Article(id=1325524241789247818, tenantId=1146029695717560320, journalId=1205116786560364546, issueId=1325524161678033072, articleNumber=null, orderNo=null, doi=10.16236/j.cnki.nrjxb.202503026, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1726675200000, receivedDateStr=2024-09-19, revisedDate=1739289600000, revisedDateStr=2025-02-12, acceptedDate=null, acceptedDateStr=null, onlineDate=1793959206292, onlineDateStr=2026-11-06, pubDate=1748102400000, pubDateStr=2025-05-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1793959206292, onlineIssueDateStr=2026-11-06, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1793959206292, creator=13701087609, updateTime=1793959206292, updator=13701087609, issue=Issue{id=1325524161678033072, tenantId=1146029695717560320, journalId=1205116786560364546, year='2025', volume='43', issue='3', pageStart='193', pageEnd='287', issueExtLink='null', onlineDate='null', pubDate='1748102400000', pubDateStr='2025-05-25', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1793959187179, creator='13701087609', updateTime=1793959945056, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1325527341178569523, tenantId=1146029695717560320, journalId=1205116786560364546, issueId=1325524161678033072, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1325527341178569524, tenantId=1146029695717560320, journalId=1205116786560364546, issueId=1325524161678033072, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=222, endPage=231, ext={EN=ArticleExt(id=1325524243806708043, articleId=1325524241789247818, tenantId=1146029695717560320, journalId=1205116786560364546, language=EN, title=Effects of air-fuel ratio on the combustion and emission characteristics of gasoline/ammonia and ethanol/ammonia engines, columnId=null, journalTitle=Transactions of CSICE, columnName=null, runingTitle=null, highlight=null, articleAbstract=

Based on a naturally aspirated four-cylinder and spark-ignition engine, the combustion and nitrogen-based emission characteristics fueled with gasoline/ammonia and ethanol/ammonia respectively, were investigated under different values of excess air ratio ϕa at the speed of 2000r/min and the indicated mean effective pressure of 0.64—0.86MPa. The experimental results show that, at ϕa=1.0, the addition of ammonia to gasoline can effectively suppress knocking and optimize combustion phase, leading to an increase of indicated thermal efficiency of 3.4%. The nitrogen-based emission patterns of gasoline/ammonia and ethanol/ammonia are similar. The blending of ammonia leads to a notable increase in NOx emissions. Especially, NOx emissions decrease with spark timing advance at ϕa=1.0, while they increase with spark timing advance at ϕa=1.2 and 1.4. Chemical kinetic analysis reveals a positively correlation between fuel-NOx and temperature, and a negative correlation with pressure, and the impact of temperature on fuel-NOx is enhanced under lean-burn conditions. The NH3 emission is controlled by both the crevice mechanism and volumetric quenching effect, with the latter being enhanced as ϕa increases. The N2O emission is controlled by the low-temperature oxidation path of ammonia and tends to increase with delayed spark timing and an increase in ϕa. After ammonia blended, the NOx conversion efficiency of the three way catalyst decreases, while the CO conversion efficiency increases at the stoichiometric ratio.

, authors=Shang Liu1, Zhelong Lin1, Yunliang Qi1, Guoxiang Lu2, Bo Wang2, Zhi Wang1, authorsList=Shang Liu, Zhelong Lin, Yunliang Qi, Guoxiang Lu, Bo Wang, Zhi Wang, authorCompany=null, correspAuthors=Zhi Wang, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1325524249401909608, articleId=1325524241789247818, tenantId=1146029695717560320, journalId=1205116786560364546, language=CN, title=空燃比对汽油/氨和乙醇/氨发动机燃烧和排放特性的影响, columnId=null, journalTitle=内燃机学报, columnName=, runingTitle=null, highlight=null, articleAbstract=

