还原剂反应性对含碳球团还原过程的影响
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摘要
焦炭、无烟煤、半焦是常用的固体还原剂,其中半焦粉是半焦生产过程中的筛下物,如果能用半焦粉代替焦粉、无烟煤等其他还原剂制作含碳球团,不仅节约了宝贵的焦炭资源也可带来一定的经济效益。
本文利用热分析仪与质谱仪联动技术,研究了半焦粉、焦粉、无烟煤等还原剂的反应性能及其还原铁矿粉的还原性能,并对还原剂还原铁氧化物的还原动力学进行了解析。通过竖式电炉还原含碳球团技术,探讨了含碳球团中还原剂的还原性能及其对含碳球团还原的影响。主要研究结果如下:
1.与焦粉和无烟煤等还原剂相比,半焦粉与CO2的反应能力较好;
2.还原剂与铁矿粉的还原机理分别为:半焦粉和无烟煤还原机理为单步形核机理,焦粉还原机理为二维扩散机理。
3.相同实验条件下,半焦粉还原铁氧化物所需能量最少,即还原反应最容易进行。
4.含碳球团内铁氧化物的碳热还原是通过碳气化和铁氧化物间接还原实现的,两个反应耦合完成的。还原前期,含碳球团的还原速率主要由碳气化速率控制,因为半焦粉比焦粉和无烟煤粉其具有良好的还原性能,还原反应一步完成,且还原最大速率对应的温度比焦粉和无烟煤粉的低150℃以上。
5.还原反应结束温度为1250℃左右。半焦粉可以代替焦粉、无烟煤等制作含碳球团。
Coke, anthracite, semi-coke are usually used as reductant ,Semi-coke powder is the siftage of semi-coke production process .If it can use semi coke powder instead of coke powder, anthracite and other reductant production carbon pellet, Not only saving coke resource also can bring certain economic benefits.
In this paper, I uses thermal analyzer and mass spectrometry technology, research the semi-coke powder, coke, anthracite reaction of a reducing agent performance and reduction of iron ore powder reduction performance, and the reduction of iron oxide reduction kinetics were analyzed. Through the reduction of carbon pellet vertical furnace technology, discusses the carbon pellet in reducing agent and its performance on the reduction of carbon pellet reduction effect. The main results are as follows:
1. compared with the different reducer as coke powder and anthracite, semi-coke powder and CO_2 response capacity is better;
2. Reducing agent with iron powder reduction mechanism respectively: semi-coke powder and anthracite reduction mechanism for single-step nucleation mechanism, coke powder reduction mechanism for only two diffusion.
3. The same experiment conditions, semi-coke powder reduction of iron oxide energy required minimal reduction reaction, The reduction reaction of the most easily.
4. Carbon pellet in iron oxide by carbon thermal reduction by carbon gasification and iron oxide indirect reduction achieved, two reaction coupled to finish. Reduction of carbon containing pellet prophase, the rate of reduction is mainly composed of carbon gasification rate control, semi coke powder than coke powder anthracite powder has good reduction performance, reduction reaction are completed in one step, and the reduction of maximum rate corresponding to the temperature range than coke powder anthracite powder low above 150℃
5. Reducing reaction temperature of 1250℃end. Semi-coke powder can replace coke, anthracite production of carbon pellet
本文利用热分析仪与质谱仪联动技术,研究了半焦粉、焦粉、无烟煤等还原剂的反应性能及其还原铁矿粉的还原性能,并对还原剂还原铁氧化物的还原动力学进行了解析。通过竖式电炉还原含碳球团技术,探讨了含碳球团中还原剂的还原性能及其对含碳球团还原的影响。主要研究结果如下:
1.与焦粉和无烟煤等还原剂相比,半焦粉与CO2的反应能力较好;
2.还原剂与铁矿粉的还原机理分别为:半焦粉和无烟煤还原机理为单步形核机理,焦粉还原机理为二维扩散机理。
3.相同实验条件下,半焦粉还原铁氧化物所需能量最少,即还原反应最容易进行。
4.含碳球团内铁氧化物的碳热还原是通过碳气化和铁氧化物间接还原实现的,两个反应耦合完成的。还原前期,含碳球团的还原速率主要由碳气化速率控制,因为半焦粉比焦粉和无烟煤粉其具有良好的还原性能,还原反应一步完成,且还原最大速率对应的温度比焦粉和无烟煤粉的低150℃以上。
5.还原反应结束温度为1250℃左右。半焦粉可以代替焦粉、无烟煤等制作含碳球团。
Coke, anthracite, semi-coke are usually used as reductant ,Semi-coke powder is the siftage of semi-coke production process .If it can use semi coke powder instead of coke powder, anthracite and other reductant production carbon pellet, Not only saving coke resource also can bring certain economic benefits.
