Article(id=1213131707662914010, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1213131702797517129, articleNumber=null, orderNo=null, doi=10.19666/j.rlfd.202307122, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1690041600000, receivedDateStr=2023-07-23, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1767162738003, onlineDateStr=2025-12-31, pubDate=1708790400000, pubDateStr=2024-02-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1767162738003, onlineIssueDateStr=2025-12-31, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1767162738003, creator=13701087609, updateTime=1767162738003, 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=184, endPage=191, ext={EN=ArticleExt(id=1213131707964903906, articleId=1213131707662914010, tenantId=1146029695717560320, journalId=1210938733613449225, language=EN, title=Effect of organic solid waste and coal mixed firing on the formation of heavy metals and particulate matter, columnId=1211002409397129992, journalTitle=Thermal Power Generation, columnName=Power generation technology forum, runingTitle=null, highlight=null, articleAbstract=

Rapidly growth of organic solid waste (OSW) has caused serious social and environmental issues. Co-combustion is an economical and environmental method to treat OSW. However, there will be a variety of heavy metals discharged with flue gas during combustion as OSW contains them. Therefore, this study conducted an experiment on the migration of heavy metals and generation of micro particles during the co-combustion of OSW and lignite. The results show that, the release of heavy metals during combustion not only depends on the concentration of heavy metal the fuel contains, but also on the chemical mechanism at high temperature. The content of Pb, Cd and As in the flue gas of blending fuel is obviously lower than that of sole OSW, but Cu, Zn, Co and Mn shows opposite tendency. In addition, the particle size distribution of the four fuels all shows a normal distribution at 800 ℃ and 850 ℃, but large particle size generates when the combustion temperature rises to 900 ℃.

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有机固体废弃物(OSW)中含有多种重金属,燃烧过程会随烟气排放,造成一定的环境危害,因此对OSW和褐煤掺混燃烧过程灰分中的重金属迁移和颗粒物生成特性进行了实验研究。结果表明:燃料在燃烧过程中各种重金属的释放不单取决于燃料本身的质量浓度,而且和高温作用下的化学机制密切相关;混合燃料烟气中产生Pb、Cd、As元素的含量明显低于典型燃料和校核燃料单独燃烧时烟气中产生的重金属元素含量;而Cu、Zn、Co、Mn在飞灰中均有较高质量分数;800、850 ℃下选用的4种燃料制得的灰分的粒径分布均大致呈现单峰正态分布;当温度升高到900 ℃后,除产生小粒径灰分外,还可能会产生较大粒径的灰分颗粒。

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吴有兵(1981),男,硕士,高级工程师,主要研究方向为火电厂热能与动力工程,

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吴有兵(1981),男,硕士,高级工程师,主要研究方向为火电厂热能与动力工程,

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吴有兵(1981),男,硕士,高级工程师,主要研究方向为火电厂热能与动力工程,

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Industrial analysis, elemental analysis and low calorific value of OSW

, figureFileSmall=null, figureFileBig=null, tableContent=
原料工业分析w/%元素分析w/%低位发热量Qnet,ar/(MJ·kg–1)
FCVAMtCHONSCl
棉布11.2587.920.835.8247.737.0043.870.430.140.16014.78
化纤6.7393.250.023.1879.8211.138.640.360.030.63027.12
EVA3.3674.7521.890.0960.039.378.310.390.010.01726.59
海绵3.9093.842.260.6469.067.2716.375.030.010.11027.46
高泡棉7.6981.9410.371.0758.035.8322.133.630.010.01822.47
聚苯乙烯8.9690.970.070.7460.075.2434.150.460.010.19017.84
竹料14.8983.801.3136.3946.635.6745.580.770.040.02510.28
木料19.0179.041.9510.5849.365.9539.812.920.010.06915.66
PVC6.4061.7131.890.6237.033.2227.810.040.0117.67012.29
再生炭黑62.619.2728.1222.8168.151.240.200.381.910.49017.26
), ArticleFig(id=1213131723458662644, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1213131707662914010, language=CN, label=表1, caption=