基于一台自然吸气4缸火花点火发动机,在转速为2000r/min、平均指示压力为0.64~0.86MPa下研究了不同过量空气系数ϕa下汽油掺氨和乙醇掺氨的燃烧和氮基污染物排放特性.结果表明:ϕa=1.0时汽油掺氨可有效抑制发动机的爆震并优化燃烧相位,指示热效率可提升约3.4%;汽油/氨和乙醇/氨的氮基污染物排放规律相近,掺氨使NOx排放大幅增加,在ϕa=1.0时NOx排放随点火提前而降低,在ϕa为1.2和1.4时NOx排放随点火提前而升高,化学动力学分析表明,燃料型NOx与温度正相关,与压力负相关,且稀燃工况下温度对燃料型NOx的影响有所增强;NH3排放受狭隙效应和体积淬熄效应控制,且体积淬熄效应的影响随ϕa增大而增强;N2O排放受NH3低温氧化路径控制,随点火推迟和ϕa增大而增加;掺氨后,三效催化剂在化学计量比下对NOx转化率降低,对CO的转化效率升高.

, authors=刘尚1, 林哲龙1, 齐运亮1, 陆国祥2, 王博2, 王志1, authorsList=刘尚, 林哲龙, 齐运亮, 陆国祥, 王博, 王志, authorCompany=null, correspAuthors=王志, authorNote=

刘尚,博士研究生,.

, correspAuthorsNote=
王志,博士,教授,.
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刘尚,博士研究生,.

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Engine specifications

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参数数值
缸径/mm72
活塞行程/mm92
排量/L1.5
压缩比15.5
喷射形式进气道喷射
点火能量/mJ90
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发动机技术参数

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参数数值
缸径/mm72
活塞行程/mm92
排量/L1.5
压缩比15.5
喷射形式进气道喷射
点火能量/mJ90
), ArticleFig(id=1325524266103628211, tenantId=1146029695717560320, journalId=1205116786560364546, articleId=1325524241789247818, language=EN, label=Tab.2, caption=

Engine specifications

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参数数值
转速/(r·min-1)2000
节气门开度/%20
IMEP(ϕa=1.0)/MPa0.85
EGR率0
氨能量占比X/%0,30
氨掺混燃料92号汽油,无水乙醇
ϕa1.0,1.2,1.4
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试验工况

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参数数值
转速/(r·min-1)2000
节气门开度/%20
IMEP(ϕa=1.0)/MPa0.85
EGR率0
氨能量占比X/%0,30
氨掺混燃料92号汽油,无水乙醇
ϕa1.0,1.2,1.4
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空燃比对汽油/氨和乙醇/氨发动机燃烧和排放特性的影响
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刘尚 1 , 林哲龙 1 , 齐运亮 1 , 陆国祥 2 , 王博 2 , 王志 1
内燃机学报 | 2025,43(3): 222-231
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内燃机学报 | 2025 , 43 (3) : 222 -231
空燃比对汽油/氨和乙醇/氨发动机燃烧和排放特性的影响
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刘尚1 , 林哲龙1, 齐运亮1, 陆国祥2, 王博2, 王志1
作者信息
  • 1.清华大学车辆与运载学院,北京 100084
  • 2.比亚迪汽车工业有限公司产品规划及新汽车技术研究院,深圳 518118
通讯作者:
王志,博士,教授,.
作者简介:

刘尚,博士研究生,.

