1. Steel slag Application in ChinaCIMM Group Co.,Ltd. International Seminar on Application of Steel Slag, November 21, 22 and 23 of 2010, Belo Horizonte MG Brazil

2. Table of contents 1. About CIMM Group 2. China Policy of solid waste treatment and comprehensive utilization 3. General- Agriculture application status in China 4. Introductiona way of application of steel slag - model of circulating economy 5. The treatment process and application of steel slag under two different slag treatment method 3. ABOUT CIMM GROUP 4. Group IntroductionCIMM Group is an integrated international conglomarate of Technology,manufacturing and trade with the process technology and projectengineering as basis.The group has been put speical emphasis on development , applicationand promotion of the environment friendly technology and applications inthe field of iron and steel industry, Cement industy and power industry interms slag treatment and application,desulfurization, dust collection,wasteheatrecovery, water treatment with a goal to contribute to a clean world.CIMM has working together with the most advanced and matured processtechnology provider in China and we introduce our achievements toworldwide mills and bring the advanced technology from overseas tofurther improve the industries in China.We hope to enjoy the progress and the achievements of Chinesedevelopment with the friends all over the world. 5. MISSIONHelp the world share the first-class technology,equipment and service from ChinaHelp China share the first-class technology,equipment and service from the world 6. VisionConstruction of Chinas new private leader in the fieldof International EPC project, to contribute to aprosperous future of human being. 7. 2. China Policy of solid waste treatment and comprehensive utilization 8. China Industry waste disposal policy On Feb. 28, 2003, The state council has issued the no.369 decree, Since July 1, 2003, the waste disposal cost will be charged. Levying criteria Slag RMB 25/t $3.8/tFly ash RMB30/t, $4.5/t Furnace slagRMB25/t Coal gangue RMB5/t, $0.8/t $3.8/t Other slagIncluding semi-solid TailingRMB15/t $2.3/t liquid wasteRMB25/t $3.8/t 9. China s Industry waste comprehensive utilizationrate2006 State National Development and ReformCommission has issued the 2010 to utilize the industry solid waste by 60% 2010 to utilize the melting slag by 86% 10. Preferential policy for comprehensivewaste utilizationState development and reform commission, Financeministration, General tax bueau jointly issued thedocuments(2004) 73 :Company who use the steel slag for production of steel andconstruction, their tax will be decreased or exempted.Steel slag powdering technology is in the name of taxreduction process and will be supported by the dedicatedfund for development 11. Circular economy law Aug. 29, 2008, Circular Economy Promotion Law of the Peoples Republic of China was issued, and was in force on Jan. 1, 2009. The law encourges to put the waste directly into production as raw or futher processed raw material, and encourages to use the no hazardous solid waste to manufacturer constrution material. 12. 3. General- Agricultureapplication status in China 13. General- Agriculture application status in ChinaAgriculture application status China is not applying in a large scale the slag fertilizer.From soil conditioning concern, the requirement is less, the acid soil is mainly in North China, but soil condition is improving due to the rain will bring the acid to the soil and improving the condition. Although the heavy chemical in the slag is containd in the form of solid solution, It can be considered as non poisonious. But systmic study on the environment impact has not been carried out, and as there are no much study has been done for its pollution effect for the underground water, and toxicological study for the biology. 