CN105271624A - Method for synergistically treating heavy metal sludge - Google Patents
Method for synergistically treating heavy metal sludge Download PDFInfo
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- CN105271624A CN105271624A CN201410235279.1A CN201410235279A CN105271624A CN 105271624 A CN105271624 A CN 105271624A CN 201410235279 A CN201410235279 A CN 201410235279A CN 105271624 A CN105271624 A CN 105271624A
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- heavy metal
- sewage sludge
- calcium
- metal sewage
- sintering
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 73
- 239000010802 sludge Substances 0.000 title claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 57
- 230000008569 process Effects 0.000 claims abstract description 40
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000011575 calcium Substances 0.000 claims abstract description 35
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000010935 stainless steel Substances 0.000 claims abstract description 25
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000428 dust Substances 0.000 claims abstract description 12
- 239000003546 flue gas Substances 0.000 claims abstract description 12
- 239000002351 wastewater Substances 0.000 claims abstract description 11
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 7
- 239000000956 alloy Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000009628 steelmaking Methods 0.000 claims abstract description 5
- 239000010801 sewage sludge Substances 0.000 claims description 63
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 38
- 239000002893 slag Substances 0.000 claims description 26
- 229910052742 iron Inorganic materials 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- 239000002250 absorbent Substances 0.000 claims description 15
- 230000002745 absorbent Effects 0.000 claims description 15
- 229910000831 Steel Inorganic materials 0.000 claims description 14
- 239000010959 steel Substances 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
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- 239000000126 substance Substances 0.000 claims description 6
- 239000002912 waste gas Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 235000012255 calcium oxide Nutrition 0.000 claims description 5
- 235000019738 Limestone Nutrition 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
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- 238000005469 granulation Methods 0.000 claims description 4
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- 238000009388 chemical precipitation Methods 0.000 claims description 3
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- 238000000576 coating method Methods 0.000 claims description 3
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- 239000008267 milk Substances 0.000 claims description 3
- 210000004080 milk Anatomy 0.000 claims description 3
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- 238000009856 non-ferrous metallurgy Methods 0.000 claims description 3
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- 239000002817 coal dust Substances 0.000 claims description 2
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- 238000005096 rolling process Methods 0.000 claims description 2
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- 239000000463 material Substances 0.000 abstract description 13
- 238000003723 Smelting Methods 0.000 abstract description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011737 fluorine Substances 0.000 abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000006477 desulfuration reaction Methods 0.000 abstract description 2
- 230000023556 desulfurization Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 23
- 239000011651 chromium Substances 0.000 description 20
- 229910052804 chromium Inorganic materials 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 14
- 239000011701 zinc Substances 0.000 description 12
- 238000005097 cold rolling Methods 0.000 description 11
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- 238000012360 testing method Methods 0.000 description 9
- 238000011084 recovery Methods 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 7
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- 239000002920 hazardous waste Substances 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 5
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- 238000012545 processing Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 240000006909 Tilia x europaea Species 0.000 description 3
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- 239000011449 brick Substances 0.000 description 3
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- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 235000011148 calcium chloride Nutrition 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
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- 230000007423 decrease Effects 0.000 description 3
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- 238000002386 leaching Methods 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 235000012149 noodles Nutrition 0.000 description 2
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- 235000009566 rice Nutrition 0.000 description 2
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- 238000001149 thermolysis Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241001417490 Sillaginidae Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000002308 calcification Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
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- 235000013339 cereals Nutrition 0.000 description 1
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- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Treatment Of Sludge (AREA)
Abstract
The present invention provides a method for synergistically treating heavy metal sludge. The method comprises: uniformly mixing heavy metal sludge with a water content of 20-50% and a calcium-based fluorine fixing agent, drying, crushing to obtain calcium-based sludge, uniformly mixing with a base sintering raw material and dust removing ash, granulating, and distributing the material, wherein a mass ratio of the base sintering raw material to the heavy metal sludge to the calcium-based fluorine fixing agent to the dust removing ash is 50-120:0.3-20:0.1-2:0.5-5; sintering the granulated mixing material to obtain sintered ore, wherein the flue gas produced during the sintering process passes through a dust removing and desulfurization device, and the purified flue gas is externally discharged through a chimney; and conveying the sintered ore into a blast furnace, and smelting, wherein the flue gas is externally discharged after the dust removing, the smelting residue is comprehensively utilized, and the alloy hot metal enters the steelmaking converter of the stainless steel enterprise. According to the present invention, dust, gas and wastewater can be discharged into the existing facilities so as to be treated; and with the synergetic treatment of the sintering process and the blast furnace smelting, most of the metal elements can be effectively recovered so as to achieve harmlessness and resources.
