Article(id=1256186030739284156, tenantId=1146029695717560320, journalId=1255847867265597444, issueId=1256186027853624275, articleNumber=null, orderNo=null, doi=10.11858/gywlxb.20251189, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1757260800000, receivedDateStr=2025-09-08, revisedDate=1760198400000, revisedDateStr=2025-10-12, acceptedDate=1768838400000, acceptedDateStr=2026-01-20, onlineDate=1777427688535, onlineDateStr=2026-04-29, pubDate=1775318400000, pubDateStr=2026-04-05, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1777427688535, onlineIssueDateStr=2026-04-29, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1777427688535, creator=13701087609, updateTime=1777427688535, updator=13701087609, issue=Issue{id=1256186027853624275, tenantId=1146029695717560320, journalId=1255847867265597444, year='2026', volume='40', issue='4', pageStart='040101-1', pageEnd='045301-13', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1777427687845, creator=13701087609, updateTime=1777427791253, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1256186461888627074, tenantId=1146029695717560320, journalId=1255847867265597444, issueId=1256186027853624275, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1256186461888627075, tenantId=1146029695717560320, journalId=1255847867265597444, issueId=1256186027853624275, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=045301-1, endPage=045301-13, ext={EN=ArticleExt(id=1256186031234212033, articleId=1256186030739284156, tenantId=1146029695717560320, journalId=1255847867265597444, language=EN, title=Inhibition Mechanism of KHCO3-Containing Water Mist on Methane-Hydrogen Premixed Deflagration, columnId=1256186031087411392, journalTitle=Chinese Journal of High Pressure Physics, columnName=High Pressure Applications, runingTitle=null, highlight=null, articleAbstract=

Explosion prevention and mitigation technologies for hydrogen-methane gas mixtures represent a critical research area for ensuring the safe application of hydrogen energy. This study systematically investigates the inhibition mechanism of potassium bicarbonate (KHCO3)-containing fine water mist on methane-hydrogen premixed deflagration using a combined approach of experiment and numerical simulation. The results indicate that KHCO3-containing fine water mist exhibits a significant inhibitory effect on methane-hydrogen premixed deflagration, with its suppression performance positively correlated to the KHCO3 mass fraction. Taking the condition of H2 volume fraction of 10% as an example, 11% KHCO3 addition resulted in reductions of the maximum explosion pressure and the average pressure rise rate by 34.64% and 44.57%, respectively. The laminar burning velocity was reduced by up to 66.43%. KHCO3 contributes to suppression through both physical and chemical mechanisms. Physically, droplet phase change (evaporation) absorbs heat and the generated steam dilutes the fuel mixture, thereby lowering the flame temperature and reducing reactant concentrations. Chemically, the decomposition of KHCO3 generates potassium compounds, which undergo the KOH→K→KOH recombination cycle to scavenge key radicals (·H, ·O, ·OH). This process competes with chain-branching reactions and interrupts the combustion chain reactions. Furthermore, the suppression process is governed by a competition between inhibitory and promotional effects. At high hydrogen blending ratios and high mass fractions of KHCO3, the physical evaporation efficiency becomes a bottleneck that constrains the chemical inhibition, leading to a saturation of the overall suppression efficiency. Nevertheless, a significant inhibitory effect is still maintained.

, correspAuthors=Peng SHAO, authorNote=null, correspAuthorsNote=null, copyrightStatement=Copyright © 2026 Chinese Journal of High Pressure Physics. All rights reserved., 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, authorCompany=null, fund=null, authors=null, authorsList=Hui HUANG, Yuanbing LI, Xia LI, Peng SHAO), CN=ArticleExt(id=1256186064960610948, articleId=1256186030739284156, tenantId=1146029695717560320, journalId=1255847867265597444, language=CN, title=含KHCO3细水雾对甲烷-氢气预混爆燃的抑制机理, columnId=1256186031326486722, journalTitle=高压物理学报, columnName=高压科学应用, runingTitle=null, highlight=null, articleAbstract=

甲烷-氢气混合气体的爆炸防控技术是保障氢能安全应用的重要课题。通过实验与数值模拟相结合的方法,系统研究了含KHCO3细水雾对甲烷-氢气预混爆燃的抑制机理。结果表明,含KHCO3细水雾对甲烷-氢气预混爆燃具有显著抑制效果,且抑制性能与KHCO3的质量分数呈正相关。以氢气体积分数为10%的混合气体为例,与对照组相比,KHCO3的质量分数为11%时,峰值压力和平均压力上升速率分别降低34.64%和44.57%,层流燃烧速度最高下降66.43%。KHCO3兼具物理与化学双重抑制效应:物理上,雾滴相变吸热和蒸气稀释效应降低火焰温度并稀释可燃物;化学上,KHCO3分解产生的钾化合物通过KOH→K→KOH重组循环消耗关键自由基(·H、·O、·OH),与链分支反应形成竞争,中断燃烧链式反应。此外,抑制过程是抑制与促进效应的竞争。高掺氢比和高KHCO3质量分数下,物理蒸发效率成为限制化学抑制作用的瓶颈,导致抑制效率出现饱和现象,但整体上仍表现出显著的抑制效果。