垃圾原料工业分析、元素分析以及低位发热量

, figureFileSmall=null, figureFileBig=null, tableContent=
原料工业分析w/%元素分析w/%低位发热量Qnet,ar/(MJ·kg–1)
FCVAMtCHONSCl
棉布11.2587.920.835.8247.737.0043.870.430.140.16014.78
化纤6.7393.250.023.1879.8211.138.640.360.030.63027.12
EVA3.3674.7521.890.0960.039.378.310.390.010.01726.59
海绵3.9093.842.260.6469.067.2716.375.030.010.11027.46
高泡棉7.6981.9410.371.0758.035.8322.133.630.010.01822.47
聚苯乙烯8.9690.970.070.7460.075.2434.150.460.010.19017.84
竹料14.8983.801.3136.3946.635.6745.580.770.040.02510.28
木料19.0179.041.9510.5849.365.9539.812.920.010.06915.66
PVC6.4061.7131.890.6237.033.2227.810.040.0117.67012.29
再生炭黑62.619.2728.1222.8168.151.240.200.381.910.49017.26
), ArticleFig(id=1213131723618046208, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1213131707662914010, language=EN, label=Tab.2, caption=

Industrial analysis and elemental analysis of OSW fuel and Indonesian coal

, figureFileSmall=null, figureFileBig=null, tableContent=
样品工业分析w/%元素分析w/%低位发热量Qnet,v,ar/(MJ·kg–1)
FCVAMtCHONSCl
典型燃料8.0788.843.093.5471.329.2215.161.150.060.50024.84
校核燃料10.0884.575.354.1569.648.6415.161.070.131.28023.98
印尼煤50.2041.718.0923.6167.234.9817.211.181.310.02119.03
), ArticleFig(id=1213131723739681031, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1213131707662914010, language=CN, label=表2, caption=

OSW燃料与印尼煤的工业分析、元素分析以及低位发热量

, figureFileSmall=null, figureFileBig=null, tableContent=
样品工业分析w/%元素分析w/%低位发热量Qnet,v,ar/(MJ·kg–1)
FCVAMtCHONSCl
典型燃料8.0788.843.093.5471.329.2215.161.150.060.50024.84
校核燃料10.0884.575.354.1569.648.6415.161.070.131.28023.98
印尼煤50.2041.718.0923.6167.234.9817.211.181.310.02119.03
), ArticleFig(id=1213131725132189962, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1213131707662914010, language=EN, label=Tab.3, caption=

Mass fractions of heavy metal elements in raw materials

, figureFileSmall=null, figureFileBig=null, tableContent=
重金属棉布化纤EVA海绵高泡棉聚苯乙烯竹料木料聚氯乙烯再生炭黑
Ti0.001 650.103 000.336 000.101 000.022 05
Fe0.006 910.006 300.020 200.008 590.006 660.005 630.004 990.026 400.012 500.196 00
Cu0.021 600.005 180.026 900.018 70
Zn0.165 000.003 000.009 841.890 00
Ba0.109 000.012 500.045 20
Mn0.008 75
Pb0.011 80
Br0.041 50
Sr0.005 51
Co0.011 60
As0.026 90
Pd0.047 00
Sn0.010 30
Cd0.052 10
), ArticleFig(id=1213131725245436172, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1213131707662914010, language=CN, label=表3, caption=

