助熔剂对煤灰渣流动性及煤气化反应性的影响
|
摘要
将两种助熔剂ADC、ADM以不同的比例加入到淮北煤Ⅰ和淮北煤Ⅱ样中,考察助熔剂对煤灰熔融温度和灰渣流动性的影响。借助XRD研究了煤灰中矿物形态的变化对煤灰熔融温度和灰渣流动性的影响。最后,采用石英弹簧热天平在还原性气氛下分析了助熔剂量对煤气化反应性的影响,主要得出结论如下:
1.助熔剂可以有效降低两种煤灰熔融温度,ADC、ADM的添加量为6%时均可把两种煤灰流动温度降到1380℃, ADM助熔剂对淮北煤Ⅰ、淮北煤Ⅱ的助熔及改善流动性效果优于ADC。
2.通过建立一种评价灰渣流动性的新方法和装置,该方法能通过温度区间直接描述灰渣流动性。结果表明,ADC、ADM助熔剂可以有效改善淮北煤Ⅰ、淮北煤Ⅱ样的灰渣流动性。
3.在高温的还原气氛下,利用XRD方法分析了两种煤样随着助熔剂量增加其矿物组成的变化,随着助熔剂的添加形成了钙长石和钠长石,随着温度的升高钙长石和钠长石的含量增加。煤灰在熔融过程形成低温共熔物,从而使煤灰的熔融温度下降。
4.在煤气化条件下,利用石英弹簧热天平研究了助熔剂量对两种煤样气化反应性的影响,结果表明,在还原气氛下,ADM的催化活性较好于ADC,通过添加ADM,ADC助熔剂提高了淮北煤Ⅰ、淮北煤Ⅱ的反应活性。
5.为了进一步研究气化条件下煤的气化反应性,根据物料和能量衡算,设计了一套煤气化实验装置。
Two fluxes, ADC and ADM were added to the two diferent types of coal samples, Huaibei coalⅠand Huaibei coalⅡwith diferent percentage respectively. Effect of flux on the ash fusion temperatrue(AFT) and fluidity of slag were studied. The impact of mineral composition on the AFT and fluidity of slag is studied by XRD. The reactivity of coals with the addition of two fluxes were also analyzed in reducing atmosphere by quartz balance. The results were shown as follows:
1. The AFT of two coal samples could be decreased remarkably to 1380℃by adding 6% of ADC or ADM . The impact of ADM on the AFT and fluidity of slag of Huaibei coalⅠand Huaibei coalⅡis better than that of ADC.
2. A new method and device for testing slag fluidity is set up, which can directly describe the slag fluidity through the whole temperature range. The results show that the the fluidity of slag of the two coal samples could be improved with the addtion of fluxes ADC and ADM.
3. In reducing conditions, the mineral transformation of two coal ash samples with the additon of ADC and ADM were studied by XRD at high temperature. The anorthite and albite were formed by adding ADC and ADM and the contents of the anorthite and albite increased with the temperature increase, which reacts with other minerals to form low melting eutectic.
4.The fluxes and their impact on reactivity of the two coal samples in coal gasification condition was studied. The reactivity of coal samples with addition of ADC and ADM were carried out by Quartz balance. ADM showed better catalytic activity than that of ADC under the reducing conditions.The gasification reactivity of Huaibei coalⅠand Huaibei coalⅡwas improved by adding of ADM and ADC.
5. In order to further study the reactivity of coal during coal gasification, a bench l scale coal gasification devices was designed based on the calculation of materail and energy balance.
