Article(id=1211002411838206592, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1210998030828958715, articleNumber=null, orderNo=null, doi=10.19666/j.rlfd.202309164, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1695312000000, receivedDateStr=2023-09-22, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1766655074319, onlineDateStr=2025-12-25, pubDate=1706112000000, pubDateStr=2024-01-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1766655074319, onlineIssueDateStr=2025-12-25, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1766655074319, creator=13701087609, updateTime=1766655074319, updator=13701087609, issue=Issue{id=1210998030828958715, tenantId=1146029695717560320, journalId=1210938733613449225, year='2024', volume='53', issue='1', pageStart='1', pageEnd='196', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1766654029805, creator=13701087609, updateTime=1766734793553, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1211336778607366994, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1210998030828958715, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1211336778611561299, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1210998030828958715, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=82, endPage=90, ext={EN=ArticleExt(id=1211002414275097234, articleId=1211002411838206592, tenantId=1146029695717560320, journalId=1210938733613449225, language=EN, title=Experimental study on sodium release characteristics during thermal conversion of high-alkali coal, columnId=1210998031487464445, journalTitle=Thermal Power Generation, columnName=High proportion combustion technology for high-alkali coal, runingTitle=null, highlight=null, articleAbstract=

In order to study release characteristics of sodium during thermal conversion of high-alkali coals, the release characteristics of sodium in high-sodium coal and low-sodium coal were compared and analyzed through combustion experiments and pyrolysis experiments of raw coal and water-washed coal, so as to explore the release law changes of different forms of sodium in coal samples during combustion and the influence of atmosphere changes on sodium release. The results show that, during the combustion experiment, the release of sodium from high-alkali coal increases slowly at 300~500 ℃ and rapidly at 500~1 100 ℃, and the release of sodium from low-alkali coal increases rapidly at 300~500 ℃ and slowly at 500~1 100 ℃. It can be seen that, coal quality is one of the main reasons affecting sodium release, and sodium release will be greatly affected by the difference in coal composition. The release law of sodium during combustion and pyrolysis is basically the same, the sodium release rate changes slowly during the pyrolysis process, and is about 7.0% lower than that of the combustion process. The release characteristics of organic sodium and water-soluble sodium are different due to different release routes.

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为研究高碱煤热转化过程中钠的释出特性,采用原煤和水萃取煤分别进行燃烧实验和热解实验来对比分析高碱煤和低碱煤中钠的释出特性,探究不同煤质的煤样在燃烧时煤样中不同赋存形态钠的释出特性变化以及气氛变化对钠释出的影响。结果表明:在进行燃烧实验时,高碱煤在300~500 ℃时钠的释出量增加缓慢,在500~1 100 ℃时钠的释出量增加较快,低碱煤在300~500 ℃时钠的释出量增加较快,在500~1 100 ℃时钠的释出量增加缓慢,由此可知煤质是影响钠释出的主要原因之一,钠的释出特性会因煤质中成分差异而受到较大影响;燃烧和热解2种不同气氛下钠释出特性相似,热解过程中钠释出率变化平缓,且热解过程中钠释出率会比燃烧过程低7.0%左右;有机钠和水溶性钠2种不同赋存形态钠因释出途径不同而导致释出特性有所差异。

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廖伟辉(1973),男,高级工程师,主要研究方向为电站锅炉设备管理及发电技术,

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廖伟辉(1973),男,高级工程师,主要研究方向为电站锅炉设备管理及发电技术,

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廖伟辉(1973),男,高级工程师,主要研究方向为电站锅炉设备管理及发电技术,

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Coal quality indicators of the experimental coal samples

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煤样工业分析元素分析
FCadVadAadMadCadHadOadNadSad
五彩湾煤46.9833.244.8914.8861.123.7511.750.640.37
天池能源煤47.7729.594.1018.5462.013.8810.650.470.53
乌东煤51.1330.4415.462.9867.484.446.791.070.68
), ArticleFig(id=1211018030524526770, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1211002411838206592, language=CN, label=表1, caption=