原料中重金属元素质量分数

, figureFileSmall=null, figureFileBig=null, tableContent=
重金属棉布化纤EVA海绵高泡棉聚苯乙烯竹料木料聚氯乙烯再生炭黑
Ti0.001 650.103 000.336 000.101 000.022 05
Fe0.006 910.006 300.020 200.008 590.006 660.005 630.004 990.026 400.012 500.196 00
Cu0.021 600.005 180.026 900.018 70
Zn0.165 000.003 000.009 841.890 00
Ba0.109 000.012 500.045 20
Mn0.008 75
Pb0.011 80
Br0.041 50
Sr0.005 51
Co0.011 60
As0.026 90
Pd0.047 00
Sn0.010 30
Cd0.052 10
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吴有兵 1 , 杨阳 2, 3 , 梁祖雄 1 , 巩鹏 1 , 王璟 2 , 王正江 2 , 张江涛 2 , 李小军 2 , 李亚娟 2 , 伊锦昊 3 , 刘虎 3
热力发电 | 发电技术论坛 2024,53(2): 184-191
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热力发电 | 发电技术论坛 2024, 53(2): 184-191
有机固废和煤掺烧对重金属及颗粒物生成的影响研究
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吴有兵1 , 杨阳2, 3, 梁祖雄1, 巩鹏1, 王璟2, 王正江2, 张江涛2, 李小军2, 李亚娟2, 伊锦昊3, 刘虎3
作者信息
  • 1.华能陇东能源有限责任公司正宁电厂,甘肃 庆阳 745306
  • 2.西安西热水务环保有限公司高效灵活煤电及碳捕集利用封存全国重点实验室,陕西 西安 710054
  • 3.西安交通大学能源与动力工程学院,陕西 西安 710049
  • 吴有兵(1981),男,硕士,高级工程师,主要研究方向为火电厂热能与动力工程,

Effect of organic solid waste and coal mixed firing on the formation of heavy metals and particulate matter
Youbing WU1 , Yang YANG2, 3, Zuxiong LIANG1, Peng GONG1, Jing WANG2, Zhengjiang WANG2, Jiangtao ZHANG2, Xiaojun LI2, Yajuan LI2, Jinhao YI3, Hu LIU3
Affiliations
  • 1.Huaneng Longdong Energy Co., Ltd., Zhengning Power Plant, Qingyang 745306, China
  • 2.Xi’an TPRI Water-Management & Environmental Protection Co., Ltd., State Key Laboratory of High-Efficiency Flexible Coal Power Generation and Carbon Capture Utilization and Storage, Xi’an 710054, China
  • 3.School of Energy and Power Engineering, Xi’an Jiaotong University, Xi’an 710049, China
出版时间: 2024-02-25 doi: 10.19666/j.rlfd.202307122
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有机固体废弃物(OSW)中含有多种重金属,燃烧过程会随烟气排放,造成一定的环境危害,因此对OSW和褐煤掺混燃烧过程灰分中的重金属迁移和颗粒物生成特性进行了实验研究。结果表明:燃料在燃烧过程中各种重金属的释放不单取决于燃料本身的质量浓度,而且和高温作用下的化学机制密切相关;混合燃料烟气中产生Pb、Cd、As元素的含量明显低于典型燃料和校核燃料单独燃烧时烟气中产生的重金属元素含量;而Cu、Zn、Co、Mn在飞灰中均有较高质量分数;800、850 ℃下选用的4种燃料制得的灰分的粒径分布均大致呈现单峰正态分布;当温度升高到900 ℃后,除产生小粒径灰分外,还可能会产生较大粒径的灰分颗粒。

有机固废  /  掺烧  /  重金属  /  灰分粒径  /  煤

Rapidly growth of organic solid waste (OSW) has caused serious social and environmental issues. Co-combustion is an economical and environmental method to treat OSW. However, there will be a variety of heavy metals discharged with flue gas during combustion as OSW contains them. Therefore, this study conducted an experiment on the migration of heavy metals and generation of micro particles during the co-combustion of OSW and lignite. The results show that, the release of heavy metals during combustion not only depends on the concentration of heavy metal the fuel contains, but also on the chemical mechanism at high temperature. The content of Pb, Cd and As in the flue gas of blending fuel is obviously lower than that of sole OSW, but Cu, Zn, Co and Mn shows opposite tendency. In addition, the particle size distribution of the four fuels all shows a normal distribution at 800 ℃ and 850 ℃, but large particle size generates when the combustion temperature rises to 900 ℃.