Description
Technical field
The invention belongs to industrial dangerous waste process and field of comprehensive utilization, particularly relate to a kind of method utilizing the existing sinter machine of stainless steel enterprises and blast-furnace smelting flow process cooperative disposal heavy metal sewage sludge.
Background technology
In the industrial production such as smelting, intermetallic composite coating, manufacture, plating, heavy-metal acid waste water source is wide, kind is many, complicated component, 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 environmental protection difficult point and the emphasis of industrial enterprise.Especially in recent years, along with the increasingly stringent day by day improving and monitor Hazardous wastes transfer, treatment and disposal of environmental regulation, the outer committee disposal costs cumulative year after year of heavy metal sewage sludge, brings heavy economical load to enterprise.
Heavy metal sewage sludge so that stainless-steel cold-rolling waste water station produces: analyze and show, 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, is attributed to HW17 and HW21 class Hazardous wastes, and process can cause poisonous metal to the secondary pollution at soil and water source accidentally.
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, CN1030219A etc.), wet underwater welding metal (CN101235439A, CN101618892A, CN101982433A, CN101618896A etc.), size mixing and reclaim chromium Ni ferrite (CN101863516A 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.
Feature as CN1733628A is the first drying of electroplating sludge, then enters smelting furnace melting after preparing burden with flux, coke and reclaim valuable metal.The main drawback that this technique exists is mud without in-depth processed, but directly carries out drying, and energy consumption is large, and production cost is high.
The feature of CN102417987A is that electroplating sludge first uses acidleach valuable metal, and solid-liquid separation after vulcanization compound sinks copper, and then carries out solid-liquid separation and obtain cupric sulfide and heavy copper mother liquor, and last step-by-step processing reclaims the valuable metal in heavy copper mother liquor.The main drawback of this technique is that technical process is long, solid-liquid separation difficulty, and recovery rate of valuable metals is lower, adopts sulfuration method to sink the operating environment of copper poor, can produce new heavy metal wastewater thereby again in production process under acidic conditions.
The feature of CN1451495A is first by industrial residue, electroplating sludge with add by a certain percentage and regulate between pH to 1.5 ~ 9, then add solidifying agent, stablizer and water and stir evenly rear molding, and be solidified into building block, finally by laying bricks or stones module finished product is built to block curing, air-dry obtaining.This technique main drawback does not recycle valuable metal wherein, do not reach the dual purpose of resource utilization and harmless treatment.
The existing document patent report of comprehensive analysis, find up to now, for having a large capacity and a wide range, the heavy metal sewage sludge that coexists of hazardness and resource, there is no the utilization ways that properly safety is economical and practical again both at home and abroad, more large utilization ways is still bakes 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 HF, SiF
4, the effusion of the gaseous state thing form such as 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.
On the other hand, 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 heavy metal sewage sludge, it itself is again a kind of renewable resources of cheapness.In view of the shortage of China metals resources, how while control secondary pollution, the heavy metals such as the chromium in effective recycling heavy metal sewage sludge, nickel, have caused the extensive concern of people.
