, so needs to drop into no small fund every year.And the scum that reclaims from the Rotary Kiln kiln slag has high-load iron, can replace this pyrite cinder just.
For smelting plumbous situation, can come some or all of replacement pyrite cinder with the scum part (i.e. first magnetic part or second magnetic part) that obtains among the present invention, can substitute 30% pyrite cinder at least.Be to use the situation of highly purified iron filings for not using pyrite cinder, scum can replace iron filings by the amount of required iron equally.
When part substitutes pyrite cinder, can be after ore storage bin mixes with pyrite cinder and scum, on expect sintered material burning slag storehouse, carry out batch mixes, granulation with unclassified stores such as lead ore concentrates, and then put into sinter machine and carry out roasting.
Because fe than plumbous preferential generation oxidizing reaction, for guaranteeing the abundant desulfurization of lead sulfide, needs to increase the air feed rate in sintering process.
This substituting has beneficial effect.At first, in existing technology, in processes of mixing and granulating, as burn the powdery substance of slag class, (～part below 0.074mm) has accounted for 90% ratio to its granularity at 200 orders, these powder material surfaces present cellular-shaped (porous), absorption speed is fast, lead ore concentrate and the back powder of trying to be the first (powder that produces when broken behind the plumbous updraught sintering) bonding is granulated, so, in processes of mixing and granulating, burning slag stops up the back powder mesoporosity, cause the granulation of lead ore concentrate to be subjected to very big influence, finally make the mixture charge balling ratio low, ventilation property is poor, intensity of roasting and caking rate that influence is baked with agglomeration.And it is thicker by the isolated scum of method of the present invention than burning slag, its particle diameter is usually about＜2mm (or 10 orders), preferably more than 1mm, the water absorbent surface speed of scum is slower, so, behind the adding scum, the mangcorn water content decreases, its balling ratio improves, and has improved breathability, and the air pressure that blasts during sintering reduces; Next owing to contain carbon in the scum, emits heat after the oxidation of coal burning, cause roasting middle part temperature to improve, thereby sintering reaction carries out well the raising of agglomerate quality; Once more because the oxidizing reaction of iron takes place comparatively fully in the sintering process, the fe that enters lead blast furnace seldom, so avoided the appearance of the long-pending iron fault of cupola well, melting production is smooth and easy; At last, contain multiple valuable metal (copper, gold and silver, indium etc.) in the scum.When scum replaced pyrite cinder to be used for plumbous the smelting, lead can dissolve valuable metals such as capturing the gold and silver that reclaim in the chalybeate, copper, indium.
In a kind of embodiment, adopt Dwight-Lloyd sintering machine to carry out the sintering that scum partly substitutes pyrite cinder, but this sinter machine comprise the chassis of 5 sintering zones long 36m, wide 2.5m, and 2 blower fans are set, and is respectively 1# blower fan, 2# blower fan.The thickness of grate-layer material during sintering (raw materials for sintering) is 250～350cm, the speed of chassis operation is 700～1000mm/ second, the particle diameter of raw materials for sintering be 3～9mm in test, pyrite cinder with 30% to 50% with among the present invention after scum that magnetic separation obtains substitutes, the raw materials for sintering water content drops to 4.8% by 5.5%; Sinter machine 1
#Blower pressure is reduced to 2.5Kpa by 2.9Kpa, and 2
#Blower pressure is reduced to 3.0Kpa by 3.5Kpa; 2
#Fan delivery is by 33000Nm
3/ h increases to 35000Nm
3/ h; Roasting middle part temperature is elevated to 550 ℃ by 480 ℃; This no change of the residual sulfenyl of agglomerate; Retailoring of blast furnace production is normal.
The applicant finds through overtesting: if can further improve iron level in the scum, after silver obtains better enrichment, scum dry measure input will reduce (1), and the blast furnace slag quantum of output is with corresponding minimizing, and economic benefit is better; (2) the scum granularity is controlled at 1～2mm, and is more favourable to the furnace charge mixing granulation, and its alternative ratio can reach 100%; (3) use scum as irony flux, silver raising recovery rate still can reach more than 95%.
