雷利利,殷俊晨,宋金甌,羅 鵬,王 攀
(1.江蘇大學(xué) 汽車與交通工程學(xué)院,江蘇 鎮(zhèn)江 212013;2. 天津大學(xué) 內(nèi)燃機(jī)燃燒學(xué)國(guó)家重點(diǎn)實(shí)驗(yàn)室,天津300072)
Mn-Ce/γ-Al2O3催化劑對(duì)柴油機(jī)碳煙的催化燃燒性能影響
雷利利1,殷俊晨1,宋金甌2,羅 鵬1,王 攀1
(1.江蘇大學(xué) 汽車與交通工程學(xué)院,江蘇 鎮(zhèn)江 212013;2. 天津大學(xué) 內(nèi)燃機(jī)燃燒學(xué)國(guó)家重點(diǎn)實(shí)驗(yàn)室,天津300072)
為了驗(yàn)證Mn-Ce/γ-Al2O3催化劑對(duì)碳煙的催化燃燒性能的影響,采用檸檬酸絡(luò)合法和溶膠-凝膠法制備了一系列不同錳、鈰摩爾比的xMnyCe/γ-Al2O3(x=4,6,8,10,y=10)催化劑,并利用X射線衍射儀、掃描電子顯微鏡、能譜儀和透射電子顯微鏡對(duì)其性能進(jìn)行表征,結(jié)果表明,MnO2和CeO2的粒徑變化范圍為5~20 nm。Mn在催化劑中主要以MnO2出現(xiàn),當(dāng)x≥6時(shí),有部分Mn2O3分散在催化劑表面。當(dāng)x=8時(shí),CeO2晶粒尺寸和分散性最好。通過熱重分析儀評(píng)價(jià)了催化劑對(duì)碳煙燃燒性能的影響。試驗(yàn)結(jié)果表明:隨著x的增加,催化劑的T10溫度呈現(xiàn)先降低后升高的趨勢(shì),8Mn10Ce/γ-Al2O3催化劑的T10溫度最低,為320.9 ℃,可以顯著降低碳煙的起燃溫度,具有最好的碳煙催化燃燒性能。
車輛工程;柴油機(jī);Mn;Ce;碳煙;催化劑
與汽油機(jī)相比,柴油機(jī)具有良好的燃油經(jīng)濟(jì)性、優(yōu)異的動(dòng)力性和較低的CO2排放。但是,柴油機(jī)的顆粒物(Particulate Matter,PM)排放是汽油機(jī)的30~100倍,且PM表面吸附有致癌物質(zhì)及重金屬,會(huì)嚴(yán)重危害人類健康和大氣環(huán)境[1-3],因此,對(duì)柴油機(jī)PM排放進(jìn)行有效控制具有重要的研究?jī)r(jià)值及實(shí)際意義[4]。目前,降低柴油機(jī)PM排放的最主要途徑是采用顆粒物捕集(Diesel Particular Filter,DPF)措施。由于PM的起燃溫度相對(duì)較高,在600 ℃左右,而通常柴油機(jī)排氣溫度較低,在200~400 ℃[5-6]。因此,如何有效降低柴油機(jī)PM的起燃溫度,對(duì)于控制DPF再生具有重要的意義。
近年來,采用催化技術(shù)降低柴油機(jī)PM排放得到了廣泛關(guān)注。A.ALINEZHADCHAMAZKETI等[7]研究了在CeO2-ZrO2中摻雜過渡金屬、堿金屬和堿土金屬氧化物對(duì)PM催化氧化的影響,發(fā)現(xiàn)在緊接觸條件下,Mn-Ce-Zr和Cu-Ce-Zr分別降低了程序升溫氧化(Temperature Programmed Oxidation,TPO)峰值溫度280和270 ℃。師少飛等[8]對(duì)Ni-La/CeXZr1-XO2催化劑部分氧化甲烷和王舒捷等[9]對(duì)Ce基復(fù)合氧化物同時(shí)催化去除碳煙-NOX的研究中,可以發(fā)現(xiàn)CeO2具有較好的儲(chǔ)放氧能力和優(yōu)良的氧化還原性質(zhì)。S.WAGLOEHNER等[10]在對(duì)錳的氧化物氧化碳煙的研究中,發(fā)現(xiàn)MnO2,Mn2O3和Mn3O4分別降低了TPO峰值溫度205,245 和255 ℃。摻雜Mn到 CeO2中形成的Ce1-XMnXO2對(duì)一些反應(yīng)表現(xiàn)出良好的催化活性[11-14]。
綜上分析可知,CeO2具有對(duì)碳煙催化燃燒具有較好的效果,但存在熱穩(wěn)定性較差的缺點(diǎn),限制了CeO2的應(yīng)用。研究發(fā)現(xiàn),通過摻雜負(fù)載等方式可改善其催化性能[15-16]。因此,筆者采用檸檬酸絡(luò)合法和溶膠-凝膠法制備了xMnyCe/γ-Al2O3(x=4,6,8,10,y=10)催化劑,用X射線衍射(X-ray diffraction,XRD)、掃描電子顯微鏡(Scanning Electron Microscope,SEM)、能譜儀(Energy Dispersive Spectroscopy,EDS)和透射電子顯微鏡(Transmission Electron Microscope,TEM)對(duì)催化劑粉體進(jìn)行表征,以及通過熱重分析儀(Thermal Gravimetric Analyzer,TG)評(píng)價(jià)催化劑對(duì)碳煙燃燒性能的影響。