实验煤种的煤质分析   单位:w/%

, figureFileSmall=null, figureFileBig=null, tableContent=
煤样工业分析元素分析
FCadVadAadMadCadHadOadNadSad
五彩湾煤46.9833.244.8914.8861.123.7511.750.640.37
天池能源煤47.7729.594.1018.5462.013.8810.650.470.53
乌东煤51.1330.4415.462.9867.484.446.791.070.68
), ArticleFig(id=1211018030616801459, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1211002411838206592, language=EN, label=Tab.2, caption=

Analysis of ash composition of experimental coal samples

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煤样Na2OFe2O3Al2O3CaOMgOK2OTiO2SO3SiO2
五彩湾煤4.888.9310.4232.708.700.490.5934.3520.02
天池能源煤6.795.0611.5310.5040.030.210.8818.6221.47
乌东煤0.686.4222.684.512.571.430.774.0056.00
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实验煤种的灰成分分析   单位:w/%

, figureFileSmall=null, figureFileBig=null, tableContent=
煤样Na2OFe2O3Al2O3CaOMgOK2OTiO2SO3SiO2
五彩湾煤4.888.9310.4232.708.700.490.5934.3520.02
天池能源煤6.795.0611.5310.5040.030.210.8818.6221.47
乌东煤0.686.4222.684.512.571.430.774.0056.00
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高碱煤热转化过程中钠的释出特性实验研究
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廖伟辉 1 , 饶勇 1 , 吕兴城 1 , 阮志龙 1 , 傅勇强 2 , 李华鸿 2 , 陈端 3 , 马帅 3 , 姚斌 3 , 赵永椿 3
热力发电 | 高比例燃烧高碱煤技术专题 2024,53(1): 82-90
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热力发电 | 高比例燃烧高碱煤技术专题 2024, 53(1): 82-90
高碱煤热转化过程中钠的释出特性实验研究
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廖伟辉1 , 饶勇1, 吕兴城1, 阮志龙1, 傅勇强2, 李华鸿2, 陈端3, 马帅3, 姚斌3, 赵永椿3
作者信息
  • 1.广东红海湾发电有限公司,广东 汕尾 516000
  • 2.湛江中粤能源有限公司,广东 湛江 524000
  • 3.华中科技大学能源与动力工程学院,湖北 武汉 430074
  • 廖伟辉(1973),男,高级工程师,主要研究方向为电站锅炉设备管理及发电技术,

Experimental study on sodium release characteristics during thermal conversion of high-alkali coal
Weihui LIAO1 , Yong RAO1, Xingcheng LYU1, Zhilong RUAN1, Yongqiang FU2, Huahong LI2, Duan CHEN3, Shuai MA3, Bin YAO3, Yongchun ZHAO3
Affiliations
  • 1.Guangdong Honghaiwan Power Generation Co., Ltd., Shanwei 516000, China
  • 2.Zhanjiang Zhongyue Energy Co., Ltd., Zhanjiang 524000, China
  • 3.School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
出版时间: 2024-01-25 doi: 10.19666/j.rlfd.202309164
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为研究高碱煤热转化过程中钠的释出特性,采用原煤和水萃取煤分别进行燃烧实验和热解实验来对比分析高碱煤和低碱煤中钠的释出特性,探究不同煤质的煤样在燃烧时煤样中不同赋存形态钠的释出特性变化以及气氛变化对钠释出的影响。结果表明:在进行燃烧实验时,高碱煤在300~500 ℃时钠的释出量增加缓慢,在500~1 100 ℃时钠的释出量增加较快,低碱煤在300~500 ℃时钠的释出量增加较快,在500~1 100 ℃时钠的释出量增加缓慢,由此可知煤质是影响钠释出的主要原因之一,钠的释出特性会因煤质中成分差异而受到较大影响;燃烧和热解2种不同气氛下钠释出特性相似,热解过程中钠释出率变化平缓,且热解过程中钠释出率会比燃烧过程低7.0%左右;有机钠和水溶性钠2种不同赋存形态钠因释出途径不同而导致释出特性有所差异。

