部分进口煤炭中氟元素的含量特征及赋存形态
|
摘要
为加强对进口高氟煤炭的管理,评价进口煤炭中氟元素的环境迁入风险,采用高温燃烧水解-氟离子选择电极法对唐山港口岸进口的225批煤炭中的氟含量进行了测定;用稳健统计描述了其整体含量水平,并根据我国煤炭行业分级标准及富集比进行了质量评价;用相关分析对氟的赋存形态进行了分析。结果表明:唐山港口进口煤炭中的氟含量可描述为(137±24)mg/kg;按我国煤炭行业标准进行质量分级评价,唐山港口进口的68%的朝鲜煤、62%的加拿大煤属于中氟煤,氟含量算术平均值高于中国煤、世界煤,其迁入风险值得关注;进口朝鲜煤中氟含量与灰分、全硫含量呈中度正相关、与磷含量呈微弱正相关,推断氟的赋存形态主要为无机硫结合态(硫化物和硫酸盐)和黏土矿物,少部分可能存在于磷酸盐类矿物及有机硫结合态中;进口澳大利亚煤中氟含量与灰分、全硫含量相关性不显著,与磷含量呈低度正相关,推断氟的赋存形态比较复杂,可能部分以磷酸盐结合态存在,赋存于氟磷灰石、磷铝钙石中;进口加拿大煤中氟含量与灰分、全硫含量相关性不显著,与磷含量的相关性系数为0.763,显著性水平为0.01,表明二者呈高度正相关,具有显著性,说明二者有很强的伴生关系,推断氟主要以磷酸盐结合态存在,赋存于氟磷灰石、磷铝钙石中。
In order to strengthen the management of imported high fluoride coals and evaluate the environment immigration risk of fluorine element in imported coals,the concentrations of fluorine element in the imported 225 batch coals of Tangshan port were determined using high temperature burning hydrolysis-ion selective electrode method.The overall content level of fluorine were described by robust statistics.The quality were evaluated by the national coal classification standard and enrichment ratio.The relevant analysis were used to study the occurrence status characteristics of fluorine.The results showed that the fluorine in coals of Jingtanggang port were( 137±24) mg/kg.According to Chinese coal industry standards for quality grading evaluation,68% of Korea coal and 62% of Canada coals were medium fluorine coal.The arithmetic average of fluorine of these two coals were higher than those of Chinese coal and the world's coal.So their environment immigration risk should be noticed.Fluorine content in Korea coals was moderate positive correlation with the ash,total sulfur and it was weak positive correlation with the phosphorus.The correlation analysis of ash,sulfur,phosphorus and fluorine content in Korea coal showed that the occurrence modes of fluorine were mainly inorganic sulfur bound( sulfides and sulfates) and clay minerals form. A small part of fluorine in Korea coals might be present in phosphate minerals and organic sulfur in bound.The correlation of ash,total sulfur and fluorine in Australian coals was not significant,and the correlation phosphorus and fluorine was low. The correlation analysis of ash,sulfur,phosphorus and fluorine content in Australian coals showed that the occurrence modes of fluorine were complex,it might be phosphate bound partly and occurred in the fluorapatite and aluminum calcium phosphate rock. The correlation of ash,total sulfur and fluorine in Canada coals was not significant,and the correlation coefficient of phosphorus content was 0. 763,significance level was 0. 01.It indicated that fluorine and phosphorus had a strong associated relationship,and it inferred that fluorine was mainly in the phosphorus bound,occurred in the fluorapatite and aluminum calcium phosphorus rock.
In order to strengthen the management of imported high fluoride coals and evaluate the environment immigration risk of fluorine element in imported coals,the concentrations of fluorine element in the imported 225 batch coals of Tangshan port were determined using high temperature burning hydrolysis-ion selective electrode method.The overall content level of fluorine were described by robust statistics.The quality were evaluated by the national coal classification standard and enrichment ratio.The relevant analysis were used to study the occurrence status characteristics of fluorine.The results showed that the fluorine in coals of Jingtanggang port were( 137±24) mg/kg.According to Chinese coal industry standards for quality grading evaluation,68% of Korea coal and 62% of Canada coals were medium fluorine coal.The arithmetic average of fluorine of these two coals were higher than those of Chinese coal and the world's coal.So their environment immigration risk should be noticed.Fluorine content in Korea coals was moderate positive correlation with the ash,total sulfur and it was weak positive correlation with the phosphorus.The correlation analysis of ash,sulfur,phosphorus and fluorine content in Korea coal showed that the occurrence modes of fluorine were mainly inorganic sulfur bound( sulfides and sulfates) and clay minerals form. A small part of fluorine in Korea coals might be present in phosphate minerals and organic sulfur in bound.The correlation of ash,total sulfur and fluorine in Australian coals was not significant,and the correlation phosphorus and fluorine was low. The correlation analysis of ash,sulfur,phosphorus and fluorine content in Australian coals showed that the occurrence modes of fluorine were complex,it might be phosphate bound partly and occurred in the fluorapatite and aluminum calcium phosphate rock. The correlation of ash,total sulfur and fluorine in Canada coals was not significant,and the correlation coefficient of phosphorus content was 0. 763,significance level was 0. 01.It indicated that fluorine and phosphorus had a strong associated relationship,and it inferred that fluorine was mainly in the phosphorus bound,occurred in the fluorapatite and aluminum calcium phosphorus rock.