1.助熔剂可以有效降低两种煤灰熔融温度,ADC、ADM的添加量为6%时均可把两种煤灰流动温度降到1380℃, ADM助熔剂对淮北煤Ⅰ、淮北煤Ⅱ的助熔及改善流动性效果优于ADC。
2.通过建立一种评价灰渣流动性的新方法和装置,该方法能通过温度区间直接描述灰渣流动性。结果表明,ADC、ADM助熔剂可以有效改善淮北煤Ⅰ、淮北煤Ⅱ样的灰渣流动性。
3.在高温的还原气氛下,利用XRD方法分析了两种煤样随着助熔剂量增加其矿物组成的变化,随着助熔剂的添加形成了钙长石和钠长石,随着温度的升高钙长石和钠长石的含量增加。煤灰在熔融过程形成低温共熔物,从而使煤灰的熔融温度下降。
4.在煤气化条件下,利用石英弹簧热天平研究了助熔剂量对两种煤样气化反应性的影响,结果表明,在还原气氛下,ADM的催化活性较好于ADC,通过添加ADM,ADC助熔剂提高了淮北煤Ⅰ、淮北煤Ⅱ的反应活性。
5.为了进一步研究气化条件下煤的气化反应性,根据物料和能量衡算,设计了一套煤气化实验装置。
Two fluxes, ADC and ADM were added to the two diferent types of coal samples, Huaibei coalⅠand Huaibei coalⅡwith diferent percentage respectively. Effect of flux on the ash fusion temperatrue(AFT) and fluidity of slag were studied. The impact of mineral composition on the AFT and fluidity of slag is studied by XRD. The reactivity of coals with the addition of two fluxes were also analyzed in reducing atmosphere by quartz balance. The results were shown as follows:
1. The AFT of two coal samples could be decreased remarkably to 1380℃by adding 6% of ADC or ADM . The impact of ADM on the AFT and fluidity of slag of Huaibei coalⅠand Huaibei coalⅡis better than that of ADC.
2. A new method and device for testing slag fluidity is set up, which can directly describe the slag fluidity through the whole temperature range. The results show that the the fluidity of slag of the two coal samples could be improved with the addtion of fluxes ADC and ADM.
3. In reducing conditions, the mineral transformation of two coal ash samples with the additon of ADC and ADM were studied by XRD at high temperature. The anorthite and albite were formed by adding ADC and ADM and the contents of the anorthite and albite increased with the temperature increase, which reacts with other minerals to form low melting eutectic.
4.The fluxes and their impact on reactivity of the two coal samples in coal gasification condition was studied. The reactivity of coal samples with addition of ADC and ADM were carried out by Quartz balance. ADM showed better catalytic activity than that of ADC under the reducing conditions.The gasification reactivity of Huaibei coalⅠand Huaibei coalⅡwas improved by adding of ADM and ADC.
5. In order to further study the reactivity of coal during coal gasification, a bench l scale coal gasification devices was designed based on the calculation of materail and energy balance.
引文
[1]姚强等编著.洁净煤技术[M].北京:化学工业出版社,2005
[2]王泉清,曾蒲君.高龄石对神木煤灰熔融性的研究[J].煤化工,1997 (3):40~45
[3]刘新兵.煤灰熔融性的研究[J].煤化工,1995,71 (2): 48~52
[4]高志武.朔州、忻州、大同与太原分公司不同煤种动力配煤的研究[[J].煤炭科学技术,2002,28 (3):32~34
[5] Privik M, Dieckmann H J. Truppat R.XRF and ICP OES comparison on the basis of a round robin and benefit for power plant chemistry[J]. Power Tech., 2002, 82 (7): 74~78