Smelt in the production layout of long flow process at stainless steel enterprises, sintering process at reduction molten iron cost, High-quality Sinters be provided, in steel mill waste resource of dissolving, enterprise energy-conserving and environment-protective level etc., play more and more important effect." sintering+blast furnace " combination has become the mainstream configuration of molten iron of high quality and at a reasonable price.
If the existing sinter machine of stainless steel enterprises, blast furnace and auxiliary facility thereof can be utilized, develop a kind of method of disposal of heavy metal sewage sludge, make it to have concurrently and pollute advantages such as thoroughly eliminating, valuable material reclaims, processing cost is cheap, the closed cycle realizing iron and steel enterprise's heavy metal sewage sludge is disposed, and iron and steel enterprise works in coordination with other industry heavy metal sewage sludge of dissolving, expands its social environment-friendly function, all significant.
Summary of the invention
Therefore, little, poor for applicability for existing art breading amount, 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, the technical problem to be solved in the present invention is to provide a kind of method polluting thorough elimination, valuable material reclaims, processing cost is cheap disposal heavy metal sewage sludge.
Technical scheme of the present invention is, a kind of method of cooperative disposal heavy metal sewage sludge, comprises drying and the pulverizing of heavy metal sewage sludge,
(1) by water ratio be the heavy metal sewage sludge of 20 ~ 50% and calcium-based absorbents mixes, dry, pulverize, obtain calcium base mud, calcium base mud and basic raw materials for sintering and dedusting ash mixed, granulation, cloth; The mass ratio of described basic raw materials for sintering, heavy metal sewage sludge, calcium-based absorbents, dedusting ash is: 50-120:0.3 ~ 20:0.1 ~ 2:0.5 ~ 5;
(2) batch mixing after granulation is sintered, obtain agglomerate; The flue gas that sintering process produces, after dedusting, desulfurizer, neat stress is arranged outward through chimney;
(3) agglomerate is sent into blast furnace, smelt, outer row after flue gas ash removal, metallurgical slag fully utilizes, and alloy hot metal enters the steel-making converter of stainless steel enterprises.
Described cloth process, the moisture content of compound, granularity, degree of mixedness comply with the requirement of normal sintering batch mixing.
Described sintering process, be the sintering operation of routine, follow-up have dedusting and desulfurizer, and sintered discharge gas is after dedusting and desulfurization, and dedusting ash returns as sintered material, and neat stress is by smoke stack emission.
Described blast furnace ironmaking process, be the stainless steel blast furnace ironmaking process of routine, follow-up have cleaning apparatus; Dedusting ash returns as sintered material, and metallurgical slag fully utilizes, and alloy hot metal is transported to steel-making converter, carries out follow-up refinement treatment.
According to the method for cooperative disposal heavy metal sewage sludge of the present invention, preferably, 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, 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 20 ~ 50% to water ratio.
According to heavy metal sewage sludge source and different in kind, when its natural mummification to water ratio is 20 ~ 50%, 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 the natural mummification cycle is long first, occupation of land is large; Second, when water ratio is too low, when pulverizing broken sieve, dust secondary pollution can be produced.
Preferably, described calcium-based absorbents is a kind of in limestone powder, ground dolomite, unslaked lime.In sewage sludge sintering high-temperature treatment process, have the effect of flux concurrently, guarantee that mud liquid phase melting process carries out smoothly, and control the volatilization of fluoro-gas.In addition, in mud mix, fluorine fixing material also can play the effect absorbing cellular moisture, reduce mud agglomerate water ratio.The concrete adding proportion of fluorine fixing material is determined according to moisture percentage in sewage sludge and composition.
Preferably, after described in step (1), heavy metal sewage sludge and calcium-based absorbents are pulverized, the size range of calcium base mud is more than 0.01 ~ 10mm (99wt%), that is mud of more than 99%, and particle size range is at 0.01 ~ 10mm.Now moisture percentage in sewage sludge is 5 ~ 20%.
