Article(id=1236372361172284400, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236372356109751006, articleNumber=null, orderNo=null, doi=10.19666/j.rlfd.202503045, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1741017600000, receivedDateStr=2025-03-04, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1772703741590, onlineDateStr=2026-03-05, pubDate=1756051200000, pubDateStr=2025-08-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1772703741590, onlineIssueDateStr=2026-03-05, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1772703741590, creator=13701087609, updateTime=1772703741590, updator=13701087609, issue=Issue{id=1236372356109751006, tenantId=1146029695717560320, journalId=1210938733613449225, year='2025', volume='54', issue='8', pageStart='1', pageEnd='174', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1772703740384, creator=13701087609, updateTime=1772788131769, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1236726319342481872, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236372356109751006, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1236726319342481873, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236372356109751006, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=160, endPage=167, ext={EN=ArticleExt(id=1236372361474273282, articleId=1236372361172284400, tenantId=1146029695717560320, journalId=1210938733613449225, language=EN, title=Experimental study on pollutants emission and ash formation characteristics during co-combustion of biomass and coal in fluidized bed, columnId=1236372358878000047, journalTitle=Thermal Power Generation, columnName=Carbon neutral fuel coupled combustion and emission control, runingTitle=null, highlight=null, articleAbstract=

Co-combustion of biomass and coal can significantly reduce the pollutants and carbon emissions. However, the pollutants emission, ash characteristics and their influence factors during co-combustion of coal and biomass are still obscure. A micro-fluidized bed reactor was used to investigate the co-combustion of rice husk (RH) and bituminous coal (SC). The effects of combustion temperature, atmosphere and blending ratio on the emission characteristics of NO, SO2 and ash were studied. The results indicated that, with the increase of temperature, the mass concentration of NO emissions during co-combustion rose at first and then fell, while the SO2 emissions mass concentration gradually increased. High temperature would promote the interaction of minerals in the ash, generating Na2Al2SiO6 and lowering the melting point of the co-combustion ash. In oxygen-deficient atmosphere, NO and SO2 emission mass concentrations increased with the O2 volume fraction. In oxygen-enriched atmosphere, the NO emission mass concentration gradually decreased as the O2 volume fraction increased, while the SO2 emission mass concentration increased at first and then decreased. The influence of reaction atmosphere on the main composition and crystal structure of the co-combustion ash was relatively minor. NO and SO2 emissions during co-combustion can be effectively reduced due to the addition of RH. As the RH blending ratio was increased, Ca3Al2O6 in ash tended to form low-melting-point compounds with SiO2, leading to a noticeable melting phenomenon.

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生物质与煤混烧可降低燃烧过程中的污染物和碳排放,但二者混烧过程中污染物排放和成灰特性及其关键影响因素仍缺乏系统的对比研究。采用小型流化床装置研究了稻壳(RH)和烟煤(SC)混烧特性,考察了燃烧温度、反应气氛和掺混比例等对混烧过程NO和SO2排放规律及成灰特性的影响。结果表明:随燃烧温度升高,混烧过程NO排放质量浓度先升高后降低,SO2排放质量浓度则逐渐升高,高温会促进灰中矿物发生相互作用,生成Na2Al2SiO6等物质,降低混烧灰熔点;贫氧气氛下提高O2体积分数会导致NO和SO2排放质量浓度升高,富氧气氛下随O2体积分数增大,NO排放质量浓度逐渐降低,而SO2排放质量浓度则先升高后降低,反应气氛对混烧灰主要组成和晶体结构的影响相对较小;添加RH能够有效降低混烧过程的NO和SO2排放,随RH掺混比例增大,灰中Ca3Al2O6易与SiO2等形成低熔点化合物,导致灰出现明显的熔融现象。

, correspAuthors=null, authorNote=null, correspAuthorsNote=
赵瑞东(1986),男,副研究员,主要研究方向为生物质热化学转化,
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许慧(1999),女,硕士研究生,主要研究方向为生物质低碳燃烧,

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许慧(1999),女,硕士研究生,主要研究方向为生物质低碳燃烧,

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许慧(1999),女,硕士研究生,主要研究方向为生物质低碳燃烧,

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1—螺旋给料机及进料管;2—石英布风板;3—K型热电偶;4—立式管式炉;5—石英外管;6—质量流量计;7—石英内管;8—烟气分析仪;9—气瓶组。

