CN104512988A - Method for treating heavy metal sludge by using stainless steel molten slag - Google Patents
Method for treating heavy metal sludge by using stainless steel molten slag Download PDFInfo
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- CN104512988A CN104512988A CN201310455243.XA CN201310455243A CN104512988A CN 104512988 A CN104512988 A CN 104512988A CN 201310455243 A CN201310455243 A CN 201310455243A CN 104512988 A CN104512988 A CN 104512988A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/248—Binding; Briquetting ; Granulating of metal scrap or alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/06—Sludge reduction, e.g. by lysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention discloses a method for treating heavy metal sludge by using stainless steel molten slag. The method comprises drying crushing, material matching mixing, pressing molding, drying, tank bottom material spreading, smelting reduction, gas purification, molten slag treating, metal recovery and other steps, and specifically comprises that: after heavy metal sludge is subjected to pre-treatment, a certain proportion of ingredients are matched, and the sludge agglomerate is adopted as the bottom spreading material and is placed into a stainless steel molten slag tank to carry out a harmless treatment on the sludge agglomerate. According to the present invention, the characteristics of high production amount, high temperature and rich sensible heat resource of the stainless steel molten slag are adopted, and the stainless steel molten slag is adopted to treat the heavy metal sludge, such that the harmless treatment on the hazardous components and the resource on the valuable material are achieved, the method is the new attempt crossing the industry, and the waste heat resource can be effectively utilized so as to achieve the waste treatment adopting the waste.
Description
Technical field
The present invention relates to industrial dangerous waste process and field of comprehensive utilization, particularly relate to a kind of method utilizing process heavy metal sewage sludge.
Background technology
Heavy metal wastewater thereby source is wide, kind is many, and its treatment process can be summarized as chemical method, Physical, physico-chemical processes and biochemical process.Take milk of lime as the chemical neutralization precipitator method of major pharmaceutical agent, because operational path is ripe, cost for wastewater treatment is low, maintenance management is convenient, level of automation high, at home and abroad be widely used, but consequent excess heavy metal sewage sludge, always be the environmental protection Focal point and difficult point of industrial enterprise.
Analysis shows, heavy metal sewage sludge water ratio 50 ~ 75% after the solid-liquid separation facilities such as filter press, vacuum filtration, diaphragm pressing, the total metal oxide content such as Cr, Ni, Zn, Pb, Fe, Cu, Ag, Cd 2 ~ 15%, calcium sulfate, Calcium Fluoride (Fluorspan), calcium chloride content 10 ~ 30%, other water soluble salts and foreign matter content about 5%.Heavy metal sewage sludge particle is comparatively thin, complicated component, Leaching are high, pollutant load fluctuation is large, be attributed to Hazardous wastes (National Hazard refuse register HW17 and HW21), process can cause poisonous metal to the secondary pollution at soil and water source accidentally, often needs the outer committee of high price have the enterprise of qualification properly to dispose.
For alleviating or eliminate the harm of heavy metal sewage sludge, recycle valuable resource wherein, avoid the secondary pollution in recycling process, Chinese scholars is with reference to electroplating sludge, the disposal and utilization experience of chromium-bearing sludge, at sludge curing/stabilizing (CN1631940A, CN101863516A, CN101921090A, CN102514079A etc.), wet underwater welding metal (CN101235439A, CN101618892A etc.), microbial acclimation leaches (CN102690956A, CN102719657A, CN101708936A etc.), roasting reduction prepares alloy (CN1733628A, CN1312391A etc.), prepare chromium system product (CN102625777A etc.), be mixed for building materials (CN101830681A, CN102414141A, CN102249730A etc.) or industrial chemicals (CN102491640A etc.), compost agricultural (CN101274861 etc.), for manufacture of cement (CN101475325A, CN102701549A etc.), metallurgical reuse (CN101805827A etc.), safe disposal (CN201560162U, CN102285743A, CN102583920A etc.) etc. aspect done a lot of useful exploration, but it is little to there is volume all to a certain extent, poor for applicability, heavy metal recovery rate is low, technical process is complicated, facility investment or working cost high, utilize process energy consumption high or easily cause secondary pollution problems.