In addition, for example also needing a certain amount of iron in plumbous dross reverberatory furnace, bismuth reverberatory furnace, the copper blast-furnace.After being made into chalybeate, can replace the iron filings of outsourcing to be used for Metal smelting at least in part by recovery scum provided by the invention.For example, in plumbous dross reverberatory furnace, scum can substitute the outsourcing iron filings fully; In the bismuth reverberatory furnace, scum can replace the outsourcing iron filings with 30% to 60% ratio; In copper blast-furnace, scum can replace the outsourcing iron filings with 20% to 50% ratio.In these substituted, melting was produced normal.
The industrial application of non-magnetic product (coke)
Coke powder is the energy of consumption maximum in the Rotary Kiln zinc metallurgy production process, and the coke powder consumption costs accounts for 20～25% of controlled processing charges.The non-magnetic product that obtains among the present invention---secondary coke powder can partly replace coke powder (coke powder), to reduce the zinc oxide production cost.
This secondary coke powder can be to dash reuse Jiao that choosing obtains through waterpower, also can be that the process carbon content that magnetic separation obtained is more than 50%, preferably at the nonmagnetic portion more than 60%, these nonmagnetic portions preferably pass through the gravity treatment operation again, with further raising carbon content.
Secondary coke powder blend proportion can account for a coke powder (the new coke powder of outsourcing) weight 5% to 25% between.The ratio of substituting is unsuitable too high.If be higher than 25%, then the Rotary Kiln working temperature does not reach requirement, influences the ordinary production of Rotary Kiln.Be the result of use of research secondary coke powder, the contriver tested respectively in zinc Rotary Kiln first workshop section and second workshop section 3～September in 2003.Concrete data are listed in table 8 and the table 9.
Table 8 first workshop section's coal, coke powder, secondary coke powder blend proportion cartogram
Table 9 second workshop section's coal, coke powder, secondary coke powder blend proportion cartogram
The use of in above-mentioned scope, the secondary coke powder being arranged in pairs or groups in Rotary Kiln, stable equipment operation was not because of the insufficient phenomenon of heat supply in the kiln took place in the utilization of secondary coke powder, during the secondary coke powder is recycled, product (ZnO) steady quality, kiln tail processing condition no change when not arranging in pairs or groups the secondary coke powder.Technology condition is in stability state.Secondary coke powder (containing fixed carbon 57～67%) can satisfy the Rotary Kiln production requirement substantially.
The applicant confirms by test, adopts scum to replace iron filings, and the plumbous grade of gained lead bullion slightly is better than existing technology.Adopt hydrodynamic cleaning, can select part secondary coke powder in Rotary Kiln flushing cinder pond; Adopt magnetic selection method,---scum and non-magnetic product---the secondary coke powder that can effectively separate the magnetic product in the Rotary Kiln kiln slag can repeat little test result.Scum can replace the iron filings in the plumbous dross reverberatory furnace batching to use.
Embodiment
Embodiment 1
The concrete composition of kiln slag sample that is adopted is: iron 35.14%, copper 1.03%, zinc 5.03%, gallium 194 gram/tons, indium 154 gram/tons, germanium 20 gram/tons, silver 160 gram/tons, sulphur 5.13%, silicon oxide 20.24%, carbon 14%.Material phase analysis shows: the iron in the kiln slag mainly is metallic iron and exists, and secondly is iron protoxide and Iron sulfuret; Copper in the kiln slag mainly is metallic copper and cupric sulfide.
