Article(id=1213131703468605769, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1213131702797517129, articleNumber=null, orderNo=null, doi=10.19666/j.rlfd.202306094, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1685894400000, receivedDateStr=2023-06-05, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1767162737003, onlineDateStr=2025-12-31, pubDate=1708790400000, pubDateStr=2024-02-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1767162737003, onlineIssueDateStr=2025-12-31, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1767162737003, creator=13701087609, updateTime=1767162737003, updator=13701087609, issue=Issue{id=1213131702797517129, tenantId=1146029695717560320, journalId=1210938733613449225, year='2024', volume='53', issue='2', pageStart='1', pageEnd='198', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1767162736844, creator=13701087609, updateTime=1767168616029, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1213156361978954089, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1213131702797517129, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1213156361978954090, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1213131702797517129, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=162, endPage=169, ext={EN=ArticleExt(id=1213131703716069708, articleId=1213131703468605769, tenantId=1146029695717560320, journalId=1210938733613449225, language=EN, title=Experimental study on high temperature reaction characteristics of H2S based on TDLAS, columnId=1211002409397129992, journalTitle=Thermal Power Generation, columnName=Power generation technology forum, runingTitle=null, highlight=null, articleAbstract=

H2S is an important product produced by power plant boilers in the process of low NOx combustion. To solve the problems that H2S may cause various hazards to thermal power plants due to its inflammability, strong corrosion and extreme toxicity, tunable diode laser absorption spectroscopy (TDLAS) method combined with multi-pass cell and computer is employed to build an online measurement system for detecting the molar fraction of low-concentration gas. By using this measurement system, accurate online measurement of H2S in the mixed gas with the molar fraction of 10–6 magnitude is realized, and the H2S high-temperature reaction experiment is carried out to explore the influence of experimental temperature and the molar fraction of O2 in the mixed gas on the reaction. The experimental results show that, under the conditions of pressure of 80 kPa and molar fraction of O2 ranging from 0 to 5%, the temperature at which H2S begins to react changes with the molar fraction of O2. On the whole, the higher the molar fraction of O2 in the mixed gas, the lower the temperature at which H2S begins to react. The experimental results can provide some data basis for the generation, transformation and harm control of H2S in boiler flue gas.

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电站锅炉在低NOx燃烧过程中因锅炉内还原性气氛浓度较高,会产生较多H2S气体。针对H2S因具有易燃、强腐蚀性、剧毒性而可能对火电厂造成多种危害的问题,采用可调谐二极管激光吸收光谱(tunable diode laser absorption spectroscopy,TDLAS)方法结合多通池和计算机搭建低气体摩尔分数在线测量系统,实现了对混合气体中摩尔分数在10–6量级H2S的精确在线测量,并利用该测量系统进行了H2S高温反应实验,探究实验温度和混合气体中O2摩尔分数对该反应的影响。实验结果展示了压力为80 kPa、O2摩尔分数为0~5%的条件下,H2S开始发生化学反应的温度随O2摩尔分数变化的变化规律,整体而言,混合气体中O2摩尔分数越高,H2S开始发生化学反应的温度越低。实验结果可以为锅炉烟气中H2S的生成、转化和危害控制提供一定数据基础。

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杜艳君(1991),女,博士,副教授,主要研究方向为基于多光谱融合的热工过程气体参数测量技术开发,
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王嘉琦(1988),男,硕士,主要研究方向为热控自动化应用与维护,

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王嘉琦(1988),男,硕士,主要研究方向为热控自动化应用与维护,

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Parameter setting and measurement result of continuous on-line measurement of H2S concentration

, figureFileSmall=null, figureFileBig=null, tableContent=
持续时
间/min
H2S流量/
(mL·min–1
N2流量/
(mL·min–1
H2S配气摩尔分数/(×10–6H2S测量摩尔分数/
(×10–6
1001 00007
100900200238
200800400473
300700600692
400600800894
5005001001 082
400600800893
300700600694
200800400476
100900200239
01 00007
), ArticleFig(id=1213131714398962357, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1213131703468605769, language=CN, label=表1, caption=