[6]李寒旭,陈方林.配煤降低高灰熔融性淮南煤灰熔融性温度的研究[J].煤炭学报,2002,27(5):529~533
[7] Steenari B M. The effect of potassium on the fusibility of coal ashes With high silica and Alumina levels[J]. Fue1, 1998, 77 (5): 407~417
[8]张德祥,龙永华.煤灰中矿物的化学组成与灰熔融性的关系[J].煤炭科学技术,2003,39(6):590～591
[9]姚星一.煤灰熔融性温度与化学成分的关系[J].燃料化学学报,1965,6 (2):151~160
[10] WinegartnerEC,RhoidesB T ,Trans[J]. ASMEJ.Eng.Powerm, 1975, 97 (3): 395
[11] Sondreal E A, Ellman R C. US Bureau of Mines Report GFERC/R1~75~1,1975
[12] Vincent R Gray. Prediction of ash fusion temperature from ash composition for some New Zealand coals [J]. Fuel, 1987, 66: 1230~1239
[13]平户瑞穗,二宫善彦.燃料协会志,1988,68 (5):393
[14] Sadriye Kueukbayrak[J]. Fuel sci. Tech. Int 1,1993,11(9): 1231
[15] Vorres K S. Mineral Matter and Ash in Coal [M]. Washington, D C: American Chemical Society, 1986
[16] Vassilev S V,Kunihiro Kitano. Influence of mineral and chemical composition of coal ashes on their fusibility [J]. Fuel Processing Technology, 1995, 45: 27～51
[17]王泉清,曾蒲君.煤灰熔融性的研究现状与分析[[J].煤炭转化,1997,20 (2):33
[18]何孝军,郑明东.煤灰熔融性测定技术的评述[[J].华东冶金学院学报,2000,17 (3): 213~214
[19]王泉清,曾蒲君.煤灰熔融性的研究现状与分析[[J].煤炭转化,1997,20 (2):34~37
[20]陈文敏,姜宁.利用煤灰成分计算我国煤灰熔融性温度[J].煤炭加工与综合利用,1998 3:13~17
[21]孔洪亮,曾荣树.煤中矿物学研究[[J].岩石矿物学杂志,2001,20 (4): 442
[22]郭崇涛.煤化学[M].北京:化学工业出版社,1992,33
[23] M .A.埃利奥特编;范辅弼译.煤利用化学[M].北京:化学工业出版社,1991,63
[24]姚多喜,支霞臣,郑宝山.煤中矿物质燃烧过程中的演化特征[J].中国煤田地质,2003,15 (2): 4~5
[25]钱觉时,吴传明.粉煤灰的矿物组成[J].粉煤灰综合利用,2001,45
[26]钱觉时等.粉煤灰的矿物组成[J].粉煤灰综合利用,2001,1:26~31
[27]川井隆夫,柴田次进.水翟会志,1985,30 (5): 325
[28] Hidero Unuma,Shohei Takeda,Takeshi Tsurus[J]. Fue1,1986,65(2):1505
[29] Kahraman, Hakan,Reifenstein, Adrian Calos. Mineralogical changes in selected Australian and overseas coals in boiler simulation test and improved ash fusion test[J]. 18th Annual International Pittsburgh Coal Conference. 2001, 70 (6) : 746~762
[30] Wall T F, False . Deformation temperature for ash fusibility associated with the conditions for ash preparation[J]. Fue1, 1998, 78 (9): 1057~1063
[31]李帆,郑瑛.煤灰助熔剂对熔融温度影响的研究[J].武汉城市建设学院学报,1997,14(1):23~27
[32]糜裕宏等.添加助熔剂降低高灰熔性淮南煤熔融温度[J].安徽理工大学学报,2003,23(3):61~63
[33]毛军等.碱性矿物质对煤灰熔融特性影响的研究[J].华中科技大学学报,2003,31(4):59~62
[34]许志琴等.助熔剂对高熔融温度煤影响的实验研究[J].煤炭转化,2005,23(3):22~25
[35]于戈文,许志琴,邓蜀平.气化条件下煤灰熔融性研究[J].煤化工,2005,10(5):27~31
[36]唐黎华,张娜等.助熔剂对煤焦高温气化反应性的影响[J].燃料化学学报,2003,3:209~214
[37]杨志忠,何秀英,沈坚勇.石灰石对CFB锅炉灰熔性影响实验研究[J].东方电气评论,2002,3(1):34~40
[38]李金锡,张鉴,Georges Urbain. MnO-SiO2,MgO-SiO2和CaO-Al2O3-SiO2熔渣粘度的计算模型[J].北京科技大学学报,1999,21(3):237～240
[39]熊友辉,孙学信.动力用煤熔体结构特性及其计算研究[J].煤炭转化,1996,19 (40): 85～91