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Proximate, ultimate and heating values analysis of the feedstocks

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项目SCRH
工业分析wad(M)/%1.322.50
wad(V)/%30.2863.36
wad(A)/%16.7018.06
wad(FC)*/%51.7016.08
元素分析wad(C)/%64.2139.43
wad(H)/%4.214.97
wad(N)/%1.040.44
wad(S)/%1.050
wad(O)*/%12.7937.10
热值分析Qad,HHV/(MJ·kg–1)26.0415.52
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原料的工业、元素及热值分析

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项目SCRH
工业分析wad(M)/%1.322.50
wad(V)/%30.2863.36
wad(A)/%16.7018.06
wad(FC)*/%51.7016.08
元素分析wad(C)/%64.2139.43
wad(H)/%4.214.97
wad(N)/%1.040.44
wad(S)/%1.050
wad(O)*/%12.7937.10
热值分析Qad,HHV/(MJ·kg–1)26.0415.52
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The occurrence forms and proportions of N in raw materials

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N-XN-QN-5N-AN-6
SC2.186.3778.3613.09
RH14.089.7313.9151.1911.09
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原料中N的赋存形态及比例

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N-XN-QN-5N-AN-6
SC2.186.3778.3613.09
RH14.089.7313.9151.1911.09
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生物质与煤流化床混烧过程污染物排放及成灰特性试验研究
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许慧 1 , 张子皓 2 , 赵瑞东 2 , 陈天举 2 , 武景丽 2 , 方龙 1 , 吴晋沪 2
热力发电 | 碳中性燃料耦合燃烧与排放控制 2025,54(8): 160-167
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热力发电 | 碳中性燃料耦合燃烧与排放控制 2025, 54(8): 160-167
生物质与煤流化床混烧过程污染物排放及成灰特性试验研究
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许慧1 , 张子皓2, 赵瑞东2 , 陈天举2, 武景丽2, 方龙1, 吴晋沪2
作者信息
  • 1.青岛大学化工学院,山东 青岛 266100
  • 2.中国科学院青岛生物能源与过程研究所,山东 青岛 266101
  • 许慧(1999),女,硕士研究生,主要研究方向为生物质低碳燃烧,

通讯作者:

赵瑞东(1986),男,副研究员,主要研究方向为生物质热化学转化,
Experimental study on pollutants emission and ash formation characteristics during co-combustion of biomass and coal in fluidized bed
Hui XU1 , Zihao ZHANG2, Ruidong ZHAO2 , Tianju CHEN2, Jingli WU2, Long FANG1, Jinhu WU2
Affiliations
  • 1.College of Chemical Engineering, Qingdao University, Qingdao 266100, China
  • 2.Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, China
出版时间: 2025-08-25 doi: 10.19666/j.rlfd.202503045
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生物质与煤混烧可降低燃烧过程中的污染物和碳排放,但二者混烧过程中污染物排放和成灰特性及其关键影响因素仍缺乏系统的对比研究。采用小型流化床装置研究了稻壳(RH)和烟煤(SC)混烧特性,考察了燃烧温度、反应气氛和掺混比例等对混烧过程NO和SO2排放规律及成灰特性的影响。结果表明:随燃烧温度升高,混烧过程NO排放质量浓度先升高后降低,SO2排放质量浓度则逐渐升高,高温会促进灰中矿物发生相互作用,生成Na2Al2SiO6等物质,降低混烧灰熔点;贫氧气氛下提高O2体积分数会导致NO和SO2排放质量浓度升高,富氧气氛下随O2体积分数增大,NO排放质量浓度逐渐降低,而SO2排放质量浓度则先升高后降低,反应气氛对混烧灰主要组成和晶体结构的影响相对较小;添加RH能够有效降低混烧过程的NO和SO2排放,随RH掺混比例增大,灰中Ca3Al2O6易与SiO2等形成低熔点化合物,导致灰出现明显的熔融现象。