, correspAuthors=邵鹏, authorNote=null, correspAuthorsNote=
邵 鹏(1997-),男,硕士,主要从事可燃气体爆燃防治研究. E-mail:
, copyrightStatement=版权所有©《高压物理学报》编辑部 2026, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=YRJyaWWLeCKxqSGlVYRWsg==, magXml=If9X8ech2xxujSRwkZJUgA==, pdfUrl=null, pdf=jKkV3rLOjlnxHEvaHIrMww==, pdfFileSize=5516690, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=pLwsznpiFOAmA3nkgJnQiA==, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=+bzvdc09Xtj5xcvxvs9U8w==, mapNumber=null, authorCompany=null, fund=null, authors=

黄 辉(1987-),男,硕士,副教授,主要从事安全智能监测和消防救援研究. E-mail:

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黄 辉(1987-),男,硕士,副教授,主要从事安全智能监测和消防救援研究. E-mail:

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黄 辉(1987-),男,硕士,副教授,主要从事安全智能监测和消防救援研究. E-mail:

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language=EN, label=Tab.1, caption=

Effects of KHCO3-containing fine water mist on the maximum explosion pressure and the average rate of pressure rise

, figureFileSmall=null, figureFileBig=null, tableContent=
$ {\varphi}_{{{\mathrm{H}}_{2}}} $/%Mass fraction of KHCO3/% $ {t}_{{{\mathrm{p}}_{\max }}} $/mspmax/kPa $ {(\mathrm{d}p/\mathrm{d}t)}_{\text{avg}} $/(MPa·s−1)
0Control37.6224.13±0.840.64±0.03
034.5421.74±0.610.63±0.03
349.8020.34±0.920.41±0.02
739.9018.71±0.410.47±0.02
1144.3615.77±0.630.36±0.01
10Control37.1826.16±0.810.70±0.03
045.1423.46±0.590.52±0.02
337.7022.16±0.950.59±0.02
734.8218.31±0.730.53±0.02
1152.1216.29±0.340.31±0.01
20Control35.5427.75±0.830.78±0.03
044.4826.95±1.120.61±0.03
342.0225.74±0.620.61±0.02
741.5026.79±1.230.65±0.02
1149.4222.40±0.720.45±0.02
30Control34.8829.92±0.780.86±0.03
039.8230.49±1.490.77±0.03
336.5226.72±0.880.73±0.02
741.5026.79±0.750.65±0.03
1141.8425.36±1.070.61±0.02
), ArticleFig(id=1256186074309714648, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1256186030739284156, language=CN, label=表1, caption=

含KHCO3细水雾对峰值压力和平均压力上升速率的影响

, figureFileSmall=null, figureFileBig=null, tableContent=
$ {\varphi}_{{{\mathrm{H}}_{2}}} $/%Mass fraction of KHCO3/% $ {t}_{{{\mathrm{p}}_{\max }}} $/mspmax/kPa $ {(\mathrm{d}p/\mathrm{d}t)}_{\text{avg}} $/(MPa·s−1)
0Control37.6224.13±0.840.64±0.03
034.5421.74±0.610.63±0.03
349.8020.34±0.920.41±0.02
739.9018.71±0.410.47±0.02
1144.3615.77±0.630.36±0.01
10Control37.1826.16±0.810.70±0.03
045.1423.46±0.590.52±0.02
337.7022.16±0.950.59±0.02
734.8218.31±0.730.53±0.02
1152.1216.29±0.340.31±0.01
20Control35.5427.75±0.830.78±0.03
044.4826.95±1.120.61±0.03
342.0225.74±0.620.61±0.02
741.5026.79±1.230.65±0.02
1149.4222.40±0.720.45±0.02
30Control34.8829.92±0.780.86±0.03
039.8230.49±1.490.77±0.03
336.5226.72±0.880.73±0.02
741.5026.79±0.750.65±0.03
1141.8425.36±1.070.61±0.02
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含KHCO3细水雾对甲烷-氢气预混爆燃的抑制机理
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黄辉 1 , 李元兵 1 , 李霞 1 , 邵鹏 2, *
高压物理学报 | 高压科学应用 2026,40(4): 045301-1-045301-13
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高压物理学报 | 高压科学应用 2026, 40(4): 045301-1-045301-13
含KHCO3细水雾对甲烷-氢气预混爆燃的抑制机理
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黄辉1 , 李元兵1, 李霞1, 邵鹏2, *
作者信息
  • 1重庆安全技术职业学院应急管理学院, 重庆 404010
  • 2西南石油大学化学化工学院, 四川 成都 610500
  • 黄 辉(1987-),男,硕士,副教授,主要从事安全智能监测和消防救援研究. E-mail:

通讯作者:

邵 鹏(1997-),男,硕士,主要从事可燃气体爆燃防治研究. E-mail:
Inhibition Mechanism of KHCO3-Containing Water Mist on Methane-Hydrogen Premixed Deflagration
Hui HUANG1 , Yuanbing LI1, Xia LI1, Peng SHAO2, *
Affiliations
  • 1School of Emergency Management, Chongqing Vocational College of Safety Technology, Chongqing 404010, China
  • 2College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, Sichuan, China
出版时间: 2026-04-05 doi: 10.11858/gywlxb.20251189
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甲烷-氢气混合气体的爆炸防控技术是保障氢能安全应用的重要课题。通过实验与数值模拟相结合的方法,系统研究了含KHCO3细水雾对甲烷-氢气预混爆燃的抑制机理。结果表明,含KHCO3细水雾对甲烷-氢气预混爆燃具有显著抑制效果,且抑制性能与KHCO3的质量分数呈正相关。以氢气体积分数为10%的混合气体为例,与对照组相比,KHCO3的质量分数为11%时,峰值压力和平均压力上升速率分别降低34.64%和44.57%,层流燃烧速度最高下降66.43%。KHCO3兼具物理与化学双重抑制效应:物理上,雾滴相变吸热和蒸气稀释效应降低火焰温度并稀释可燃物;化学上,KHCO3分解产生的钾化合物通过KOH→K→KOH重组循环消耗关键自由基(·H、·O、·OH),与链分支反应形成竞争,中断燃烧链式反应。此外,抑制过程是抑制与促进效应的竞争。高掺氢比和高KHCO3质量分数下,物理蒸发效率成为限制化学抑制作用的瓶颈,导致抑制效率出现饱和现象,但整体上仍表现出显著的抑制效果。