organic solid waste  /  mixing firing  /  heavy metal  /  ash particle size  /  coal
吴有兵, 杨阳, 梁祖雄, 巩鹏, 王璟, 王正江, 张江涛, 李小军, 李亚娟, 伊锦昊, 刘虎. 有机固废和煤掺烧对重金属及颗粒物生成的影响研究. 热力发电, 2024 , 53 (2) : 184 -191 . DOI: 10.19666/j.rlfd.202307122
Youbing WU, Yang YANG, Zuxiong LIANG, Peng GONG, Jing WANG, Zhengjiang WANG, Jiangtao ZHANG, Xiaojun LI, Yajuan LI, Jinhao YI, Hu LIU. Effect of organic solid waste and coal mixed firing on the formation of heavy metals and particulate matter[J]. Thermal Power Generation, 2024 , 53 (2) : 184 -191 . DOI: 10.19666/j.rlfd.202307122
随着经济高速发展,城市有机固体废弃物(OSW)的持续快速增长已成为全球关注的问题。大量的OSW占据了大量土地,且对环境、人体健康和安全有严重的负面影响。因此,必须提出合理的处理方法,实现OSW减量,并使OSW成为无害化资源。
在众多的OSW处理技术中,焚烧处理越来越受到关注,因为它能够最大化减少废物体积并实现能量回收[1-2]。OSW可以在多种焚烧炉中燃烧,尤其流化床,因为它具有良好的燃料适应性,良好的混合和温度控制,以及高转化效率和低污染物排放[3-4]。近期研究和商业运行经验表明,通过将OSW和煤粉混烧,能够提高能量转化效率,降低投资成本。混烧对处理来源于生产生活中的低热值OSW具有显著优势[5-6]
与煤相比,多数OSW含有大量S和Cl,如橡胶和塑料。相对含量较高的S和Cl会促进碱金属氯化物和硫化物等低熔点成分的产生,不仅造成严重结渣和腐蚀问题[7-10],同时蒸发的无机成分被认为是灰气溶胶的主要先驱物。混烧OSW不但影响灰形成和积聚特性,还会增强亚微米颗粒物的生成,而亚微米颗粒物很难被发电厂的电除尘器捕捉。另外,相对含量较高的S和Cl可能加速混烧过程中重金属蒸发,造成飞灰或底灰(或灰渣)中重金属聚集,产生严重环境危害[11-12]
很多学者对可吸入颗粒物(PM)的生成和排放特性开展了研究[13-15]。文献[16]发现混烧过程颗粒演变被OSW和煤中矿物交互作用主导。对于富含外在矿物的OSW,大量团聚导致细颗粒向粗颗粒转变;然而对于富含内在矿物的OSW,这些矿物的演化过程是独立的。对于含有高比例外在矿物质的煤和高比例内在矿物质的污泥掺烧,矿物质之间的交互作用增强了PM生成。对排放颗粒物矿物组成的研究表明,将P和S由亚微米颗粒转变为超微米颗粒有助于减少PM1的排放[13]。燃烧炉底灰中高浓度Cl和重金属的析出,可能成为底灰再利用的障碍。文献[17]指出,尽管燃烧后大多数重金属残留在灰渣中不会排入大气,但Cu和Zn不稳定,进入飞灰中的成分达到86.21 mg/kg和939.46 mg/kg,会造成环境污染。文献[18]分析聚焦于塑料的重金属析出特性,发现Ba、Zn、Cu和Mn在塑料样品中的含量较高。
颗粒尺寸也对含OSW和煤混烧燃烧产物浸出毒性有重要影响。挥发性重金属会在小颗粒中聚集,这增加了小颗粒的环境风险[19]。文献[20]表征了4种粒径的OSW(0~0.5 mm,0.5~2.0 mm,2.0~ 4.0 mm,4.0~16.0 mm)颗粒燃烧后晶体和元素组成,发现细颗粒比粗颗粒浸出更高比例的重金属元素,使得细颗粒危害更大。
因此,本文研究了OSW和褐煤在流化床中混烧时重金属和飞灰颗粒排放特性,为OSW和煤在CFB锅炉中焚烧利用提供支撑。
