熱裂解-在線(xiàn)真空紫外光電離質(zhì)譜法研究固體物熱裂解

第36卷第6期質(zhì)譜學(xué)報Vol, 36 No 62015年11月Journal of Chinese Mass Spectrometry SocietyNov.2015熱裂解-在線(xiàn)真空紫外光電離質(zhì)譜法研究固體物熱裂解王健!,王毓,胡永華2,文武!,黃鵲,潘洋1(1.中國科學(xué)技術(shù)大學(xué)國家同步輻射實(shí)驗室,安徽合肥230026;2.安徽中煙工業(yè)有限責任公司技術(shù)中心,安徽合肥230088)摘要:為了實(shí)時(shí)、在線(xiàn)研究一些固體物質(zhì)的熱裂解產(chǎn)物,自行搭建了一套熱裂解在線(xiàn)真空紫外光電離質(zhì)譜裝置。利用真空紫外燈作為電離源,并結合垂直引人飛行時(shí)間質(zhì)譜,初步研究了聚丙烯在400600℃和卷煙煙絲在400~700℃熱解時(shí)釋放的氣相產(chǎn)物。本實(shí)驗不僅在線(xiàn)獲得了一系列熱解氣相產(chǎn)物的光電離質(zhì)譜圖,還了解了各產(chǎn)物,如丙烯(m/z42)、戊二烯(m/z68)等在不同溫度下隨時(shí)間的變化曲線(xiàn),從而獲知熱解反應的動(dòng)態(tài)變化過(guò)程。結果表明,真空紫外光電離質(zhì)譜法是研究固體物熱裂解的重要手段,可以為研究熱解動(dòng)態(tài)變化和產(chǎn)物形成機理提供重要信息。關(guān)鍵詞:固體物;光電離質(zhì)譜;熱裂解;氣相產(chǎn)物;實(shí)時(shí)研究中圖分類(lèi)號:O657.63文獻標志碼:A文章編號:10042997(2015)06-0513-08doi: 10.7538/zpb youxian 2015. 0035Study on the Pyrolysis of Solid Materials with Pyrolysis-OnlineVacuum Ultraviolet Photoionization Mass SpectrometryWANG Jian, WANG Yu, HU Yong-hua2, WEN Wu'HUANG Que, PAN Yang(l National Synchrotron Radiation LaboratoryUniversity of Science and Technology of China, Hefei 230026, China2. Center of Technology, China Tobacco Anhui Industrial Co, Ltd, Hefei 230088, China)Abstract: An online pyrolysis-vacuum ultraviolet photoionization mass spectrometer(PY-VUV PIMS) was built for the analysis of pyrolysis products of solid materials.Vacuum ultraviolet photoionization is a soft "ionization method producing few or nofragments of molecular ions, making the identification and interpretation of complex pyrolysis products in real time possible. In this work, the gaseous pyrolysis of polypropylene at the temperatures range of 400C to 600 C were firstly studied with this new-builtsetup A series of mass spectra of gaseous products were obtained, and the time-evolved收稿日期:2014-1226;修回日期:201503-11基金項目:國家自然科學(xué)基金(11175185、U1432128)資助作者簡(jiǎn)介:王健(1986-),男(漢族),安徽淮南人博士研究生從事光電離質(zhì)譜技術(shù)及應用研究。Emal: wang86@mal.ustc.edu通信作者:潘洋(1976—),男(漢族),安徽蚌埠人,副研究員,從事光電離質(zhì)譜技術(shù)及應用研究。 