According to the method for cooperative disposal heavy metal sewage sludge of the present invention, preferably, described basic raw materials for sintering at least comprise fine ore, solid fuel, containing calcium flux, return mine, steel scale of steel rolling, bof sludge one or more; Described dedusting ash is flue gas ash removal ash.
Further, in described dedusting ash Zn content lower than 1.0%.Further, the dedusting ash that can collect from sintered discharge gas, blast furnace or converter waste gas for cleaning apparatus of this dedusting ash.Also can be environmental dust removal ash.
One or more or described fuel is selected from coke powder, coal dust, in carbon dust; The described calcium flux that contains is selected from ground dolomite, limestone powder, unslaked lime.
According to the method for cooperative disposal heavy metal sewage sludge of the present invention, preferably, the mass ratio of described basic raw materials for sintering, heavy metal sewage sludge, calcium-based absorbents, dedusting ash is: 100:0.3 ~ 10:0.1 ~ 2:0.5 ~ 5.
Heavy metal sewage sludge and calcium-based absorbents are in blending process, water ratio reduces further, sludge character (plasticity-, cohesiveness etc.) improves further, the calcium base mud obtained again with mixing, the cloth process of basic raw materials for sintering, dedusting ash, mixing and the distribution device of existing sinter machine can be made full use of; In sintering zone, heavy metal sewage sludge is heated to more than 1600 DEG C gradually, and keeps 30 ~ 60min, and in the process, metal in sludge element (representing with the Me of divalence) recurs oxyhydroxide thermolysis (Me (OH)
2=MeO+H
2o), Reduction of Oxide (MeO+CO=Me+CO
22MeO+C=2Me+CO
2) and slag making reaction (MeO+SiO
2=MeOSiO
22MeO+SiO
2=2MeOSiO
2meO+Me'O+SiO
2=MeOMe'OSiO
2).During this period, the metals such as most chromium, nickel, iron form agglomerate after high temperature action, and the sintered discharge gas produced is (containing dust, SO
2, NO
x, Dioxins, HF, HCl, SiF
4deng) drain into follow-up dedusting and desulfurizer through main exhauster, utilize existing smoke eliminator, purification is carried out to sintered discharge gas and disposes.
After sintering preliminary treatment, the agglomerate containing heavy metal sewage sludge enters blast furnace, is further processed, and under blast furnace strong reducing property condition, in agglomerate, the inorganics such as calcium, silicon, phosphorus, sulphur of more than 90% enters slag phase, ZnO, PbO, Na
2o, K
2the volatile gaseses such as low melting point such as O and dust enter in high-temperature gas, and after dedusting, low zinc dedusting ash is returned and done sintered material recycle.
For heavy metal element chromium representational in mud, set forth the rule of chromium in sintering, blast furnace ironmaking process in mud further: in sintering process, chromium hydroxide, after thermolysis, redoxomorphism, enters agglomerate; Under the strong reductive condition of blast-furnace smelting, about have the chromium of 90% to enter molten iron, less than 10% in agglomerate and enter slag, 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 the addition of heavy metal sewage sludge in sintered material is less than 10%, can not impact slag.
Because the present invention relies on " sintering+blast furnace " technique and the auxiliary facility of existing stainless steel enterprises maturation, in whole process, dust, gas and discharge of wastewater can include existing utility disposal process in; For harmful element in heavy metal sewage sludge, the cooperative disposal of sintering process and blast-furnace smelting, can make most metallic element obtain efficient recovery, thus realizes its innoxious and resource utilization; And the metallic elements such as Cr, Ni of minute quantity enter in slag, basic impact can not be produced on slag.Therefore, from the angle of dissolve process and safe disposal heavy metal sewage sludge, this is one, and removing toxic substances is the most thorough, cost is most economical, the simplest approach of technique.