高碱煤  /  钠释出  /  赋存形态  /  燃烧  /  热解

In order to study release characteristics of sodium during thermal conversion of high-alkali coals, the release characteristics of sodium in high-sodium coal and low-sodium coal were compared and analyzed through combustion experiments and pyrolysis experiments of raw coal and water-washed coal, so as to explore the release law changes of different forms of sodium in coal samples during combustion and the influence of atmosphere changes on sodium release. The results show that, during the combustion experiment, the release of sodium from high-alkali coal increases slowly at 300~500 ℃ and rapidly at 500~1 100 ℃, and the release of sodium from low-alkali coal increases rapidly at 300~500 ℃ and slowly at 500~1 100 ℃. It can be seen that, coal quality is one of the main reasons affecting sodium release, and sodium release will be greatly affected by the difference in coal composition. The release law of sodium during combustion and pyrolysis is basically the same, the sodium release rate changes slowly during the pyrolysis process, and is about 7.0% lower than that of the combustion process. The release characteristics of organic sodium and water-soluble sodium are different due to different release routes.

high-alkali coal  /  sodium release  /  occurrence form  /  combustion  /  pyrolysis
廖伟辉, 饶勇, 吕兴城, 阮志龙, 傅勇强, 李华鸿, 陈端, 马帅, 姚斌, 赵永椿. 高碱煤热转化过程中钠的释出特性实验研究. 热力发电, 2024 , 53 (1) : 82 -90 . DOI: 10.19666/j.rlfd.202309164
Weihui LIAO, Yong RAO, Xingcheng LYU, Zhilong RUAN, Yongqiang FU, Huahong LI, Duan CHEN, Shuai MA, Bin YAO, Yongchun ZHAO. Experimental study on sodium release characteristics during thermal conversion of high-alkali coal[J]. Thermal Power Generation, 2024 , 53 (1) : 82 -90 . DOI: 10.19666/j.rlfd.202309164