H2S气体摩尔分数连续在线测量实验参数设置与测量结果

, figureFileSmall=null, figureFileBig=null, tableContent=
持续时
间/min
H2S流量/
(mL·min–1
N2流量/
(mL·min–1
H2S配气摩尔分数/(×10–6H2S测量摩尔分数/
(×10–6
1001 00007
100900200238
200800400473
300700600692
400600800894
5005001001 082
400600800893
300700600694
200800400476
100900200239
01 00007
), ArticleFig(id=1213131714499625660, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1213131703468605769, language=EN, label=Tab.2, caption=

Process parameters of H2S high-temperature reaction experiment (take 3% concentration O2 as an example)

, figureFileSmall=null, figureFileBig=null, tableContent=
持续时间/min温度/KP/kPa99.99%N2流量/(mL·min–1)20%O2流量/(mL·min–1)0.1% H2S流量/(mL·min–1)
1530080280120400
5<180000
1535080280120400
5<180000
1540080280120400
5<180000
1545080280120400
5<180000
15~3050080280120400
5<180000
15~3555080280120400
5<180000
15~3060080280120400
5<180000
1565080280120400
5<180000
1570080280120400
), ArticleFig(id=1213131714633843398, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1213131703468605769, language=CN, label=表2, caption=

H2S高温反应实验过程参数(以O2摩尔分数3%为例)

, figureFileSmall=null, figureFileBig=null, tableContent=
持续时间/min温度/KP/kPa99.99%N2流量/(mL·min–1)20%O2流量/(mL·min–1)0.1% H2S流量/(mL·min–1)
1530080280120400
5<180000
1535080280120400
5<180000
1540080280120400
5<180000
1545080280120400
5<180000
15~3050080280120400
5<180000
15~3555080280120400
5<180000
15~3060080280120400
5<180000
1565080280120400
5<180000
1570080280120400
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基于TDLAS的H2S高温反应特性实验研究
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王嘉琦 1 , 田思迪 2 , 高东波 1 , 田志伟 1 , 彭志敏 2 , 杜艳君 3
热力发电 | 发电技术论坛 2024,53(2): 162-169
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热力发电 | 发电技术论坛 2024, 53(2): 162-169
基于TDLAS的H2S高温反应特性实验研究
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王嘉琦1 , 田思迪2, 高东波1, 田志伟1, 彭志敏2, 杜艳君3
作者信息
  • 1.京能秦皇岛热电有限公司,河北 秦皇岛 066003
  • 2.清华大学能源与动力工程系电力系统及发电设备控制与仿真国家重点实验室,北京 100084
  • 3.华北电力大学控制与计算机工程学院,北京 102206
  • 王嘉琦(1988),男,硕士,主要研究方向为热控自动化应用与维护,

通讯作者:

杜艳君(1991),女,博士,副教授,主要研究方向为基于多光谱融合的热工过程气体参数测量技术开发,
Experimental study on high temperature reaction characteristics of H2S based on TDLAS
Jiaqi WANG1 , Sidi TIAN2, Dongbo GAO1, Zhiwei TIAN1, Zhimin PENG2, Yanjun DU3
Affiliations
  • 1.Jingneng Qinhuangdao Thermal Power Co., Ltd., Qinhuangdao 066003, China
  • 2.State Key Laboratory of Power Systems, Department of Energy and Power Engineering, Tsinghua University, Beijing 100084, China
  • 3.School of Control and Computer Engineering, North China Electric Power University, Beijing 102206, China
出版时间: 2024-02-25 doi: 10.19666/j.rlfd.202306094
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电站锅炉在低NOx燃烧过程中因锅炉内还原性气氛浓度较高,会产生较多H2S气体。针对H2S因具有易燃、强腐蚀性、剧毒性而可能对火电厂造成多种危害的问题,采用可调谐二极管激光吸收光谱(tunable diode laser absorption spectroscopy,TDLAS)方法结合多通池和计算机搭建低气体摩尔分数在线测量系统,实现了对混合气体中摩尔分数在10–6量级H2S的精确在线测量,并利用该测量系统进行了H2S高温反应实验,探究实验温度和混合气体中O2摩尔分数对该反应的影响。实验结果展示了压力为80 kPa、O2摩尔分数为0~5%的条件下,H2S开始发生化学反应的温度随O2摩尔分数变化的变化规律,整体而言,混合气体中O2摩尔分数越高,H2S开始发生化学反应的温度越低。实验结果可以为锅炉烟气中H2S的生成、转化和危害控制提供一定数据基础。