Effects of air-fuel ratio on the combustion and emission characteristics of gasoline/ammonia and ethanol/ammonia engines
Shang Liu1 , Zhelong Lin1, Yunliang Qi1, Guoxiang Lu2, Bo Wang2, Zhi Wang1
Affiliations
  • 1.School of Vehicle and Mobility,Tsinghua University,Beijing 100084,China
  • 2.Automotive Product Strategy and New Technology Research Institute,BYD Auto Industry Company Limited,Shenzhen 518118,China
出版时间: 2025-05-25 doi: 10.16236/j.cnki.nrjxb.202503026
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基于一台自然吸气4缸火花点火发动机,在转速为2000r/min、平均指示压力为0.64~0.86MPa下研究了不同过量空气系数ϕa下汽油掺氨和乙醇掺氨的燃烧和氮基污染物排放特性.结果表明:ϕa=1.0时汽油掺氨可有效抑制发动机的爆震并优化燃烧相位,指示热效率可提升约3.4%;汽油/氨和乙醇/氨的氮基污染物排放规律相近,掺氨使NOx排放大幅增加,在ϕa=1.0时NOx排放随点火提前而降低,在ϕa为1.2和1.4时NOx排放随点火提前而升高,化学动力学分析表明,燃料型NOx与温度正相关,与压力负相关,且稀燃工况下温度对燃料型NOx的影响有所增强;NH3排放受狭隙效应和体积淬熄效应控制,且体积淬熄效应的影响随ϕa增大而增强;N2O排放受NH3低温氧化路径控制,随点火推迟和ϕa增大而增加;掺氨后,三效催化剂在化学计量比下对NOx转化率降低,对CO的转化效率升高.

氨气  /  稀薄燃烧  /  氮基排放  /  化学反应动力学

Based on a naturally aspirated four-cylinder and spark-ignition engine, the combustion and nitrogen-based emission characteristics fueled with gasoline/ammonia and ethanol/ammonia respectively, were investigated under different values of excess air ratio ϕa at the speed of 2000r/min and the indicated mean effective pressure of 0.64—0.86MPa. The experimental results show that, at ϕa=1.0, the addition of ammonia to gasoline can effectively suppress knocking and optimize combustion phase, leading to an increase of indicated thermal efficiency of 3.4%. The nitrogen-based emission patterns of gasoline/ammonia and ethanol/ammonia are similar. The blending of ammonia leads to a notable increase in NOx emissions. Especially, NOx emissions decrease with spark timing advance at ϕa=1.0, while they increase with spark timing advance at ϕa=1.2 and 1.4. Chemical kinetic analysis reveals a positively correlation between fuel-NOx and temperature, and a negative correlation with pressure, and the impact of temperature on fuel-NOx is enhanced under lean-burn conditions. The NH3 emission is controlled by both the crevice mechanism and volumetric quenching effect, with the latter being enhanced as ϕa increases. The N2O emission is controlled by the low-temperature oxidation path of ammonia and tends to increase with delayed spark timing and an increase in ϕa. After ammonia blended, the NOx conversion efficiency of the three way catalyst decreases, while the CO conversion efficiency increases at the stoichiometric ratio.