1.1 催化劑的制備
筆者采用檸檬酸和溶膠-凝膠法制備了一系列的xMn10Ce/γ-Al2O3(x=4,6,8,10)催化劑。首先,按照不同錳/鈰摩爾比稱取一定量的Ce(NO3)3·6H2O,C4H6MnO4·4H2O和γ-Al2O3,分別溶于適量的去離子水中制成溶液;加入Ce3+和Mn2+離子摩爾總量?jī)杀兜臋幟仕岷?,再加?0%檸檬酸質(zhì)量的聚乙二醇,80 ℃磁力攪拌,直至形成透明凝膠,110 ℃干燥24 h,自然冷卻,再研磨成粉末,最后將粉末放于馬弗爐中300 ℃焙燒1 h,后升溫至500 ℃繼續(xù)焙燒5 h,冷卻至室溫,利用球磨機(jī)研磨制成xMn10Ce/γ-Al2O3催化劑粉末。
1.2 催化劑的表征方法
XRD在德國(guó)Bruker/D8 ADVANCE型X射線衍射儀上進(jìn)行測(cè)試,輻射源采用CuKα(λ=0.154 068 nm),掃描角速度為7°/min,20°~80°掃描,晶粒大小根據(jù)Scherrer公式進(jìn)行計(jì)算:
式中:K為Scherrer常數(shù);D為晶粒尺寸,nm;β為實(shí)測(cè)樣品衍射峰的半高寬度,rad;θ為衍射角,°;λ為X射線波長(zhǎng),nm。
TEM測(cè)試在荷蘭Philips公司的Tecnai 12的透射電鏡(TEM)上進(jìn)行,點(diǎn)分辨率為0.24 nm;線分辨率為0.14 nm;加速電壓為120 kV。SEM和EDS測(cè)試在日本電子株式會(huì)社(JEOL)的JSM-7001F型掃描電鏡(SEM)上進(jìn)行,加速電壓0.5~30 kV,放大倍數(shù)10~800 K,分辨率1.2 nm(30 kV)/3.0 nm(1 kV)。
1.3 催化劑活性評(píng)價(jià)
Degussa公司生產(chǎn)的Printex-U色素碳黑在950 ℃時(shí)揮發(fā)份為5%,灰份的含量低于0.02%,原生粒徑在25 nm左右,性質(zhì)較為穩(wěn)定,其物化特性與柴油機(jī)PM排放物近似,故采用其作為模擬碳煙[17]。TG試驗(yàn)的樣品由模擬碳煙與催化劑按照1∶10的質(zhì)量比混合而成,研磨5 min達(dá)到緊密接觸后,裝樣保存以備測(cè)試性能。
采用Pyris 1熱重分析儀來評(píng)價(jià)催化劑對(duì)碳煙燃燒性能的影響,初始的進(jìn)樣量約為15 mg,置于熱平衡反應(yīng)室里,N2氣流為50 mL/min,O2氣流為20 mL/min,程序升溫范圍為40~750 ℃,升溫速率為10 ℃/min。
2.1 催化劑的性能表征
2.1.1 催化劑XRD表征
xMn10Ce/γ-Al2O3(x=4,6,8,10)催化劑的XRD譜圖如圖1。
圖1 xMn10Ce/γ-Al2O3催化劑XRD譜圖Fig.1 XRD spectrum of xMn10CeO/γ-Al2O3 catalysts
由圖1可見,在2θ為25.74°,5.32°,37.93°,43.53°,53.72°,57.65°,66.68°和68.36°(JCPDS:PDF 10-0173)處出現(xiàn)了γ-Al2O3的特征衍射峰;CeO2的特征衍射峰與純CeO2(JCPDS:PDF 34-0394)較為接近,但存在向高角度偏移現(xiàn)象;MnO2的特征衍射峰與純MnO2(JCPDS:PDF 65-7467)幾乎完全重合。催化劑在2θ為27.32°處存在一個(gè)較寬的衍射峰,類似于A.M.T.SILVA等研究的XRD表征結(jié)果[18],說明在催化劑中Ce的主要存在形式為α無定型結(jié)構(gòu)。當(dāng)x≥6時(shí),在2θ為31.84°處出現(xiàn)了明顯的Mn2O3特征衍射峰,與文獻(xiàn)[19-20]表述相一致。隨著x值增加,2θ為31.84°處的Mn2O3特征衍強(qiáng)度先變強(qiáng)后變?nèi)酰?θ為47.58°處的CeO2特征衍射峰先變寬后變窄,強(qiáng)度先變?nèi)鹾笞儚?qiáng)。x=8時(shí),2θ為31.84°處的Mn2O3特征衍強(qiáng)度最強(qiáng),說明催化劑表面游離的Mn2O3結(jié)晶度最好; 2θ為76.98°處的CeO2特征衍射峰最寬,且強(qiáng)度最弱,說明CeO2晶粒尺寸細(xì)小且分散性最好,運(yùn)用Scherrer方程估算CeO2晶粒尺寸為26 nm。CeO2衍射峰角度的偏移現(xiàn)象主要因?yàn)镃eO2中半徑較大的Ce4+被半徑較小的Mn4+和Mn3+所取代形成固溶體,引起的晶胞收縮所致[21],這有助于形成氧空位,從而對(duì)催化燃燒碳煙起作用。此外其表面分散的MnO2和Mn2O3有利于氧氣在催化劑表面活性解離后與碳煙反應(yīng)。