TDLAS  /  H2S  /  在线测量  /  高温反应  /  O2摩尔分数

H2S is an important product produced by power plant boilers in the process of low NOx combustion. To solve the problems that H2S may cause various hazards to thermal power plants due to its inflammability, strong corrosion and extreme toxicity, tunable diode laser absorption spectroscopy (TDLAS) method combined with multi-pass cell and computer is employed to build an online measurement system for detecting the molar fraction of low-concentration gas. By using this measurement system, accurate online measurement of H2S in the mixed gas with the molar fraction of 10–6 magnitude is realized, and the H2S high-temperature reaction experiment is carried out to explore the influence of experimental temperature and the molar fraction of O2 in the mixed gas on the reaction. The experimental results show that, under the conditions of pressure of 80 kPa and molar fraction of O2 ranging from 0 to 5%, the temperature at which H2S begins to react changes with the molar fraction of O2. On the whole, the higher the molar fraction of O2 in the mixed gas, the lower the temperature at which H2S begins to react. The experimental results can provide some data basis for the generation, transformation and harm control of H2S in boiler flue gas.

TDLAS  /  H2S  /  on-line measurement  /  high temperature reaction  /  O2 molar fraction
王嘉琦, 田思迪, 高东波, 田志伟, 彭志敏, 杜艳君. 基于TDLAS的H2S高温反应特性实验研究. 热力发电, 2024 , 53 (2) : 162 -169 . DOI: 10.19666/j.rlfd.202306094
Jiaqi WANG, Sidi TIAN, Dongbo GAO, Zhiwei TIAN, Zhimin PENG, Yanjun DU. Experimental study on high temperature reaction characteristics of H2S based on TDLAS[J]. Thermal Power Generation, 2024 , 53 (2) : 162 -169 . DOI: 10.19666/j.rlfd.202306094