ammonia  /  lean-burn  /  nitrogen-based emissions  /  chemical reaction kinetics
刘尚, 林哲龙, 齐运亮, 陆国祥, 王博, 王志. 空燃比对汽油/氨和乙醇/氨发动机燃烧和排放特性的影响. 内燃机学报, 2025 , 43 (3) : 222 -231 . DOI: 10.16236/j.cnki.nrjxb.202503026
Shang Liu, Zhelong Lin, Yunliang Qi, Guoxiang Lu, Bo Wang, Zhi Wang. Effects of air-fuel ratio on the combustion and emission characteristics of gasoline/ammonia and ethanol/ammonia engines[J]. Transactions of CSICE, 2025 , 43 (3) : 222 -231 . DOI: 10.16236/j.cnki.nrjxb.202503026
氢火焰速度快、可燃范围宽及所需点火能低,具有优异的燃烧性能[1].但氢安全性差、体积能量密度较低,使得其在制储运方面存在较大挑战[2-3].相比于氢,氨的体积能量密度较高、爆燃安全性好,原料来源广泛,制备工艺成熟,储运成本较低[4].同时,氨的氢含量较高,理论上完全燃烧产物为N2和H2O,是一种较优的氢能载体,且辛烷值高、抗爆性好.但氨所需点火能高,火焰传播速度慢,纯氨需采用进气加热[5-6]、高能点火[7]、主动射流[6]和多火花塞点火[8]等技术以提高点火或燃烧的稳定性,这会导致发动机制造成本的大幅增加和可靠性的降低,同时氨相比碳氢燃料可能产生更多的NOx、未燃NH3和N2O排放,难以在发动机中直接使用[9].对于点燃式发动机,较多的研究聚焦于氨与高火焰速度燃料的掺混燃烧,如氨/氢、氨/天然气和氨/汽油等.Mørch等[10]在进气道中引入不同掺混比的氨/氢混合气表明,氢气体积分数为10%时,发动机热效率最高.Grannell等[11]在一台可变压缩比发动机中研究了汽油掺氨条件下发动机的燃烧特性表明,在大负荷下掺氨燃烧可有效抑制爆震并提高热效率.Ryu等[12]利用缸内直喷氨气进气道喷射汽油,实现了较高的发动机充量系数,提高了氨/汽油发动机的动力输出.Ariemma等[13]在旋流燃烧器中开展了氨/甲烷在不同化学计量比下的燃烧特性试验表明,天然气的引入可以大幅度拓展氨的可燃极限,但会造成NOx的大幅增加.
作为最具代表性的含氧燃料,乙醇来源广泛,可由生物质转化而来,制备工艺成熟,是一种具有碳中和潜力的燃料.乙醇火焰速度快、辛烷值高,可以有效地抑制发动机爆震,改善燃烧稳定性和提高热效率[14-15].Li等[16]在激波管中测量了氨/乙醇混合燃料的滞燃期表明,燃烧初期乙醇产生的大量自由基是促进氨燃烧的关键因素.乙醇燃料可有效降低发动机碳排放[17],乙醇的高火焰速度和含氧特性相比于汽油可能对氨的燃烧起到促进作用,随着绿氨的生产规模逐渐扩大[18],生物乙醇与绿氨掺混燃烧,可大幅降低发动机的CO2排放[19].掺氨发动机的排放问题也日益受到关注,由于氨燃烧时会产生燃料型NOx,使得总NOx排放大幅增高[20],且NOx的影响机制更加复杂.此外,氨的低温氧化路径会产生一定量的N2O,其温室效应约是CO2的近300倍[21].
目前,氨与汽油类燃料的掺混燃烧聚焦于发动机整机性能的变化,缺少对燃烧特性和排放特性的详细分析,且研究工况聚焦于化学计量比[12, 19-20],但对于汽油机特别是稀燃工况,有关掺氨条件下的发动机燃烧和污染物排放规律的研究较少.笔者通过一台4缸四冲程高压缩比汽油机,探究了不同过量空气系数ϕa条件下汽油掺氨和乙醇掺氨对燃烧和氮基污染物排放的影响,并结合化学动力学分析讨论了NOx和N2O排放的生成规律,旨在为掺氨发动机燃烧及氮基污染物排放控制提供参考.