细水雾  /  KHCO3  /  甲烷-氢气  /  预混爆燃  /  抑制机理

Explosion prevention and mitigation technologies for hydrogen-methane gas mixtures represent a critical research area for ensuring the safe application of hydrogen energy. This study systematically investigates the inhibition mechanism of potassium bicarbonate (KHCO3)-containing fine water mist on methane-hydrogen premixed deflagration using a combined approach of experiment and numerical simulation. The results indicate that KHCO3-containing fine water mist exhibits a significant inhibitory effect on methane-hydrogen premixed deflagration, with its suppression performance positively correlated to the KHCO3 mass fraction. Taking the condition of H2 volume fraction of 10% as an example, 11% KHCO3 addition resulted in reductions of the maximum explosion pressure and the average pressure rise rate by 34.64% and 44.57%, respectively. The laminar burning velocity was reduced by up to 66.43%. KHCO3 contributes to suppression through both physical and chemical mechanisms. Physically, droplet phase change (evaporation) absorbs heat and the generated steam dilutes the fuel mixture, thereby lowering the flame temperature and reducing reactant concentrations. Chemically, the decomposition of KHCO3 generates potassium compounds, which undergo the KOH→K→KOH recombination cycle to scavenge key radicals (·H, ·O, ·OH). This process competes with chain-branching reactions and interrupts the combustion chain reactions. Furthermore, the suppression process is governed by a competition between inhibitory and promotional effects. At high hydrogen blending ratios and high mass fractions of KHCO3, the physical evaporation efficiency becomes a bottleneck that constrains the chemical inhibition, leading to a saturation of the overall suppression efficiency. Nevertheless, a significant inhibitory effect is still maintained.