目前煤炭在我国一次能源消费中仍占据大半份额,化石燃料消费也处于持续缓慢增长的过程中[1-3]。由于燃煤技术较为成熟、供能稳定,长期看来,煤电将在能源结构低碳转型和保障能源安全方面继续发挥不可替代的作用。煤炭的燃烧会生成大量含氮、硫、汞的污染物,为了控制火电机组运行时产生的NOx、SOx、烟尘等大气污染物排放,我国实施了超低排放和节能改造[4-6]。针对火电厂的NOx排放问题,目前的解决方案主要是在锅炉内部采用分级燃烧、烟气再循环等低氮燃烧技术以及在烟气排放前进行脱硫、脱硝处理[7-11]。但是锅炉中O2摩尔分数降低同时导致还原性气氛(H2S和CO)摩尔分数明显增加,炉膛贴壁烟气中还原性气体摩尔分数尤其高[12-14]。在长期运行条件下,锅炉辐射和对流换热面上会形成灰、渣等积垢。在还原性气氛中,煤灰渣中铁主要以低熔点的FeS和FeO形式存在,导致灰熔点较低、更易在水冷壁表面结渣,进而加剧水冷壁腐蚀[15-18]
H2S作为一种剧毒、易燃、易腐蚀的酸性气体,与燃烧状态紧密相关,是锅炉燃烧产生的重要还原性气体之一,在能源电力、化工生产等多个领域中都是重要的中间产物或排放物质[19-21]。因此,在线精确测量H2S摩尔分数并探究其化学反应过程对工业安全生产、生态环境保护和人体健康安全有重要意义[22-23]。同时,在锅炉贴壁气氛中,O2摩尔分数、温度、H2O摩尔分数等因素对H2S摩尔分数影响相关的定量实验研究较少,与该气体对水冷壁材料腐蚀速率影响的相关研究同样较少且缺乏可靠的定量实验分析。如果能够实现实时测量H2S摩尔分数变化,则可以进行定量实验探究H2S与O2的高温反应特性。
目前可用于测量H2S气体的方法主要包括以下几种:1)气相色谱检测,对气体摩尔分数具有较高测量精度,但预处理系统复杂,测量中存在样气失真、响应速度慢等问题,不适合用于气体摩尔分数在线测量监测;2)电化学气体传感器,响应范围比较宽、稳定性强、技术成熟、操作简单,缺点是传感器材料会被消耗和污染,并且实际应用中容易受到其他气体组分和环境干扰,如部分H2S传感器也会与SO2发生反应;3)比较先进的荧光探针法,主要用于对等离子体中H2S的分析,难以应用到工业现场在线监测,不符合工业应用条件;4)可调谐二极管激光吸收光谱(tunable diode laser absorption spectroscopy,TDLAS)技术,在均匀气态物质的温度、摩尔分数等参数检测方面具有灵敏度高、选择性强、易实现低检测限等优势,适用于多组分气体中的痕量H2S摩尔分数测量[24-27]
因此,本文采用TDLAS测量方法结合多通池和计算机实现对多组分中H2S气体的测量,在此基础上利用高温炉进行了H2S与O2的高温反应实验,实验结果将有助于锅炉运行时的各项参数设置优化,并给炉膛内燃烧状况判断提供一种指示标准,同时有助于预防或减轻水冷壁的结渣、腐蚀现象。
频率为ν的激光经过含有待测气体介质的腔室时,出射光强It和入射光强I0满足Beer-Lambert定律:
α(v)=ln(ItI0)=pLS(T)χφ(ν)
式中:p为腔室内总气压;L为光程,cm;S(T)为待测气体吸收谱线的线强度;T为环境温度,K;χ为气体摩尔分数;α(ν)为谱线的吸收率;φ(ν)为线型函数。
因此,通过探测激光通过吸收物质后的光强度衰减量可以计算得到物质在该光谱区域的吸收率,进而获得气体摩尔分数、温度等参数。
线型函数φ(ν)用于描述单个吸收谱线的轮廓,目前被广泛应用的一种模型是Voigt线型(Voigt profile,VP),其表达式如下:
φV(x,y)=ARe[W(x,y)]
其中W(x,y)为:
W(x,y)=iπ+exp(t2)x+iytdt
式中:A=ln2/π/ΔvDy=ln2ΔvC/ΔvDx=ln2(vv0)/ΔvDΔvC=Pkχkγk(T)γk(T)为物质k的碰撞展宽系数。
二次速度相关的Voigt模型(quadratic speed-dependent Voigt profile,qSDVP)提供一个解释与分子速度相关的碰撞展宽的参数ΔνC,2(cm-1)比VP更符合实际谱线轮廓,其表达式如下:
φqSDVP(z,z+)=ARe[w(iz)w(iz+)]
式中:z±=X+Y±YXY的表达式如式(5)。
X=[i(vv0)+ΔνC3ΔνC,2/2]/ΔνC,2Y=(ΔvD/ΔvC,2)2/4/ln2
直接吸收光谱(direct absorption spectroscopy,DAS)是用波长可调谐连续激光扫描待测物质因能级跃迁得到的吸收光谱。以H2S分子在近红外波段的一个跃迁直接吸收光谱测量结果为例,图1展示了当扫描信号为正弦波时对该跃迁的It信号(蓝色)的测量结果,以及用干涉仪对该扫描信号波长标定(橙色)的测量结果,干涉仪自由光谱区(FSR)为0.05 cm–1,图中红点为测量所得相对波长数值,绿色线条是根据波长测量值对光束波长的反演值。