试验在一台1.5L、4缸火花点火发动机中进行,进气方式为自然吸气,液体燃料采用进气道喷射的方式自进气歧管雾化后进入缸内;在进气总管安装气体喷嘴以0.45MPa压力喷射氨气,氨气与新鲜空气在进气总管和混合腔中混合均匀,通过进气歧管进入缸内.试验中对液氨罐表面进行50℃温度控制,以保证氨气喷射压力的稳定.图1为发动机台架示意,表1为发动机技术参数.
试验台架配备有凯迈CJ160电力测功机用于转速控制,缸内压力由AVL ZI33火花塞式缸内压力传感器进行测量,并由Kistler Kibox燃烧分析仪进行采集分析,缸内压力记录连续的200个循环.ECU可以实现喷油量和喷氨量的调节,从而控制掺氨比和整体ϕa;排放由AVL FTIR(型号SESAM 4.0)进行采集分析,该排放仪可测量NOx(仅包含NO和NO2)、N2O、NH3、CO和总碳氢(THC)等排放,对于每一个试验工况点,连续采集约50s的排放数据.试验中对排放采样管进行加热和温控,以防止水蒸汽冷凝吸收氨气,试验中所测排放为体积分数.液体燃料流量由MAX P001体积式油耗仪测量,氨流量由TSK521ML热式质量流量计测量.试验工况如表2所示,试验中在ϕa和掺氨比不变的条件下进行了点火时刻(ST)的扫掠,燃烧重心(CA50)位于0~5° CA ATDC区间或缸内发生明显爆震时,该工况即认为是最大点火提前角工况.使用输入缸内的氨能量占总燃料能量的比例作为掺氨比X,计算式为
X=(m1LVH1)/(m1LVH1+m2LVH2)
式中:m1为氨的质量流量;LVH1为氨的低热值;m2为汽油或乙醇的质量流量;LVH2为汽油或乙醇的低热值.对于一个工作循环,CA10、CA50和CA90分别为累计放热量达到总放热量10%、50%和90%对应的曲轴转角.
使用化学动力学计算软件Chemkin-Pro中的一维火焰速度模型展开计算,机理采用Wang等[22]开发的CEU-NH3,该机理包含91个组分和444步基元反应,该机理对乙醇/氨的火焰速度等进行了相关的验证[22].计算域长度设为1.0cm,最大网格数量设为500,并采用200个网格的自适应加密进行网格细化.仿真中采用的燃料为乙醇和氨,在入口边界改变燃料的摩尔分数和可燃混合气的空燃比.改变未燃混合气的初始温度、压力和各组分比例,以探究压力、温度、掺氨比和ϕa对NOx排放的影响.掺氨比采用氨的摩尔分数Y表示,其与X的换算方法为
w1=XLVH1−1XLVH1−1+(1−X)LVH2−1
w2=1−w1
Y=(w1M1−1)/(w1M1−1+w2M2−1)
式中:w1为氨在混合燃料中的质量分数;w2为乙醇在混合燃料中的质量分数;M1为氨的相对分子质量;M2为乙醇的相对分子质量.
图2示出汽油/氨和乙醇/氨在X为0%和30%最大点火提前角工况下的缸内压力与放热率曲线.对于汽油,其辛烷值相对较低,在ϕa=1.4,ST为-12° CA ATDC工况下,缸内仍会出现明显的爆震现象,压力曲线出现了较为剧烈的振荡,放热率曲线表现出明显的自燃特征.掺氨后,氨的化学惰性有效地延长了混合气的滞燃期,爆震被抑制,试验中各ϕa工况下均未出现爆震现象.对于乙醇燃料,其辛烷值高达108[3],抗爆性较强,在试验工况下缸内基本无爆震现象.乙醇掺氨后火焰速度降低,表现为缸内爆压和放热率峰值的降低.
图3和图4分别展示了汽油/氨和乙醇/氨混合燃料的指示平均有效压力(IMEP)和指示热效率.图5为最佳热效率工况点的燃烧相位.对于汽油,随着稀燃程度增加,IMEP降低.在ϕa不变的条件下,由于发动机充量系数降低,且相比汽油和乙醇,氨具有较低的体积能量密度,使得掺氨后负荷稍有降低;乙醇燃料辛烷值高,使得缸内爆震倾向低,掺氨无燃烧相位优化作用,且掺入气态氨导致发动机充量系数降低,因此,X=30%工况下的IMEP相比X=0%工况有较大幅度的降低.