14. General- Agriculture application status in ChinaField Study on Silica & Phosphorus slag fertilizerThe major chemical that is useful for plant growth is Si, P,Ca andMg, besides there are Zn, Mn, Fe, Cu etc. will be helpful to improvethe fertilile conditon of the soil.Si, is the major nutrition content for rice growth, Field test has beenconducted by the scientist : to apply the steel slag with SiO2 >15%grinded to size less 60mesh( 4%,when use the high content P hot iron to produce steel, if didnt putthe fluospar for slagging, the slag generated can be used toproduce Phosphorus slag fertizer. As the F can reduce the restraint-dissolveing ability of P2O5, so the F content requires to be less than0.5%., the higher the CaO/SiO2 value, the higher restraint abilitycan be achieved.The temperary standard for Phosphorus slag fertilizer in Maanshansteel requires the P2O5 >10%. The Phosphorus slag fertilizer isgood for acid soil , it can also be applied in the alkaline soil short ofP, it can be used in the paddy field, it can have effect in glebe field. 15. 4 Introduction aboutcirculating economy- a wayof application of steel slag. 16. Circular Economy PrincipalTurn the waste into resources is the focus of thecircular economy under development in China now.The core of cirular economy is to improve theefficiency of natural resources utilization, reduce theresources consumption and environment cost, tomake the social economy system in harmony withthe nature ecosystem and to maintain thesustainable development of the society.in China ,this industry will undegone huge developmentdriven both at the Policy stimulation and enonomystimulation. 17. An circulating enomonic model for steelslag application 18. Circular Economic Technology The principal of use waste to treat waste is relized in this process The steel slag has been used as the absolvent of the SO2 from the sinter plant, the SO2 emission is reduced, the steel slag is used, while the outcome of the desulpurazation can be used as fertilizer and conditioning material for the saline and alkaline soil 19. SO2 absorbent can be adjustable to localconditions:SlagGrain slagAnd many other industrial solid waste such as flying ash, redearth from alumina plant can be used as solvent.Outcome of desulfurization:Sulphur-silicon fertilizer (base fertilizer)Land conditionaing materialModification of saline and alkaline 20. Recycling Economic Technology SO2 air pollution control Comprehensive use of solid industrial wastes Soil Sandy and wasteland modificationimprovement Fertilizer Deal with 3 hardest world wide issues.Desulferization Product Recycling useSolid DesulfurizationIndustrial WastesRecycling Economic Technology Flow Process 21. Current Situation ofDesulfurization At present, 90% desulfurization system adopt the limestone/gypsum process FGD(Flue Gas Desulfurization) Advantages:The natural limestone is rich, wide distributionThe purchasing cost of absorbent is lessThe technology is comparatively matureThe system investment is small disadvantages:Fire of limestone consumes a mass of resourcesDischarges a large numbers of CO2synchronouslyThe outcome of desulfurization can not betreatedMost of desulfurized gypsum are piled up 22. Desulfurization process introduction 23. The process flow 24. Feature of sinter waste gas Big volume of fumeabout 40006000m3 will be generated for 1t sinter High fume temperature, the fume temperature is around 150C under different operation conditions Quantity of dust in the fume is high High moisture, about 10& of water by volume. With corrosive gas, during BF gas burning and sinter process, SOxNOx will be generated, it will turn in to acid when meet water, it will erode the steel structure. low SO2 contentfor different raw matriaql and fuel, it will be aroud 10003000 mg/m3 25. The feature of slagThe steel slag is composed of different ore bodies, its main chemical composition are Ca, Fe, Si, Mg oxide and traces of Al, Mn, P oxide. the main ore phase are tricalcium silicate (3CaOSiO2)dicalcium silicate 2CaOSiO2monticellite (CaOMgOSiO2 manganolite (MnO,MgO,CaO) gehlenite SiO2 2CaOXAl2O3(1-X)Fe2O3) and Si, Mg, Fe, Mn, P oxide are in the form of solid solvent, and free CaO and metal Fe are also exist. 