Up to now, for having a large capacity and a wide range, the heavy metal sewage sludge that coexists of hazardness and resource, more large utilization ways is still baked bricks or is used as cement spike, but because in heavy metal sewage sludge, the volatile substances such as fluorine, chlorine content is higher, under the high temperature conditions, fluorine, chlorine can with the effusions of the gaseous state thing form such as HF, SiF4, HCl, not only etching apparatus, cause kilneye ring formation, also can endanger surrounding environment, even can cause the sericulture industry underproduction in the neighbourhood.Meanwhile, when mud volume is more than 2%, need to be assessed further to the environmental safety risk brought in cement or brick and tile use procedure because mixing burning Hazardous wastes.
In sum, heavy metal sewage sludge output is large, complicated component, harm are serious, there is no the utilization ways that properly safety is economical and practical again both at home and abroad, simultaneously, containing various metals composition (as chromium, nickel, copper, lead, iron, zinc etc.) and Non-metallic components (as Calcium Fluoride (Fluorspan), calcium sulfate, calcium carbonate, calcium chloride etc.) in mud, it itself is a kind of renewable resources of cheapness.In view of the shortage of China metals resources, how effectively to reduce discharging and recycle the heavy metal such as chromium, nickel in heavy metal sewage sludge, control mud environmental pollution oneself cause the very big concern of people.
On the other hand, in stainless steel enterprises smelting process, smelt slag temperatures as high 1600 DEG C, generation accounts for 20 ~ 30% of output of steel, and sensible heat resource is very abundant, conventional stainless steel slag handling technology, as " air cooling+spray/immersion/hot application " etc., fail effectively to utilize valuable sensible heat resource.
Review heavy metal sewage sludge process and apply more high-temperature roasting technique, power consumption is not only needed to heat, to guarantee chromium in mud, nickel, copper, plumbous, iron, the thorough reduction of the heavy metals such as zinc and harmlessness disposing, also complex structure will be equipped with, smelting furnace (the CN102433437A of investment and working cost costliness, CN101376926A etc.), if stainless steel dross sensible heat and existing slag ladle equipment can be utilized, develop a kind of heavy metal sewage sludge high-temperature processing technology, then have melting slag waste heat concurrently to utilize, valuable material reclaims, pollute and thoroughly eliminate, the advantages such as processing cost is cheap, can be rated as and use for reference the innoxious and resource utilization experience of traditional Hazardous wastes, again in conjunction with sludge components and the feature of Iron And Steel Industry own, the Tiao Xin road walked out.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is to provide a kind of heavy metal-polluted mud resource and innoxious treatment process, overcome that existing art breading amount is little, poor for applicability, heavy metal recovery rate is low, technical process is complicated, facility investment or working cost high, utilize that process energy consumption is high, innoxious does not thoroughly easily cause the defects such as secondary pollution.
Technical scheme of the present invention is, a kind of method utilizing stainless steel slag treatment heavy metal sewage sludge, comprises the following steps:
(1) mummification is pulverized: heavy metal sewage sludge, after solid-liquid separation, natural mummification, is down to 50 ~ 65% to water ratio, pulverizes broken sieve, for subsequent use;
(2) batching mixing: by the heavy metal sewage sludge after above-mentioned pulverizing and carbonaceous powder, containing calcium flux, siliceous binder formulation and/or contain heavy industries waste material and mix in proportion; Described heavy metal sewage sludge and carbonaceous powder, be 50 ~ 100:30 ~ 80:10 ~ 50:10 ~ 50 containing calcium flux, containing the part by weight of silicon bonding; Described heavy industries waste material is waste oil mud and desulphurize fly ash, and the part by weight of described heavy metal sewage sludge and waste oil mud, desulphurize fly ash is 50 ~ 100:1 ~ 20:1 ~ 20;
(3) compression moulding: the batching of mixing is pressed into agglomerate;
(4) dry: above-mentioned agglomerate is dried further;
(5) stone at the bottom of tank: using mud agglomerate as grate-layer material, inserts in stainless steel slag slag ladle; Described mud agglomerate accounts for 0.5% ~ 15% of the rear mud agglomerate of mixing and stainless steel slag gross weight;
(6) smelting reduction: by the heat of high temperature stainless steel slag, carries out smelting reduction to mud agglomerate;
(7) gas sweetening: tail gas clean-up process, discharges after removing the pollutent such as dust, halogenide;
(8) slag treatment: after slag temperature is down to 1000 ~ 1200 DEG C, pyroreaction terminates, by original measure process slag;
(9) metal recovery: through high melt reduction treatment, the most metallic elements in mud agglomerate enter in liquid alloy molten iron, after alloy mouth is released, recycle as Fe alloy slag steel full dose.