[40]熊友辉,孙学信.基于熔体结构的高温灰渣粘度模型[J].华中理工大学学报,1998,26 (10):79～81
[41]陈惠钊,吕仲芝.升球法高温粘度测量影响因素的研究[J].分析仪器,1997,1:48～51
[42]陈惠钊.粘度测量[M].北京:中国计量出版社,1964
[43] ChuShaojun, LiuHaihong, DiaoShuheng et al. Discrimination between long slag and short slag[J]. Journal of Univerity of Science and Technology Beijing, 1995, 2 (1): 19～23
[44] British Pant 2458 ( 1867)
[45] Given P H.The ditribution of hydrogen in coals and its relation to coal structure[J]. Fuel, 1960, 39: 147
[46] Veraa M J,Bell A T,Effect of alkali metal catalysts on gasification of coal char[J]. Fuel, 1978, 57: 194
[47] Kouichi M,Masaru A,Takao N,Kenji H,Steam gasification of carbon effect of several metals on the rate of gasification and the rates of CO and CO2 formation[J]. Fuel,1986, 65: 407
[48] Lang R J,Neavel R C.Behavior of calcium as a steam gasification catalysts[J]. Fuel, 1982, 61:620
[49] Yoshiyuki Nishiyama. Catalytic gasification of coals-Features and possibilities[J]. Fuel Processing Technology, 1991, 29: 31～42
[50] Yasuo Ohtsuka,Kenji Asami. Highly active catalysts from inexpensive raw Materials for coal gasification[J]. Catalysis Today, 1997,39:111～125
[51] Dimple Mody Quyn, Hongwei Wu, Jun-ichiro Hayashi et al. Volatilisation and catalytic effects of alkali and alkaline earth metallic species during the pyrolysis and gasification of Victorian brown coal. Part IV. Catalytic effects of NaCl and ion-exchangeable Na in coal on char reactivity[J]. Fuel, 2003, 82: 587～593
[52] Yaw D. Yeboah, Yong Xu, Atul Sheth, et al, Catalytic gasification of coal using eutectic salts: identification of eutectics[J]. Carbon,2003, 41: 203～214
[53]寇公.煤炭气化工程[M].北京:机械工业出版社,1992
[54]冯杰,李文英,谢克昌.石灰石在煤的水蒸气气化中的催化作用[J].太原工业大学学报,1996,27(4):50～60
[55]朱廷玉. CaO催化温和气化研究[J].燃料化学学报,2000,28 (1):36～39
[56]田原宇.一种新型煤提升管催化气化装置[P]. CN 2511486Y,2002
[57]曾才.工业废碱对福建无烟煤水蒸汽催化气化的研究[D].福州:福州大学,2000
[58]张泽凯.煤炭的催化气化及其反应动力学研究[D].西安:西安交通大学,2003
[59]刘艳.利用热重分析仪研究煤的催化气化[D].西安:西北大学,2007
[60]董众兵,胡振,曹晏等.石英弹簧热天平在热分析中的应用[J].化工自动化及仪表,2002,29(3):66～67
[61]周志杰,范晓雷,张薇等.非等温热重分析研究煤焦气化动力学[J].煤炭学报,2006,31(2):219～222
[62]罗鸣,张建民,高梅杉等.不同方法求取活性焦气化反应动力学参数比较[J].上海理工大学学报,2006,21(2):136～146
[63]周建明,公旭中,王永刚等.煤焦-CO2气化反应性及其动力学模型[J].中国煤炭,2005,31(5):52～54
[64] Robert J.Lang and Richard C.Neave.Behaviour of calcium as a steam gasification catalyst[J]. 1982, 7 (61): 620～626
[65]赵新法,杨黎燕,石振海.煤中矿物质在气化反应中的催化作用分析[J].煤炭技术,2005,1 (24):103～104
[66]王福明.气流床高温煤气化的研究[D].上海:华东理工大学,2004
[67]刘吉堂,张成恩.有限元法在电厂热力设备传热计算中的应用[J].东北电力技术,1999,12:1～2
[68]贾英全.硅钼棒电炉的设计与制造[J].中国陶瓷,2000,36 (5):27～28
[2]王泉清,曾蒲君.高龄石对神木煤灰熔融性的研究[J].煤化工,1997 (3):40~45
[3]刘新兵.煤灰熔融性的研究[J].煤化工,1995,71 (2): 48~52
[4]高志武.朔州、忻州、大同与太原分公司不同煤种动力配煤的研究[[J].煤炭科学技术,2002,28 (3):32~34