E-mail: panyang@ustc.edu網(wǎng)絡(luò )出版時(shí)間:2015-06-02;網(wǎng)絡(luò )出版地址:htp:∥www.cnki.net/kcms/detail,/11.2979.TH.20150602.0851.005.html中國煤化工CNMHG514質(zhì)譜學(xué)報第36卷curves for the products like propylene(m/z 42)and pentadiene(m/z 68) were also re-corded. It was found that the increase of temperature can dramatically shorten the reac-tion time Due to the effect of secondary reactions, the formation time of pentadiene is alittle later than that of propylene produced only from primary reaction. Reactions likechain fission, back-biting, and A-scission contribute to most of the primary reactions.The pyrolysis of tobacco was also performed with PY-VUV PIMS in the temperaturerange from 400C to 700 C, and the effects of reaction temperature on the pyrolysisproducts intensity were studied. For relative small molecular weight compounds likepropylene(m/z 42), their relative intensities increase all the time as pyrolysis temperature rises. As for acetone/propanal (m/z 58)and some other compounds, their relativeintensities first rise to the maximum and then decrease. In the case of relatively largemolecular weight compounds like nicotine (m/z 162), they decrease with temperatureincreases, indicating that it have suffered secondary reactions under high temperatureand decomposed into small molecules. Results show that vacuum ultraviolet photoionzation mass spectrometry is a powerful method for pyrolysis study, which can offer im-portant information for learning the pyrolysis mechanisms and dyKey words: solid materials; photoionization mass spectrometry; pyrolysis; gaseousproducts; online熱裂解是研究有機高分子材料和生物質(zhì)材視。德國的Adam等5基于激光光電離和電料的組成、結構、性質(zhì)及轉化利用的一種重要的子束泵浦(EBEL)技術(shù)開(kāi)展了大量的創(chuàng )新性工技術(shù)手段。熱裂解過(guò)程中會(huì )產(chǎn)生和釋放大量的作;國內的李海洋、周振和程平等也開(kāi)發(fā)了利用氣相和顆粒相產(chǎn)物,獲得這些產(chǎn)物的信息可為真空紫外燈的質(zhì)譜檢測技術(shù)67;此外,還有研究熱裂解機理提供直接的依據和幫助。目些基于光電離質(zhì)譜的實(shí)驗方法開(kāi)始逐漸被應用前,分析熱裂解產(chǎn)物的方法主要包括氣相色譜于固體樣品的熱解研究,并獲得了許多重要的法紅外光譜法以及色譜質(zhì)譜聯(lián)用法等[1。