(1) technical process of stainless steel associated enterprises is long, existing sinter machine and blast furnace and auxiliary facility configuration is complete, environmental protection facility is complete, sensible heat aboundresources, there is high temperature reducing conditions, can cooperative disposal heavy metal sewage sludge, realizing that hazard component is innoxious, valuable material resource utilization, is that iron and steel enterprise's heavy metal sewage sludge closed cycle is disposed and the Beneficial of social large Hazardous wastes of dissolving.
(2) this technique can utilize stainless steel enterprises existing installation and flow process, without the need to building special treatment plant and smelting device, simple to operate, 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 grain slag performance and later use, be Hazardous wastes resource utilization and innoxious effective ways.
(3) heavy metal sewage sludge and calcium-based absorbents mix, dry, pulverizes after the calcification mud that obtains, not only reduce sludge drying cost, also effectively can improve vertical sintering speed, yield rate and utilization coefficient during agglomerate sintering, the flux add-on in raw materials for sintering can also be reduced simultaneously, reduce raw materials cost, and in sintering process, reduce the volatile quantity of vapor-phase fluoride, achieve many things at one stroke.
(4) under " sintering+blast furnace " hot 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.
(5) 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 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.
Accompanying drawing explanation
Fig. 1 is technical process of the present invention.
Embodiment
Embodiment 1
Heavy metal sewage sludge comes from certain stainless steel enterprises cold rolling wastewater treatment 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 (3.0%), Ni (0.7%), Zn (0.02%), Pb (0.03%), Fe (22.4%), Si (3.1%), K (0.03%), Na (0.01%), total carbon (2.0%), scaling loss (15%), CaSO4 (22%), CaF2 (18%), CaCl2 (2%), heavy metal sewage sludge particle is thinner, complicated component, Leaching is high, be attributed to Hazardous wastes (National Hazard refuse register HW17 and HW21), according to environmental requirement, outer committee is needed to have the enterprise of qualification properly to dispose.
As shown in Figure 1, when the mummification of 1000 tons of cold rolling mud natures is to water ratio 50%, mix with 100 tons of unslaked limes (calcium-based absorbents), dry, pulverize, obtaining water ratio is 20%, size range is the calcium base mud of 0.01 ~ 5mm, in the commerical test of month by a definite date, calcium base mud and 10000 tons of basic raw materials for sintering are (by 80 parts of fine ores, 5 parts of coke powders, 8 parts of ground dolomites and 7 parts of compositions of returning mine, wherein fine ore adds this powder by 13 parts of OK a karaoke clubs respectively, 22 parts of CVRD powder, 3.5 parts of PB powder, 8.5 parts of oblique three ore deposits, 3 parts of assorted ore deposits, 14 parts of Mike's powder, spread out ore deposit, river for 5 parts, 31 parts of Yang Di powder compositions), 500 tons of dedusting ash (are made up of by a certain percentage the low zinc dedusting ash from sintered discharge gas cleaning apparatus and blast furnace waste gas cleaning apparatus, Zn content is lower than 1.0%) mixing after, carry out cloth and stoking, agglomerate, after fragmentation, screening, enters blast furnace as iron-smelting raw material and smelts, the waste gas sintering and produce in iron manufacturing process, respectively after dust-removal and desulfurizing and dedusting, neat stress is arranged outward, and dedusting ash returns the raw material making sintered material, agglomerate is through blast furnace high temperature reduction, and the alloy hot metal of generation enters the steel-making converter of stainless steel enterprises, refines further, stainless steel slag fully utilizes.
In sintering commerical test, after adding calcium base mud, in basic raw materials for sintering, lime adding amount decreases 1.2%, sintering finished rate increases 3.0%, and sintering utilization coefficient increases 10%, and solid burnup reduces 0.6kg/T, sintering performance significantly improves, and sintering cost significantly reduces.