fine water mist  /  KHCO3  /  methane-hydrogen  /  premixed deflagration  /  inhibition mechanism
黄辉, 李元兵, 李霞, 邵鹏. 含KHCO3细水雾对甲烷-氢气预混爆燃的抑制机理. 高压物理学报, 2026 , 40 (4) : 045301-1 -045301-13 . DOI: 10.11858/gywlxb.20251189
Hui HUANG, Yuanbing LI, Xia LI, Peng SHAO. Inhibition Mechanism of KHCO3-Containing Water Mist on Methane-Hydrogen Premixed Deflagration[J]. Chinese Journal of High Pressure Physics, 2026 , 40 (4) : 045301-1 -045301-13 . DOI: 10.11858/gywlxb.20251189
氢气(H2)作为一种清洁高效的燃料及重要的工业原料,被认为是实现能源转型的重要载体[12]。然而,相比纯甲烷(CH4),氢气的加入会显著提高混合气体的层流燃烧速度,拓宽爆炸极限,使爆炸冲击危害增加[35]。在该背景下,传统天然气安全防控体系面临新的挑战,如何有效抑制爆燃过程,保障工程安全成为目前关注的焦点。
针对气体爆炸的防护,目前常用的方法有惰性气体稀释、金属盐粉体喷射以及细水雾抑制等。惰性气体能通过降低氧浓度减缓反应,但在实际场景中,常受到储运和成本的限制[68]。干粉灭火剂依赖化学抑制机制,在火焰区表现出较强的抑制能力,但粉体的沉积和污染会带来二次风险[910]。细水雾具有高潜热和强蒸汽稀释效应,因而引起学者的广泛关注。有学者指出,细水雾可有效缓解爆炸风险,但其性能依赖于雾滴粒径和喷雾密度[1112]。然而,在实际工业应用中,仅依靠物理效应难以保证抑制效果,因此,需要寻找高效的抑制剂。
为克服这一局限性,学者们尝试在细水雾中引入碱金属盐添加剂。其中,钾盐在多项实验中显示出优于钠盐的抑制性能[13]。Zhang等[14]指出,添加钾盐的细水雾能够显著降低火焰的传播速度;王晓玲等[15]发现,草酸钾等钾盐细水雾可以显著延缓火焰反应速率;Pei等[16]、Hu等[17]证实,钾盐的抑制效果不仅体现在热分解吸热和稀释效应,还可以通过在气相中释放K和KOH等活性物质消耗火焰中的自由基,削弱链分支反应。上述研究证实了含钾盐细水雾物理-化学双重抑制效应的优势。
碳酸氢钾(KHCO3)因具有良好的溶解性和分解特性,被广泛应用于防灭火领域。KHCO3在火焰中分解产生K2CO3、CO2和H2O,其中CO2和水蒸气参与气相稀释和冷却,而钾化合物则发挥自由基清除效应[13]。Jia等[18]证实了KHCO3粉体在甲烷爆炸中的抑制效果,并指出其性能受粉体粒径和喷射条件的影响。然而,与喷射粉体相比,含KHCO3细水雾的抑制表现尚未得到系统研究,特别是在甲烷-氢气预混气体条件下的作用机理仍需深入探讨。
据报道,细水雾在某些条件下可能产生复杂的抑制-促进双重效应。Van Wingerden等[19]发现,粒径较大的水雾通过增强湍流强度可能加速火焰传播。Cheikhravat等[20]也观察到了细水雾喷射系统产生的湍流导致的火焰加速现象。Zhang等[21]指出,43.3和28.2 μm的液滴均能削弱爆炸超压,但前者引起的湍流特征更显著,在一定程度上促进了火焰传播。这表明,细水雾的最终作用效果是抑制与促进机制竞争的结果。
然而,现有研究主要关注细水雾的整体抑制效果,缺乏对抑制-促进竞争机理的深入理解。特别是在含KHCO3细水雾体系中,化学抑制效应的发挥程度往往受到物理蒸发过程的制约。当蒸发效率受限时,未完全蒸发的雾滴不仅无法充分释放KHCO3,还可能充当“流体障碍物”,通过增强火焰的Darrieus-Landau(D-L)不稳定性来促进燃烧,从而进一步削弱甚至抵消化学抑制效应。
基于上述科学问题,本工作拟系统研究含KHCO3细水雾对甲烷-氢气预混爆燃的抑制-促进竞争机理,通过实验测量火焰结构、爆炸压力及压力上升速率,结合化学反应动力学深入分析含KHCO3细水雾的化学抑制机理,并揭示蒸发过程与气相反应耦合下抑制-促进效应的竞争关系及其主导因素,旨在为掺氢天然气的爆炸防控提供理论支撑。
爆炸实验装置如图1所示,该装置主要由可视化管道、配气系统、细水雾喷洒系统、点火与同步控制系统以及数据采集系统构成。可视化管道为方形,尺寸为100 mm×100 mm×1000 mm。为保障实验安全,管道末端(距离点火端96 cm)设置由0.5 mm厚聚四氟乙烯(polytetrafluoroethylene, PTFE)膜密封的G1泄爆口。数据采集系统包括高速摄像机和压力采集系统。高速摄像机(Phantom EVO 710L)以2 000 s–1的采样速率采集火焰传播过程。压力信号由安装在距离点火端90 cm处的PCB(113B21)压力传感器采集,采样频率为5 000 Hz。点火与同步控制系统通过12 V直流变压器和脉冲发生器控制电极产生电火花。为实现同步控制,采用延迟继电器设定细水雾喷洒1 s后启动电火花,并持续放电50 ms。细水雾喷洒系统由超声波雾化喷头、空压机和水泵组成,喷头安装于距离点火端37.5 cm处。实验中,空气驱动压力固定为0.3 MPa,对应的喷雾流量为325 mL/min。Ingram等[22]和Shao等[23]的研究表明,碱金属盐的质量分数对喷雾粒径无显著影响。基于此,本研究仅对纯细水雾的粒径分布进行测试(由美泰喷雾科技有限公司测量,设备型号为OMEC DP-02),结果如图2所示(D10D50D90分别为细水雾累积分布达到10%、50%和90%时对应的粒径),在后续分析中不考虑粒径分布的影响。实验环境温度约为298 K,此外,每个工况下重复3次以上实验,以保证结果的可靠性。