煤  /  生物质  /  混烧  /  污染物  /  成灰特性

Co-combustion of biomass and coal can significantly reduce the pollutants and carbon emissions. However, the pollutants emission, ash characteristics and their influence factors during co-combustion of coal and biomass are still obscure. A micro-fluidized bed reactor was used to investigate the co-combustion of rice husk (RH) and bituminous coal (SC). The effects of combustion temperature, atmosphere and blending ratio on the emission characteristics of NO, SO2 and ash were studied. The results indicated that, with the increase of temperature, the mass concentration of NO emissions during co-combustion rose at first and then fell, while the SO2 emissions mass concentration gradually increased. High temperature would promote the interaction of minerals in the ash, generating Na2Al2SiO6 and lowering the melting point of the co-combustion ash. In oxygen-deficient atmosphere, NO and SO2 emission mass concentrations increased with the O2 volume fraction. In oxygen-enriched atmosphere, the NO emission mass concentration gradually decreased as the O2 volume fraction increased, while the SO2 emission mass concentration increased at first and then decreased. The influence of reaction atmosphere on the main composition and crystal structure of the co-combustion ash was relatively minor. NO and SO2 emissions during co-combustion can be effectively reduced due to the addition of RH. As the RH blending ratio was increased, Ca3Al2O6 in ash tended to form low-melting-point compounds with SiO2, leading to a noticeable melting phenomenon.