2.1.2 催化劑8Mn10Ce/γ-Al2O3的SEM和EDS表征
8Mn10Ce/γ-Al2O3催化劑的SEM和EDS譜圖如圖2。
圖2 8Mn10Ce/γ-Al2O3催化劑的SEM和EDS譜圖Fig.2 SEM and EDS spectrum of 8Mn10Ce/γ-Al2O3
由圖2(a)可見,催化劑表面分布有許多不規(guī)則狀的顆粒物,這些顆粒物主要由許多細(xì)微顆粒團(tuán)聚形成,主要成分是Ce,Mn氧化物。顆粒物的分散性較好,粒徑約在10~100 nm之間。催化劑表面的顆粒能與PM充分接觸,從而降低PM的起燃溫度,有利于PM催化燃燒。從圖2(b)可見,催化劑的主要成分為C,Al,O,Ce和Mn,其中C主要可能為C4H6MnO4·4H2O和檸檬酸高溫分解后,未被完全氧化的殘留物。
2.1.3 催化劑8Mn10Ce/γ-Al2O3的TEM表征
8Mn10CeO/γ-Al2O3催化劑的TEM譜圖如圖3。由圖3可見,圓圈內(nèi)的顆粒物即為MnO2,Mn2O3和CeO2顆粒,在γ-Al2O3載體表面存在有粒徑大約10 nm的半球狀顆粒物。此外,大量半球狀MnO2,Mn2O3和CeO2顆粒均勻分布在γ-Al2O3載體表面,粒徑在5~20 nm不等,分散性好,在TG試驗(yàn)中可以與碳煙充分接觸。圖上顏色較深的區(qū)域可能是多個(gè)催化劑活性顆粒疊加所造成的。
圖3 8Mn10Ce/γ-Al2O3催化劑TEM譜圖Fig.3 TEM spectrum of 8Mn10Ce/γ-Al2O3 catalyst
2.2 催化劑活性評(píng)價(jià)
通過對(duì)催化劑與碳煙進(jìn)行TG試驗(yàn),可以考察催化劑對(duì)碳煙燃燒性能的影響。為清楚比較各催化反應(yīng)的失重規(guī)律,將碳煙失重10%時(shí)的對(duì)應(yīng)溫度標(biāo)記為T10,碳煙的氧化速率達(dá)到峰值時(shí)的對(duì)應(yīng)溫度標(biāo)記為Tm。圖4為4Mn10Ce/γ-Al2O3和8Mn10Ce/γ-Al2O3催化劑作用下碳煙的熱失重曲線。
圖4 催化劑作用下的碳煙TG-DTG圖Fig.4 TG-DTG picture of soot under the effect of catalysts
由圖4可見,在T10溫度前TG曲線呈緩慢下降趨勢(shì),DTG曲線基本保持穩(wěn)定,該過程主要是吸附水的脫除以及碳煙中部分物質(zhì)受熱揮發(fā)。之后,隨著溫度的升高,碳煙開始氧化且氧化速率不斷加快,在Tm溫度時(shí)達(dá)到峰值。在高于680 ℃后,失重率基本保持不變。
表1給出了各催化劑作用下碳煙催化燃燒的T10和Tm溫度。
表1 催化劑催化燃燒碳煙的T10及Tm
由表1可見,xMn10Ce/γ-Al2O3(x=4,6,8,10)催化劑都能有效降低碳煙的起燃溫度,使碳煙起燃溫度降低至柴油機(jī)尾氣溫度范圍內(nèi)。其中,8Mn10Ce/γ-Al2O3催化劑的T10溫度為320.9 ℃,較4Mn10Ce/γ-Al2O3,6Mn10Ce/γ-Al2O3和10Mn10Ce/γ-Al2O3分別降低了139.3,42.1,53.1 ℃,表明8Mn10Ce/γ-Al2O3具有較好的碳煙催化燃燒性能。
1)對(duì)于xMnyCe/γ-Al2O3催化劑而言,當(dāng)x=8時(shí),CeO2晶粒尺寸和分散性最好;Mn在催化劑中主要以MnO2出現(xiàn),當(dāng)x≥6時(shí),有較多Mn2O3晶體出現(xiàn)。
2)8Mn10Ce/γ-Al2O3催化劑中Mn4+和Mn3+進(jìn)入CeO2晶胞中形成固溶體,有效減小了CeO2晶粒尺寸,催化劑表面的氧空位及其表面分散的Mn2O3,使氧氣在催化劑表面活性解離后與碳煙反應(yīng)。
3)xMn10Ce/γ-Al2O3(x=4,6,8,10)催化劑能有效降低碳煙的起燃溫度,其中,8Mn10Ce/γ-Al2O3具有較好的碳煙催化燃燒性能,可以實(shí)現(xiàn)在柴油機(jī)正常排溫范圍內(nèi)對(duì)碳煙排放的有效脫除。