Described heavy metal sewage sludge is one or more of the by product from industry milk of lime-chemical precipitation art breading heavy metal wastewater therebies such as iron and steel, chemical industry, petrochemical industry, coloured, plating, nonferrous metallurgy, intermetallic composite coating, machinofacture.Mud, after the mechanical solid-liquid separation facilities such as filter press, diaphragm pressing, vacuum press filtration, can be taked naturally to store up mummification in canopy or in storehouse, be down to 50 ~ 65% to water ratio, pulverize broken sieve, for subsequent use;
According to heavy metal sewage sludge source and different in kind, when its natural mummification to water ratio is 50 ~ 65%, appearance is comparatively hard, convenient conveying, storage, broken and follow-up mixing.Water ratio is too high, wet sticky shapeless, pulverizes broken sieved journey and has some setbacks, cause adhering device or putty; Water ratio is too low, and heat drying cost is high first, when second water ratio is too low, can produce dust secondary pollution when pulverizing broken sieve.
Described carbonaceous powder, as reductive agent in follow-up smelting reducing process, guarantees the reduction ratio under metal in sludge (Cr, Ni, Fe etc.) high temperature.Above-mentioned carbonaceous powder can be coal dust, also can with coke powder or carbon dust, and concrete adding proportion is determined according to metal in sludge composition and content.
Described containing calcium flux, as flux in follow-up smelting reducing process, guarantee that sludge liquid phase slagging course carries out smoothly, and control the volatilization of fluoro-gas.In addition, in mud batching briquetting, the effect absorbing cellular moisture, reduce mud agglomerate water ratio and binding agent can also be played containing calcium flux (such as unslaked lime).Can be unslaked lime containing calcium flux, also can use Wingdale, rhombspar, concrete adding proportion be determined according to moisture percentage in sewage sludge and composition.
Described containing silicon bonding, in mud batching briquetting, play the effect increasing cold strength, absorb moisture and assistant formation.Can select cement containing silicon bonding, also can use wilkinite, attapulgite, flyash, adding proportion requires according to moisture percentage in sewage sludge and green ball strength and determines.
Described waste oil mud is the bed mud after waste lubricating oil natural subsidence or refining regeneration.Solid load is more than 20%, and in thick, color and luster is dark, oil content is large, heavy metal content is high, is a kind of industrial dangerous waste being difficult to utilize; Waste oil mud, as mud agglomerate batching, has contribution calorific value and metallic element, bonding agglomerate, regulates the effect such as moisture and auxiliary briquette formation, in high-temperature slag while recycling, also achieve the innoxious of self.The adding proportion of waste oil mud, requires according to waste oil mud composition, moisture percentage in sewage sludge and green ball strength and determines.
Described desulphurize fly ash is the by product of coal-burning power plant or steel enterprise sintering operation dry fume/semi-dry desulfurizing process.Main component is the impurity such as CaSO31/2H2O, CaSO42H2O, CaCO3, f-CaO, Ca (OH) 2 and a small amount of flying dust, alkalescence high, complicated component, poor stability, utilizes difficulty large, utilizes enterprise to bring heavy burden to downstream sources.Desulphurize fly ash, as mud agglomerate batching, has absorption moisture, provides calcium source and the effect such as metallic element, increase agglomerate green ball strength, in high-temperature slag while recycling, also achieve the innoxious of self.The adding proportion of desulphurize fly ash, determines according to factors such as its composition, moisture percentage in sewage sludge, unslaked lime adding proportion and green ball strength requirements.