In this paper, I uses thermal analyzer and mass spectrometry technology, research the semi-coke powder, coke, anthracite reaction of a reducing agent performance and reduction of iron ore powder reduction performance, and the reduction of iron oxide reduction kinetics were analyzed. Through the reduction of carbon pellet vertical furnace technology, discusses the carbon pellet in reducing agent and its performance on the reduction of carbon pellet reduction effect. The main results are as follows:
1. compared with the different reducer as coke powder and anthracite, semi-coke powder and CO_2 response capacity is better;
2. Reducing agent with iron powder reduction mechanism respectively: semi-coke powder and anthracite reduction mechanism for single-step nucleation mechanism, coke powder reduction mechanism for only two diffusion.
3. The same experiment conditions, semi-coke powder reduction of iron oxide energy required minimal reduction reaction, The reduction reaction of the most easily.
4. Carbon pellet in iron oxide by carbon thermal reduction by carbon gasification and iron oxide indirect reduction achieved, two reaction coupled to finish. Reduction of carbon containing pellet prophase, the rate of reduction is mainly composed of carbon gasification rate control, semi coke powder than coke powder anthracite powder has good reduction performance, reduction reaction are completed in one step, and the reduction of maximum rate corresponding to the temperature range than coke powder anthracite powder low above 150℃
5. Reducing reaction temperature of 1250℃end. Semi-coke powder can replace coke, anthracite production of carbon pellet
引文
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[4] Patrick.J,W.Wilkinson,H.C,1978.Analysis of metallurgical cokes.In:Karr.Jr,C.(Ed.), Analytical Methods for Coal and Coal Products [J],vol.II.Academic Press,New York:339– 370.
[5] Ragan.S. Marsh, H.1980. A critique of industrial methods of measurement of strength of metallurgical coke. [J] J.Phys.D: Appl. Phys.13:983–993.
[6] Loison. R, Foch, P.Boyer, A.1989. Coke. Quality and Production.Butterworth [J], London, p.178– 189.
[7] Alvarez.R,D?′ez,M.A.2000.Chemistry of production of metallurgical coke.In:Marsh,H. Rodr?′guez-Reinoso, F. (Eds.), Sciences of Carbon Materials, Chap. 18. Secretariado de Publicaciones [J], The University of Alicante, Spain:595– 635.
[8]高正阳,方立军,叶学民,闫维平.无烟煤与烟煤混煤燃烧性能的热重实验研究[J].华北电力大学学报,2001,(28):39-42.
[9] Gale. T K, Bartholomew .C H, Fletcher T H [J].Energy and Fuels,1996,10: 766.
[10] Skorupska .N M, Sanayal. A, Hesselman. G J, Crelling. J C,Edwards .I A S, Marsh H. In: Moulijn J A,Nater K A,Chermin H A G, eds.Proceeding of the International Conferenceon Coal Science.Maastricht,The Netherland [J]: Elsevier SciencePublishing Company Inc. September 1987:827.
[11] Bailey. J G, Tate. A, Diessel. C F K, Wall .T F. A char morphology system with applications to coal combustion [J]. Fuel,1990,69(2): 225~239.