實(shí)驗結果610為了減少二次反應,獲得熱解產(chǎn)物初生狀態(tài)的本工作將自行搭建的真空紫外光電離質(zhì)譜信息,理想的熱解產(chǎn)物分析方法應該建立在在與一套新近設計的管式熱解爐相結合,對聚丙線(xiàn)和實(shí)時(shí)分析的基礎上。雖然氣相色譜法能對烯和煙草樣品的裂解進(jìn)行初步研究,希望為深熱解產(chǎn)物進(jìn)行在線(xiàn)分析,但是由于產(chǎn)物在色譜開(kāi)展固體樣品的熱裂解研究奠定基礎。柱中的分離時(shí)間長(cháng),因而無(wú)法實(shí)現實(shí)時(shí)分析;紅外光譜法是依據化合物的特定吸收波長(cháng)進(jìn)1實(shí)驗部分行定性,對于復雜的熱解產(chǎn)物而言,由于譜峰1.1主要儀器與裝置之間的重疊和干擾,該方法通常只能對少數熱裂解-在線(xiàn)真空光電離質(zhì)譜裝置主要由的揮發(fā)性物質(zhì)進(jìn)行分析;而傳統質(zhì)譜技術(shù)采臺自制管式熱解爐、產(chǎn)物傳輸管道以及一套用70eV的轟擊電離會(huì )產(chǎn)生大量的碎片,對于自制光電離垂直引入飛行時(shí)間質(zhì)譜儀組成,其復雜的分析體系,其譜圖的解析非常困難,甚裝置示意圖示于圖1。管式爐的溫度上限為至是不可能的5。1000℃,內部石英管內徑為18mm,有效加熱由于光電離幾乎不產(chǎn)生碎片離子,且在很區域長(cháng)度為170mm,熱解爐溫度由控溫儀控短的時(shí)間即可獲得只含復雜產(chǎn)物分子離子峰的制。爐體達到設定溫度后,樣品由一根石英進(jìn)質(zhì)譜圖,因而在燃燒熱裂解產(chǎn)物的實(shí)時(shí)在線(xiàn)分樣舟導入熱解管內進(jìn)行加熱反應,反應析方面顯示出了良好的應用前景。近年來(lái),真過(guò)程中的中國煤化工帶出,流量空紫外光電離質(zhì)譜技術(shù)越來(lái)越受到人們的重為200mLCNMHG一根內徑第6期王健等:熱裂解在線(xiàn)真空紫外光電離質(zhì)譜法研究固體物熱裂解515MCP檢測區離子軌道至真空泵狹縫單透鏡昌■校準氣熱電偶鎳制漏勺粒子濾波聚焦板毛細管防水板管式爐熱傳輸線(xiàn)至真空泵氨燈排氣孔樣品舟圖1熱裂解-在線(xiàn)真空紫外光電離質(zhì)譜裝置示意圖Fig. 1 Schematic of pyrolysis-online vacuum ultraviolet photoicmass spectrometry為100μm的熔融石英毛細管,其末端導人飛2結果與討論行時(shí)間質(zhì)譜儀光電離室。為防止氣相產(chǎn)物冷2.1聚丙烯的熱解凝,整個(gè)傳輸管道被加熱至250℃。產(chǎn)物傳輸聚合物在惰性氣氛下熱解可以轉化為輕質(zhì)管道與熱解爐之間設有玻璃纖維濾片(研究聚氣體和其他化工原料,是處理廢棄聚合物的丙烯時(shí)濾片孔徑為1.2pm,研究煙絲熱解所用種很有前景的方法121),人們已經(jīng)應用GC/劍橋濾片孔徑為0.2pm),以濾掉產(chǎn)物中的顆Ms和PyGC/MS方法做了大量聚丙烯熱解的粒物,防止毛細管堵塞。研究工作116。裂解產(chǎn)物探測使用的自制光電離飛行時(shí)聚丙烯在400℃和600℃熱解后獲得的間質(zhì)譜儀由光電離室(壓力為0.75Pa)和質(zhì)光電離質(zhì)譜圖示于圖2。由圖中可以看出,譜室(壓力為1.5×105Pa)兩個(gè)腔體構成。由于真空紫外光電離是軟電離方法,幾乎不光電離室有一只商用直流放電氪燈作為電離產(chǎn)生碎片,所以譜峰基本都是熱解產(chǎn)物的分源,能量為10.6eV。中性分子在推斥電極子離子峰。聚丙烯在400℃熱解后,生成從(6.0V)和聚焦電極(5.5V)之間發(fā)生電離C3(m/z42)至C21(m/z294)一系列不飽和后,在電場(chǎng)作用下經(jīng)過(guò)鎳制漏勺進(jìn)入質(zhì)譜室;烯烴,最高峰位于m/z126。前人已經(jīng)使用漏勺后設置有一組離子光學(xué)透鏡和狹縫,用GC/MS法對一些主要的熱解產(chǎn)物進(jìn)行了歸于將離子垂直引入質(zhì)譜儀而引出電場(chǎng)區;飛屬,結果列于表11181。