高碱煤是中国一种十分丰富的煤矿资源,目前新疆准东地区已经勘探到的高碱煤量大概有3 000多亿t,能充分保证我国的能源供应。并且高碱煤有着良好的着火性能和燃烧性能,灰分较低,含有的有害物质较少,在未来有很大的发电潜力[1-3]。但是高碱煤中钠质量分数较高,会使高碱煤在锅炉内燃烧时受热面发生比较恶劣的沾污结渣,影响电站锅炉的运行安全,这也是阻碍高碱煤被广泛使用的主要原因之一[4-6]。目前在电厂主要是燃用高碱煤时掺混一些低碱煤来进行燃烧[7],而在准东附近地区低碱煤储量十分有限,这就导致电厂在未来会全部燃用高碱煤[8]。且掺混钠含量低碱煤燃烧只能起到缓解沾污结渣的作用[9],无法从本质上解决沾污结渣的问题。
国内外有许多学者研究分析高碱煤中钠的赋存形态和钠的释出,王运泉和张军营等[10-11]认为煤中的微量元素能够通过逐级萃取分离法将微量元素分离,不同的萃取液可以萃取不同的微量元素。张军等[12]认为有机钠和水溶性钠是钠在煤中2种主要存在形态。郭帅等[13]通过研究发现水溶性钠以水合离子和氯化钠晶体形式存在居多,有机钠大多以羧基钠形式为主。阿斯亚·巴克等[14]对准东高钠煤进行了提取实验,并选择盐酸、醋铵、去离子水作为提取剂,发现高碱煤中水溶性钠在钠中占比较高。李想等[15]认为煤中含有的水溶性钠主要源自煤吸收水分而含有的无机盐以及因海水而滞留在煤中的盐分。Nasir等人[16]通过对煤样进行充分水洗发现,通过水洗可以较好地将煤样中的水溶性钠分离,并将煤中灰分降低。王长安等[17]通过水洗煤样发现,煤在经过水洗之后,其中大多数钠都能由水洗分离出来。张军等[18]认为氯化钠是水溶性钠从煤中释出的主要方式,而当有机钠是钠的赋存形式时,其主要会随挥发分一起释出。刘敬等[19]在进行燃烧实验后观察到在400~600 ℃时煤中的钠主要以水溶性钠形式释出,并且在这个阶段钠的释出速度最快,同时钠的释出主要发生在燃烧后期。Wibberley等人[20]认为钠的转化形式在燃烧后期受燃煤的种类、气氛等多重因素影响而存在差异。Schafer等人[21]认为因煤中对钠具有吸收作用的物质质量分数不同,钠的释出会由于煤质成分不同而存在较大差异。本文通过高碱煤和高碱水萃取煤的燃烧和热解实验来对比分析高碱煤和低碱煤钠的释出特性,以此探究不同燃煤中不同赋存形态钠的释出特性以及气氛变化对钠释出的影响,为工业应用中减少钠释出的方案提供理论指导。
本文选取了乌东煤(WD)、天池能源煤(TCNY)、五彩湾煤(WCW)作为实验研究对象。表1为实验煤种的煤质分析,表2为实验煤种的灰成分分析。从表1表2可以看出,高碱煤五彩湾煤和高碱煤天池能源煤在煤质特性上较为一致,低碱煤乌东煤与上述2种煤的煤质特性有所差别。
对上述煤进行水洗处理得到水萃取煤。将去离子水和煤以40:1的质量配比来混合,保持温度恒定在70 ℃,在磁力搅拌器中24 h不间断地以400 r/min的搅拌速度搅拌,萃取出煤中的水溶性钠,并在105 ℃的条件下将残渣烘干8 h,得到乌东水萃取煤(WDSCQ)、天池能源水萃取煤(TCNYSCQ)、五彩湾水萃取煤(WCWSCQ)。得到3种水洗煤后,分别从中取出一定量的水洗煤继续采用逐级萃取分离法,用一定浓度的醋酸铵溶液、盐酸溶液依次洗煤,将盐酸萃取过的煤样置于105 ℃烘箱中干燥8 h,并对其进行消解处理后得到消解液,使用电感耦合等离子体发射光谱仪(ICP-OES)对萃取液和消解液进行检测和定量分析,从而得到原煤中总钠质量分数Wt(mg/g,后同)、水溶性钠的质量分数W1、有机钠的质量分数W2及不溶性钠的质量分数W3