[12] H Y. Cai, Kandiyoti R. Effect of Changing Inertinite Concentration on Pyrolysis Yields and Char Reactivities of Two South African Coals [J].Energy and Fuels,1995,9(6): 965~961.
[13] Thomas C G, Hollombe D, Shibaoka M, Young B C BrunckHorst L F, Gawronski E. In: Sponsored by Member Countriesof the International Energy Agency, eds. Proceeding of theInternational Conference on Coal Science [J]. Tokyo: September1989:257.
[14] Thomas.CG,Shibaoka.M,Gawronski .E,Gosnell.M E,Phong -anant .D,Brunckhorst .L F, Salehi. M E. In: Sponsored byMember Countries of the International Energy Agency, eds[J].Proceedings of the International Conference on Coal Science.Tokyo: September 1989:213.
[15]杜铭华,俞珠峰.3种低阶煤热解半焦CO2反应性的研究[J].煤炭科学技术,1996,24(1) :34-37.
[16]马兴亚,汪琦,姜茂发.含碳球团还原技术研究现状[J].烧结球团, 1999,24(3): 24~26.
[17]黄典冰,杨学民,杨天钧等.含碳球团还原过程动力学及模型[J].金属学学报, 1996,32(6): 629~636.
[18]汪琦.含碳球团还原反应及其技术[J].鞍钢技术,2009,(4): 1~9.
[19] S.SUN et al.Building of a mathematical model for the reduction of iron ore in ore/coal composites [J]. ISIJ International,1999,39(2): 130~138.
[20] N.S.Studies on the reduction of hematite by carbon. Srinivasan et al.Met [J]. Trans,1977, 8B(3): 175~178.
[21]杜挺,杜昆.含碳球团—铁浴熔融还原法关键技术的应用基础研究[J].金属学报, 1997,33(7):719~729.
[22] C.E.Seaton et al. Structural-changes occurring during reduction of hematite andmagnetite pellets containing coal char.Trans [J]. Iron Steel Inst. Jpn,1983,23: 497~503.
[23] M.C.Abraham et al. Kinetics of reduction of iron oxide by carbon [J].Ironmaking and Steelmaking.1979,6(l): 15.
[24] N.S.Studies on the reduction of hematite by carbon.Srinivasan et al [J].Met. Trans,1977, 8B(3): 175~178.
[25] G. V. Reddy et al. Kinetic rate equation for direct reduction of iron ore by non-coking coal[J]. Ironmaking and Steelmaking, 1991, (3): 221.
[26] S.Prakash.Nonisothermal kinetics of iron-ore reduction[J]. Ironmaking and Steelmaking, 1994,21(3): 237~243.
[27] C.E.Seaton et al.Reduction kinetics of hematite and magnetite pellets containing coal char.Trans[J].Iron Steel Inst. Jpn,1983,23:490.
[28] Q.Wang et al.mechanisms of reduction in iron ore-coal composite pellet[J].Ironmaking and Steelmaking,6(1997):457.
[29] W.M.McKewan,Reduction of iron oxide reduction.Trans[J].TMS-AIME,1960,2:2.
[30] J. Szekely et al.Gas-Solid Reduction, Academic Press[R], New York, NY:1976.
[31] S.Prakas et al. Reduction of iron ore under rising temperature and fluctuating temperature conditions[J]. Thermochimica Acta,1987,(111):143~166.
[32] E.Donskoi et al.Estimation and modeling of Parameters for Direct Reduction in Iron Ore/Coal Composites:PartⅡ.Kinetics Parameters[J]. Met.Trans. B,2003,34(2):255~266.
[33] C. E. Seaton et al.Structural-changes occurring during reduction of hematite and magnetite pellets containing coal char. Trans[J]. Iron Steel Inst.Jpn,1983, 23:p.497~503.
[34] Zsako,J.Kinetic analysis of thermogravimetric data,J.Phys[J].Chem,1968,72:p.2406~2411
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