预混气体反应式为
$ \begin{aligned}{\varphi}_{{{\mathrm{H}}_{2}}}{\mathrm{H}}_{2}+\left(1-{\varphi}_{{{\mathrm{H}}_{2}}}\right){\text{CH}}_{4}+\frac{4-3{\varphi}_{{{\mathrm{H}}_{2}}}}{2}\left({\mathrm{O}}_{2}+3.76{\mathrm{N}}_{2}\right)\rightarrow \\ \left(1-{\varphi}_{{{\mathrm{H}}_{2}}}\right){\text{CO}}_{2}+\left(2-{\varphi}_{{{\mathrm{H}}_{2}}}\right){\mathrm{H}}_{2}\mathrm{O}+3.76\times\frac{4-3{\varphi}_{{{\mathrm{H}}_{2}}}}{2}{\mathrm{N}}_{2} \end{aligned}$
其中
$ {\varphi}_{{{\mathrm{H}}_{2}}}=\frac{{n}_{{{\mathrm{H}}_{2}}}}{{n}_{{{\mathrm{H}}_{2}}}+{n}_{{{\text{CH}}_{4}}}}\times 100\text{%} $
式中:$ {\varphi}_{{{\mathrm{H}}_{2}}} $为氢气在混合气体中的体积分数,$ {n}_{{{\mathrm{H}}_{2}}} $为氢气的物质的量,$ {n}_{{{\text{CH}}_{4}}} $为甲烷的物质的量。
数值模拟使用ANSYS Chemkin-Pro 24R2中的Premixed Laminar FIame Speed Calculation模型。为保证计算的精确度,网格细化参数梯度(Grad)和曲率(Curv)分别设置为0.01和0.05。计算域的距离为0~10 cm,网格数量为1500。初始温度为298 K,压力为0.1 MPa。此外,计算过程中还考虑了热扩散(Soret效应)对甲烷-氢气-空气燃烧的影响。模拟所用的机理文件由3部分组成,其中甲烷-氢气的机理由GRI 3.0与San Diego机制耦合,KHCO3的机理可以从Babushok等[24]的研究中获取。机理耦合后,选取3种当前主流机理的层流燃烧速度进行对比验证,验证结果如图3所示。
一维稳态层流火焰的主要控制方程有连续性方程、物种守恒方程、能量守恒方程。
连续性方程
$ \dot{M}=\rho uA={C} $
式中:$\dot{M} $为质量流率;$ \rho $为混合物密度;uA为体积流量,u为轴向速度,A为横截面积;C为常数。
物种守恒方程
$ \dot{M}\frac{\mathrm{d}{Y}_{k}}{\mathrm{d}x}+\frac{\mathrm{d}}{\mathrm{d}x}\left(\rho A{Y}_{k}{v}_{k}\right)-A{\dot{\omega }}_{k}{W}_{k}=0\,\;\;\;\;\;\;\;\;k=1,2,\cdots ,{K}_{g} $
能量守恒方程
$ \dot{M}\frac{\mathrm{d}T}{\mathrm{d}x}-\frac{1}{{c}_{p}}\frac{\mathrm{d}}{\mathrm{d}x}\left(\lambda A\frac{\mathrm{d}T}{\mathrm{d}x}\right)+\frac{A}{{c}_{p}}\sum \limits_{k=1}^{K}\rho {Y}_{k}{v}_{k}{c}_{p,k}\frac{\mathrm{d}T}{\mathrm{d}x}+\frac{A}{{c}_{p}}\sum \limits_{k=1}^{K}{\dot{\omega }}_{k}{h}_{k}{W}_{k}=0$
式中:YkvkWkhk分别为物种k的质量分数、扩散速度、摩尔质量和质量比焓,Kg为气相物种总数,$ {\dot{\omega }}_{k} $为物种k的净化学反应生成速率,T为温度,$ {c}_{p}\text{、}\lambda $分别为混合物的比定压热容和热导率。
图4(a)展示了在无细水雾作用下(对照组),$ {\varphi}_{{{\mathrm{H}}_{2}}} $=20%时火焰结构的演化过程。火焰呈现出从半球形到郁金香火焰的典型形态演变。此外,还观测到扭曲的郁金香火焰(t=50 ms),这可以归因于火焰前锋受流场、压力波之间非对称耦合作用的影响[25]
喷洒细水雾显著改变了火焰前锋的结构。如图4(b)所示,当细水雾中不添加KHCO3时,雾滴与火焰的持续作用导致郁金香火焰消失,并造成火焰在传播过程中出现褶皱和胞状结构(25~35 ms)。此外,雾滴与火焰持续接触并发生热交换,还会导致火焰颜色发生变化。雾滴进入火焰后,郁金香火焰消失,与图4(a)相比,火焰传播至尾端的时间提前6.47%。这可归因于火焰区中未蒸发雾滴充当障碍物,增强了火焰的D-L不稳定性[26]。如图4(c)图4(d)图4(e)所示,当KHCO3的质量分数分别为3%、7%和11%时,火焰表面产生胞状结构,且胞状结构特征的显著性与其质量分数呈正相关。虽然胞状结构可以通过增大火焰表面积提升火焰燃烧速度,但却显著延长了火焰传播至尾端的时间。这表明,含KHCO3的细水雾对火焰传播兼具抑制与促进效应,且在添加KHCO3后,抑制效应占据主导。