In the compression moulding of step (3), compression moulding process, twin rollers can be taked to extrude (pressure is 2000 ~ 4000N), and as relied on the existing moulded coal processing unit (plant) of Steel Plant, its intensity should be able to meet transport, dump, dries and store up not broken, fissureless requirement in process.
Described drying course, thermal source can draw the waste heat reclaiming high-temperature gas from smelting reduction process, as this flue gas heat is inadequate, also can take outside heat supply.
In step (6), the temperatures as high of stainless steel slag 1600 DEG C, conventional process is after being accepted by slag with slag ladle, be dragged to slag field and carry out wet processed, whole transportation about 10 ~ 30min, this technique just in time make use of during this period of time, carries out high temperature (1200 ~ 1600 DEG C) smelting reduction process to mud agglomerate.
Smelting reduction is the core procedure of this technique, metallic element (representing with the Me of divalence) in heavy metal sewage sludge, in slag ladle, recurs oxyhydroxide thermolysis (Me (OH) 2=MeO+H2O), Reduction of Oxide (MeO+CO=Me+CO22MeO+C=2Me+CO2) and slag making reaction (MeO+SiO2=MeOSiO22MeO+SiO2=2MeOSiO2MeO+Me'O+SiO2=MeOMe'OS iO2).In smelting reduction process, mud agglomerate is heated to rapidly more than 1200 DEG C by slag, and keep 10 ~ 30min, during this period, the metals such as the overwhelming majority chromium, nickel, iron enter in Stainless Steel Alloy molten iron after high temperature reduction, the inorganics such as calcium, silicon, phosphorus, sulphur of more than 90% enters slag phase, the volatile gaseses such as low melting point such as HF, HCl, SiF4, ZnO, PbO, Na2O, K2O and dust enter in high-temperature gas, and the objectionable impurities in mud agglomerate realizes resource utilization and innoxious under the high temperature conditions simultaneously.
For chromium, further elaboration mud agglomerate resource utilization and innoxious process in slag slag ladle: the achievement in research before contriver shows (CN101805827A), under the strong reductive condition of smelting, about there is the chromium of 90% to enter molten iron, less than 10% and enter slag, the a small amount of chromium entering slag can only exist with trivalent, can not cause secondary pollution.The same slag composition of the allocation proportion of concrete chromium in slag, iron, hot metal composition and slag iron temperature are relevant, when chromium too high levels, may also affect the performance of slag; And when mud pelletizing addition is less than 15%, can not impact slag.Meanwhile, in view of this technique relies on existing stainless steel smelting to slag tap technique, Cr, Ni of minute quantity enter in slag, more can not produce basic impact to molten iron and slag.From the angle of dissolve process and safe disposal heavy metal sewage sludge, this is a suitable approach.
For shortening the high melt recovery time, also can increase pneumatic blending facility in slag ladle, impel three-phase thoroughly to react, but the air capacity passed into should be appropriate.Crossing conference causes slag to lower the temperature, and too small do not have stirring action.
In step (7), described gas sweetening, is to drying machine flue gas out, takes the one in dust removal with machine, bag-type dust, alkali liquor absorption, deodorization and combination thereof, after purifying, discharged by chimney.
In step (8), the existing facility of slag treatment, comprises air cooling+spray, air cooling+hot application, air cooling+immersion etc.After slag treatment, cold slag can be adopted further to utilize.Cold slag utilizes: detect cold slag ingredient, especially Leaching, to determine whether to belong to Hazardous wastes; If the Leaching of main metal element (as chromium, lead, nickel, copper, zinc, cadmium, arsenic, silver etc.) is lower than GB (GB5085.3-2007), the stainless steel slag that this technique produces can follow original Land use models, as tailings Development and Production complex cement and concrete additive after magnetic separation, as pavement construction material, bituminous concrete, cement concrete, cement products etc.After special processing, also can make the additive of high value added product, as rust cleaning sandblasting, rubber filling material, cement stopping composition, pitch stopping composition, agricultural soil ameliorant and fertilizer additive etc.