coal  /  biomass  /  co-combustion  /  pollutants  /  ash formation characteristics
许慧, 张子皓, 赵瑞东, 陈天举, 武景丽, 方龙, 吴晋沪. 生物质与煤流化床混烧过程污染物排放及成灰特性试验研究. 热力发电, 2025 , 54 (8) : 160 -167 . DOI: 10.19666/j.rlfd.202503045
Hui XU, Zihao ZHANG, Ruidong ZHAO, Tianju CHEN, Jingli WU, Long FANG, Jinhu WU. Experimental study on pollutants emission and ash formation characteristics during co-combustion of biomass and coal in fluidized bed[J]. Thermal Power Generation, 2025 , 54 (8) : 160 -167 . DOI: 10.19666/j.rlfd.202503045
我国能源结构主要以煤炭等化石能源为主,面临较大的污染物和碳减排压力。积极发展可再生能源是实现我国能源结构转型和“双碳”目标的重要途径之一[1]。生物质作为一种可再生的碳中性能源,与煤混烧可显著降低燃烧过程的碳排放,同时也可在一定程度上降低SO2和NOx等污染物的排放[2],受到了学者的广泛关注。谭厚章等[3]在660 MW燃煤机组上开展了生物质与煤混烧研究,发现当生物质掺混比例低于20%时,锅炉能够保持稳定燃烧,燃烧效率约为94%。李春建等[4]利用热重分析仪和固定床反应器考察了煤和木屑混燃和污染物排放特性,发现当木屑的掺混比例从10%升到70%时,燃料的综合燃烧特性逐渐提高,燃料氮向NO的转化率逐渐降低。
与煤相比,生物质中碱金属和碱土金属含量较高,混烧过程中易与灰中组分发生相互作用,促进低熔点共熔物的生成,导致锅炉受热面出现结渣和腐蚀等问题[5]。但不同种类生物质的灰存在较大差别,对混烧过程结渣特性的影响也不尽相同。张勇等[6]利用沉降炉研究了生物质与神华煤掺烧过程的积灰特性,发现生物质中的碱金属会显著增加受热面的积灰。随生物质掺混比例增加,其灰分中富集的钙元素会生成低熔点化合物,导致灰颗粒熔融粘连加剧。Liu等人[7]发现随水葫芦的掺混比例增加,其与无烟煤混烧过程的结渣倾向逐渐增大,添加高岭土和CaO可抑制混烧过程的结渣。Han等人[8]研究了富硅生物质与煤混烧对成灰和结渣特性的影响,发现添加富硅生物质可降低煤灰的结渣倾向。
此外,气氛对混烧过程的成灰特性也有重要影响。特别是随着富氧燃烧技术成为一种重要的碳捕集手段,生物质与煤富氧混烧过程的成灰特性也受到了学者的广泛关注。Wu等人[9]研究了富氧气氛下稻壳与烟煤混烧过程的灰分沉积特性,发现与空气燃烧相比,富氧燃烧会促进灰分中矿物质间的相互作用,增加灰沉积倾向。
现有对生物质与煤混烧利用研究,多侧重于考察其单一的污染物排放特性或成灰特性等,对二者的综合研究相对较少,尤其缺乏贫氧气氛等复杂因素对其排放和成灰特性影响的研究。基于此,本文利用小型流化床实验装置,开展了稻壳与烟煤混烧特性研究,考察了不同掺混比例、反应气氛和燃烧温度下混烧过程污染物排放及成灰特性的综合变化规律,揭示了复杂反应气氛等关键参数对其影响机制,研究结果可为燃煤循环流化床锅炉大规模混烧生物质提供基础技术支撑。
实验所用的稻壳(RH)采集自东北某地区,烟煤(SC)来自广西柳州某水泥公司,其工业、元素和热值分析见表1。2种原料先经过烘干和破碎预处理,筛分出粒径为1~2 mm的RH颗粒和0.6~ 1.0 mm的SC颗粒,然后按不同RH掺混比例(质量比)混合均匀。
混烧实验在小型流化床反应装置上进行,其示意如图1所示。该装置主要由配气系统、进料系统、流化床反应器和烟气分析系统组成。流化床反应器由石英外管、石英内管和管式炉组成,石英外管和内管的内径分别为50 mm和40 mm,二者通过磨砂口连接和密封。燃烧段高约450 mm,内管中焊接石英布风板(孔径0.5 mm),主要用于均匀布风并支撑反应原料。
实验过程中,原料通过螺旋给料机从反应器顶部加入,沿进料管到达布风板上方(进料量为0.35 g/min),与底部通入的流化气体接触并发生燃烧反应,燃烧产生的烟气由石英外管顶部排出,进入在线烟气分析仪C600(意大利Seitron公司),分析其中的CO、CO2、SO2、O2和NO等组分含量(采样间隔为2 s)。每组实验持续20 min,待实验结束和灰渣冷却后,移出石英内管并收集布风板上的灰渣,用于分析混烧过程的成灰特性。