本文所采用的实验系统如图1所示。石英管反应器呈圆柱形,为了使风向较均匀,在石英管反应器的下端设置了均相导流隔板,在石英管的中间加热段利用带孔的石英隔板布置流化反应区域。石英主管外径为35 mm,内径30 mm,石英支管的外径为8 mm,内径为5 mm。加热段长度为325 mm,最高使用温度为1 200 ℃,最大加热功率2 kW。实验总气流量为22.87 L/min,其中一次风流量为7.60 L/min,一次风压力为0.7 MPa,二次风(在图中标明)流量为15.27 L/min,二次风的压力为0.1 MPa。流量通过流量计控制,以达到最终流化风速0.54 m/s。
实验之前,在反应器的挡板处铺设石英纤维滤膜,并将1 g实验燃料与5 g石英砂(石英砂粒径大于1 mm)床层颗粒混合均匀后放入料仓中,关闭上、下阀门。混合石英砂一方面可以减小样品落入床层后的不均匀性对实验结果的影响,另一方面可以避免高温下样品之间的凝聚结块。石英砂使用前在1 273 K温度下进行1 h热处理,因此可认为热反应实验过程中,石英砂颗粒不会再发生任何化学反应。反应器与垂直管式炉的周围用石英棉填满,起到保温和隔热的作用。实验操作过程:首先打开温控系统,待温控系统升至指定工况温度,打开提供一次风流量的阀门,通过调节减压阀和一次风流量控制器至指定工况下的压力和流量,之后再打开冷冻干燥机、空气压缩机的阀门,调节二次风流量控制器的阀门至指定工况;然后,打开烟气分析仪记录反应器出口气体组分的变化过程,待一次风气体和二次风气体吹扫反应器一定时间后,打开下阀门,待气体组分趋于不变时认为反应完成;最后,关闭烟气分析仪、加热器,待温度降到室温后,取出反应器并清扫反应器内的石英砂、石英纤维滤膜以及燃烧之后的灰渣。
实验燃料以及混合比例由福建某电厂提供。实验用OSW为2种不同的混合燃料,分别命名为典型燃料与校核燃料,其成分主要包括棉布、化纤布料、乙烯-醋酸乙烯共聚物(EVA)、海绵、高泡棉、聚苯乙烯、竹料、木料、聚氯乙烯、再生炭黑。典型燃料和校核燃料具体成分如图2所示。本研究选取的实验燃料为典型燃料、校核燃料、混合燃料1(w(典型燃料):w(印尼煤)=3:7)以及混合燃料2(w(校核燃料):w(印尼煤=3:7),分别在800、850、900 ℃下测量收集4种燃料灰渣,并对其进行重金属元素分布特性和灰渣粒度分析,确定灰渣特性。
垃圾原料破碎后原始OSW外观如图3所示。实验研究前将竹料、木料及再生炭黑利用磨煤机粉碎至粒径0.3 mm以下,其他原料由于硬度较低,利用液氮粉碎机粉碎至粒径2.0 mm以下。燃料的工业分析和元素分析见表1表2
重金属指密度大于4.5 g/cm的金属。根据挥发特性可以将燃料重金属分为3类:高挥发性重金属、中度挥发性重金属和低挥发性重金属。Ba、Cr、Co、Cu和Ni等元素属于低挥发性重金属元素,这些重金属主要存在于底灰中。Pb、Cd、Zn、As、Sn和Ti则属于中度挥发性重金属。这些重金属主要通过挥发冷凝富集在飞灰中。重金属中挥发性最高的Hg和Se在低温仍具有很高的饱和蒸气压,因而主要存在于气相中。
燃料重金属含量测量方法:采用粉末压片法进行样品制备,先将塑料环放在模具上,称取粒径75 um左右的不同质量分数元素标准样品(至少20个)4 g放于塑料环内铺平,再将塑料环放于压片机上压制成≥7 mm厚度的薄片;在仪器的最佳工作条件下,依次上机分析记录X射线荧光强度,以X射线荧光强度(CPS)为纵坐标,以对应各元素的质量分数为横坐标,建立标准曲线,将待测原料样品按照与建立标准曲线相同的条件进行测定,记录X射线荧光强度;最后进行原料样品中重金属元素质量分数的计算。
飞灰重金属含量测量方法:
1)飞灰样品消解