In this technique, because of factors such as Seasonal Temperature Difference, procedure connection, organizational schedulings, as very fast in the cooling of stainless steel slag, for guaranteeing that the slag after lowering the temperature still can be poured out from slag ladle (entering conventional Slag treatment operation), in slag ladle, the mud agglomerate of shop fixtures can reduce the amount of inserting, or take disposable shop fixtures, multiple tank high temperature reduction, until mud agglomerate all melts.
In this technique, for collecting gas, toppling over slag or alloy hot metal convenience, have selected stainless steel slag slag ladle as high temperature reduction device.Also can suit measures to local conditions, replace slag ladle (mud pelletizing still does grate-layer material) with slag pan, tray, but operating process may form fugacity airborne dust or high temperature fumes, make troubles to site environment management.
According to a kind of method utilizing stainless steel slag treatment heavy metal sewage sludge of the present invention, preferably, step (2) described mixing process, takes the powerful mixed grind mode of Double-axis screw mixing machine.
According to a kind of method utilizing stainless steel slag treatment heavy metal sewage sludge of the present invention, preferably, in the described gas sweetening process of step (7), the high-temperature gas that smelting reduction produces is back to the drying course of mud agglomerate.
Above-mentioned high-temperature gas is back in drying course and adopts gas waste-heat retrieving arrangement, and gas waste-heat retrieving arrangement can close hood configuration for negative-pressure dense, is placed in above slag slag ladle, high-temperature flue gas can be caused mud agglomerate drying system in time.
Waste heat recovery is indirectly, directly or one of built-up type heat exchange mode; The one in hollow blade dryer, conveyor dryer, vertical polydisc drying machine, disc dryer can be taked.
In a preferred embodiment, described carbonaceous powder is selected from one or more in coal dust, coke powder, carbon dust.
In a preferred embodiment, described containing calcium flux be selected from unslaked lime, Wingdale, rhombspar one or more.
In another preferred embodiment, described containing silicon bonding be selected from cement, wilkinite, attapulgite, flyash one or more.
Preferably, step (3) described mud agglomerate size is 5 ~ 50mm.In this technique, mud agglomerate size is 5 ~ 50mm, and shape is not limit, and can be spherical, strip, one of ellipticity or bulk; Particle diameter is less than 5mm, easily produces dust in transhipment, drying course; Particle diameter is greater than 50rnm, then affect slag ladle inner transmission matter, heat transfer and speed of response.
Preferably, step (4) by mud agglomerate dry to water ratio be 8 ~ 33wt%.
Further, step (4) by mud agglomerate dry to water ratio be 10 ~ 30wt%.
The invention has the beneficial effects as follows:
(1) stainless steel slag generation is large, temperature is high, and sensible heat aboundresources, processes heavy metal sewage sludge with it, realizes that hazard component is innoxious, valuable material resource utilization, is inter-trade new try, effectively can utilizes residual heat resources, realize the treatment of wastes with processes of wastes against one another.
(2) this technique can utilize the existing slag ladle equipment of stainless steel enterprises, mixing briquetting apparatus and Slag treatment flow process, without the need to building special smelting shop and smelting device, simple to operate, technical process is short, metal recovery rate is high, investment and working cost low, mud handling capacity is large, be easy to industrialization promotion, can the various heavy metal sewage sludge of in situ remediation, and considerable influence is not produced to stainless steel slag performance and later use, be Hazardous wastes resource utilization and innoxious effective ways.
(3) under high temperature reducing conditions, metallic element in heavy metal sewage sludge, inorganic component and combustibleconstituents, fully can there is physical-chemical reaction, participate in the synthesis of clinker mineral, and wherein the unwanted component such as foreign metal and fluorine element also can be solid-solution in clinker mineral structure and high-temperature liquid-phase, realize stable solidification.
(3) metallic element such as chromium, nickel, iron enters in stainless steel molten iron, it is the useful supplement to molten iron alloy mass, therefore this technique suitability is strong, except processing stainless-steel cold-rolling mud, the cold rolling mud of carbon steel, the cold rolling mud of special steel, electroplating sludge, nonferrous metallurgy mud, wiring board mud, waste oil mud, desulphurize fly ash etc. containing heavy metal waste, also can to dissolve general industry refuse simultaneously, to make it be converted into recycling and be worth the stainless steel slag comparatively large, the scope of application is wider.