实验主要考察燃烧温度、掺混比例和反应气氛对混烧过程的影响。其中,燃烧温度分别为700、800、900和1 000 ℃、掺混比例(SC与RH的质量比)分别为10:0、9:1、8:2、7:3、5:5、0:10,反应气氛分别采用空气、富氧气氛(φ(O2):φ(CO2)为21:79、30:70、40:60,分别表示为21%O2、30%O2、40%O2)和贫氧气氛(φ(O2):φ(CO2):φ(N2)为6:15:79、11:10:79、16:5:79,分别表示为6%O2、11%O2、16%O2)。富氧气氛主要用于模拟富氧燃烧工况,采用氧体积分数21%是为了与常规空气燃烧对比,进一步考察N2和CO2对混烧过程的影响。贫氧气氛则主要用于模拟空气气氛下炉内的贫氧燃烧区域。
实验过程中保持过量空气系数为1.3不变,不同反应气氛下的过量空气系数由式(1)计算。气体污染物排放量取稳定实验过程中烟气分析仪检测数据的平均值,并利用式(2)将体积分数转换为质量浓度。实验装置运行过程中,NO、CO和SO2污染物排放质量浓度的波动较小(在±7%以内)。
λ=φ1(O2)φ1(O2)φ2(O2)
式中:λ为过量空气系数;φ1(O2)为燃烧反应前氧气的体积分数,%;φ2(O2)为燃烧反应后烟气中氧气的的体积分数,%。
X0=MX×XV×273.15Vm×T
式中:X0为标准状态下污染物排放质量浓度,mg/m3MX为污染物摩尔质量,g/mol;XV为体积分数,μL/L;T为室温;Vm为标态下气体摩尔体积。
利用X射线光电子能谱XPS(赛默飞公司Thermo ESCALAB 250Xi)对SC和RH原料中氮赋存形态进行表征,其中主要含氮官能团的特征峰如下:吡啶氮(N-6,(398.8±0.2) eV)、氨氮(N-A,(399.9±0.2) eV)、吡咯氮(N-5,(400.4±0.2) eV)、季氮(N-Q,(401.4±0.2) eV)和氮氧化物(N-X,402~405 eV)[10]。利用X射线荧光光谱仪XRF(理学公司ZSX Primus IV)分析燃烧后灰分的主要组成;采用X射线衍射仪XRD(理学公司Smart Lab 9 kW)对灰分进行晶体结构分析;采用扫描电镜SEM(蔡司公司Gmini SEM 360)分析灰分的微观形貌。
图2为SC和RH原料的N 1s谱图及各含氮官能团分峰拟合曲线,各官能团的比例见表2。由图2表2可知:SC中的N主要以N-5形式存在,含量达到78.36%,其余为N-6、N-Q和N-X;而RH中的N则主要以N-A(51.19%)的形式存在,其余为N-X、N-6、N-5和N-Q。
图3为RH掺混比例50%时,温度对混烧过程CO、NO和SO2排放质量浓度的影响。图3表明:当燃烧温度为700 ℃时,CO排放质量浓度接近1 000 mg/m3;随燃烧温度升高,CO的排放量迅速降低,1 000 ℃时CO排放质量浓度约为70 mg/m3,气体不完全燃烧热损失大幅降低。
随燃烧温度升高,NO的排放呈现先增大后减小的趋势,在900 ℃时NO排放质量浓度达到最高为227 mg/m3。混烧过程中,燃料氮首先以挥发分氮(NH3、HCN)形式析出,然后再经氧化和还原等共同作用生成NO。低温下,受反应动力学限制,燃料氮的析出和氧化速率较低,导致NO的排放量略低。随燃烧温度升高,混合燃料的燃烧更加剧烈,加快了燃料氮的析出和氧化,致使NO质量浓度上升。但当温度进一步升高至1 000 ℃时,高温会促进燃料中挥发分的快速释放,使局部还原性气氛增强,同时强化了NO的还原反应[11],导致NO排放质量浓度又逐渐降低至195 mg/m3
随燃烧温度升高,SO2的排放质量浓度由700 ℃时的976 mg/m3逐渐升高至1 000 ℃时的1 513 mg/m3。特别是当燃烧温度超过900 ℃时,SO2排放质量浓度的增长幅度较快。分析认为,煤中的硫主要以有机硫和黄铁矿硫等可燃硫以及硫酸盐等不可燃硫的形式存在。提高燃烧温度会促进混合燃料中可燃硫的析出和氧化,增大SO2排放质量浓度。当燃烧温度为800~900 ℃左右时,硫酸盐分解率较低,灰分的固硫作用也较强,导致SO2的增长幅度相对较慢。而当燃烧温度为1 000 ℃时,灰分的固硫作用减弱,特别是硫酸盐分解率升高,重新释放出SO2,导致其排放质量浓度迅速升高[12]
图4为RH掺混比例50%时,温度对燃烧过程灰分组成和晶体结构的影响。由图4a)可知,混烧灰中酸性氧化物SiO2的含量最高,随燃烧温度的升高,其质量分数略有波动,基本维持在75%左右。而SO3的质量分数则从3.49%逐渐下降至1.99%,这主要是由于CaSO4等硫酸盐在高温下分解造成的[13]。此外,不同燃烧温度下Na2O、K2O和MgO的含量基本不变。
图4b)可知,当燃烧温度为700 ℃和800 ℃时,混烧灰中晶体结构主要为方石英(SiO2)、石英(SiO2)和硬石膏(CaSO4)。燃烧温度为900 ℃时,灰中SiO2和Al2O3发生化学反应,生成了熔点较高的莫来石(3Al2O3·2SiO2)。当燃烧温度继续升高至1 000 ℃时,高温促进了灰中Na2O与SiO2和Al2O3的反应,生成低熔点共熔物钠长石(Na2Al2SiO6),降低了灰分的结渣温度[14]。此外,随燃烧温度的升高,灰中方石英的衍射峰强度增大,说明高温时SiO2主要以方石英的形式存在。