胞状结构的产生主要归因于扩散-热不稳定性和D-L不稳定性[27]。需要注意的是,含KHCO3细水雾在火焰区域的不完全和不均匀蒸发强化了这2种因素。KHCO3的不均匀分布一方面造成了局部温度梯度和反应物浓度的差异,强化了扩散-热不稳定性;另一方面,未蒸发的雾滴充当障碍物对气流产生湍流扰动,加剧了局部火焰拉伸,从而增强了D-L不稳定性。然而,这种由不稳定性导致的促进效应,远不及含KHCO3细水雾的抑制效应。物理上,KHCO3雾滴相变蒸发降低了火焰区的温度,同时产生的水蒸气和CO2稀释了可燃物浓度。化学上,KHCO3分解产生的气相钾化合物(K、KOH等)则通过消耗维持燃烧链式反应的核心自由基(H、OH)延缓反应速率[24]。在不同的掺氢比条件下,含KHCO3细水雾对火焰结构也表现出类似的影响规律。
图5展示了不同掺氢比下含KHCO3细水雾对爆燃压力的影响。可以看出,压力的变化趋势相似,其特征是由密封膜的破裂导致初始压力峰值,并随着压力发展至最大压力后逐渐衰减。压力在衰减过程中受火焰与管壁的热声耦合效应影响,呈现亥姆霍兹型振荡[2829]
表1所示,纯细水雾的加入显著改变了爆炸进程。与对照组相比,纯细水雾几乎在所有掺氢比下均导致了峰值压力($ {p}_{\max } $)和平均压力上升速率($ {(\mathrm{d}p/\mathrm{d}t)}_{\text{avg}} $)的下降。以${\varphi}_{{{\mathrm{H}}_{2}}} $=10%为例,与对照组相比,$ {p}_{\max } $$ {(\mathrm{d}p/\mathrm{d}t)}_{\text{avg}} $分别下降了10.32%和26.13%。这表明雾滴相变吸热与蒸汽稀释所构成的物理抑制是爆燃抑制效应的基础。KHCO3的加入带来了高效且显著的化学抑制效应。同样以$ {\varphi}_{{{\mathrm{H}}_{2}}}$=10%为例,当KHCO3质量分数为11%时,与纯细水雾相比,$ {p}_{\max } $$ {(\mathrm{d}p/\mathrm{d}t)}_{\text{avg}} $分别下降了34.64%和44.57%。这表明抑制效果与KHCO3质量分数整体呈正相关。同时,无论掺氢比如何,KHCO3的质量分数为11%时均表现出最佳的抑制性能,对应着最低的$ {p}_{\max } $$ {(\mathrm{d}p/\mathrm{d}t)}_{\text{avg}} $
尽管抑制效果与KHCO3质量分数呈正相关,但其抑制效率在高掺氢比下表现出非单调性:当$ {\varphi}_{{{\mathrm{H}}_{2}}}$=0%、KHCO3的质量分数为11%时,相较于对照组,$ {p}_{\max } $下降了34.64%;当$ {\varphi}_{{{\mathrm{H}}_{2}}}$为20%和30%、KHCO3的质量分数为11%时,相较于对照组,$ {p}_{\max } $分别下降了19.27%和15.22%;而当$ {\varphi}_{{{\mathrm{H}}_{2}}} $=20%、KHCO3的质量分数从3%增至7%时,$ {p}_{\max } $不仅没有下降,反而从25.74 kPa增至26.79 kPa,同时$ {(\mathrm{d}p/\mathrm{d}t)}_{\text{avg}} $也从0.61 MPa/s增至0.65 MPa/s。这表明,KHCO3细水雾对爆燃存在抑制和促进双重竞争效应。此外,在高掺氢比下还观察到了KHCO3抑制效果的饱和性。以$ {\varphi}_{{{\mathrm{H}}_{2}}} $=30%为例,将KHCO3的质量分数从7%提升至11%,$ {(\mathrm{d}p/\mathrm{d}t)}_{\text{avg}} $从0.65 MPa/s降至0.61 MPa/s,抑制效率远不如其在$ {\varphi}_{{{\mathrm{H}}_{2}}} $=0%下显著。这可能归因于气相KOH在空气中存在最大饱和浓度,进而导致抑制效率出现饱和性[30]
总体而言,压力分析证实了KHCO3兼具物理和化学的双重抑制机制。但抑制效应的非单调性和饱和性表明,存在一个关键瓶颈因素阻碍了KHCO3化学抑制潜力的完全发挥,这一限制因素的作用机理将在后续的化学动力学分析中深入探讨。
层流燃烧速度(laminar burning velocity,LBV)是可燃混合物的固有特性,被认为是评估抑制剂抑制效率的关键参数[31]。如图6所示,不同质量分数的KHCO3均能对LBV产生显著的抑制作用。具体来说,当$ {\varphi}_{{{\mathrm{H}}_{2}}} $=20%、KHCO3的质量分数为0%时,LBV从无细水雾的41.72 cm/s降至34.77 cm/s,降幅约为16.65%。KHCO3的加入进一步提高了化学抑制能力,并且其效果与质量分数呈正相关。当$ {\varphi}_{{{\mathrm{H}}_{2}}} $=20%时,随着KHCO3的质量分数从3%增至11%,LBV进一步降低至14.00 cm/s,与对照组相比,总降幅高达66.43%。
净热释放速率(net heat release rate,NHRR)同为可燃混合物的固有特性,与化学反应速率和热释放相关[32]。而LBV的降低则与火焰区能量释放的减弱密切相关。如图7所示,NHRR峰值的变化规律与LBV相似,即KHCO3的质量分数为0%时,对照组的NHRR峰值显著降低,而KHCO3则进一步加剧了这种抑制。当$ {\varphi}_{{{\mathrm{H}}_{2}}} $=20%、KHCO3的质量分数为11%时,NHRR峰值从对照组的5.09×109 J/(m3·s)显著降低至7.60×108 J/(m3·s)。此外,需要注意的是,KHCO3的加入显著提高了热释放速率达到峰值的温度。具体表现为,NHRR达到峰值所需的温度随KHCO3质量分数的增加而升高,从对照组的1 664.84 K升至11%时的1 814.10 K。这可能归因为KHCO3分解产生的钾化合物降低了火焰中的自由基浓度,延缓了链式反应的进程,进而降低了反应放热。
需要注意的是,无论氢气体积分数如何,LBV随着KHCO3质量分数的增加更加接近,出现趋同效应,表明此时影响燃烧强度的主控因素已经从燃料自身的反应活性转变为抑制剂的化学抑制效应,类似的结果在NHRR中也有发现。