引文
[1]刘雪锋.煤中氟的迁徙演化行为及含硫大分子结构的研究[D].武汉:华中理工大学,2009.
[2]Geng W H,Nakajima T,Takanashi H.Determination of total fluorine in coal by use of oxygen-flask combustion method with catalyst[J].Fuel,2007,86(5/6):715-721.
[3]齐庆杰,刘建忠,曹欣玉,等.煤中氟分布与燃烧排放特性[J].化工学报,2002,53(6):572-577.Qi Qingjie,Liu Jianzhong,Cao Xinyu,et al.Fluorine distribution characteristics in coal and behavior of fluorine during coal combustion[J].Journal of Chemical Industry and Engineering(China),2002,53(6):572-577.
[4]刘雪锋,郑楚光,刘晶,等.贵州煤中氟赋存形态分析[J].中国电机工程学报,2008,28(8):46-51.Liu Xuefeng,Zheng Chuguang,Liu Jing,et al.Analysis on fluorine speciation in coals from Guizhou province[J].Proceedings of the Chinese Society for Electrical Engineering,2008,28(8):46-51.
[5]吴代赦,郑宝山,唐修义,等.中国煤中氟的含量及其分布[J].环境科学,2005,26(1):7-11.Wu Daishe,Zheng Baoshan,Tang Xiuyi,et al.Content and Distribution of fluorine in Chinese coals[J].Environmental Science,2005,26(1):7-11.
[6]陈萍,唐修义.中国煤中的氟[J].中国煤田地质,2002,14(7):25-28.Chen Ping,Tang Xiuyi.Fluorine in coal of China[J].Coal Geology of China,2002,14(7):25-28.
[7]刘曙,李晨,诸秀芬,等.上海口岸进口煤炭总汞含量的分布特征[J].岩矿测试,2014,33(5):730-736.Liu Shu,Li Chen,Zhu Xiufen,et al.Distribution characteristics of total mercury in imported coals at Shanghai port[J].Rock and Mineral Analysis,2014,33(5):730-736.
[8]Finkelman R B,Belkin H E,Zheng B S.Health impacts of domestic coal use in China[J].Proceedings National Academy of Science,1999,96(7):3427-3431.
[9]刘桂建,彭子成,王桂梁,等.煤中微量元素研究进展[J].地球科学进展,2002,17(1):53-62.Liu Guijian,Peng Zicheng,Wang Guiliang,et al.Study on trace elements in coal[J].Advance in Earth Sciences,2002,17(1):53-62.
[10]Wang Xiaobo,Dai Shifeng,Sun Yingying,et al.Modes of occurrence of fluorine in the Late Paleozoic No.6 coal from the Haerwusu Surface mine,Inner Mongolia,China[J].Fuel,2011,90(1):248-254.
[11]刘曙,沈劼,周海明,等.电感耦合等离子体质谱原子荧光光谱法研究上海口岸进口印度尼西亚煤炭微量元素的赋存形态特征[J].岩矿测试,2015,34(4):436-441.Liu Shu,Shen Jie,Zhou Haiming,et al.Study on occurrence status characteristics of trace elements in imported indonsia coals of Shanghai port using inductively coupled plasma-mass spectrometry and atomic fluorescence spectrometry[J].Rock and Mineral Analysis,2015,34(4):436-441.
[12]Dai Shifeng,Li Dan,Zhou Chenlin,et al.Mineralogy and geochemistry of boehmite-rich coals:new insights from the Haerwusu Surface mine,Jungar coalfield,Inner Mongolia,China[J].International Journal of Coal Geology,2008,74:185-202.