图5为RH掺混比例50%、燃烧温度900 ℃时,反应气氛对混烧过程CO、NO和SO2排放质量浓度的影响。由图5可知,贫氧和富氧气氛下,随O2体积分数升高,混合燃料的燃烧性能改善,CO的排放质量浓度逐渐降低,但均高于空气气氛下的排放质量浓度。这主要是由于贫氧气氛下,混合燃料的燃烧速率较慢,气体不完全燃烧热损失较高。而富氧气氛则因为高含量的CO2促进了C与CO2的气化反应,增加了CO的排放。
贫氧和富氧气氛下,随O2体积分数增大,NO的排放质量浓度逐渐升高。高O2体积分数下,混合燃料的燃烧反应较为剧烈,一方面促进了其中燃料氮的析出和氧化;另一方面加快了固定碳的消耗,减少了CO生成,削弱了NO还原反应[15]。与空气气氛相比,当φ(O2)≤30%时,富氧气氛下混烧过程的NO排放量相对较低。这一方面是由于没有N2参与反应,减少了热力型氮氧化物的生成;另一方面,富氧气氛下CO等还原性组分含量增加,强化了NO的还原反应。
贫氧气氛下,随O2体积分数的升高,促进了混合燃料中硫的析出和氧化,导致SO2的排放质量浓度从359 mg/m3升高至797 mg/m3。与此不同的是,在富氧气氛中,SO2的排放质量浓度呈先升高后降低的趋势,推测可能是由于混合燃料灰分的固硫效应与硫释放间的相互作用导致。O2体积分数升高,一方面会加快混合燃料的燃烧,促进其中硫的析出和转化,增大SO2的排放量。但另一方面,富氧气氛可减缓灰中CaO等组分的烧结,提高其固硫反应速率。同时,富氧气氛下高含量的CO2会增强CaO的碳酸化反应,生成的CaCO3进一步与SO2发生直接硫化反应并释放CO2,可提高脱硫产物的孔隙率,增强混合燃料中灰分的固硫效应,从而降低其SO2排放[16]
图6为RH掺混比例50%、燃烧温度900 ℃时,反应气氛对灰分组成和晶体结构的影响。由图6a)可知,贫氧气氛下,随氧气体积分数增大,SiO2的含量呈先降低后升高的趋势,而Al2O3含量的变化则恰好相反。富氧气氛下,随氧气体积分数升高,SiO2的含量总体呈降低趋势,Al2O3含量则逐渐增加。其余氧化物含量受反应气氛的影响相对较小。
图6b)可知,不同反应气氛下,灰分的晶体结构均以石英、方石英、硬石膏和莫来石为主,这说明气氛对RH与SC混烧过程灰分晶体结构的影响较小。但值得注意的是,在贫氧气氛下,灰分中还存在一定量的CaO。随氧气体积分数升高,其衍射峰强度逐渐减弱,在富氧气氛下未发现相应的衍射峰,这主要是由于氧气体积分数高促进了SO2与CaO的反应导致[17]
图7为空气气氛下,燃烧温度为900 ℃时,掺混比例对混烧过程CO、NO和SO2排放质量浓度的影响。由图7可知,SC单独燃烧时CO、NO和SO2的排放质量浓度较高,分别为444、263和2 128 mg/m3。随RH掺混比例的增加,混烧过程CO、NO和SO2的排放质量浓度均逐渐降低,说明SC与RH混烧可显著降低污染物的排放,这主要是由于RH原料中碳、氮和硫元素的含量较低。此外,其还可能受RH和SC间相互作用的影响。
为进一步验证这一点,图7还对比了混烧过程污染物排放计算值与实验值。其中,计算值是假定SC和RH混烧过程不存在相互作用时,二者单独燃烧时污染物排放量与其各自掺混比例的加权和,其计算公式如式(3)所示。
Xcal=αSCXSC+αRHXRH
式中:Xcal为混合燃料燃烧时污染物排放质量浓度的计算值,mg/m3XSCXRH分别为SC和RH单独燃烧时的污染物排放质量浓度,mg/m3αSCαRH分别为混合燃料中SC和RH的质量分数。
图7可以发现,不同掺混比例下CO排放质量浓度的实验值均低于计算值,这说明SC与RH混烧可显著改善混合燃料的燃烧性能,降低其不完全燃烧损失。当RH掺混比例不大于30%时,混烧过程NO排放质量浓度的实验值低于计算值,而当RH掺混比例大于30%时,结果恰好相反。这说明RH掺混比例低会抑制混烧过程NO排放,而高掺混比例下RH与SC混烧会促进NO的排放。这主要是因为当RH掺混比例较低时,混合燃料中固定碳含量较高,增强了NO还原反应,因此抑制了NO的排放。而当RH掺混比例较高时,一方面混合燃料燃烧性能改善,促使更多的燃料氮析出并进一步转化为NO;另一方面燃料中固定碳含量显著降低,削弱了已生成NO的还原反应。
SO2排放质量浓度实验值与计算值的变化规律与NO相反,当RH掺混比例不大于30%时,混烧会促进SO2的排放,而当RH掺混比例大于30%时则存在抑制作用,这可能是由于混合燃料灰分的固硫作用变化导致。由2.4.2节的分析可知,SC灰中含有较多的CaO,而RH灰中K2O等碱金属含量较高,二者均具有一定的固硫效应[18]。随RH掺混比例增加,混合燃料中CaO含量降低,导致固硫效应减弱,但同时K2O含量升高又增强了固硫效应,二者共同作用,导致SO2排放质量浓度的实验值和计算值出现上述变化。