As shown in Figure 1, with the particle diameter of kiln slag powder essence into about 2mm, magnetic separator carries out primary election with jaw crusher, and the field intensity that is adopted is 1500 oersteds, obtains first nonmagnetic portion (mine tailing I) and first magnetic part (rough concentrate I).Again with rough concentrate I ball milling to about 200 purpose fineness, it is selected to carry out dry type with the low intensity magnetic separation machine under the field intensity of 600 oersteds, obtains second nonmagnetic portion (mine tailing II) and second magnetic part (concentrate I)
Embodiment 2
The concrete composition of kiln slag sample that is adopted is: iron 35.14%, copper 1.03%, zinc 5.03%, gallium 194 gram/tons, indium 154 gram/tons, germanium 20 gram/tons, silver 160 gram/tons, sulphur 5.13%, silicon oxide 20.24%, carbon 14%.Material phase analysis shows: the iron in the kiln slag mainly is metallic iron and exists, and secondly is iron protoxide and Iron sulfuret; Copper in the kiln slag mainly is metallic copper and cupric sulfide.
As shown in Figure 1, with the particle diameter of kiln slag powder essence into about 2mm, magnetic separator carries out primary election with jaw crusher, and the field intensity that is adopted is 1500 oersteds, obtains first nonmagnetic portion (mine tailing I ') and first magnetic part (rough concentrate I ').Again with the fineness of rough concentrate I ' ball milling to about 200, it is selected to carry out wet type with the low intensity magnetic separation machine under the field intensity of 600 oersteds, obtains second nonmagnetic portion (mine tailing II ') and second magnetic part (concentrate I ')
Embodiment 1 and 2 the results are shown in Table 10.
Table 10 embodiment 1 and 2 magnetic separation test-results
As seen from Table 10, wet magnetic separation is better than dry type magnetic separation, and the grade of iron reaches 76.65%.Silver also concentration and separation is better, though copper enrichment to some extent is not ideal enough.
Embodiment 3
As shown in Figure 2, kiln slag from Rotary Kiln dashes choosing through waterpower in the flushing cinder pond, tell part coke powder (reuse Jiao) afterwards, kiln slag is become the kiln slag of particle diameter less than 2mm by comminution, carry out magnetic separation with dry-type magnetic extractor, its magneticstrength is the 800-1800 oersted, most preferably is 1000 Austria, obtains secondary Jiao and scum.Scum can be as returning plumbous batching.The results are shown in Table shown in 11.Magnetic part (scum) productive rate is 60%, and the iron grade can bring up to 60.21%, and carbon can drop to 2.36%; A large amount of carbon, silicon, magnesium, calcium, aluminium etc. are enriched among nonmagnetic portion secondary Jiao, productive rate 40%, and the rate of recovery of carbon is 87.7%, its carbon containing 25%.
Table 11 embodiment 3 test-results
Nonmagnetic portion secondary Jiao who obtains in the present embodiment is contained the carbon of the about 20-30% of weight ratio, and the carbon taste is lower.Its main a certain amount of iron, silicon-dioxide and a small amount of other metals or metallic compound, can not be directly used in the fuel of Rotary Kiln, carry out gravity treatment with table concentration carbon again, the casting yield that carbon enters mine tailing is 88.7%, and carbon containing 50.55% can be used for the fuel of Rotary Kiln, concentrate and tailings is used for steel-making ironmaking, sees table 12 for details.