溫度升至600℃后,行時(shí)間質(zhì)譜儀采用反射式結構,質(zhì)量分辨率獲得的聚丙烯熱解光電離質(zhì)譜圖示于圖2b,約為1500,離子在質(zhì)譜儀中引出后加速,經(jīng)可見(jiàn),隨著(zhù)熱解溫度的提高,長(cháng)鏈碳氫化合過(guò)漂移管、反射電場(chǎng)后,最終被微通道板探測物進(jìn)一步裂解,質(zhì)譜圖中的熱解產(chǎn)物以短器接收。離子信號經(jīng)預放大器放大,被一套鏈C3(m/z42)至C6(m/z84)為主。在此超快數據采集卡采集記錄m。溫度下,可以觀(guān)察到進(jìn)一步裂解產(chǎn)生的乙1.2主要材料與試劑烯(m/z28)。聚丙烯:均為全同立構,粒徑小于180m,光電離質(zhì)譜是一種在線(xiàn)質(zhì)譜方法,不需要上海勵陽(yáng)機電有限公司產(chǎn)品;實(shí)驗用某烤煙型色譜分離即可實(shí)時(shí)獲得待測物隨時(shí)間的變化情卷煙:購自國內市場(chǎng),實(shí)驗前將煙支置于22℃、況,非常適合于研究熱解反應的動(dòng)態(tài)過(guò)程。聚相對濕度60%的恒溫恒濕箱中恒定48h;每次丙烯在不同溫度下的熱解產(chǎn)物丙烯(m/z42)熱解實(shí)驗樣品用量均為40mg;高純氮氣和乙和戊二烯中國煤化工曲線(xiàn)示于烯:南京特種氣體公司產(chǎn)品圖3由圖CNMHG兩種熱解16質(zhì)譜學(xué)報第36卷30002000010000圖2聚丙烯在400℃(a)和600℃(b)熱解后獲得的光電離質(zhì)譜圖Fig 2 Photoionization mass spectra for the pyrolysis productsolypropylene at400℃(a)and600℃(b)表1聚丙烯的部分熱解產(chǎn)物Table 1 Some major pyrolysis products of polypropylene化合物名稱(chēng)化合物名稱(chēng)乙烯 Ethylene丙烯 Propylene戊二烯2-戊烯2- Pentene2-甲基1戊烯2- Methy-1- pentene2,4-二甲基-1-庚烯2,4 Dimethyl-1- heptene4-甲基-2-戊烯4 Methy-2- pentene4,6-二甲基2-庚烯4,6- Dimethy-2- heptene1124-甲基2-庚烯4- Methyl-2 hepter2,4,6-三甲基1庚烯2,4,6- Trimethyl-l- heptene4,6-二甲基2-壬烯4,6- Dimethyl-2- nonene4,6,8-三甲基2十一烯4,6,8 Trimethyl-2 undecene16824,6三甲基-1-壬烯2,4,6- Trimethyl-1- nonene‖2102,4,6,8四甲基1-+一烯2,4,6,8- Tetramethyl-1- undecene168468三甲基1壬烯4,6,8 Trimethyl2 nonene2104,6,8,10四甲基2+一烯4,68,10- Tetramethyl2 undecene400℃2040608010012014020406080100120140t/S注;a.丙烯;b.戊二烯圖3熱解產(chǎn)物在400,500和600℃隨時(shí)間的變化曲線(xiàn)Fig 3 Timeevolved profiles for the pyrolysis prodat the temperature of 400, 500YH中國煤化工CNMHG第6期王健等:熱裂解-在線(xiàn)真空紫外光電離質(zhì)譜法研究固體物熱裂解517產(chǎn)物的生成時(shí)間大大縮短。例如,400℃時(shí),丙次反應和二次反應,而戊二烯則來(lái)自于熱解烯在熱解40s后開(kāi)始出現,到90s時(shí)濃度達到次反應。已有研究表明,聚丙烯的一次熱解峰值;而當溫度提高至600℃時(shí),丙烯在熱解后反應產(chǎn)物主要來(lái)源于鏈斷裂、回咬( back bit0s即開(kāi)始出現,并在30s時(shí)達到峰值。從圖ing)和B斷裂過(guò)程,主要反應過(guò)程示于圖4中還可以看出,在任何溫度下丙烯的生成都要其一次產(chǎn)物再經(jīng)過(guò)其他化學(xué)過(guò)程生成更加復雜略早于戊二烯,這是因為丙烯來(lái)源于熱解后的的產(chǎn)物。1.鏈斷裂2.