[13]袁晓鹰,张永春,姜涛.进口煤炭中有害微量元素的风险类别[J].煤炭科技,2013(1):95-96.Yuan Xiaoying,Zhang Yongchun,Jiang Tao.Risk classification of harmful microelement in imported coal[J].Coal Science and Technology,2013(1):95-96.
[14]Swaine D J.Trace elements in coal[M].London:Butterworths,1990:278.
[15]齐庆杰,于贵生,李芳玮,等.煤中氟的无机/有机亲和性与洗选特性[J].辽宁工程技术大学学报,2006,2(4):481-484.Qi Qingjie,Yu Guisheng,Li Fangwei,et al.Inorganic/organic affinity and washing floatation characteristic of fluorine in coal[J].Journal of Liaoning Technical University,2006,2(4):481-484.
[16]刘桂建,杨萍月.济宁煤田煤中微量元素的地球化学研究[J].地质地球化学,1999,24(4):77-89.Liu Guijian,Yang Pingyue.Geochemistry of trace elements in Jining coalfield[J].Geology-Geochemistry,1999,24(4):77-89.
[17]刘桂建,杨萍月.唐口区煤中微量元素的分布特征[J].煤田地质与勘探,1999,27(2):13-15.Liu Guijian,Yang Pingyue.The distribution characteristics of trace elements in the coal of Tangkou district[J].Coal geology and Exploration,1999,27(2):13-15.
[18]刘桂建,杨萍月,彭子成,等.兖州矿区煤中某些微量元素的赋存状态研究[J].地球化学,2002,31(1):85-89.Liu Guijian,Yang Pingyue,Peng Zicheng,et al.Occurrence of trace elements in coal of Yanzhou mining district[J].Geochimica,2002,31(1):85-89.
[19]Dai Shifeng,Ren Deyi,Tang Yuegang,et al.Concentration and distribution of elements in Late Permian coals from western Guizhou province,China[J].International Journal of Coal Geology,2005,61(1):119-137.
[20]Vassilev S V,Kitano K,Vassileva C G.Relations between ash yield and chemical and mineral composition of coals[J].Fuel,1997,76(1):3-8.
[21]刘建忠,盛军杰,齐庆杰,等.煤燃烧干法除氟技术的研究[J].热力发电,2004,33(8):32-34.Liu Jianzhong,Sheng Junjie,Qi Qingjie,et al.Study on dry method for fluorine-eliminating technology during combustion of coal[J].Thermal Power Generation,2004,33(8):32-34.
[22]Harrison C D,Akers D J,Raleigh C E,et al.Hazardous air pollutant precursors(HAPs):Advanced Coal Based Power and Environmental Systems'97 Conference[C].Pittsburgh:[s.n.],1997.
[23]Martinez Tarazona M R,Suarea Fernandez G P,Gardin J M.Fluorine in Asturian coals[J].Fuel,1994,73(7):1209-1213.
[2]Geng W H,Nakajima T,Takanashi H.Determination of total fluorine in coal by use of oxygen-flask combustion method with catalyst[J].Fuel,2007,86(5/6):715-721.
[3]齐庆杰,刘建忠,曹欣玉,等.煤中氟分布与燃烧排放特性[J].化工学报,2002,53(6):572-577.Qi Qingjie,Liu Jianzhong,Cao Xinyu,et al.Fluorine distribution characteristics in coal and behavior of fluorine during coal combustion[J].Journal of Chemical Industry and Engineering(China),2002,53(6):572-577.
[4]刘雪锋,郑楚光,刘晶,等.贵州煤中氟赋存形态分析[J].中国电机工程学报,2008,28(8):46-51.Liu Xuefeng,Zheng Chuguang,Liu Jing,et al.Analysis on fluorine speciation in coals from Guizhou province[J].Proceedings of the Chinese Society for Electrical Engineering,2008,28(8):46-51.
[5]吴代赦,郑宝山,唐修义,等.中国煤中氟的含量及其分布[J].环境科学,2005,26(1):7-11.Wu Daishe,Zheng Baoshan,Tang Xiuyi,et al.Content and Distribution of fluorine in Chinese coals[J].Environmental Science,2005,26(1):7-11.
[6]陈萍,唐修义.中国煤中的氟[J].中国煤田地质,2002,14(7):25-28.Chen Ping,Tang Xiuyi.Fluorine in coal of China[J].Coal Geology of China,2002,14(7):25-28.
[7]刘曙,李晨,诸秀芬,等.上海口岸进口煤炭总汞含量的分布特征[J].岩矿测试,2014,33(5):730-736.Liu Shu,Li Chen,Zhu Xiufen,et al.Distribution characteristics of total mercury in imported coals at Shanghai port[J].Rock and Mineral Analysis,2014,33(5):730-736.