Carry out in process in commerical test, to flue gas after sintering device handpiece flue gas, dust-removal and desulfurizing, BF Gas Washing water, blast furnace slag quenching water, carry out tracking monitor, to find in flue gas that the compositions such as SO2, NOX, fluorochemical, HCl, sulfuric acid mist are all in normal range, lower than " steel sintering, pelletizing industrial air pollution thing emission standard " (GB28662-2012) emission limit set, discharge of wastewater index meets " Iron And Steel Industry pollution discharge standard " (GB13456-2012).
Detect stainless steel slag composition, 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.
Contrast blank group, based on heavy metal sewage sludge treatment capacity and composition (with Fe, Cr, Ni) and stainless steel slag generation and composition, the rate of recovery of Theoretical Calculation three kinds of major metals is respectively 92%, 95% and 93%.
Embodiment 2
When the mummification of 1000 tons of stainless-steel cold-rolling mud natures is to water ratio 45%, mix with 200 tons of ground dolomites (calcium-based absorbents), dry, pulverize, obtaining water ratio is 15%, size range is the calcium base mud of 1 ~ 5mm, in the commerical test of month by a definite date, calcium base mud and 15000 tons of basic raw materials for sintering are (by 85 parts of fine ores, 5 parts of coal dusts, 5 parts of ground dolomites and 5 parts of compositions of returning mine, wherein fine ore adds this powder by 15 parts of OK a karaoke clubs respectively, 20 parts of CVRD powder, 5 parts of PB powder, 10 parts of oblique three ore deposits, 3 parts of assorted ore deposits, 17 parts of Mike's powder, spread out fried rice noodles for 9 parts, 31 parts of Yang Di powder compositions), 400 tons of dedusting ash are (by from sintered discharge gas cleaning apparatus, the low zinc dedusting ash of blast furnace waste gas cleaning apparatus and converter dust-removing device forms by a certain percentage, Zn content is lower than 1.0%) mixing after, carry out cloth and stoking, other processes are with embodiment 1.
In sintering commerical test, after adding calcium base mud, in basic raw materials for sintering, lime adding amount decreases 1.5%, sintering finished rate increases 2.5%, and sintering utilization coefficient increases 8%, and solid burnup reduces 0.9kg/T, sintering performance significantly improves, and sintering cost significantly reduces.
In commerical test process, waste water, exhaust gas emission all meet GB, slag quality meets requirements of comprehensive utilization, contrast blank group, based on heavy metal sewage sludge treatment capacity and composition (with Fe, Cr, Ni) and slag generation and composition, the rate of recovery of Theoretical Calculation three kinds of major metals is respectively 90%, 92% and 95%.
Other are with embodiment 1.
Embodiment 3
When the mummification of 1000 tons of stainless-steel cold-rolling mud natures is to water ratio 35%, mix with 250 tons of ground dolomites (calcium-based absorbents), dry, pulverize, obtaining water ratio is 18%, size range is the calcium base mud of 0.5 ~ 5mm, in the commerical test of month by a definite date, calcium base mud and 18000 tons of basic raw materials for sintering are (by 82 parts of fine ores, 8 parts of coal dusts, 7 parts of ground dolomites and 3 parts of compositions of returning mine, wherein fine ore adds this powder by 10 parts of OK a karaoke clubs respectively, 25 parts of CVRD powder, 15 parts of PB powder, 5 parts of oblique three ore deposits, 5 parts of assorted ore deposits, 10 parts of Mike's powder, spread out fried rice noodles for 10 parts, 20 parts of Yang Di powder compositions), 350 tons of dedusting ash are (by from sintered discharge gas cleaning apparatus, the low zinc dedusting ash of blast furnace waste gas cleaning apparatus and converter dust-removing device forms by a certain percentage, Zn content is lower than 1.0%) mixing after, carry out cloth and stoking, other processes are with embodiment 1.
In sintering commerical test, after adding calcium base mud, in basic raw materials for sintering, lime adding amount decreases 2.5%, sintering finished rate increases 1.2%, and sintering utilization coefficient increases 7%, and solid burnup reduces 0.7kg/T, sintering performance significantly improves, and sintering cost significantly reduces.
