微波协同化学助剂强化脱除煤中硫
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摘要
硫是煤中主要有害元素,煤炭利用过程中硫的排放是酸雨的重要成因,脱硫是煤炭洁净利用的研究热点之一。微波具有促进反应发生、加快反应速率的作用,微波协同化学助剂脱硫是煤炭脱硫的重要手段。本文通过微波辐照结合3种化学助剂研究煤中硫的脱除效果,利用正交试验考察微波辐照时间、化学助剂种类和煤种对脱硫效果的影响。结果表明,煤种对微波协同不同助剂的脱硫效率影响较大,所选3种煤样的最佳辐照时间各不相同;硝酸与微波联合的脱硫效果最好,其中贵州(GZ)煤在微波协同硝酸作用下,全硫脱除率可达71. 2%。形态硫测试分析表明煤样经脱硫后无机硫脱除效率较高,最高可达90. 5%,有机硫脱除效率在20%～40%。XRD谱图分析显示微波协同化学助剂脱硫后,煤中主要矿物和煤质结构没有明显变化,微波在脱除煤中硫分的同时可保持煤炭基质稳定。XPS谱图分析表明,煤样硫醚(醇)类有机硫脱除效果较好,脱除率可达49. 4%,亚砜类略低,脱除率为23%～28%,噻吩类有机硫脱除效果最差,脱除率在10%～20%。
Sulfur is the main harmful element in coal.The emission of sulfur during coal utilization is an important cause of acid rain.Desulfurization is one of the research hotspots for clean utilization of coal.Microwave has the function of promoting the reaction and accelerating the reaction rate.Microwave combined with chemical auxiliaries is an important means of coal desulfurization. In this paper,the effects of sulfur removal in coal were studied by microwave irradiation combined with three chemical additives.The effects of microwave irradiation time,chemical additives types and coal types on desulfurization were investigated by orthogonal test. The results show that the coal types have a great influence on the desulfurization efficiency of microwave assisted additives,and the optimum irradiation time of the selected three coal samples is different.Among the three chemical additives selected,the desulfurization effect of nitric acid combined with microwave is the best.The removal rate of total sulfur in Guizhou( GZ) coal can reach 71.2% under the action of microwave combining with nitric acid.The morphological sulfur test analysis shows that the removal efficiency of inorganic sulfur after coal desulfurization is higher,up to 90.5%,and the removal efficiency of organic sulfur is between 20% and 40%.XRD spectrum analysis shows that after the desulfurization of microwave assisting chemical additives,there is no significant change in the main minerals and coal structure in the coal.The microwaves can maintain the stability of coal matrix while removing sulfur from coal.Through the analysis of XPS spectrum,it is known that the removal of sulphur thioethers and organic sulphur from coal samples is better,the removal rate can reach 49.4%,the sulfoxides are slightly lower,the removal rate is 23%-28%,the removal of the thiophene organic sulfur is the worst,and the removal rate is between 10% and 20%.
Sulfur is the main harmful element in coal.The emission of sulfur during coal utilization is an important cause of acid rain.Desulfurization is one of the research hotspots for clean utilization of coal.Microwave has the function of promoting the reaction and accelerating the reaction rate.Microwave combined with chemical auxiliaries is an important means of coal desulfurization. In this paper,the effects of sulfur removal in coal were studied by microwave irradiation combined with three chemical additives.The effects of microwave irradiation time,chemical additives types and coal types on desulfurization were investigated by orthogonal test. The results show that the coal types have a great influence on the desulfurization efficiency of microwave assisted additives,and the optimum irradiation time of the selected three coal samples is different.Among the three chemical additives selected,the desulfurization effect of nitric acid combined with microwave is the best.The removal rate of total sulfur in Guizhou( GZ) coal can reach 71.2% under the action of microwave combining with nitric acid.The morphological sulfur test analysis shows that the removal efficiency of inorganic sulfur after coal desulfurization is higher,up to 90.5%,and the removal efficiency of organic sulfur is between 20% and 40%.XRD spectrum analysis shows that after the desulfurization of microwave assisting chemical additives,there is no significant change in the main minerals and coal structure in the coal.The microwaves can maintain the stability of coal matrix while removing sulfur from coal.Through the analysis of XPS spectrum,it is known that the removal of sulphur thioethers and organic sulphur from coal samples is better,the removal rate can reach 49.4%,the sulfoxides are slightly lower,the removal rate is 23%-28%,the removal of the thiophene organic sulfur is the worst,and the removal rate is between 10% and 20%.
引文
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[11]张秀文,董宪姝,樊玉萍,等.微波联合酸性助剂对高硫无烟煤脱硫效果及机理的研究[J].中国煤炭,2018,44(2):95-99.ZHANG Xiuwen,DONG Xianshu,FAN Yuping,et al. Study on desulfurization efficiency of high-sulfur anthracite by microwave combined with acid additive and its mechanism[J]. China Coal,2018,44(2):95-99.