(4) high, the thin thickness of grain of waste oil mud solid load, color and luster is dark, oil content is large, heavy metal component is complicated is a kind of industrial dangerous waste being difficult to utilize; And using waste oil mud as mud agglomerate batching, calorific value and metallic element not only can be contributed, bond agglomerate in addition, regulate the effect such as moisture and auxiliary briquette formation.Therefore, this technique can effectively realize the innoxious of waste oil mud and resource utilization.
(5) desulphurize fly ash alkalescence high, complicated component, poor stability, utilize difficulty large, mud agglomerate is it can be used as to prepare burden, can be played it absorb moisture, calcium source and the effect such as metallic element, increase agglomerate green ball strength are provided, effectively realize the innoxious of Hazardous wastes and resource utilization.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Embodiment 1
Heavy metal sewage sludge comes from stainless-steel cold-rolling waste water processing station, for the by product (being called for short cold rolling mud) of milk of lime-chemical precipitation art breading cold rolling wastewater, cold rolling mud is after filter press, heap is stored in substrate antiseepage, in draughty warehouse, this mud Exemplary chemical component is: Cr(0.5 ~ 5%), Ni(0.1 ~ 1.0%), Zn(0.05 ~ 0.5%), Pb(0.05 ~ 0.5%), Fe(10 ~ 25%), CaSO4 (5 ~ 25%), CaF2 (5 ~ 15%), CaCl2 (1 ~ 5%), other (5 ~ 10%), heavy metal sewage sludge particle is thinner, complicated component, Leaching is high, be attributed to Hazardous wastes (National Hazard refuse register HW17 and HW21), outer committee is needed to have the enterprise of qualification properly to dispose.
As shown in Figure 1, when the mummification of cold rolling mud nature is to water ratio 55%, pulverize broken sieve, with coal dust, unslaked lime, cement, waste oil mud, desulphurize fly ash, (cold rolling mud 50% in proportion, coal dust 15%, unslaked lime 10%, cement 10%, waste oil mud 10%, desulphurize fly ash 5%), adopt Double-axis screw mixing machine to mix.
By mixing dosage, take twin rollers extrude (pressure is 2000 ~ 4000N) shaping, obtain granularity major diameter 50mm, the ellipsoid agglomerate of minor axis 30mm, this ellipsoid mud agglomerate is dried further to water ratio be 20%; The thermal source that drying needs draws the waste heat reclaiming high-temperature gas from smelting reduction process.
By the mud agglomerate after oven dry, according to the ratio of 5%, about 1.5t inserts bottom stainless steel slag slag ladle.
In stainless steel smelting process, tapping temperature about 1600 DEG C, slag ladle volume 17 ~ 18m3, actual weight of load is about 30t, mud agglomerate is heated to rapidly more than 1200 DEG C by slag in slag ladle, oxyhydroxide thermolysis is gone through in 20min, the serial reaction such as Reduction of Oxide and slag making, overwhelming majority chromium, nickel, the metals such as iron enter in Stainless Steel Alloy molten iron after high temperature reduction, the calcium of more than 90%, silicon, phosphorus, the inorganicss such as sulphur enter slag phase, HF, HCl, SiF4, ZnO, PbO, Na2O, the volatile gaseses such as low melting point such as K2O and dust enter in high-temperature gas, objectionable impurities in mud agglomerate realizes resource utilization and innoxious under the high temperature conditions simultaneously.
The high-temperature gas that smelting reduction produces, cause mud agglomerate drying system by the airtight hood configuration of negative pressure be placed in above slag slag ladle, conveyor dryer direct heating mode is taked in waste heat recovery; Conveyor dryer flue gas out, takes the mode of " cyclone dust removal+alkali liquor absorption ", is discharged after purification by chimney.
When slag temperature is down to about 1100 DEG C, pyroreaction terminates, and slag treatment still adopts original " air cooling+spray " to process.