H2S分子在近-中红外波段谱线吸收强度较弱且容易受到CO2、CO、H2O等常见气体分子谱线干扰,这4种气体的一个标准大气压下谱线线强度分布如图2所示。
图2中H2S在2.5 μm处一个标准大气压下谱线线强度最大,达到4.5×10–2 cm–2,但该波段谱线在实际测量中,尤其是应用于大气环境监测或工业气体分析时极容易受到CO2、H2O等气体干扰,即使在低压条件下也难以单独、准确地测量H2S;同时中红外激光器及探测系统不仅技术成熟度较差,而且价格昂贵。相较而言,H2S分子在1.58 μm波段虽然线强度较小(约为2.5 μm处的1/10),但受其他气体分子吸收光谱干扰较小,具有在复杂工业现场中用于测量H2S气体的潜力。经过仿真和实验分析,选择中心频率为6 336.62 cm–1的谱线作为实验测量吸收谱线。
气体摩尔分数在线测量及高温反应实验系统如图3所示,可分为气路和光路2部分。在气路部分,采用H2S标准气体(H2S摩尔分数2×10-3,N2作为稀释气体),N2标准气体(N2摩尔分数99.99%)和经过配气的O2用质量流量计进行流动配气,气体在混合气室中混合均匀后输入到高温管式炉加热的不锈钢容器(容积约535 mL)中,从高温容器流出的反应后气体产物进入Herriott池(光程为48.27 m),利用吸收光谱检测混合物中剩余H2S的摩尔分数,气体流出Herriott池后经过碱性溶液将剩余酸性气体吸收后将废气排出;在光路部分,采用DAS方法进行摩尔分数测量,中心频率为1 578 nm的DFB激光器在控制器的作用下输出扫描波长信号为正弦波的激光。激光在分束器的作用下分为2束,在Herriott池中经过吸收的透射光束被探测器探测后转化为电信号传输到采集卡,由采集卡转化为数字信号后输入计算机;经过干涉仪的光束用于校准激光相对波长,同样被探测后经过采集卡传输到计算机中进行处理。
在进行高温实验前,进行常温下流动气体摩尔分数在线测量实验以验证整个实验系统的测量精度和灵敏度。气体摩尔分数连续在线测量实验的配气总流量设置为1 L/min,H2S气体的配比摩尔分数设置为0~1×10–3等差分布取6个值,在每个摩尔分数下流动配气的时间为10 min,设定H2S摩尔分数从低到高再到低变化,具体如表1所示。表1的前4列展示了流动配气过程中H2S和N2标准气体所采用的质量流量控制器的参数设置以及混合气体中H2S的理论摩尔分数。表1的最后一列展示了每个阶段混合气体中H2S摩尔分数的实时测量值的平均值,本次实验在室温下(295 K)进行。
图4展示了实验全程H2S摩尔分数的实时测量值以及每个摩尔分数,即配气参数下气体摩尔分数的平均测量值,此系统每0.3 s可获取1个气体摩尔分数数据。由图4可知,H2S摩尔分数的测量值与流动配气的理论摩尔分数存在一定偏差。当H2S配气摩尔分数为0时,测量摩尔分数的平均值为7×10–6,考虑到质量流量计存在1%满量程的流量误差,此结果在合理范围内。为了减小实验仪器引起的误差,实验系统的气路始终保持H2S和N2 2路转接为一路,质量流量计入口处也始终处于正压状态,流量计中阀门无法完全闭合就会导致混合气体中始终存在一定量的H2S;并且在不设置H2S气路、仅使用单气路输送N2流经Herriott池时,程序显示H2S摩尔分数测量值在1×10–15量级波动,可看做是0,此条件下H2S的理论摩尔分数和实际测量摩尔分数都是0,说明程序对摩尔分数的空白值分析是准确的。
对不同配气条件下的H2S摩尔分数平均值和理论上H2S标准气体稀释比例进行线性分析,结果显示其线性相关系数R2=0.998 2,说明H2S的实际测量摩尔分数与其标准气体稀释比例确实存在线性相关关系,这证明实验误差不包含较大的随机误差和粗大误差;该线性关系的斜率为2 160×10–6,此斜率的物理意义是由实验测量结果推算出配气所采用的H2S标准气体的摩尔分数值。考虑到H2S气体具有吸附性,在管路以及气室中流动时容器壁面上会发生H2S吸附和解吸附的过程,这可能导致混合流动气体中H2S的实际摩尔分数与设置配气比例时的理论值不符,以及测量值与实际摩尔分数之间也会存在一定误差。