燃烧实验和热解实验是在高温管式电加热实验系统上进行,图1为实验系统示意。加热管由内径为10 cm、长度为100 cm的刚玉管组成。
炉内两端用炉塞密封,确保内外空间的隔离,同时内部气体有均匀的流速。通过设置管式炉的控温程序,可在管炉中部形成一个保温区域,进行燃烧实验时,在300~1 100 ℃的温度条件下,每隔100 ℃设置一个实验温度,并将盛有1 g原煤煤粉样品的瓷舟置于保温区域内以确保其能够充分燃烧。将氮气和氧气按照4:1的比例组成混合气体从炉的一端通入。放置实验样品在炉内1 h后,将灰样冷却至25 ℃并将灰样取出。将取出的灰样进行消解,通过ICP-OES对得到的消解液进行检测和定量分析,从而得到原煤在燃烧后所剩灰样中钠的质量分数W3a,进而得到燃烧过程中高碱煤的总钠释出率R1,其计算式为:
R1=WtW3aWt
式中:WtW3a为1 g原煤在燃烧时释出的总钠量。
再对1 g原煤样品进行上述水洗处理并烘干,此时原煤中的水溶性钠被水萃取液完全分离出来,水萃取煤中仅剩有机钠,其释出的有机钠量即为1 g原煤在燃烧过程中所释出的有机钠量。将水萃取煤按照上述相同的实验条件和步骤进行燃烧实验,并通过ICP-OES对消解灰样的消解液进行检测和定量分析从而得到煤在燃烧后所剩灰样中钠的质量分数W3b(mg/g)。进而得到燃烧过程中高碱水萃取煤的有机钠释出率R2,其计算式为:
R2=W2W3bW2
式中:W2W3b为1 g原煤在燃烧时所释出的有机钠量。
在得到1 g原煤燃烧时所释出的总钠量和有机钠量后,即可计算得出1 g原煤燃烧时所释出的水溶性钠量,以及高碱煤中的水溶性钠释出率R3,其计算公式如下:
R3=(WtW3a)(W2W3b)W1
式中:(WtW3a)–(W2W3b)为1 g原煤在燃烧时所释出的水溶性钠。
热解实验是在300、500、700、900 ℃ 4个温度条件中进行,使用氮气作为气氛,将盛有1 g原煤煤粉样品的瓷舟放置于保温区域,并对煤粉样品进行热解,在煤焦冷却至25 ℃后将煤焦取出,并对其进行消解,通过ICP-OES对得到的消解液进行检测和定量分析。后面的计算过程与上述原煤进行燃烧实验时的计算过程相同。
煤中钠的释出受多种因素影响,煤质、矿物质含量、水分含量、挥发分量等都会对钠的释出造成较大影响[22-25],来自不同矿区的3种煤样因煤质成分不同,钠的释出会有区别,其中低碱煤乌东煤与另2种高碱煤在煤质成分上差别较大。
图2为高碱煤燃烧实验过程中的钠释出率。由图2可知,实验温度从300 ℃上升到500 ℃时,五彩湾煤总钠释出率由5.0%增长至9.0%,天池能源煤总钠释出率由10.0%增长至16.3%,总钠释出量小幅上升。这是因为在此温度条件下煤样中会有水分蒸发以及挥发分的脱除,在水分蒸发时水溶性钠会被水分带至煤粉表面并释出,或粘黏在表面上并在之后的燃烧阶段中释出。实验温度从600 ℃上升到800 ℃时,五彩湾煤总钠释出率从16.8%增长至34.0%,天池能源煤总钠释出率从21.4%增长至38.7%。此温度条件下,由于固定碳的燃烧,水溶性钠和有机钠都会随着燃烧而较多释出。实验温度从900 ℃上升到1 100 ℃时,五彩湾煤总钠释出率从40.0%增长至67.7%,天池能源煤总钠释出率从47.3%增长至63.3%,2种煤样在该阶段含钠矿物质熔化蒸发,导致无机矿物质中的残渣态钠挥发是总钠释出率增长较大的主要原因。五彩湾煤、天池能源煤在1 100 ℃时钠并未完全释出,这是因为一定量钠因反应生成含钠的硅铝酸盐,变成不溶性钠而无法释出。
图2可以看出:实验温度从300 ℃上升到500 ℃时,乌东煤总钠释出量明显上升,钠释出率从28.5%增长至50.0%,在该温度条件下水溶性钠和有机钠会随水分蒸发挥发分脱除而释出,且在500 ℃下大部分钠已经释出;实验温度从500 ℃上升到1 100 ℃时,乌东煤总钠释出率从50.0%增长至66.2%,钠释出量缓慢增加,乌东煤在此阶段大部分可释出钠并不是直接释出,而是因为附着在碳粒子上随固定碳燃烧与可燃物一同释出。