回咬3.B斷裂過(guò)程圖4聚丙烯一次熱解產(chǎn)物涉及的主要反應Fig 4 Mechanisms for the pyrolysis of major products of polypropylene2.2卷煙煙絲的熱裂解某種卷煙煙絲在400℃和700℃熱裂解在煙草研究中,熱裂解是接近卷煙燃燒過(guò)后得到的光電離質(zhì)譜圖示于圖5。從圖5a可程的一種實(shí)驗方法。研究表明,煙草的燃燒會(huì )見(jiàn),在400℃時(shí),煙草樣品的熱解會(huì )產(chǎn)生豐富產(chǎn)生數千種產(chǎn)物1,在這些產(chǎn)物中,一方面包的產(chǎn)物,其中可被觀(guān)察到的最小質(zhì)量數產(chǎn)物括大量的香氣成分,滿(mǎn)足了消費者的需求;另為氨氣(m/z17),最大產(chǎn)物為尼古丁(m/z方面也存在著(zhù)有害物質(zhì),吸煙與健康的矛盾由162)。由于使用了劍橋濾片,更大質(zhì)量的半此而產(chǎn)生。因此,開(kāi)展煙草熱解方面的研究是揮發(fā)物和不揮發(fā)物無(wú)法透過(guò),因此不能被檢一項十分有意義的工作,不僅有助于了解煙氣測到。從質(zhì)譜圖中還可發(fā)現,除了存在煙草中香味成分和有害成分的形成機理和規內源化合物,如尼古丁外,還有許多煙草生物律320,同時(shí)也可為卷煙生產(chǎn)以及減害降焦提聚合物,如纖維素、半纖維素、木質(zhì)素和蛋白供理論依據和方法途徑。質(zhì)等的裂解產(chǎn)物(如m/z43、48、58、68、84、98、16212648800054120140160180圖5卷煙煙絲在400C(a)和700C(b)熱解后得到的光電離質(zhì)譜圖Fig 5 Photoionization mass spectra for the pyH中國煤化工of tobacco at 400C(a) and 700 CCNMHG518質(zhì)譜學(xué)報第36卷110等)。此前,已有文獻利用同步輻射光電離歸屬21),結合以前的工作,將部分煙絲熱裂解技術(shù)對卷煙氣相燃燒產(chǎn)物進(jìn)行了詳細的研究和產(chǎn)物可能的歸屬情況列于表2。表2卷煙煙絲主要熱解產(chǎn)物Table 2 Some major pyrolysis products of tobacco化合物名稱(chēng)化合物名稱(chēng)氨氣 Ammonia甲苯 Phenol/丙三醇 Glycerol丙烯 Propylene甲基呋喃 Dimethylfuran/糠醛 Furfural乙烯胺 Vinylamine乙基苯 Ethylbenzene/二甲苯 Xylene乙醛 Acetaldehyde110甲基糠醛 Methylfurfural/2乙酰呋喃甲硫醇 Methyl Mercaptan2- Acetylfuran/苯二酚 Dihydroxybenzene58丙酮 Acetone/丙醛 Propanal/乙二酸 Ethanedial122乙基苯酚 Ethylphenol/苯甲酸 Benzoic acid68呋喃 Furan/異戊二烯 Isoprene/環(huán)戊烯 Cyclopentene1244-甲氧基苯酚4 Methoxyphenol2-甲基呋喃2 Methylfuran2,3二氫-1茚酮1- Indanone/3-甲基呋喃3- Methylfuran/2,5-二甲基苯乙烯2,5- Methylstyrene/3-已炔3- Hexyne2乙基5甲酚2-Ethy-5- methylphenol/2甲基-1,3戊二烯2- Methyl-1,3- pentadiene/甲氧基苯甲醛 Methoxybenzaldehyde/檸檬烯 Limon3-甲基2-丁烯醛3- Methyl-2- butenal1-萘酚1- Naphtha/2-己烯2- Hexene162尼古丁 Nicotine對比圖5a和圖5b可以發(fā)現,當熱解溫度同溫度條件下的產(chǎn)物實(shí)時(shí)分析結果,可以推從400℃升高到700℃時(shí),多數低質(zhì)量數產(chǎn)導產(chǎn)物的形成機理物的質(zhì)譜峰強度會(huì )明顯提高,而一些分子質(zhì)量相對較大的產(chǎn)物峰強度則有所降低。進(jìn)400℃步研究表明,不同的熱解產(chǎn)物隨溫度的變化有一定的規律性。400℃至700℃部分煙絲熱解產(chǎn)物強度變化圖示于圖6。