26. Converter slag compostion in 4 different steelmills in China( % Steel mill CaO MgOSiO2Al2O3 FeO Fe2O3MnOP2O5 f-CaO A40-49 4-713-171-311-22 4-105-61-1.4 2-9.5 B45-50 4-510-111-410-18 7-10 0.5-2.53-511-5 C45-51 5-12 8-100.6-1 5-205-10 1.5-2.52-34-10 D42-54 3-812-202-64-182.5-131-20.2-1.3 2-10 27. Steel slag composition in EAF%Steel Slag typeCaO MgO SiO2 FeOAl2O3 MnO P A Oxidize slag29-33 12-14 15-17 19-223-44-5 0.2-0.4 BReduction slag 44-55 8-1311-20 0.5-1.5 10-18 28. The process and Principal of steel slagdesulpuration By the previous analysis of the composition, the steel slag composition will be different in different process and different stage of smelting, but the differents mainly differs in quantity, the chemical content is almost the same, and the ore composed of the steel slag are also similar The reaction of steel slag as absolvent with theSO2 can be realized in several phase 29. SO2 dissolving and oxidizing in waterwhen SO2 dissolving in the water, it will firsly turn into H2SO3, in theform of ion in waterSO2H2OH2SO3(HSO3(H) 1(HSO3)(SO32(H) 2as there are superfluous o2 in the fume, so part of the (SO3)2will beoxidized to (SO4)2(SO3)2+(1/2O2SO42(3) 30. ReactionThe free CaO, Mgo and MnO etc in the steel slag will be reacted withthe SO2 in the solventCaO+SO32CaSO3(4)MgO+SO32MgSO3- (5) 31. The reaction with the Ores in the steel slagThe ore bodys of the steel slag will react with the SO2 solvent3CaOSiO2+3H2SO33CaSO3+SiO2+3H2O 6)2CaOSiO2+2H2SO32CaSO3+SiO2+2H2O 7)CaOMgOSiO2+2H2SO3CaSO3+MgSO3+SiO2+2H2O (8)(MnO,MgO,CaO)SiO2+H2SO3(Mn,Mg,Ca)SO3+H2O(9)(2CaOXAl2O3(1-X)Fe2O3)+2H2SO32CaSO3+ XAl2O3+(1-X)Fe2O3)+2H2O (10) 32. The reaction with the Ores in the steel slag3CaOSiO2+3H2SO43CaSO4+SiO2+3H2O(11)2CaOSiO2+2H2SO42CaSO4+SiO2+2H2O (12)CaOMgOSiO2+2H2SO4CaSO4+MgSO4+SiO2+2H2O (13)(MnO,MgO,CaO)SiO2+H2SO4(Mn,Mg,Ca)SO4+H2O (14)(2CaOXAl2O3(1-X)Fe2O3)+2H2SO42CaSO4+XAl2O3 +(1-X)Fe2O3)+2H2O (15)there are superfluous O2 in the fume, the SO3 will be futher oxidized in to SO4, the reaction is as following: MeSO3+1/2O2MeSO4 (16) 33. Tangshan Delong Steel Co., Ltd.230m sinter Flue Gas desulfurization ProjectFume temperature180Moisture content6%SO2content1000-3000mg/Nm Fume volume1440000/mh Desulphrizaiton rate95-99%Annual SO2 emission reduction: around 6600TAnnual CO2 emission reduction: around 4600TAnnual Slag consumption: around 20000TAnnual Outcome of desulfurization slag: 23000TAnnual lime stone saving: about 16000TAnnual saving of coal: around 1200T st.Annual saline and alkaline soil treatment: 1, 67000m2Operation cost: $0.6-0.7 /T sinter outputThe traditional operation cost is at $1.8-4/T 34. Tangshan Delong saline land improved by thedesulfurization slag 35. Saline, Alkaline and Sandy land modification project:Delong Steel Co., Ldt, Tangshan 36. Sandy wasteland modificationThe original appearance of sandy After- After-modification of sandy wasteland ofJing-wasteland of Shougang Jing-TangShougang Jing-Tang Company in CaofeidianJing-Company in Caofeidian. 37. Fertilizer and soil improvementDr. Mazharh. Naqyi ,the world-known saline and Project site of saline and alkaline land alkaline expert is investigating the result of modification of the south bank ofsaline and alkaline land modification in Cixi Shitangjiang in Cixi. 38. Jinhua Soil Improving ProjectVarious kinds of vegetables growing on the sandywasteland which have been modified successfully:Projects of Jinhua Soil Modification:The output of rape, letuce, watermelon and cotton etc. were increased by 15-20%. 39. Delong steel 230msinter desulphurzationDS RecyclingLimestone MethodsMethod Econimic Technology (MgO 85%) (CaO 80%) CaO 5%5% Unit price of agentUse the steel slag 850 yuan/ton 350 yuan/ton Consumption per 1 3 ton 0.735 ton1.14 tontSO2desulpurization Quantity of desulpurization unit3.43 tondry basebase 1.9 or 3.84 ton 2.43 ton put output Absorvent total consumption About 20,000 ton About 5,000 ton About 8,000 tonTotal desulphurization12,500-About 12,500-25,000output About 23,000 tontonAbout 16,000 ton MgSO4The place ofsaline and alkaline treatmentDischarge to GypsumFinal recidues go Cement additives waste waterdisposaltreatment Energy saving1,200 ton/year00Standard CoalCoalTotal cost for reaction agent 04.25 million2.63 million 40. Benefits comparison of different soil modificationmethodsTraditional SoilModification MethodsSecondary salification will be 2-occurred after 2-3 years.Soil changing, 1mu(667m2) salineand alkaline land