对比天池能源煤与五彩湾煤这2种高碱煤可知,2种煤样在燃烧过程中钠的释出特性相似。低碱煤乌东煤与另2种高碱煤相比,钠的释出特性差异较大,由此可见煤质不同对钠释出的影响较大。
图3为高碱水萃取煤燃烧过程中有机钠释出率。由图3可知:实验温度从300 ℃上升到500 ℃时,五彩湾水萃取煤中有机钠释出率会从9.5%小幅增长至13.1%,此时的有机钠随着挥发分脱除而释出,部分有机钠由于附着在碳颗粒上而无法释出;在600~800 ℃时,五彩湾水萃取煤中因有机物燃烧而释出的有机钠有限,同时一定量的有机钠在固定碳燃烧时会反应形成不溶性钠而无法释出,此温度范围内的有机钠释出率在11.0%~13.0%,释出率依然较低;在1 100 ℃时五彩湾水萃取煤的有机钠释出率仅有32.0%,煤中仍有较多的有机钠未释出,这是由于五彩湾煤中铁和钙的质量分数较高,有机钠会由于含铁和含钙矿物质与钠之间的反应,而导致释出受到抑制。
图3可以看出:实验温度从300 ℃上升到500 ℃时,天池能源水萃取煤中钠的释出率从16.7%增长至31.0%,且增长速度较快,这是因为有机钠在脱挥发分阶段迅速分解并释出;实验温度从600 ℃上升到1 100 ℃时有机钠释出率会因固定碳燃烧从31.7%增长至51.2%,并高于同为高碱煤的五彩湾水萃取煤,这是由于2种煤样的成分不同而导致水萃取煤有机钠释出率的差异。
实验温度从300 ℃上升到500 ℃时,乌东水萃取煤有机钠释出率从10.3%增长至38.5%,增长明显。通过与原煤的总钠释出率对比分析可知,在该温度条件下乌东煤中钠释放量的提高,是因为有机钠释出量上升;在500~1 100 ℃时乌东水萃取煤的有机钠释出率会随碳燃烧而从38.5%平缓增长至53.2%,在3种煤样中钠释出率最高。
图4为高碱煤在燃烧过程中水溶性钠的释出特性。由图4可知:实验温度从300 ℃上升到500 ℃时,由于水分蒸发,五彩湾煤中水溶性钠释出量会从2.4%小幅增长至8.4%,但此时没有剧烈燃烧,所以只有较少的水溶性钠释出;实验温度从600 ℃上升到1 100 ℃时,五彩湾煤水溶性钠释出量会逐渐升高,并且随着燃烧愈发剧烈,五彩湾煤中水溶性钠释出率从19.2%持续上升至90.0%,上述现象表明在燃烧初期并不会直接释出大量水溶性钠,水溶性钠会先在煤粉表面上黏附,到燃烧中后期才会随着固定碳燃烧而大量释出;在800~1 100 ℃时煤中有机物燃烧完全,此时有部分水溶性钠未释出,这是因为在燃烧时这部分水溶性钠转化成不溶性钠而无法释出。同时从图4中可以看出,同为高碱煤的天池能源煤与五彩湾煤水溶性钠的释出特性相似。
图4可知,实验温度从300 ℃上升到500 ℃时,乌东煤中水溶性钠释出率从54.0%增长至66.6%,并且在300 ℃的温度条件下就已超过50.0%,远高于另2种高碱煤煤样。随着实验温度逐渐升高,水溶性钠会因有机物燃烧而持续释出。由于乌东煤中钠含量较低,所以在释出过程中水溶性钠释出率增长缓慢。在800~1 100 ℃的温度条件下,乌东煤中可燃物燃烧完全,但仍有水溶性钠未释出,这是因为一定量水溶性钠在燃烧时因反应形成含钠的硅铝酸盐,变成不溶性钠而无法释出。
图5为高碱煤热解过程中总钠的释出特性。钠在燃烧气氛中主要以气化成钠氧化物形式释出;而钠在热解气氛中主要是以氯化钠和钠原子形式释出。煤中水溶性钠在热解过程中被蒸发水分带至煤粉表面,并在煤粉表面粘黏或者释出。天池能源煤和五彩湾煤在300 ℃时只能通过水分蒸发释出部分钠,所以总钠释出率偏低,均在10.0%以下。在300 ℃的温度条件下,乌东煤由于水分蒸发比例较大,因此总钠释出率较高,达到了21.0%,在水分完全蒸发后,因乌东煤能较好地脱除挥发分,所以在乌东煤中占比较高的有机钠会随之大量释出,在500 ℃的温度条件下乌东煤的总钠释出率会上升至43.7%。由于乌东煤中挥发分在700 ℃和900 ℃的温度条件下脱除充分。所以总钠释出率会在温度上升到700 ℃和900 ℃时进一步上升,并最终达到55.6%。通过对比可知,热解时总钠释出率比燃烧时低,这是因为在热解过程中缺乏氧气,所以热解过程较为缓慢,并且煤中的钠可能因为热解过程中燃烧不剧烈在碳颗粒上粘黏而无法释出。由图5可知,钠在上述2种气氛的同一高温条件下总钠释出率差别不大,而钠在900 ℃的温度下仍未完全释出,这是因为煤中一部分有机钠和水溶性钠转化为不溶性钠。