Detect cold slag ingredient, the Leaching of its main metal element (as chromium, lead, nickel, copper, zinc, cadmium, arsenic, silver etc.) is all lower than GB (GB5085.3-2007), this stainless steel slag illustrating that this technique produces can follow original building materials Land use models, as road administration material, concrete and cement products raw material.
Through high melt reduction treatment, the most metallic elements (rate of recovery of chromium, nickel, iron is all more than 90%) in mud agglomerate enter in liquid alloy molten iron, after alloy mouth is released, can be used as Fe alloy slag steel full dose and recycle.
Embodiment 2
Heavy metal sewage sludge comes from electroplating wastewater processing process.The mummification of mud nature, to water ratio 60%, pulverizes broken sieve, with coke powder, rhombspar, attapulgite, waste oil mud, desulphurize fly ash, and (mud 40% by weight proportion, coke powder 15%, rhombspar 15%, attapulgite 15%, waste oil mud 10%, desulphurize fly ash 5%), adopt Double-axis screw mixing machine to mix.
By mud agglomerate dry to water ratio be 33%.In compression moulding technique, mud agglomerate size is the pelletizing of particle diameter 15mm.
By the mud pelletizing after oven dry, the ratio (mud pelletizing accounts for the ratio of stainless steel slag and mud pelletizing gross weight in slag ladle) according to 15%, about 4.5t inserts bottom stainless steel slag slag ladle.
The other the same as in Example 1.
Embodiment 3
Heavy metal sewage sludge comes from chemical wastewater treatment process.The mummification of mud nature, to water ratio 50%, pulverizes broken sieve, with coal dust, Wingdale, wilkinite, waste oil mud, desulphurize fly ash, and (mud 30% by weight proportion, coal dust 10%, Wingdale 25%, wilkinite 15%, waste oil mud 5%, desulphurize fly ash 15%), adopt Double-axis screw mixing machine to mix.
By mud agglomerate dry to water ratio be 8%.In compression moulding technique, mud agglomerate size is the pelletizing of particle diameter 20mm.
By the mud pelletizing after oven dry, the ratio (mud pelletizing accounts for the ratio of stainless steel slag and mud pelletizing gross weight in slag ladle) according to 10%, about 3t inserts bottom stainless steel slag slag ladle.
The other the same as in Example 1.
Embodiment 4
Heavy metal sewage sludge comes from nonferrous metallurgy wastewater treatment process.The mummification of mud nature, to water ratio 55%, pulverizes broken sieve, with coke powder, coal dust, unslaked lime, flyash, waste oil mud, desulphurize fly ash, and (mud 35% by weight proportion, coke powder 10%, coal dust 15%, unslaked lime 10%, flyash 25%, desulphurize fly ash 15%), adopt Double-axis screw mixing machine to mix.
By mud agglomerate dry to water ratio be 10%.In compression moulding technique, mud agglomerate size is the strip agglomerate of granularity major diameter 50mm, minor axis 30mm
By the mud pelletizing after oven dry, the ratio (mud pelletizing accounts for the ratio of stainless steel slag and mud pelletizing gross weight in slag ladle) according to 0.5%, about 0.15t inserts bottom stainless steel slag slag ladle.
The other the same as in Example 1.
Embodiment 5
Heavy metal sewage sludge comes from intermetallic composite coating wastewater treatment process.The mummification of mud nature, to water ratio 60%, pulverizes broken sieve, with coke powder, rhombspar, wilkinite, flyash, by weight proportion (mud 40%, coke powder 15%, rhombspar 15%, wilkinite 10%, flyash 20%), adopts Double-axis screw mixing machine to mix.
By mud agglomerate dry to water ratio be 20%.In compression moulding technique, mud agglomerate size is the strip agglomerate of granularity major diameter 40mm, minor axis 20mm.
By the mud pelletizing after oven dry, the ratio (mud pelletizing accounts for the ratio of stainless steel slag and mud pelletizing gross weight in slag ladle) according to 8%, about 2.4t inserts bottom stainless steel slag slag ladle.
The other the same as in Example 1.