用H2S平均摩尔分数为7×10–6阶段的摩尔分数值计算该阶段数据的标准差为1.4×10–6。如果按照检出限为空白平均值与3倍标准偏差之和的标准,则该实验系统对H2S摩尔分数的最低检出限为4.2×10–6。从图4中各个配气摩尔分数阶段的测量结果可以看出H2S摩尔分数从低到高再到低过程中配气参数相同的阶段摩尔分数测量平均值也基本相同,计算结果显示偏差不超过3×10–6,考虑到质量流量控制器本身的流量误差,该偏差可以忽略,可以认为该实验系统对H2S摩尔分数测量的复现性比较好。
为进一步验证该系统的检测限,对该阶段摩尔分数数据的Allan标准差进行分析,结果如图5所示。图5中横坐标τ为时间簇,表示对H2S摩尔分数数据进行平均分组时每一组的平均时间长度,纵坐标σ(τ)为Allan标准差,由图5可知,当τ在10~ 20 s范围内σ(τ)较小,τ=13.5 s时,σ(τ)达到极小值,为3×10–7,说明此实验系统在对固定气体摩尔分数进行连续测量时,可以准确分辨摩尔分数在10–7量级的H2S气体摩尔分数变化。实验结果说明此实验系统具有较高的精度和灵敏度。
为探究反应物中O2摩尔分数和温度对H2S高温反应的影响,依托高温管式炉开展H2S高温氧化反应实验,其中高温炉加热温度范围设置为300~700 K(间隔50 K),O2摩尔分数为0~5%,H2S气体分数为500×10–6,气体总流量为800 mL/min,高温炉内的不锈钢反应容器、Herriott池以及管路部分的压力值恒定为80 kPa。
H2S高温反应实验过程参数设置见表2表2中第1列为每个设定温度下实验持续的时间;第2列为高温管式炉的设定温度,其中,空白处表示高温炉处于升温加热状态,加热5 min后进入下一温度;第3列为容器内压力参数,当温度达到指定数值时保持容器内压力为80 kPa,此阶段结束后将整个管路中的压力降低至1 kPa以下,目的是加快管路中气体的更替速率;第4列为摩尔分数为99.99%的氮气标准气体的配气流量参数,当处于稳定温度阶段时,该参数配合氧气和H2S的流量,使气体总流量恒定;第5列为摩尔分数为20%的O2配气流量,其流量设置与实验要求的O2摩尔分数相关,以摩尔分数3% O2的氧化反应实验为例,温度稳定时其流量为120 mL/min,加热阶段流量为0;最后一列是不同温度阶段的摩尔分数0.1% H2S标准气体配气流量。实验过程中对管路和容器内压力的控制通过调整Herriott池出口阀门进行,对不同气体的流量控制通过调整质量流量控制器实现。
对经过不同温度状态下包含H2S的混合气体进行连续测量,结果如图6所示。图中横坐标为时间,纵坐标为混合物中H2S摩尔分数实时检测结果,其中高位摩尔分数值表示处于设定温度值,此时H2S摩尔分数测量值为其在反应后生成物中的剩余含量,相邻2个高位摩尔分数值之间的低摩尔分数阶段(H2S摩尔分数近似为0)为升温阶段,此时管路抽真空后用氮气清洗,避免前一反应温度下残留的混合气体对后续气体摩尔分数测量的影响。反应物在每个温度下的持续流动时间设置为15 min。但是从实验过程中可以发现在某些温度下,生成物中的H2S摩尔分数不能在此时间范围内达到稳定值,因此需延长高温炉在该温度下的恒温持续时间,直至H2S摩尔分数保持在同一数值(±2×10–6)超过3 min。当测量H2S摩尔分数小于4×10–6时,认为H2S已经完全反应。在高温富氧条件下,H2S氧化过程的总包反应可表示如下:
H2S+1.5O2H2O+SO2
因此,可认为本实验条件下H2S与O2反应后的主要产物为SO2
图6可知,O2在摩尔分数1%~5%,当温度小于450 K时,H2S摩尔分数变化量小于5%,说明此温度条件下40 s内H2S几乎不发生氧化反应;当温度大于等于650 K时,生成物中的H2S摩尔分数近似为0,说明此温度条件下H2S的转化率约为100%,且氧化反应在40 s内达到平衡。在H2S发生氧化反应阶段,可以看出生成物中H2S的摩尔分数先达到最大值再缓慢降低、最后达到稳定,推测其主要原因是:改变温度时,在高温反应容器达到指定温度后开始通入混合气体,由于此前管路中充满氮气,虽然压力未发生突变,但是H2S摩尔分数发生了突变,所以在初始阶段H2S会迅速扩散至Herriott池达到摩尔分数均匀状态,部分H2S由于在高温反应容器中停留时间过短、来不及达到氧化反应平衡的条件就先进入Herriott池被检测到。因此初始阶段H2S摩尔分数会升高直至最大值,而后在管路中H2S摩尔分数达到均匀后,流动混合气体在高温反应容器中的停留时间不再发生突变,此时流出气体中的H2S即为真实的剩余摩尔分数,该值需要管路中的气体被缓慢地完全替代后才能较为准确地测量。