[12]许宁,陶秀祥,杨彦成.微波联合碱液煤炭脱硫研究[J].中国矿业,2015,24(4):117-120.XU Ning,TAO Xiuxiang,YANG Yancheng. Coal desulfurization under microwave irradiation combined with Na OH solution[J].China Mining Magazine,2015,24(4):117-120.
[13] USLU T,ATALAY U. Microwave heating of coal for enhanced magnetic removal of pyrite[J]. Fuel Processing Technology,2004,85(1):21-29.
[14] YAMADA K,NAGASHIMA I,HACHISU M,et al.Efficient solidphase synthesis of cyclic RGD peptides under controlled microwave heating[J].Tetrahedron Letters,2012,53(9):1066-1070.
[15]谢广元.选矿学[M].徐州:中国矿业大学出版社,2001.
[16] CHOU C L.Sulfur in coals:A review of geochemistry and origins[J].International Journal of Coal Geology,2012,100:1-13.
[2]樊东方.对目前我国煤炭能源低碳发展的思考分析[J].煤矿现代化,2018(1):123-124,127.FAN Dongfang.Analysis on the low carbon development of coal resources in China[J]. Coal Mine Modernization,2018(1):123-124,127.
[3]严东,周敏.煤炭微波脱硫技术研究现状与发展[J].煤炭科学技术,2012,40(7):125-128.YAN Dong,ZHOU Min.Study status and development on coal microwave desulfurization technology[J].Coal Science and Technology,2012,40(7):125-128.
[4]袁鉴.煤炭脱硫技术研究进展[J].洁净煤技术,2015,21(4):99-103.YUAN Jian. Research progress of coal desulfurization[J]. Clean Coal Technology,2015,21(4):99-103.
[5]丁乃东,傅家伟,李兆鑫,等.微波驱动的煤炭脱硫研究[J].洁净煤技术,2010,16(4):49-52.DING Naidong,FU Jiawei,LI Zhaoxin,et al. Study on microwavepromoted desulfurization of coal[J].Clean Coal Technology,2010,16(4):49-52.
[6]刘松,张明旭,黄少飞.微波氢氧化钠联合脱硫及机理分析[J].煤炭转化,2016,39(1):92-96.LIU Song,ZHANG Mingxu,HUANG Shaofei. Desulfurization by microwave irradiation combined with sodium hydroxide and mechanism for reaction[J]. Coal Conversion,2016,39(1):92-96.
[7]赵景联,张银元,陈庆云,等.微波辐射氧化法联合脱除煤中有机硫的研究[J].微波学报,2002,18(2):80-84.ZHAO Jinglian,ZHANG Yinyuan,CHEN Qingyun,et al. The desulfurization of high organic sulfur coal by oxidation under microwave radiation[J].Journal of Microwaves,2002,18(2):80-84.
[8]程刚,王向东,蒋文举,等.微波预处理和微生物联合煤炭脱硫技术初探[J].环境工程学报,2008,2(3):408-412.CHENG Gang,WANG Xiangdong,JIANG Wenju,et al.Preliminary study on biodesulfurization technology of coal in combination with microwave pretreatment[J].Chinese Journal of Environmental Engineering,2008,2(3):408-412.
[9]白景启.利用超声波-微波技术脱除煤中有机硫的研究[J].选煤技术,2017(1):17-19.BAI Jingqi.Study on removal of organic sulfur in coal using ultrasonic wave-microwave combined technique[J]. Goal Preparation Technology,2017(1):17-19.
[10] CHEHREH S C,JORJANI E.Microwave irradiation pretreatment and peroxyacetic acid desulfurization of coal and application of GRNN simultaneous predictor[J]. Fuel,2011,90(14):3156-3163.
[11]张秀文,董宪姝,樊玉萍,等.微波联合酸性助剂对高硫无烟煤脱硫效果及机理的研究[J].中国煤炭,2018,44(2):95-99.ZHANG Xiuwen,DONG Xianshu,FAN Yuping,et al. Study on desulfurization efficiency of high-sulfur anthracite by microwave combined with acid additive and its mechanism[J]. China Coal,2018,44(2):95-99.
[12]许宁,陶秀祥,杨彦成.微波联合碱液煤炭脱硫研究[J].中国矿业,2015,24(4):117-120.XU Ning,TAO Xiuxiang,YANG Yancheng. Coal desulfurization under microwave irradiation combined with Na OH solution[J].China Mining Magazine,2015,24(4):117-120.
[13] USLU T,ATALAY U. Microwave heating of coal for enhanced magnetic removal of pyrite[J]. Fuel Processing Technology,2004,85(1):21-29.
[14] YAMADA K,NAGASHIMA I,HACHISU M,et al.Efficient solidphase synthesis of cyclic RGD peptides under controlled microwave heating[J].Tetrahedron Letters,2012,53(9):1066-1070.
[15]谢广元.选矿学[M].徐州:中国矿业大学出版社,2001.
[16] CHOU C L.Sulfur in coals:A review of geochemistry and origins[J].International Journal of Coal Geology,2012,100:1-13.