火焰厚度是火焰锋面内化学反应速率和热释放速率的宏观体现[33]。如图8所示,添加KHCO3显著增加了热厚度($ {\delta }_{\mathrm{T}} $)和扩散厚度($ {\delta }_{\mathrm{D}} $),并且其与质量分数呈正相关。具体来说,当$ {\varphi}_{{{\mathrm{H}}_{2}}} $=10%时,相较于对照组,KHCO3的质量分数分别为0%、3%、7%和11%时,$ {\delta }_{\mathrm{T}} $分别增加了14.45%、49.76%、93.67%和139.62%,$ {\delta }_{\mathrm{D}} $分别增加了17.37%、61.72%、119.39%和182.12%。火焰厚度的增加意味着传热传质驱动力的减弱和反应区域的扩展,即KHCO3通过降低火焰锋面内的温度梯度和质量浓度梯度,削弱了火焰锋面内传热传质驱动力和速率,进而实现抑制效果。
火焰厚度的增加有利于提高火焰的本征稳定性。然而,如2.1节所观测到的火焰褶皱和胞状结构,KHCO3雾滴的不均匀分布则会导致相反的结果。KHCO3所在的局部高浓度区虽然可以增强局部稳定性,但同时在周围区域产生了更强的拉伸率,导致了火焰表面不稳定性。此外,添加KHCO3$ {\delta }_{\mathrm{D}} $的增幅强于$ {\delta }_{\mathrm{T}} $,表明其对传质的抑制作用更强,从而成为诱发扩散-热不稳定性的主要因素。值得注意的是,如图4(d)中26.5~40.5 ms和图4(e)中25.5~41.5 ms所示,火焰表面褶皱和胞状结构的显著性随KHCO3质量分数的增加而增强。这表明,由$ {\delta }_{\mathrm{D}} $$ {\delta }_{\mathrm{T}} $抑制差异性引起的不稳定性与实验中胞状结构的形成实现了良好对应,从而进一步解释了KHCO3作用下扩散-热不稳定性对火焰不稳定演化的主导作用。
火焰厚度的变化直接影响反应物的传质速率和自由基的扩散行为,而自由基浓度的变化是控制链式反应进程的关键因素[32]。如图9所示,KHCO3对3种关键自由基摩尔分数均产生了显著的抑制效果,且抑制效果与KHCO3质量分数呈正相关。以${\varphi}_{{{\mathrm{H}}_{2}}} $=30%为例,与对照组相比,当KHCO3的质量分数为11%时,H自由基的峰值摩尔分数从7.51×10−3降至8.67×10−4,下降约88.46%;O和OH自由基分别下降90.55%和64.52%。此外,KHCO3对自由基的抑制表现出显著的差异性。H自由基的降幅最显著,其次为O自由基,OH自由基的降幅相对较小。这可能是由钾化合物参与反应路径循环的差异性造成的[13]
需要注意的是,尽管KHCO3可以通过钾化合物(K、KOH等)建立催化循环,对所有掺氢比下的关键自由基摩尔浓度实现线性抑制效果[14],但2.2节对爆炸压力的分析表明,KHCO3细水雾存在抑制瓶颈。在低掺氢比下(0%和10%),火焰传播相对缓慢,火焰锋面较厚。此时,雾滴有相对充足的时间在火焰锋面前沿蒸发,其物理(冷却、稀释)和化学(自由基清除)的抑制效应远大于流体力学扰动带来的促进作用,因此,抑制效应占据绝对主导。而在高掺氢比下(20%和30%),火焰速度更快,火焰厚度更薄,缩短了雾滴的有效停留时间[34],并且KHCO3的加入会降低液滴的饱和蒸气压,两者共同导致蒸发效率下降[35],降低了钾化合物参与气相抑制反应的强度,从而削弱了物理和化学抑制效果。另一方面,未及时蒸发的雾滴充当“障碍物”,对更不稳定的高掺氢火焰产生了更显著的流体力学扰动。减弱的抑制效应与增强的促进效应相互抵消,导致抑制效率呈现非单调性。当KHCO3的质量分数进一步增加到11%时,化学抑制剂足够多,化学抑制作用重新占据主导地位,压倒了促进作用,表现为宏观爆炸参数再次下降。因此,高掺氢比和高KHCO3质量分数条件下,抑制效果下降的瓶颈因素从化学反应动力学层面转向物理蒸发效率层面。这2个因素共同构成的物理限制最终导致宏观层面的抑制效率下降。
自由基浓度的改变是基元反应竞争的结果,为深入理解各基元反应对燃烧过程的影响程度,对层流燃烧速度进行敏感性分析。正负系数分别代表相应反应对层流速度的促进或抑制作用。图10展示了含KHCO3细水雾对层流速度敏感性的影响。反应R38(H+O2$\Leftrightarrow $O+OH)是最重要的链分支反应,随着KHCO3质量分数的增加,该反应的敏感性系数显著上升,表明其在燃烧过程中变得更加关键。反应R52(H+CH3(+M)$\Leftrightarrow $CH4(+M))和R53(H+CH4$\Leftrightarrow $CH3+H2)是重要的链终止反应,与R38直接竞争H自由基,阻碍链分支反应的进行,最终导致链式反应速率降低。
加入KHCO3后,新增的含钾反应是主要抑制机制。反应R221(K+OH+M$\Leftrightarrow $KOH+M)呈现强负敏感性,表明其成为OH自由基的主要消耗途径。更关键的是,R221(K+OH+M$\Leftrightarrow $KOH+M)在三体碰撞作用下与R259(H+KOH$\Leftrightarrow $K+H2O)形成了KOH→K→KOH自由基重组循环。Badhuk等[3637]指出,该循环将活性自由基·H和·OH转化为稳定的H2O分子,这种催化特性使其比传统链终止反应H+OH+M$\Leftrightarrow $H2O+M更为高效。对比$ {\varphi}_{{{\mathrm{H}}_{2}}}$=0%,当$ {\varphi}_{{{\mathrm{H}}_{2}}}$=30%时,R38(H+O2$\Leftrightarrow $O+OH)和R221(K+OH+M$\Leftrightarrow $KOH+M)的敏感性系数同步增加,表明氢气增强了KOH→K→KOH重组循环和链分支反应对H自由基的消耗竞争。氢气的加入还新增了R84(OH+H2$\Leftrightarrow $H+H2O),与含钾反应形成双重自由基消耗机制。此外,Slack等[38]的研究表明,钾化合物还可通过K→KO2→KO→KOH→K循环进一步消耗自由基。