对于汽油,ϕa为1.0和1.2工况下掺氨均可提高发动机指示热效率,这得益于燃烧相位的优化(点火范围被拓宽)和传热损失的降低(燃烧温度降低);而ϕa进一步增加至1.4后,虽能实现较优燃烧相位,但掺氨后缸内的燃烧速度降幅较大,使得X为0%和30%工况下发动机指示热效率处于同一水平.稀燃同样能够提高燃用乙醇时发动机的指示热效率,但掺氨无燃烧相位优化作用.ϕa=1.0时,尽管掺氨降低燃烧速度,但较低的燃烧温度使得传热损失降低,X为0%和30%工况下的指示热效率处于同一水平,但随着稀燃程度增加,燃烧速度逐渐降低,未燃损失有所升高,掺氨使得指示热效率降低,且ϕa=1.4工况下的降幅最大.
由图5可知,从燃烧相位的角度,由于掺氨后汽油/氨混合燃料的点火角范围被大幅拓宽,其CA50得以优化,但对于乙醇,ϕa相同时,X为0%和30%工况下CA50处于同一水平.从燃烧速度看,掺氨主要导致燃烧初期(CA10~ST)和燃烧后期(CA90~CA50)火焰速度变慢,而燃烧前期火焰速度(CA50~CA10)基本不变.
图6为三效催化剂(TWC)前汽油/氨和乙醇/氨的NOx排放(包含NO和NO2,主要为NO).X=0%时,NOx主要为热力型NOx,与温度和氧气浓度相关.因而无论是汽油还是乙醇,NOx排放随点火提前而增加.掺氨后NOx排放大幅增加,此时NOx由热力型NOx和燃料型NOx组成,且由于燃烧温度的降低,热力型NOx排放降低.在ϕa=1.0时,NOx排放随点火提前而降低,此时燃料型NOx处于主导地位.相关研究表明,燃料NOx与氨的氧化密切相关[13, 20].
无论汽油还是乙醇,一定程度的稀燃导致NOx排放大幅增加,汽油在ϕa=1.2时的爆震工况可达0.45%,乙醇在ϕa=1.2时的最大点火提前角工况可达0.35%.而引入氨后,相比X=0%工况,稀燃会造成NOx更大幅度地增加,NOx排放可达0.5%以上.在稀燃、X=30%工况,NOx排放随点火提前而增加.一方面,过量的氧气促进了热力型NOx和燃料型NOx的产生;另一方面,在稀混合气条件下,燃料型NOx对温度的变化可能更为敏感,即增加相同的温度,稀燃条件下燃料型NOx增幅比例可能增大.富燃时,NH3氧化会产生大量的中间产物如NH2和NH,从而促进了de-NOx反应[23]:NH2+NO=NNH+OH,NH+NO=N2+H2O,进一步降低了NOx排放,且明显低于ϕa=1.0工况下的NOx排放.
TWC前汽油/氨和乙醇/氨的NH3和N2O排放分别如图7和图8所示.化学计量比条件下,未燃NH3排放主要来源于狭隙效应[21],即未燃氨在压缩冲程末期和燃烧过程初期,近壁处的氨受到活塞压缩和火焰压缩的作用被挤入活塞与缸壁、气门阀座与缸盖等之间的间隙,并在膨胀冲程再次进入缸内,而此时缸内温度较低,未燃氨无法燃烧,在排气冲程被排出缸内.狭隙效应随着压力升高而增强,因而ϕa=1.0时,未燃NH3排放随着点火提前而增加.
稀燃条件下,燃烧温度降低,缸内压力降低,狭隙效应减弱,未燃NH3排放更多地受体积淬熄效应的影响,即火焰未传播到壁面时发生淬熄而产生未燃NH3,火焰淬熄距离随着压力和温度升高而降低,因而ϕa=1.4工况下,点火提前,未燃NH3排放降低.富燃时,过量的NH3无法燃烧完全,ϕa=0.9工况较ϕa=1.0工况NH3排放大幅升高.乙醇的含氧特性有助于氨的氧化.因此,在ϕa相同条件下,乙醇/氨的NH3排放略低于汽油/氨.
N2O排放受氨低温氧化路径的控制[21],随着ϕa增大,缸内燃烧温度降低,N2O排放升高;随着点火提前,缸内燃烧温度升高,N2O排放降低.富燃时,虽然燃烧温度较低,但N2O排放反而较低.N2O排放主要通过NHi组分与NO在低温反应下生成[21],NO摩尔分数的降低造成了N2O排放的降低.
汽油机保持化学计量比燃烧,目的是使用TWC即可满足较为严格的排放法规,后处理系统简单且成本较低.图9示出了汽油/氨混合燃料在X为0%和30%时TWC的空燃比特性.随着ϕa自0.9增加至1.0,X=0%条件下TWC入口排气温度由828.4K逐渐增加至862.6K;X=30%条件下TWC入口排气温度由768.3K逐渐增加至792.2K.随着ϕa自1.0增加至1.1,X=0%条件下TWC入口排气温度逐渐降低至844.8K;X=30%条件下TWC入口排气温度逐渐降低至767.7K.X=0%时,TWC的高效转化区位于ϕa=1.0附近;而X=30%时,化学计量比工况下TWC对NOx的转化率低于80%,但掺氨燃烧产生的大量NOx排放使得CO的转化效率有所升高.