[5] Privik M, Dieckmann H J. Truppat R.XRF and ICP OES comparison on the basis of a round robin and benefit for power plant chemistry[J]. Power Tech., 2002, 82 (7): 74~78
[6]李寒旭,陈方林.配煤降低高灰熔融性淮南煤灰熔融性温度的研究[J].煤炭学报,2002,27(5):529~533
[7] Steenari B M. The effect of potassium on the fusibility of coal ashes With high silica and Alumina levels[J]. Fue1, 1998, 77 (5): 407~417
[8]张德祥,龙永华.煤灰中矿物的化学组成与灰熔融性的关系[J].煤炭科学技术,2003,39(6):590～591
[9]姚星一.煤灰熔融性温度与化学成分的关系[J].燃料化学学报,1965,6 (2):151~160
[10] WinegartnerEC,RhoidesB T ,Trans[J]. ASMEJ.Eng.Powerm, 1975, 97 (3): 395
[11] Sondreal E A, Ellman R C. US Bureau of Mines Report GFERC/R1~75~1,1975
[12] Vincent R Gray. Prediction of ash fusion temperature from ash composition for some New Zealand coals [J]. Fuel, 1987, 66: 1230~1239
[13]平户瑞穗,二宫善彦.燃料协会志,1988,68 (5):393
[14] Sadriye Kueukbayrak[J]. Fuel sci. Tech. Int 1,1993,11(9): 1231
[15] Vorres K S. Mineral Matter and Ash in Coal [M]. Washington, D C: American Chemical Society, 1986
[16] Vassilev S V,Kunihiro Kitano. Influence of mineral and chemical composition of coal ashes on their fusibility [J]. Fuel Processing Technology, 1995, 45: 27～51
[17]王泉清,曾蒲君.煤灰熔融性的研究现状与分析[[J].煤炭转化,1997,20 (2):33
[18]何孝军,郑明东.煤灰熔融性测定技术的评述[[J].华东冶金学院学报,2000,17 (3): 213~214
[19]王泉清,曾蒲君.煤灰熔融性的研究现状与分析[[J].煤炭转化,1997,20 (2):34~37
[20]陈文敏,姜宁.利用煤灰成分计算我国煤灰熔融性温度[J].煤炭加工与综合利用,1998 3:13~17
[21]孔洪亮,曾荣树.煤中矿物学研究[[J].岩石矿物学杂志,2001,20 (4): 442
[22]郭崇涛.煤化学[M].北京:化学工业出版社,1992,33
[23] M .A.埃利奥特编;范辅弼译.煤利用化学[M].北京:化学工业出版社,1991,63
[24]姚多喜,支霞臣,郑宝山.煤中矿物质燃烧过程中的演化特征[J].中国煤田地质,2003,15 (2): 4~5
[25]钱觉时,吴传明.粉煤灰的矿物组成[J].粉煤灰综合利用,2001,45
[26]钱觉时等.粉煤灰的矿物组成[J].粉煤灰综合利用,2001,1:26~31
[27]川井隆夫,柴田次进.水翟会志,1985,30 (5): 325
[28] Hidero Unuma,Shohei Takeda,Takeshi Tsurus[J]. Fue1,1986,65(2):1505
[29] Kahraman, Hakan,Reifenstein, Adrian Calos. Mineralogical changes in selected Australian and overseas coals in boiler simulation test and improved ash fusion test[J]. 18th Annual International Pittsburgh Coal Conference. 2001, 70 (6) : 746~762
[30] Wall T F, False . Deformation temperature for ash fusibility associated with the conditions for ash preparation[J]. Fue1, 1998, 78 (9): 1057~1063
[31]李帆,郑瑛.煤灰助熔剂对熔融温度影响的研究[J].武汉城市建设学院学报,1997,14(1):23~27
[32]糜裕宏等.添加助熔剂降低高灰熔性淮南煤熔融温度[J].安徽理工大学学报,2003,23(3):61~63
[33]毛军等.碱性矿物质对煤灰熔融特性影响的研究[J].华中科技大学学报,2003,31(4):59~62
[34]许志琴等.助熔剂对高熔融温度煤影响的实验研究[J].煤炭转化,2005,23(3):22~25
[35]于戈文,许志琴,邓蜀平.气化条件下煤灰熔融性研究[J].煤化工,2005,10(5):27~31
[36]唐黎华,张娜等.助熔剂对煤焦高温气化反应性的影响[J].燃料化学学报,2003,3:209~214
[37]杨志忠,何秀英,沈坚勇.石灰石对CFB锅炉灰熔性影响实验研究[J].东方电气评论,2002,3(1):34~40