图8为空气气氛下,燃烧温度900 ℃时,掺混比例对燃烧过程灰分组成和晶体结构的影响。由图8a)可知,RH灰中SiO2质量分数较高,达到83.8%,其余以Al2O3和K2O为主。而SC灰中Al2O3和SiO2的质量分数接近,均在40%左右,其余以CaO和Fe2O3为主。随RH掺混比例增加,混烧灰中SiO2质量分数逐渐增高,Al2O3质量分数渐降低,特别是K2O的质量分数由0.491%升高至4.680%。
图8b)可知,不同RH掺混比例下,混烧灰中的SiO2主要以石英和方石英的形式存在。随RH掺混比例增加,石英衍射峰的强度逐渐减弱,方石英衍射峰的强度逐渐增加。当RH掺混比例不小于30%时,混烧灰中还出现了铝酸三钙(Ca3Al2O6)。铝酸三钙易与碱金属氧化物(SiO2、MgO、R2O)等进一步形成低熔点的共熔物,导致混烧灰熔点降低[19],因此RH掺混比例不宜过高。
图9为燃烧温度900 ℃时,不同RH掺混比例下混烧灰微观形貌的变化。由图9可知,SC单独燃烧后的灰分呈不规则块状结构,表面较粗糙,部分颗粒出现熔融现象。而RH单独燃烧后的灰分颗粒为片状结构,表面相对光滑,呈多孔蜂窝状,熔融和玻璃化现象更加显著。当RH掺混比例为不大于20%时,混烧灰结构基本保持松散,无明显熔融迹象。当RH掺混比例为30%时,混烧灰颗粒边缘开始圆滑并伴随局部熔融粘连,颗粒间形成联结网络。进一步提高RH掺混比例,混烧灰开始呈现明显的熔融现象。这与XRD的结果基本一致,说明当RH掺混比例超过30%时,会显著降低混烧灰的熔点,诱发团聚和结渣等问题。
本文采用小型流化床实验装置开展了SC与RH混烧特性研究,考察了燃烧温度、反应气氛和掺混比例对混烧过程污染物排放及成灰特性的影响规律,主要结论如下。
1)SC与RH混烧过程中,随燃烧温度升高,受燃料氮析出与NO还原共同作用,NO排放质量浓度呈先升高;后降低趋势,SO2排放质量浓度则随温度升高而逐渐增大,尤其是高温下增长幅度较大。SC与RH的混烧灰主要由SiO2、Al2O3和CaSO4等组成,燃烧温度对灰中碱金属和碱土金属含量的影响较小。但当燃烧温度为1 000 ℃时,高温会促进灰中Na2O与SiO2和Al2O3的反应,生成低熔点共熔物Na2Al2SiO6,降低灰的熔点。
2)贫氧气氛下,O2体积分数升高促进了燃料的燃烧,导致NO和SO2排放质量浓度升高。富氧气氛下,随O2体积分数增大,NO排放质量浓度逐渐降低,而SO2排放质量浓度则先升高后降低。反应气氛对混烧灰主要组成和晶体结构的影响相对较小,但高体积分数O2混烧灰中CaO的衍射峰强度明显减弱。
3)增大RH掺混比例,由于混合燃料中C、N和S元素含量减少,混烧过程CO、NO和SO2的排放量逐渐降低。RH掺混比例不大于30%时,混烧可抑制NO的生成,但同时会促进SO2排放,RH掺混比例高时结果恰好相反。当RH掺混比例不小于30%时,混烧灰中会产生Ca3Al2O6,易与SiO2等形成低熔点共熔物,显著降低灰的熔点,导致其出现明显的熔融现象。
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doi: 10.19666/j.rlfd.202503045
  • 接收时间:2025-03-04
  • 首发时间:2026-03-05
  • 出版时间:2025-08-25
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  • 收稿日期:2025-03-04
基金
Key Research and Development Program of Guangxi Province(AB24010075)
广西省重点研发计划项目(AB24010075)
作者信息
    1.青岛大学化工学院,山东 青岛 266100
    2.中国科学院青岛生物能源与过程研究所,山东 青岛 266101

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赵瑞东(1986),男,副研究员,主要研究方向为生物质热化学转化,
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2种不同金属材料的力学参数

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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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