使用电子天平准确称取0.05 g飞灰样品,置于聚四氟乙烯(PTEE)消解罐中,再往消解罐中加入消解液(6 mL浓HNO3溶液(质量分数68%)、2 mL浓HCl溶液(质量分数37%)、2 mLH2O2溶液(质量分数30%)),消解液与飞灰样品均匀混合后密封消解罐,并将消解罐放至微波消解仪中开始消解。微波消解仪以20 ℃/min速率升温至100 ℃,并在此温度下保持2 min;此后再以10 ℃/min速率升至150 ℃,并在此温度下保持3 min;最后再以6 ℃/min速率升至180 ℃,并在180 ℃的温度下保持25 min。
2)飞灰样品重金属测量
消解结束后,使用ICP-MS对溶液中的重金属采用标准曲线法进行测定。首先配置3—5个不同质量浓度的标准重金属元素溶液,选择合适的光谱线波长,在适当的分析条件下激发样品,以不含被测组分的空白溶液(去离子水)作为原点,测量每个标准溶液待测元素的光谱强度,以该元素标准样品的质量浓度值作为横坐标,以光谱仪测得的各标准溶液中待测的光谱强度作为纵坐标,绘制具有良好线性关系的标准曲线;然后将分析飞灰样品得到的光谱强度代入标准曲线方程,即可计算该样品中重金属元素质量浓度。表3给出了不同OSW中重金属质量浓度,可以看出,不同OSW所含重金属种类及质量浓度差别很大。
4种燃料不同温度下的燃烧时间约为300 s,认为此时4种燃料释放到烟气中的重金属趋于完全。图4展示了900 ℃燃烧温度下烟气中重金属质量浓度分布情况。从图4可以看出,900 ℃下重金属元素Pb在烟气中的质量浓度较高,典型燃料和校核燃料燃烧过程中释放的Pb质量浓度几乎一致,接近0.45 mg/m3
印尼煤分别掺烧典型燃料、校核燃料(混合燃料1和混合燃料2)烟气中Pb、Cd、As元素的质量浓度明显低于典型燃料和校核燃料烟气。校核燃料释放的重金属元素Cd质量浓度比其他燃料高,达到了0.23 mg/m3。推测在800∼850 ℃条件下Cd主要以CdCl2(g)形式存在,文献[20-21]也得到类似的结论。As在2种混合燃料燃烧产生的烟气中质量浓度较低,而典型燃料和校核燃料单独燃烧释放到烟气中的As质量浓度相对较高,但仅为0.037 mg/m3和0.035 mg/m3。此时,烟气温度为300~1 300 K,大部分As以稳定形态Ca3(AsO4)存在。重金属元素Sn只在2种混合燃料燃烧的烟气中出现,质量浓度分别为0.45、0.41 mg/m3;相反重金属元素Sr只在典型燃料和校核燃料燃烧产生的烟气中存在,但质量浓度较低,分别为0.006、0.005 mg/m3
2种混合燃料中重金属元素Sn质量浓度低于典型燃料和混合燃料,而典型燃料和校核燃料重金属元素Sr质量浓度远低于2种混合燃料,但烟气中相应重金属质量浓度则相反。这说明燃料在燃烧过程中各种重金属的释放不单取决于燃料本身的质量浓度[22],而且和高温作用下的化学机制密切相关。燃料中S与Cl质量浓度可能是影响因素之一。典型燃料和校核燃料中Cl质量浓度相对较高,2种混合燃料中S质量浓度也相对较高,但S元素质量分数的增加会导致部分重金属的挥发性减弱,相反在燃烧过程中,Cl元素极易与重金属发生反应,形成更易于挥发的重金属氯化物,重金属硫酸盐比重金属氯化物挥发性差,每种重金属氯化物以颗粒夹带的形式向飞灰或烟气中迁移。重金属元素Sn可能更易于与Cl元素结合形成重金属氯化物扩散至烟气中,而重金属元素Sr更易与S元素结合形成重金属硫化物。另外,烟气中均未检测到Cu、Zn、Co、Mn 4种重金属元素,他们主要富集在飞灰中。
图5展示了不同燃烧温度下飞灰中Cu质量分数。由图5可见:典型燃料和校核燃料燃烧形成的飞灰中Cu质量分数较高,并且这一现象并不随燃烧温度的改变而变化,甚至在900 ℃下典型燃料燃烧形成的飞灰中重金属Cu质量分数为30.17 mg/g;随燃烧温度的增加,2种混合燃料飞灰中Cu的富集呈上升趋势,900 ℃下混合燃料1和混合燃料2形成的飞灰中重金属Cu质量分数分别达到了12.74 mg/g和11.74 mg/g。文献[23]研究塑料垃圾在900 ℃燃烧时Cu的挥发率时发现,塑料垃圾中Cu的挥发率甚至高达60%。其原因可能主要与燃料中的Cl含量有关,塑料垃圾中的Cl含量较高,此时会形成大量CuCl(g)和少量Cu3Cl3(g)气相产物,它们易被烟气带走,而在本实验中Cu为难挥发性金属,在流化床内未经历蒸发过程,Cu分别以氧化物或CuFe2O4(c)的形式存在于固体或凝聚相中。另外,热力学模拟还指出900 ℃以下时,Cu在局部还原条件下会形成稳定的铜金属,还会与飞灰中的矿物质成分形成CuO•Al2O3(s)、CuO•Fe2O3(s)和CuO•CuSO4(s)等非挥发性物质存在,抑制了Cu的挥发。