图6为高碱水萃取煤在热解过程中的有机钠释出率。由图6可知:在900 ℃时五彩湾水萃取煤在热解过程中有机钠释出率比另2种煤样低23.0%左右,这是因为五彩湾水萃取煤中含钙和含铁等矿物质质量分数较高,煤中钠和含钙、含铁矿物质反应,导致有机钠释出减少;天池能源水萃取煤与五彩湾水萃取煤相比,只有少量有机钠会发生反应,所以有机钠释出率更高;乌东水萃取煤中有机钠在热解时会转变为羧酸钠等,并进一步分解释出[23],乌东水萃取煤中有机钠质量在总钠中占比较高,其释出率也会高于五彩湾水萃取煤并在燃烧后期与天池能源水萃取煤相近。
图6也可知,水萃取煤在900 ℃的温度条件下有机钠未能完全释出,这说明在释出过程中,煤中有一定量有机钠转化为不溶性钠而无法释出。
图7为高碱煤热解过程中水溶性钠的释出率。由图7可知,在热解过程中,2种高碱煤水溶性钠的释出特性相似,热解时因缺乏固定碳燃烧阶段而导致水溶性钠与煤粉黏合无法释出,所以热解时的水溶性钠释出率要比燃烧时低。
从上述分析可知,钠释出量会因热解过程而减少,通过热解提质煤能得到热值较高的煤,并使钠的释出量降低。3种煤中水溶性钠在燃烧和热解时的释出特性相似,这说明无论煤质中钠含量高低,其水溶性钠在燃烧时的释出特性与热解时基本一致,这是因为水溶性钠释出路线简易,赋存方式相对单一。
钠的释出途径会因气氛不同而存在差异,本文将水溶性钠和有机钠在热解气氛和燃烧气氛下的释出特性进行比较。图8为五彩湾煤中2种不同赋存形态钠的释出特性。
图8可知,在300~500 ℃的温度条件下,有机钠在燃烧气氛下的释出率高于水溶性钠,而水溶性钠释出率随着温度上升也会快速增长,在500 ℃之后高于有机钠释出率。煤中不同赋存形态钠会以氧化物形式或者以钠原子形式释出,从而导致二者释出特性差别较大。有机钠会分解并且转化为挥发分释出,而水溶性钠的释出主要是以氯化钠的形式[26],释出途径与有机钠相比更加简单,所以水溶性钠释出率更高,五彩湾煤中钠以水溶性钠形式释出为主。有机钠需要经过分解转化,导致其释出过程更加复杂,有机钠在释出过程中会与固定碳黏连,与煤中的物质发生反应,同时其与乌东煤和天池能源煤相比,含有较高的钙和铁,导致有机钠释出量明显减少,由此看出有机钠的释出受煤质的影响较大。在热解气氛下,钠的释出途径和转化物会发生变化,但是释出特性仍与燃烧时相似,说明气氛改变对钠的释出影响较小,同时由于在热解气氛下燃烧较为平和,钠会和含钙、铁等矿物质发生反应并会有一定量钠附着在煤粉上而无法释出,所以在热解气氛下钠释出率会比燃烧气氛低。
图9为天池能源煤有机钠和水溶性钠在燃烧和热解气氛下的释出率。
图9可知:在300~900 ℃时,燃烧气氛下天池能源煤中水溶性钠释出率会低于有机钠,水溶性钠在实验温度上升时,释出速度会迅速提升;而气氛不同对天池能源煤有机钠的释出影响较小,与燃烧气氛相比,热解气氛下有机钠的释出只在转化的含钠化合物形式和释出途径上有所差异。
图10为乌东煤有机钠和水溶性钠在燃烧和热解气氛下的释出率。由图10可知,在全部实验温度条件下乌东煤中有机钠释出率一直低于水溶性钠。水溶性钠释出率在起始温度下较高,燃烧和热解气氛下分别超过了50.0%和35.0%,这是因为乌东煤中水分蒸发比例较高,在燃烧气氛下钠随水分来到煤粉表面并释出或者附着在煤粉表面,在固定碳燃烧时释放而在热解气氛下,水溶性钠会随蒸发水分至煤粉表面并直接释放,所以在相同的实验条件下水溶性钠释出率会高于有机钠;在实验温度从300 ℃上升至500 ℃时,燃烧气氛下的有机钠释出率会因固定碳燃烧从10.7%大幅增长至42.0%,热解气氛下随着挥发分脱除量的增加,有机钠释出率也会从9.2%增长至34.0%。可以看出,有机钠和水溶性钠在2种不同气氛下的释出途径会发生变化,但释出特性相似。