Table 12 embodiment 3 nonmagnetic portion gravity treatment results
Embodiment 4
As shown in Figure 3 and Figure 4, kiln slag from Rotary Kiln dashes choosing through waterpower in the flushing cinder pond, tell part coke powder (reuse Jiao) afterwards, rest part is loaded into the feed bin bucket, feed into the raw material conveyor by oscillating feeder, flow to double-geared roller crusher, become the kiln slag of particle diameter less than 2mm by comminution, by magnetic separation conveyor I magnetic separation (field intensity 1000 oersteds), obtain scum I and coke I.Scum I iron-holder height is carried by scum conveyor I, makes chalybeate and stores standby.Remain a large amount of scums among the coke I that sub-elects,, obtain scum II and coke II so carry out the magnetic separation second time (magnetic separation II) (field intensity 600 oersteds) by magnetic separation conveyor II.Scum II iron content carbon content is not high, can sell in addition, is used for steel-making, steel-making.The coke II that sub-elects is through vibratory screening apparatus, sub-elect particle diameter greater than thick Jiao of 2mm and particle diameter less than thin Jiao of 2mm, see off by thick burnt conveyor and thin burnt conveyor respectively, thick Jiao returns Rotary Kiln and partly substitutes carbon source, thin burnt pin substitutes carbon source to brick field.One-level magnetic separation scum I, secondary magnetic separation scum II, the copper in the coke, lead, silver, iron, carbon content see Table 14.Main equipment list sees Table 13.
Table 13 embodiment 4 major equipments
| Sequence number | Title | Specification |
| ??1 | The feed bin bucket | Pile high volume 4.2M3 δ 10 |
| ??2 | Oscillating feeder | ??50#380V(2×0.2kw) |
| ??3 | Bidentate wheel crusher | ??450×500A(11kw) |
| ??4 | Magnetic separation conveyor I | ??B1000L11455(5.5kw) |
| ??5 | Scum conveyor I | ??B500L11295(2.2kw) |
| ??6 | Magnetic separation conveyor II | ??B1000L7147(4kw) |
| ??7 | Scum conveyor II | ??B500L11295(2.2kw) |
| ??8 | Vibratory screening apparatus | 0821 designs 6 * 6 voluntarily |
| ??9 | Thin burnt conveyor | ??B500L16700 |
| ??10 | Thick burnt conveyor |
Copper, lead, silver, iron, carbon content (wt%) in the table 14 kiln slag magnetic separation product
| Magnetic separation product | ??Cu | ??Pb | ??Ag | ??Fe | ??C |
| Scum I | ??1.58 | ??0.61 | ??0.06 | ??65.18 | ??2.90 |
| Scum II | ??0.55 | ??0.28 | ??0.018 | ??25.85 | ??8.95 |
| Coke | ??0.19 | ??0.15 | ??0.009 | ??9.35 | ??61.59 |
In the product of this embodiment, the composition of one-level magnetic separation scum is: Fe50～65%, be stabilized in more than 60% usually, Ag300～600g/t can use as the substitute of pyrite cinder for plumbous smeltery.Coke powder fixed carbon is 60～65%, and particle diameter is extremely about 2mm of about 1mm, can be used as the secondary coke powder and uses.
Embodiment 5 (technology of the second stage of the project in 2004, ball milling-gravity treatment-magnetic separation)
The main component of the kiln slag that uses is: iron is about 30%, coking coal is about 20%, about 2%, the about 260g/ ton of silver of plumbous about 1%, the zinc of valuable metal.Technical process as shown in Figure 5.
Block kiln slag, evenly to deliver to a formula double-deck screen shale shaker by rotary conveyor and carry out the one-level screening, screen overflow carries out coarse breaking with alligator; Material after the coarse breaking is made vibratory screening apparatus by oneself with the seat formula and is carried out the secondary screening; One deck screen underflow (particle diameter＜2mm, 10 orders) of the screen overflow of secondary screening and one-level screening carries out fine crushing with hammer mill; The two layers of screen underflow of the material behind the fine crushing and one-level screening and the screen underflow (particle diameter＜0.154mm of secondary screening, 100 orders) be transported to the intermediate buffering storehouse with chapelet, then material by feeding machine under the intermediate buffering storehouse even feeding in wet type (Ф 2100 * 5500) ball mill; Material behind the ball milling sieves once more with high frequency shale shaker, screen overflow is got to little ball mill (wet type) with sand pump and is carried out once more ball milling (Ф 1500 * 3000), material behind the ball milling is returned high frequency shale shaker and is sieved, screen underflow (particle diameter＜0.074mm that high frequency shale shaker is sieved, 200 orders) carry out gravity treatment with spiral gravity concentrator, heavy material is silver-colored iron ore, light material then carries out one-level wet magnetic separation (1000 oersted) with circle roller magnetic separator (Ф 1050 * 2400), and the magnetic separation thing is iron mud; Material remaining after the one-level magnetic separation carries out secondary wet magnetic separation (operational condition 600 oersteds) with circle roller magnetic separator (Ф 600 * 1500) again, and the magnetic separation thing is an iron mud also, and the remaining thing after the secondary magnetic separation is the finished product coal slimes.