不同燃烧温度下飞灰中Zn质量分数如图6所示。从图6可见,Zn基本全部存在于飞灰中,校核燃料燃烧形成的飞灰中Zn质量分数较高;随着燃烧温度的升高,飞灰中富集的Zn质量分数降低,在800 ℃时Zn质量分数为60.5 mg/g;典型燃料、混合燃料1和混合燃料2在燃烧温度为850 ℃时形成的飞灰中Zn的富集程度最高,分别为13.0、14.5、11.3 mg/g。Zn元素属于中等挥发性重金属,但是在烟气中基本未检测到,可能是因为ZnCl2的熔点仅为283 ℃,ZnCl2会与灰分中的Al2O3成分发生熔融现象,这一方面加快了ZnCl2与Al2O3反应速率,生成的难挥发物质ZnAl2O4抑制了ZnCl2的挥发,同时熔融的ZnCl2堵塞了灰分颗粒中的微孔,使得更多的Zn富集在飞灰中。
不同燃烧温度下飞灰中Co质量分数如图7所示。由图7可见:Co在飞灰中的质量分数远低于Cu、Zn;燃烧温度为850 ℃时,典型燃料、校核燃料和混合燃料1的飞灰中Co质量分数最大,分别为2.9、9.7、1.4 mg/g;混合燃料2则在燃烧温度900 ℃时最大,为4.3 mg/g。Co总是作为固体存在,它会与灰分中的矿物质Fe2O3存在相互作用,并形成固体化合物CoFe2O4(s),同时也会与床料中的SiO2反应生成晶体类物质Co2SiO4(c)。无论燃料中的Co质量分数如何变化,Co几乎都以晶体类物质Co2SiO4(c)稳定存在,这使得Co在烟气中的质量分数较低。
不同燃烧温度下飞灰中Mn质量分数如图8可见。Mn在烟气中的质量分数也相对较低,但在飞灰中的富集程度略高于Co。从图8可见,在不同燃烧温度下,4种燃料飞灰中的Mn质量分数差异较小,并且质量分数随燃烧温度的增加而增加。在燃烧温度为900 ℃时飞灰中重金属Mn质量分数达到了最大,典型燃料、校核燃料、混合燃料1和混合燃料2燃烧形成的飞灰中Mn质量分数分别为6.7、8.7、12.9、17.0 mg/g。同时还发现2种混合燃料形成的飞灰中Mn质量分数略高于典型燃料和校核燃料燃烧形成的飞灰。原因在于2种混合燃料中的水分(17.77%、17.59%)高于典型燃料和校核燃料的水分(3.54%、4.15%)。重金属氧化物与烟气中HCl气体反应生成重金属氯化物和水蒸气,如果燃料的水分较高,在高温条件下形成的水蒸气会使得平衡逆向移动,较多的重金属氯化物将会转变成重金属氧化物停留在飞灰中,降低重金属在烟气中的挥发率。因此,2种混合燃料燃烧烟气中的水蒸气质量分数较高,Mn更多以氧化物的形式停留在灰分中。
图9为800 ℃下灰分粒径分布。从图9可以看出:800 ℃下4种燃料制得的灰分粒径呈现正态分布,典型燃料和校核燃料燃烧形成的灰分粒径分别分布在955∼1 720 nm、710∼1 490 nm,并且2种灰分的粒径分别在1 280、1 105 nm附近达到各自的最大比例;混合燃料1在800 ℃下灰分粒径分布范围更大,粒径跨度范围约为1 035 nm,但混合燃料2灰分的粒径分布更为集中,颗粒大小较为均匀,主要集中在820~1 105 nm,粒径跨度范围减小至280 nm。
图10为850 ℃下灰分粒径分布。由图10可见,当燃烧温度增加至850 ℃时,典型燃料所制得的灰分粒径分布范围更大,灰分中最小的粒径为531 nm,最大的颗粒直径达到5 560 nm,其他3种燃料灰分粒径分布范围也有不同程度的扩大。