对比图9(a)和图9(b)可知,掺氨后NOx高效转化区小幅向富燃偏移,化学计量比下掺氨后NOx排放大幅升高,过量NOx难以被完全转化,同时未燃NH3在TWC中的高温环境中可能部分转化为NOx.尽管轻度富燃时NOx可被高效转化,但此工况下NH3和CO的转化效率也大幅降低,因而需要优化TWC催化剂配方等,使其匹配发动机掺氨燃烧.在富燃时,TWC起到了恶化NH3排放的负面作用,这与掺混氨无关,而是通过CO+H2O=H2+CO、2NO+2CO+3H3=2CO2+2NH3和NO+5H2=2NH3+2H2O等反应生成[24];在稀燃时,TWC起到了恶化NOx排放的负面作用,这可能是由于部分未燃的NH3在催化剂作用下被氧化为NO.
图10示出了Y为0、0.6和1.0条件下乙醇/氨混合燃料在不同ϕa条件下已燃区NO的摩尔分数.对于3种燃料,其已燃区NO摩尔分数均随着温度的升高而增大,但对于Y为0.6和1.0两种燃料,其已燃区NO摩尔分数则随着压力升高而降低,Y=0的燃料已燃区NO摩尔分数随着压力升高而增大,这与试验现象相一致,即燃料型NO摩尔分数与温度呈正相关关系,与压力呈负相关关系,但温度和压力对NO摩尔分数变化率的影响在不同ϕa下有所不同,即NO摩尔分数随温度和压力变化曲线的斜率有所不同.掺氨燃烧时,NO摩尔分数最大值出现在ϕa=1.2;而Y=0时,NO摩尔分数最大值出现在ϕa=1.1,一定程度的稀燃会促进整体NOx的生成[21].
对上述曲线利用最小二乘法进行线性拟合,取斜率的绝对值表征不同ϕa条件下温度和压力对NO摩尔分数变化率的影响,如图11所示.在掺氨燃烧(Y为0.6,1.0)时,随稀燃程度增加,温度对NO摩尔分数的影响逐渐增大,压力对NO摩尔分数的影响则基本不变.而对于乙醇,温度和压力在ϕa=1.1时对NO摩尔分数的影响最大.这解释了图6中所示掺氨稀燃工况下NOx排放随点火提前而增大的现象.
图12示出了ϕa为0.8、1.0和1.2工况下NO最大产率截面NH3的氧化路径.无论是富燃、化学计量比燃烧还是稀燃,NH3的氧化总是始于NH3与OH等活性自由基反应脱氢,且NO的生成主要通过NH-HNO-NO、NH-NO和NH-N-NO等路径,OH、H和O等自由基在其中起了关键作用.不同的是浓燃时NH2/NH-N2H2的路径被大幅加强,这是因为富燃时OH等自由基浓度较低,NH3向NO的转化被抑制,但该转化路径中H自由基的贡献有所增强,这是因为富燃时氨会产生部分氢[25];而在稀燃时,氨氧化路径中OH和O自由基的贡献有一定的增加.
从氧化路径分析中可知,N2O是由NO与NH或NH2自由基反应生成,NH自由基浓度与掺氨比、ϕa和温度等密切相关.高掺氨比时,过量的氨无法被完全氧化,产生大量的NHi中间组分,NO向N2O的转化被加强,同时NO-NNH-N2和NO-N2路径的de-NOx反应也会被加强.稀燃工况下,燃烧温度降低,易导致NH3氧化不完全,增加NHi组分的摩尔分数,促进NO向N2O转化.图13示出了Y=0.6、T=700K和不同ϕa条件下OH摩尔分数随压力的变化关系,随着压力的升高,在不同ϕa条件下OH摩尔分数均呈现出降低趋势,这是燃料型NOx与压力呈负相关的原因.
在T=700K、p=4.5MPa和Y=0.6工况下分别对NO和N2O产率最大截面进行敏感性分析,如图14所示.不同ϕa下,链分支反应H+O2=O+OH对NO和N2O的促进作用最大,因该反应使得活性基浓度增加,促进了氨的氧化.而NH+NO=N2O+H在NO消耗中起到极大的促进作用,也是生成N2O的最主要反应,但N2O绝大部分会被转化为N2见图12.
对于NO,其对涉及OH、O和H生成和消耗反应的敏感性较大,因上述自由基在氨氧化过程中起重要作用.而在对NO生成起到抑制作用的反应中包含大量的三体反应,高压下三体反应向生成物分子数少的方向进行,此过程中,大量的OH、H等自由基被消耗,使得氨氧化过程被抑制,进而降低了燃料型NO的产率.