有机钠和水溶性钠的释出过程有所不同,有机钠会分解并且转化为挥发分释出,释出过程较为复杂;而水溶性钠的释出主要由蒸发水分带至煤粉颗粒表面并直接释放,或者是附着在煤粉颗粒表面在固定碳燃烧时释放,释出过程简易,从而2种不同赋存形态的钠释出率有所差异。
同时有机钠释出率在不同气氛的高温条件下均低于水溶性钠,钠的转化物和释出途径会因不同气氛而有所差异。在燃烧气氛下,钠气化的主要形式是钠的氧化物,在还原气氛下钠气化的主要形式是钠原子。而不同气氛的释出途径会由于还原气氛下缺乏氧气,没有固定碳的燃烧阶段而有所不同,但煤中钠的释出依然遵循相似的释出特性,这说明钠释出受气氛变化的影响较小,赋存状态和煤质的不同是影响钠释出的主要原因。
1)五彩湾煤和天池能源煤2种高碱煤的钠释出特性基本一致,高碱煤在进行燃烧实验时,在300~500 ℃时钠的释出量增加缓慢,500~1 100 ℃时钠的释出量增加较快;低碱煤在300~500 ℃时钠的释出量增加较快,500~1 100 ℃时钠的释出量增加缓慢。高碱煤和低碱煤钠释放的过程差异明显,可以看出煤质不同是影响钠释出的主要原因之一,钠释出会因煤质中成分差异而受到较大影响。
2)高碱煤和低碱煤中钠在热解和燃烧过程中释出特性基本一致,钠释出受气氛影响较小,不同气氛主要是对钠释出形成的含钠生成物有所影响,热解过程中钠释出率会比燃烧过程低7.0%左右,这是因为热解过程钠更容易附着在煤焦颗粒上,减少了释出。
3)有机钠和水溶性钠因释出途径不同,有机钠会分解并且转化为挥发分释出,释出过程较复杂,而水溶性钠的释出主要由蒸发水分带至煤粉颗粒表面并直接释放,或者是附着在煤粉颗粒表面在固定碳燃烧时释放,释出过程简易,因此二者释出特性会有所差异,高温条件下有机钠释出率低于水溶性钠。有机钠和水溶性钠在热解和燃烧过程中都不会完全释出,有一定量的钠向不溶性钠转化而无法释出。
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2024年第53卷第1期
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doi: 10.19666/j.rlfd.202309164
  • 接收时间:2023-09-22
  • 首发时间:2025-12-25
  • 出版时间:2024-01-25
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  • 收稿日期:2023-09-22
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National Key Research and Development Program(2022YFB4202000)
国家重点研发计划项目(2022YFB4202000)
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    1.广东红海湾发电有限公司,广东 汕尾 516000
    2.湛江中粤能源有限公司,广东 湛江 524000
    3.华中科技大学能源与动力工程学院,湖北 武汉 430074
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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