图11为900 ℃下灰分粒径分布。由图11可见,当流化床燃烧温度继续增加到900 ℃时,典型燃料和2种混合燃料灰分的粒径分布明显存在2个峰值,此时灰分的粒径分布集中在2个范围内。典型燃料燃烧产生的灰分粒径集中在825~2 305 nm和5 560 nm附近,混合燃料1燃烧产生的灰分粒径分布集中在530~1 485 nm和4 800~5 560 nm 2个范围内。另外,混合燃料2燃烧产生的灰分粒径分布极不均匀,范围极广,存在3个明显的峰值,小颗粒粒径集中在220~400 nm,中颗粒粒径范围集中在530~2 670 nm,大颗粒粒径集中分布在4 800~5 560 nm。2种混合燃料产生的灰分中大颗粒粒径存在一定的相似性。
本文通过实验室小型流化床研究了OSW和煤混烧过程中飞灰的粒径分布及重金属特性,对比了OSW单独燃烧及OSW和煤混烧过程重金属迁移及飞灰颗粒分布特性,主要得到以下结论。
1)印尼煤分别掺烧典型燃料、校核燃料的烟气中产生Pb、Cd、As元素的含量明显低于典型燃料和校核燃料烟气中产生的重金属元素含量。
2)燃料在燃烧过程中各种重金属的释放不单取决于燃料本身的质量浓度,还与高温作用下的化学机制密切相关。重金属元素Sn可能更易于与Cl元素结合形成重金属氯化物扩散至烟气中,而重金属元素Sr更易与S元素结合形成重金属硫化物。飞灰中Cu、Zn、Co、Mn质量分数均较高。
3)800、850 ℃下4种燃料制得灰分的粒径分布均呈现单峰正态分布;当温度升高到900 ℃后,除了产生小粒径灰分外,还可能会产生较大粒径的灰分颗粒。
  • 中国华能集团有限公司总部科技项目(HNKJ21-H44)
  • 陕西省自然科学基金项目(2020JQ-063)
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2024年第53卷第2期
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doi: 10.19666/j.rlfd.202307122
  • 接收时间:2023-07-23
  • 首发时间:2025-12-31
  • 出版时间:2024-02-25
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  • 收稿日期:2023-07-23
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Science and Technology Project of China Huaneng Group Co., Ltd.(HNKJ21-H44)
中国华能集团有限公司总部科技项目(HNKJ21-H44)
Natural Science Foundation of Shaanxi Province(2020JQ-063)
陕西省自然科学基金项目(2020JQ-063)
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    1.华能陇东能源有限责任公司正宁电厂,甘肃 庆阳 745306
    2.西安西热水务环保有限公司高效灵活煤电及碳捕集利用封存全国重点实验室,陕西 西安 710054
    3.西安交通大学能源与动力工程学院,陕西 西安 710049
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2种不同金属材料的力学参数

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属数
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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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