In commerical test process, waste water, exhaust gas emission all meet GB, slag quality meets requirements of comprehensive utilization, contrast blank group, based on heavy metal sewage sludge treatment capacity and composition (with Fe, Cr, Ni) and slag generation and composition, the rate of recovery of Theoretical Calculation three kinds of major metals is respectively 91%, 93% and 96%.
From above embodiment, utilize the existing sinter machine of stainless steel enterprises and blast-furnace smelting flow process cooperative disposal heavy metal sewage sludge, can economical, realize dissolving and disposing of mud effectively, safely, to environment, alloy hot metal and stainless steel slag without negative impact, therefore, this technique is the Beneficial of iron and steel enterprise's heavy metal sewage sludge closed cycle disposal and social large Hazardous wastes of dissolving.
Claims (9)
1. a method for cooperative disposal heavy metal sewage sludge, comprises drying and the pulverizing of heavy metal sewage sludge, it is characterized in that:
(1) by water ratio be the heavy metal sewage sludge of 20 ~ 50% and calcium-based absorbents mixes, dry, pulverize, obtain calcium base mud, calcium base mud and basic raw materials for sintering and dedusting ash mixed, granulation, cloth; The mass ratio of described basic raw materials for sintering, heavy metal sewage sludge, calcium-based absorbents, dedusting ash is: 50-120:0.3 ~ 20:0.1 ~ 2:0.5 ~ 5;
(2) batch mixing after granulation is sintered, obtain agglomerate; The flue gas that sintering process produces, after dedusting, desulfurizer, neat stress is arranged outward through chimney;
(3) agglomerate is sent into blast furnace, smelt, outer row after flue gas ash removal, metallurgical slag fully utilizes, and alloy hot metal enters the steel-making converter of stainless steel enterprises.
2. the method for cooperative disposal heavy metal sewage sludge according to claim 1, it is characterized in that, 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, plating, nonferrous metallurgy, intermetallic composite coating, machinofacture.
3. the method for cooperative disposal heavy metal sewage sludge according to claim 1, is characterized in that, described calcium-based absorbents is a kind of in limestone powder, ground dolomite, unslaked lime.
4. the method for cooperative disposal heavy metal sewage sludge according to claim 1, is characterized in that, after described in step (1), heavy metal sewage sludge and calcium-based absorbents are pulverized, the size range of more than 99wt% calcium base mud is 0.01 ~ 10mm.
5. the method for cooperative disposal heavy metal sewage sludge according to claim 1, is characterized in that, described basic raw materials for sintering at least comprise fine ore, solid fuel, containing calcium flux, return mine, steel scale of steel rolling, bof sludge one or more; Described dedusting ash is flue gas ash removal ash.
6. the method for cooperative disposal heavy metal sewage sludge according to claim 5, is characterized in that, in described dedusting ash, Zn content is lower than 1.0%.
7. the method for the cooperative disposal heavy metal sewage sludge according to claim 5 or 6, is characterized in that, described dedusting ash is the dedusting ash that cleaning apparatus is collected from sintered discharge gas, blast furnace or converter waste gas.
8. the method for cooperative disposal heavy metal sewage sludge according to claim 5, is characterized in that, described fuel is selected from coke powder, coal dust, one or more in carbon dust; The described calcium flux that contains is selected from ground dolomite, limestone powder, unslaked lime.
9. the method for cooperative disposal heavy metal sewage sludge according to claim 1, is characterized in that, the mass ratio of described basic raw materials for sintering, heavy metal sewage sludge, calcium-based absorbents, dedusting ash is: 100:0.3 ~ 10:0.1 ~ 2:0.5 ~ 5.
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| CN105907950A (en) * | 2016-04-29 | 2016-08-31 | 浙江大学 | Treatment method for metallurgy sintering of abandoned SCR flue gas denitrification catalyst |
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