[8]Finkelman R B,Belkin H E,Zheng B S.Health impacts of domestic coal use in China[J].Proceedings National Academy of Science,1999,96(7):3427-3431.
[9]刘桂建,彭子成,王桂梁,等.煤中微量元素研究进展[J].地球科学进展,2002,17(1):53-62.Liu Guijian,Peng Zicheng,Wang Guiliang,et al.Study on trace elements in coal[J].Advance in Earth Sciences,2002,17(1):53-62.
[10]Wang Xiaobo,Dai Shifeng,Sun Yingying,et al.Modes of occurrence of fluorine in the Late Paleozoic No.6 coal from the Haerwusu Surface mine,Inner Mongolia,China[J].Fuel,2011,90(1):248-254.
[11]刘曙,沈劼,周海明,等.电感耦合等离子体质谱原子荧光光谱法研究上海口岸进口印度尼西亚煤炭微量元素的赋存形态特征[J].岩矿测试,2015,34(4):436-441.Liu Shu,Shen Jie,Zhou Haiming,et al.Study on occurrence status characteristics of trace elements in imported indonsia coals of Shanghai port using inductively coupled plasma-mass spectrometry and atomic fluorescence spectrometry[J].Rock and Mineral Analysis,2015,34(4):436-441.
[12]Dai Shifeng,Li Dan,Zhou Chenlin,et al.Mineralogy and geochemistry of boehmite-rich coals:new insights from the Haerwusu Surface mine,Jungar coalfield,Inner Mongolia,China[J].International Journal of Coal Geology,2008,74:185-202.
[13]袁晓鹰,张永春,姜涛.进口煤炭中有害微量元素的风险类别[J].煤炭科技,2013(1):95-96.Yuan Xiaoying,Zhang Yongchun,Jiang Tao.Risk classification of harmful microelement in imported coal[J].Coal Science and Technology,2013(1):95-96.
[14]Swaine D J.Trace elements in coal[M].London:Butterworths,1990:278.
[15]齐庆杰,于贵生,李芳玮,等.煤中氟的无机/有机亲和性与洗选特性[J].辽宁工程技术大学学报,2006,2(4):481-484.Qi Qingjie,Yu Guisheng,Li Fangwei,et al.Inorganic/organic affinity and washing floatation characteristic of fluorine in coal[J].Journal of Liaoning Technical University,2006,2(4):481-484.
[16]刘桂建,杨萍月.济宁煤田煤中微量元素的地球化学研究[J].地质地球化学,1999,24(4):77-89.Liu Guijian,Yang Pingyue.Geochemistry of trace elements in Jining coalfield[J].Geology-Geochemistry,1999,24(4):77-89.
[17]刘桂建,杨萍月.唐口区煤中微量元素的分布特征[J].煤田地质与勘探,1999,27(2):13-15.Liu Guijian,Yang Pingyue.The distribution characteristics of trace elements in the coal of Tangkou district[J].Coal geology and Exploration,1999,27(2):13-15.
[18]刘桂建,杨萍月,彭子成,等.兖州矿区煤中某些微量元素的赋存状态研究[J].地球化学,2002,31(1):85-89.Liu Guijian,Yang Pingyue,Peng Zicheng,et al.Occurrence of trace elements in coal of Yanzhou mining district[J].Geochimica,2002,31(1):85-89.
[19]Dai Shifeng,Ren Deyi,Tang Yuegang,et al.Concentration and distribution of elements in Late Permian coals from western Guizhou province,China[J].International Journal of Coal Geology,2005,61(1):119-137.
[20]Vassilev S V,Kitano K,Vassileva C G.Relations between ash yield and chemical and mineral composition of coals[J].Fuel,1997,76(1):3-8.
[21]刘建忠,盛军杰,齐庆杰,等.煤燃烧干法除氟技术的研究[J].热力发电,2004,33(8):32-34.Liu Jianzhong,Sheng Junjie,Qi Qingjie,et al.Study on dry method for fluorine-eliminating technology during combustion of coal[J].Thermal Power Generation,2004,33(8):32-34.
[22]Harrison C D,Akers D J,Raleigh C E,et al.Hazardous air pollutant precursors(HAPs):Advanced Coal Based Power and Environmental Systems'97 Conference[C].Pittsburgh:[s.n.],1997.
[23]Martinez Tarazona M R,Suarea Fernandez G P,Gardin J M.Fluorine in Asturian coals[J].Fuel,1994,73(7):1209-1213.