In the present embodiment, obtain three kinds of products altogether, be respectively coal slime, iron mud and silver-colored iron ore.Wherein, silver-colored iron ore can be used for the plumbous recovery silver of smelting; Coal slime can export trade brick field or smeltery; Iron mud (iron content about 65%) can be sold to Steel Plant's iron and steel smelting.
Table 15 is listed the equipment that present embodiment adopts.
The equipment of table 15 embodiment 5
Embodiment 6
At 9.6m
2In the plumbous dross reverberatory furnace, test in the ratio in the table 16 with the scum of embodiment 3 resulting iron grades about 60%.The gained test-results sees Table 17, and the production test situation is normal.
Table 16 raw material is packed into and quantum of output
The Chemical Composition (wt%) of table 17 output material
Effect of the present invention
(1) owing to kiln slag process high-temperature calcination, valuable metal retains complicated in the kiln slag, content is low, inertia is strong, if take pyrogenic process, hydrometallurgic recovery, all cost is high, the cycle is long, treating capacity is low, and feasibility is not high, and benefit is not sure. Pyrogenic process can generate new waste residue, the waste residue that produces and former slag weight do not have much differences, still need to drop into huge disposal costs, but the valuable metal that adopts large equipment investment to reclaim in the kiln slag is not good selection. Taking the method for " Gravity separation silver, magnetic separation divide tap a blast furnace, enrichment silver, separation of iron coal ", is the selection of processing the rational faculty of kiln slag.
(2) carbon in the kiln slag and iron-based originally are recycled utilization; Secondary Jiao that magnetic separation is separated returns Rotary Kiln Partial Replacement once burnt (coke), the coal slime export trade to brick field or smeltery as the part solid fuel. Gravity treatment silver-colored iron ore out is used for plumbous the smelting, utilizes on the one hand iron, reclaims on the other hand the valuable metals such as wherein silver, copper, indium, and the export trade of iron mud is to steel plant's iron and steel smelting.
Claims (18)
1. method of recycling kiln slag of zinc hydrometallurgy volatilizing kiln may further comprise the steps:
(1) kiln slag is crushed to the particle size range of about 0.01-2mm, carries out primary election in the magneticstrength of 800-1800 oersted, kiln slag first magnetic part and first nonmagnetic portion;
(2) described first magnetic part is crushed to 50-60 weight %200 purpose size range, carries out selectedly with 500-1090 oersted magneticstrength, obtain second magnetic part and second nonmagnetic portion;
(3) described first nonmagnetic portion is partly replaced the fuel of Metal smelting process as the secondary coke powder.
2. method according to claim 1 further may further comprise the steps:
(4) described first magnetic part or described second magnetic part are used as the source of iron in the heavy metal smelting process.
3. method according to claim 1 wherein, is used for slag making as source of iron with described first magnetic part or described second magnetic part in lead blast furnace retailoring.
4. method according to claim 3 wherein, substitutes pyrite with described first magnetic part or described second magnetic part with at least 30% weight ratio.
5. method according to claim 4 wherein, substitutes pyrite with described second magnetic part with 100% weight ratio.
6. according to each described method of claim 1 to 5, wherein, with described first magnetic part or described second magnetic with after pyrite mixes, on expect that sintered material burns the slag storehouse, carry out batch mixes, granulation with lead ore concentrate and unclassified stores, and then put into sinter machine and carry out roasting, corresponding increase air feed rate when roasting.