[38]李金锡,张鉴,Georges Urbain. MnO-SiO2,MgO-SiO2和CaO-Al2O3-SiO2熔渣粘度的计算模型[J].北京科技大学学报,1999,21(3):237～240
[39]熊友辉,孙学信.动力用煤熔体结构特性及其计算研究[J].煤炭转化,1996,19 (40): 85～91
[40]熊友辉,孙学信.基于熔体结构的高温灰渣粘度模型[J].华中理工大学学报,1998,26 (10):79～81
[41]陈惠钊,吕仲芝.升球法高温粘度测量影响因素的研究[J].分析仪器,1997,1:48～51
[42]陈惠钊.粘度测量[M].北京:中国计量出版社,1964
[43] ChuShaojun, LiuHaihong, DiaoShuheng et al. Discrimination between long slag and short slag[J]. Journal of Univerity of Science and Technology Beijing, 1995, 2 (1): 19～23
[44] British Pant 2458 ( 1867)
[45] Given P H.The ditribution of hydrogen in coals and its relation to coal structure[J]. Fuel, 1960, 39: 147
[46] Veraa M J,Bell A T,Effect of alkali metal catalysts on gasification of coal char[J]. Fuel, 1978, 57: 194
[47] Kouichi M,Masaru A,Takao N,Kenji H,Steam gasification of carbon effect of several metals on the rate of gasification and the rates of CO and CO2 formation[J]. Fuel,1986, 65: 407
[48] Lang R J,Neavel R C.Behavior of calcium as a steam gasification catalysts[J]. Fuel, 1982, 61:620
[49] Yoshiyuki Nishiyama. Catalytic gasification of coals-Features and possibilities[J]. Fuel Processing Technology, 1991, 29: 31～42
[50] Yasuo Ohtsuka,Kenji Asami. Highly active catalysts from inexpensive raw Materials for coal gasification[J]. Catalysis Today, 1997,39:111～125
[51] Dimple Mody Quyn, Hongwei Wu, Jun-ichiro Hayashi et al. Volatilisation and catalytic effects of alkali and alkaline earth metallic species during the pyrolysis and gasification of Victorian brown coal. Part IV. Catalytic effects of NaCl and ion-exchangeable Na in coal on char reactivity[J]. Fuel, 2003, 82: 587～593
[52] Yaw D. Yeboah, Yong Xu, Atul Sheth, et al, Catalytic gasification of coal using eutectic salts: identification of eutectics[J]. Carbon,2003, 41: 203～214
[53]寇公.煤炭气化工程[M].北京:机械工业出版社,1992
[54]冯杰,李文英,谢克昌.石灰石在煤的水蒸气气化中的催化作用[J].太原工业大学学报,1996,27(4):50～60
[55]朱廷玉. CaO催化温和气化研究[J].燃料化学学报,2000,28 (1):36～39
[56]田原宇.一种新型煤提升管催化气化装置[P]. CN 2511486Y,2002
[57]曾才.工业废碱对福建无烟煤水蒸汽催化气化的研究[D].福州:福州大学,2000
[58]张泽凯.煤炭的催化气化及其反应动力学研究[D].西安:西安交通大学,2003
[59]刘艳.利用热重分析仪研究煤的催化气化[D].西安:西北大学,2007
[60]董众兵,胡振,曹晏等.石英弹簧热天平在热分析中的应用[J].化工自动化及仪表,2002,29(3):66～67
[61]周志杰,范晓雷,张薇等.非等温热重分析研究煤焦气化动力学[J].煤炭学报,2006,31(2):219～222
[62]罗鸣,张建民,高梅杉等.不同方法求取活性焦气化反应动力学参数比较[J].上海理工大学学报,2006,21(2):136～146
[63]周建明,公旭中,王永刚等.煤焦-CO2气化反应性及其动力学模型[J].中国煤炭,2005,31(5):52～54
[64] Robert J.Lang and Richard C.Neave.Behaviour of calcium as a steam gasification catalyst[J]. 1982, 7 (61): 620～626
[65]赵新法,杨黎燕,石振海.煤中矿物质在气化反应中的催化作用分析[J].煤炭技术,2005,1 (24):103～104
[66]王福明.气流床高温煤气化的研究[D].上海:华东理工大学,2004
[67]刘吉堂,张成恩.有限元法在电厂热力设备传热计算中的应用[J].东北电力技术,1999,12:1～2
[68]贾英全.硅钼棒电炉的设计与制造[J].中国陶瓷,2000,36 (5):27～28