modificaiton = 1mu(667m2) fertile land destroying. By desulfurization slag soilimprovement method Only need 30% investment cost of the traditional one. Once modification without secondary alkalinization No need of changing soil 41. Field test has been carried out since 2002 in thesaline and alkaline land.every year the sample is collected and the resultshowsPH value has been steady decreased and nosecondary alcalination has take placesoil fertile condition is imporved and ion has beenreduced.soil partical size is increased 42. Safty concern in the soil condition materialthe desulfurization slag may contain heavy metal such as: CuZnPbCdHgCrAsThere are risk of pollution of the soil by the heavymetal, when applying the slag into the soil, we mustmake sure there will be no heavy metal pollution tothe soil, other wise the conditioning will be no sense. 43. 1)heavy metal limitUp to now, there are no national standard for the heavy metal limit regulation for the slag soil conditioner, but with reference to two national standard for heavy metal content in GB8173-87pollution control standard for agriculture application purpose fly ashandGB 4284-84pollutant control standard for agriculture mudwith reference fo this two national standard, we have set up the heavy metal limmit for slag soil conditioner 44. slag desulfurization conditionaer heavy metal limitmg/kgdry base item Metal limit in the soild Cd incluidng cd in the compound10 Hg including Hg in the compound15 pb including Pb in the compound 500 Cr including Cr in the compount 500 As including As in the compount75 B incluidng B in the compound50 Cu incluidng Cu in the compount 500 Zn including Zn in the compount 1000 Ni including Ni in the compound 200 Mo including Mo in the compound10 Se incluidng Se in the compound15 the quantity of the slag in compliance with above limitshould not over 30000kg within 10 years( dry base) 45. 5. Treatment process andapplication of steel slag undertwo different slag treatmentmethod 46. two advanced treament method-- Granulating -- Slag Granulation Plant-- Powdering -- Splashing in closed box 47. SGP Process Principal 48. Slag Granulation Plant Merits of SGPShort FlowDwell time: 2 minutesSmall land occupation10m10mCleanlinessCentralized exhaust of steam, good for installation of dedusting deviceQualified SlagGood separation of slag from scrapRecovery rate of iron 85% for A type slagEven granulated slageasy for post-treatment & utilizationHigh Safety Slag Granulation Plant 49. Particle Size Distribution of SGP Finished Slag70 58.7605040 wt %3020 13.714.110.5103.00>105-10 1. 25- 5 0. 3- 1. 25 0. 3Particle Size (mm) 50. PrincipleSteam Molten Slag Use of different contractionCoolingof slag and ironWaterGood Separation of Slag from IronCrushing Use of medium for primarySudden cooling & crushing, and useCoolingof separated space High Safety SolidificationAdequate granulation Good StabilityGranulated Slag 51. StackSGPSlag potSlag skimmer Slag pottilting machineDedusting device Slag pot & carriageDrivingBucket Drumelevator assembly CoolingSlag Storagewaterbin WatertreatmentsystemSewageElectric control systemGranulated iron Magnetic separator 52. CompositionMain BodyAuxiliary SystemFeeding SystemWater Treatment SystemSteam Exhausting SystemFinished Slag Transporting & Processing SystemElectric Control System 53. Job Site PhotosTilting machine Slag skimmer Tilting machine Slag skimmer 54. Processing of 1 ton slag Water0.25-0.3 tElectricityApprox. 6kWhCompressed AirUnder 800m3/h (TYPE-B) 55. SGP Slag Application 56. Production Rate & Classification of BOF SlagSlag Production Rate8-12%Classification Slag of Low Viscosity A TypeB Type Thickness: 3080mm Thickness: 80120mm Slag of High ViscosityD TypeC TypeThickness: 200450mm Thickness: 120200mm 57. In general, during the production of steel, wecan encounter all kind of slag as A, B, C, D,according the stability of different kind of steelslag, we select different different directions ofapplication( by the SGP process, it is easy tocontrol and realize): 58. Slag application according size- taken a 500000million ton slag treatment for an example categoryapplicationSize specification1 Agriculture6mm 30%3-6mm40%