The present invention utilizes that stainless steel slag generation is large, temperature is high, and the resourceful feature of sensible heat, processes heavy metal sewage sludge with it, realize that hazard component is innoxious, valuable material resource utilization, be inter-trade new try, effectively can utilize residual heat resources, realize the treatment of wastes with processes of wastes against one another.The present invention is simple to operate, technical process is short, metal recovery rate is high, investment and working cost low, mud handling capacity is large, be easy to industrialization promotion, can the various heavy metal sewage sludge of in situ remediation, and considerable influence is not produced to stainless steel slag performance and later use, be Hazardous wastes resource utilization and innoxious effective ways.
Claims (9)
1. utilize a method for stainless steel slag treatment heavy metal sewage sludge, comprise the following steps:
(1) mummification is pulverized: heavy metal sewage sludge, after solid-liquid separation, natural mummification, is down to 50 ~ 65% to water ratio, pulverizes broken sieve, for subsequent use;
(2) batching mixing: by the heavy metal sewage sludge after above-mentioned pulverizing and carbonaceous powder, containing calcium flux, siliceous binder formulation and/or contain heavy industries waste material and mix in proportion; Described heavy metal sewage sludge and carbonaceous powder, be 50 ~ 100:30 ~ 80:10 ~ 50:10 ~ 50 containing calcium flux, containing the part by weight of silicon bonding; Described heavy industries waste material is waste oil mud and desulphurize fly ash, and the part by weight of described heavy metal sewage sludge and waste oil mud, desulphurize fly ash is 50 ~ 100:1 ~ 20:1 ~ 20;
(3) compression moulding: the batching of mixing is pressed into agglomerate;
(4) dry: above-mentioned agglomerate is dried further;
(5) stone at the bottom of tank: using mud agglomerate as grate-layer material, inserts in stainless steel slag slag ladle; Described mud agglomerate accounts for 0.5% ~ 15% of the rear mud agglomerate of mixing and stainless steel slag gross weight;
(6) smelting reduction: by the heat of high temperature stainless steel slag, carries out smelting reduction to mud agglomerate;
(7) gas sweetening: tail gas clean-up process, discharges after removing the pollutent such as dust, halogenide;
(8) slag treatment: after slag temperature is down to 1000 ~ 1200 DEG C, pyroreaction terminates, by original measure process slag;
(9) metal recovery: through high melt reduction treatment, the most metallic elements in mud agglomerate enter in liquid alloy molten iron, after alloy mouth is released, recycle as Fe alloy slag steel full dose.
2. a kind of method utilizing stainless steel slag treatment heavy metal sewage sludge according to claim 1, is characterized in that: step (2) described mixing process, takes the powerful mixed grind mode of Double-axis screw mixing machine.
3. a kind of method utilizing stainless steel slag treatment heavy metal sewage sludge according to claim 1, is characterized in that: in the described gas sweetening process of step (7), and the high-temperature gas that smelting reduction produces is back to the drying course of mud agglomerate.
4. a kind of method utilizing stainless steel slag treatment heavy metal sewage sludge according to claim 1, is characterized in that: described carbonaceous powder be selected from coal dust, coke powder, carbon dust one or more.
5. a kind of method utilizing stainless steel slag treatment heavy metal sewage sludge according to claim 1, is characterized in that: described containing calcium flux be selected from unslaked lime, Wingdale, rhombspar one or more.
6. a kind of method utilizing stainless steel slag treatment heavy metal sewage sludge according to claim 1, is characterized in that: described containing silicon bonding be selected from cement, wilkinite, attapulgite, flyash one or more.
7. a kind of method utilizing stainless steel slag treatment heavy metal sewage sludge according to claim 1, is characterized in that: step (3) described mud agglomerate size is 5 ~ 50mm.
8. a kind of method utilizing stainless steel slag treatment heavy metal sewage sludge according to claim 1, is characterized in that: step (4) by mud agglomerate dry to water ratio be 8 ~ 33wt%.
9. a kind of method utilizing stainless steel slag treatment heavy metal sewage sludge according to claim 8, is characterized in that: step (4) by mud agglomerate dry to water ratio be 10 ~ 30wt%.
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