7. method according to claim 2 wherein, is used as source of iron described first magnetic part or described second magnetic part in plumbous dross reverberatory furnace, bismuth reverberatory furnace, copper blast-furnace.
8. method according to claim 7 wherein, is used described first magnetic part or the alternative fully iron filings of described second magnetic part in plumbous dross reverberatory furnace.
9. method according to claim 7 wherein, replaces iron filings to use in the bismuth reverberatory furnace with 30% to 60% ratio described first magnetic part or described second magnetic part.
10. method according to claim 7 wherein, replaces iron filings to use in copper blast-furnace with 20% to 50% ratio described first magnetic part or the described second magnetic part scum.
11. method according to claim 1, wherein, described first nonmagnetic portion is used for Rotary Kiln zinc metallurgy as the secondary coke powder with the weight ratio substituting disposable coke powder with respect to a coke powder 5% to 25%.
12. method according to claim 1, wherein, described selected be to carry out with the magneticstrength of 500-1090 oersted.
13. method according to claim 1 wherein, comprised that before described preliminary magnetic one is carried out the step that waterpower is dashed choosing with described kiln slag, with a part of coke of direct recovery, is used for the part alternative fuel of Metal smelting.
14. method according to claim 1 wherein, comprises described second nonmagnetic portion obtaining rich carbonaceous recovery coke powder with the step that shaking table carries out gravity treatment, is used for the part alternative fuel of Metal smelting.
15. method according to claim 1 wherein, also is included in the step of carrying out gravity treatment after the described kiln slag fragmentation, to obtain the step of rich argentiferous silver-colored iron ore, is used for refining silver.
16. method according to claim 15, wherein, described fragmentation is to use the wet ball-milling crusher machine, and particle size after cracking is-200 orders, and described gravity treatment is to be undertaken by spiral gravity concentrator.
17. method according to claim 1, wherein, with the described selected secondary magnetic separation that comprises,
Wherein, first step magnetic is to carry out with the magneticstrength of 800-1800 oersted; Second stage magnetic separation is to carry out with the magneticstrength of 500-1090 oersted.
18. method according to claim 1, wherein, the described selected secondary magnetic separation that comprises,
Wherein, first step magnetic is to carry out with the magneticstrength of 1050 oersteds; Second stage magnetic separation is to carry out with the magneticstrength of 650 oersteds.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102814228A (en) * | 2012-08-30 | 2012-12-12 | 湖南省中杰科技发展股份有限公司 | Method for recycling nickel from low-grade nickel smelting slag |
| CN107470016A (en) * | 2017-08-30 | 2017-12-15 | 云南楚丰新材料集团有限公司 | A kind of method that chemical industry iron powder is prepared using zinc kiln slag as raw material |
| CN111495588A (en) * | 2020-04-27 | 2020-08-07 | 汉源县伟业环保科技有限公司 | Method for recycling, reducing and harmlessly treating lead-zinc smelting slag |
-
2009
- 2009-09-08 CN CN200910259547A patent/CN101781709A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102814228A (en) * | 2012-08-30 | 2012-12-12 | 湖南省中杰科技发展股份有限公司 | Method for recycling nickel from low-grade nickel smelting slag |
| CN107470016A (en) * | 2017-08-30 | 2017-12-15 | 云南楚丰新材料集团有限公司 | A kind of method that chemical industry iron powder is prepared using zinc kiln slag as raw material |
| CN107470016B (en) * | 2017-08-30 | 2019-09-20 | 云南楚丰新材料集团有限公司 | A method of chemical industry iron powder is prepared by raw material of zinc kiln slag |
| CN111495588A (en) * | 2020-04-27 | 2020-08-07 | 汉源县伟业环保科技有限公司 | Method for recycling, reducing and harmlessly treating lead-zinc smelting slag |
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