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Effect of Mn-Ce/γ-Al2O3Catalysts on Catalytic Combustion Performance of Diesel Engine Soot
LEI Lili1, YIN Junchen1, SONG Jin’ou2, LUO Peng1, WANG Pan1
(1. School of Automotive and Traffic Engineering, Jiangsu University, Zhenjiang 212013, Jiangsu, P. R. China; 2. State Key Laboratory of Engines, Tianjin University, Tianjin 300072, P. R. China)
In order to investigate the effect of Mn-Ce/γ-Al2O3catalysts on catalytic combustion performance of soot, a series ofxMnyCe/γ-Al2O3(x=4, 6, 8, 10,y=10) catalysts with different ratio of Mn and Ce were prepared by an acid-aided sol-gel method. The effect of metallic Mn and Ce on their microstructure and catalytic properties was investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and transmission electron microscope (TEM) analysis. According to the analysis results, it is indicated that the diameter variation range of MnO2and CeO2is from 5 nm to 20 nm. Mn appears as MnO2in the catalyst. Some Mn2O3disperses on the catalyst surface, when the value ofxis 6 or higher. The grain size and dispersion of CeO2are the best, when the value ofxis 8. Effect of the catalysts on combustion performance of soot is analyzed by TG (thermal gravimetric analyzer). Test results show that: with the increase ofx, the temperature of the catalystT10decreases firstly and then increases;T10temperature of 8Mn10Ce/γ-Al2O3catalyst is the lowest among the catalysts, that is 320.9 ℃, which can significantly reduce the ignition temperature of soot and have the best catalytic combustion performance of soot.
vehicle engineering; diesel engines; Mn; Ce; soot; catalysts
2015-10-21;
2016-05-23
國(guó)家自然科學(xué)基金項(xiàng)目(51206068);江蘇省自然科學(xué)基金項(xiàng)目(BK2015040369);天津大學(xué)內(nèi)燃機(jī)燃燒學(xué)國(guó)家重點(diǎn)實(shí)驗(yàn)室開放基金資助項(xiàng)目(k15-07)
雷利利(1982—),女,江蘇鎮(zhèn)江人,講師,博士,主要從事發(fā)動(dòng)機(jī)排放控制方面的研究。E-mail:yutian820817@126.com。
10.3969/j.issn.1674-0696.2016.06.33
U473;TK421.5
A
1674-0696(2016)06-163-05