总体而言,KHCO3抑制机理的本质是含钾反应与链分支反应R38(H+O2$\Leftrightarrow $O+OH)之间的竞争,钾化合物通过重组循环消耗关键自由基来中断燃烧链式反应,从而减缓链式反应速率,最终导致层流燃烧速度和火焰传播能力下降。
图11给出了含KHCO3细水雾抑制机理示意图。分析表明,含KHCO3细水雾对甲烷-氢气预混爆燃表现出显著的抑制效果,源于物理抑制与化学抑制的协同作用,同时也受两者竞争与制约的影响。
含KHCO3细水雾的物理抑制主要通过热力学效应和稀释效应实现。雾滴在火焰区发生相变蒸发,消耗大量潜热并降低火焰温度;同时,KHCO3热分解反应为吸热过程,进一步削弱火焰的热释放强度。此外,分解产生的CO2和H2O参与气相稀释,降低了可燃气体浓度。
KHCO3的化学抑制是其核心抑制效应,依赖其分解产生的钾化合物对燃烧链式反应的影响。KHCO3对关键自由基·H、·O和·OH均产生显著的清除效果,其中对H自由基的抑制最显著。虽然主链分支反应R38(H+O2$\Leftrightarrow $O+OH)和含钾反应形成直接竞争,但是R221(K+OH+M$\Leftrightarrow $KOH+M)和R259(H+KOH$\Leftrightarrow $K+H2O)形成KOH→K→KOH重组循环,以及K→KO2→KO→KOH→K重组循环,实现了对自由基的高效清除,从而阻断链式反应的传播。
然而,最终的抑制效果并非2种机制的简单叠加,而是协同与竞争的综合。在多数情况下,物理抑制为化学抑制提供了有利条件。温度降低和反应物稀释使得链分支反应活性下降,从而增强了含钾反应的竞争优势。同时,火焰厚度增加延长了反应物在火焰区的停留时间,为钾化合物与自由基的清除反应提供了更充分的条件。未蒸发的液滴对火焰锋面产生扰动,从而促进燃烧的竞争效应。在高掺氢比下,火焰速度过快缩短了雾滴停留时间,而高浓度KHCO3又阻碍蒸发,使得钾化合物无法及时参与气相化学反应。此时,物理蒸发效率成为瓶颈,限制并削弱化学抑制的发挥,并可能放大促进效应,最终导致宏观抑制效率的非单调性和饱和现象。
总体而言,KHCO3细水雾抑制剂作用存在复杂性,它不是简单的浓度线性关系,而是物理蒸发、化学抑制以及流体力学不稳定性之间相互协同与竞争的复杂过程。物理与化学的协同作用确保了其高效的抑制性能,但物理蒸发瓶颈则限制了其抑制效率的上限。
(1) 含KHCO3细水雾对甲烷-氢气预混爆燃表现出显著的物理与化学双重抑制效果。其抑制性能与KHCO3的质量分数整体呈正相关。以$ {\varphi}_{{{\mathrm{H}}_{2}}}$=0%为例,相较于对照组,$ {p}_{\max } $$ {(\mathrm{d}p/\mathrm{d}t)}_{\text{avg}} $最高分别下降34.64%和44.57%,LBV和NHRR最高分别降低63.4%和82.77%。
(2) KHCO3细水雾同时存在抑制和促进的竞争关系。KHCO3细水雾显著增加了火焰厚度,$ {\delta }_{\mathrm{T}} $$ {\delta }_{\mathrm{D}} $最大分别增加139.62%和182.12%。KHCO3雾滴的不均匀分布影响了传热传质过程,使得传质效应主导了火焰结构的局部失稳,耦合D-L不稳定性导致火焰表面出现褶皱和胞状结构。
(3) 含KHCO3细水雾兼具物理和化学双重抑制效应,后者占主导地位。物理上,雾滴相变吸热和蒸汽稀释效应降低火焰温度并稀释可燃物;化学上,R221(K+OH+M$\Leftrightarrow $KOH+M)和R259(H+KOH$\Leftrightarrow $K+H2O)通过KOH→K→KOH重组循环高效消耗关键自由基,与链分支反应R38(H+O2$\Leftrightarrow $O+OH)形成竞争,中断燃烧链式反应。
(4) KHCO3细水雾的最终效果是抑制与促进双重效应竞争的结果。在高掺氢比和高KHCO3质量分数下,雾滴的物理蒸发效率成为限制化学抑制作用发挥的瓶颈,进而导致整体抑制效率出现饱和现象。
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2026年第40卷第4期
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doi: 10.11858/gywlxb.20251189
  • 接收时间:2025-09-08
  • 首发时间:2026-04-29
  • 出版时间:2026-04-05
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  • 收稿日期:2025-09-08
  • 修回日期:2025-10-12
  • 录用日期:2026-01-20
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    1重庆安全技术职业学院应急管理学院, 重庆 404010
    2西南石油大学化学化工学院, 四川 成都 610500

通讯作者:

邵 鹏(1997-),男,硕士,主要从事可燃气体爆燃防治研究. E-mail:
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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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