对于N2O,除涉及到OH等自由基的反应外,其对NH2和NH生成和消耗反应的敏感性也较大,这进一步说明了NHi在N2O生成过程中起重要作用.此外,富燃条件下N2O对产生或消耗H自由基的反应更敏感,链终止反应H+CH3=CH4和NH2+HO2=NH3+O2的敏感性系数在富燃时增加.
(1) 相比乙醇,汽油掺氨可以有效地抑制发动机化学计量比和轻度稀燃(ϕa=1.2)、中高负荷工况下的爆震,并拓展点火时刻范围,优化CA50位于5°~10° CA ATDC范围,从而有助于提高发动机燃油经济性;ϕa为1.0和1.2时,掺混30%氨气可使发动机指示热效率分别提高约3.4%和1.8%.
(2) 无氨掺混时,NOx排放受热力型NOx机理控制,引入30%氨后,NOx排放大幅增加,同时受热力型和燃料型NOx生成路径控制;掺氨后,ϕa=1.0时,NOx排放随点火提前而降低,ϕa为1.2和1.4时,NOx排放随点火提前而升高;化学计量比条件下掺氨使得TWC对NOx的转化率降低,对CO的转化率升高.
(3) NH3排放受狭隙效应和体积淬熄效应控制,在ϕa为1.0和1.2工况下,NH3排放随点火提前而增加,此时狭隙效应起主导作用,体积淬熄效应的影响随ϕa增加而加强,且在ϕa=1.4时占主导作用;N2O排放随点火角推迟和ϕa增大而增加.
(4) 化学动力学分析结果表明,不同ϕa下,燃料型NOx与温度呈正相关,与压力呈负相关;ϕa自1.0逐渐增加,温度对NO摩尔分数的影响增大,导致稀燃工况下NOx排放随点火提前而增加;OH、H和O等组分在NO和N2O的生成中起关键作用,NHi组分在N2O的生成中起关键作用.
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2025年第43卷第3期
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doi: 10.16236/j.cnki.nrjxb.202503026
  • 接收时间:2024-09-19
  • 首发时间:2026-11-06
  • 出版时间:2025-05-25
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  • 收稿日期:2024-09-19
  • 修回日期:2025-02-12
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国家自然科学基金资助项目(T2241003)
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    1.清华大学车辆与运载学院,北京 100084
    2.比亚迪汽车工业有限公司产品规划及新汽车技术研究院,深圳 518118

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王志,博士,教授,.
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2种不同金属材料的力学参数
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属
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种数
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species
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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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