图6a)图6b)图6c)中,在温度为550 K时停留时间比其他温度下要长,约为30~35 min,表明此温度下H2S氧化反应速率迅速增大,导致反应前后气体中的H2S摩尔分数变化较大,因此需要更长时间达到稳定摩尔分数状态。出乎意料的是,图6d)中结果表明,在理论上反应物中不包含O2的条件下,当温度足够高(>500 K)时,生成物中的H2S摩尔分数仍然有明显降低,并且该实验进行时去除了O2气路分支以避免由质量流量控制器的误差带来的影响。推测导致该现象的原因可能有3个:1)由于管路并非完全密封装置且实验条件为负压,反应物中可能混入了极少部分来自空气中的O2;2)作为配气源头的N2和H2S标准气体中本身存在痕量的O2成分;3)反应物中的H2S在高温不锈钢容器中与其他成分发生了化学反应,如与金属或可能存在的水蒸气发生了壁面反应,真实情况可能是上述理由中一种或多种情形共同发生的结果。
图7综合展示了H2S经过反应后的剩余摩尔分数与温度和反应物中O2摩尔分数的关系。结果表明,同一O2摩尔分数条件下,温度越高,H2S转化率越高;同一温度阶段下,O2摩尔分数越高,H2S转化率越高。在压力为80 kPa、O2摩尔分数为1%~5%的条件下,H2S转化率的变化速率的温度转折点在500~600 K左右。
本文利用TDLAS技术结合Herriott池设计搭建了能够对混合气体中低摩尔分数H2S进行准确在线测量的气体测量实验系统,结合火电燃煤锅炉实际情况,以O2摩尔分数和温度为变量进行了H2S与O2的高温反应实验。实验结果表明,H2S转化率随温度和O2摩尔分数的升高而升高,在压力80 kPa、O2摩尔分数为1%~5%的条件下,H2S转化率发生变化的温度转折点大概在500~600 K,当温度达到600 K以上时H2S有很大概率不仅与O2发生反应,同时还自身发生裂解或与水冷壁壁面物质发生反应。实验结果可以为火电行业燃煤锅炉燃烧状态的检测、优化以及水冷壁高温腐蚀在线预警提供参考。
  • 中国华能集团有限公司总部科技项目(HNKJ22-H105)
  • 清华大学山西研究院种子基金项目(041509005)
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2024年第53卷第2期
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doi: 10.19666/j.rlfd.202306094
  • 接收时间:2023-06-05
  • 首发时间:2025-12-31
  • 出版时间:2024-02-25
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  • 收稿日期:2023-06-05
基金
Science and Technology Project of China Huaneng Group Co., Ltd.(HNKJ22-H105)
中国华能集团有限公司总部科技项目(HNKJ22-H105)
Tsinghua University Seed Fund of Shanxi Research Institute(041509005)
清华大学山西研究院种子基金项目(041509005)
作者信息
    1.京能秦皇岛热电有限公司,河北 秦皇岛 066003
    2.清华大学能源与动力工程系电力系统及发电设备控制与仿真国家重点实验室,北京 100084
    3.华北电力大学控制与计算机工程学院,北京 102206

通讯作者:

杜艳君(1991),女,博士,副教授,主要研究方向为基于多光谱融合的热工过程气体参数测量技术开发,
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2种不同金属材料的力学参数

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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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