由圖6可以看出,丙烯(m/z42)、甲苯(m/z92)以及二甲苯/乙基苯(m/z106)等的強度隨溫度升高而⊥.a增加;丙酮/丙醛(m/z58)、呋喃/異戊二烯/4248688496110136162環(huán)戊烯(m/z68)等的強度隨溫度升高先增加再下降;而3-甲基-2-丁烯醛(m/z162)和尼古圖6卷煙煙絲部分熱解產(chǎn)物丁(m/z162)等的強度則一直降低。 Evans在400℃~700℃的變化趨勢等2曾經(jīng)指出,在煙草的熱解過(guò)程中,產(chǎn)物的ig. 6 Effect of temperature(400-700 C)特性與裂解的強烈程度有明顯的相關(guān)性。通n the intensities of some pyrolysis products常,中等強度的溫度會(huì )導致初級產(chǎn)物的形成;隨著(zhù)溫度的進(jìn)一步升高,初級產(chǎn)物會(huì )發(fā)生裂3結論解生成次級產(chǎn)物;而次級產(chǎn)物進(jìn)一步裂解和具有高溫熱合成會(huì )產(chǎn)生三級產(chǎn)物。因此,結合不行時(shí)間質(zhì)MYH中國煤化工電燈與飛CNMHG的分析手第6期王健等:熱裂解-在線(xiàn)真空紫外光電離質(zhì)譜法研究固體物熱裂解519段。本工作利用自行搭建的一套熱裂解在線(xiàn)Application of time-of-flight mass spectrometry真空紫外光電離質(zhì)譜裝置對固體物聚丙烯和卷with laser-based photoionization methods for ana-煙煙絲熱解的氣相產(chǎn)物進(jìn)行實(shí)時(shí)、在線(xiàn)研究,通lytical pyrolysis of PvC and tobacco[J].Journal過(guò)獲得的一系列質(zhì)譜圖,對聚丙烯和卷煙煙絲of Analytical and Applied Pyrolysis, 2005, 74 (1/的主要熱解產(chǎn)物進(jìn)行了分析。2):454-464實(shí)驗準確地鑒定了聚丙烯在不同溫度下6]wUQ,HUAL,HoUK,etal. A combinedingle photon ionization and photoelectron ionia熱解后的一次反應和二次反應產(chǎn)物,并觀(guān)察tion source for orthogonal acceleration time-of到熱解產(chǎn)物丙烯(m/z42)和戊二烯(m/z68)flight mass spectrometer[J]. International Jour-隨時(shí)間的變化情況,深入了解了聚丙烯材料nal of Mass Spectrometry, 2010, 295(1/2):60-中不同組分的受熱分解特性?？傮w來(lái)看,聚丙烯在400℃熱解后生成從C3(m/z42)至7] TANGE,GAOW, HUANG ZX,etal.acuC21(m/z294)的一系列不飽和烯烴;隨著(zhù)熱um ultraviolet single- photon ionization time-of-解溫度進(jìn)一步提高至600℃,長(cháng)鏈碳氫化合flight mass spectrometer[J]. Chinese Journal of物進(jìn)一步裂解成短鏈產(chǎn)物。該結果可以直觀(guān)Analytical Chemistry, 2011, 39(10):1470-地反映聚丙烯熱解產(chǎn)物的形成時(shí)間和變化規律,有助于驗證和推測反應機理。而對于卷81J,cAu,yw,a. A thermal dec煙煙絲熱解,本實(shí)驗快速地鑒定了其在不同by tunable synchrotron vacuum ultraviolet photoionization mass溫度下的熱解、聚合等化學(xué)反應產(chǎn)物,并對主etry[J]. Rapid Communications in Mass要熱解產(chǎn)物進(jìn)行歸納總結,通過(guò)觀(guān)察不同溫Spectrometry,2009,23(9):1269-1274.度條件下煙絲熱裂解產(chǎn)物的實(shí)時(shí)分析結果,[9]JAL.Y, WENG J J, WANG Y,etal. 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