新疆托里油砂分段熱解機理

第66卷第11期化工學(xué)報Vol. 66 No 112015年1I月CIESC Journalovember 2015研究論文新疆托里油砂分段熱解機理白翔,馬鳳云,劉景梅,鐘梅(新疆大學(xué)化學(xué)化工學(xué)院,新疆烏魯木齊830046)摘要:在熱重分析儀中考察了不同升溫速率下油砂的熱解特性,結果表眀:油砂樣品失重過(guò)程分為少量氣體脫附低溫熱解、主要熱解、半焦縮聚4個(gè)階段。通過(guò)微型固定床與在線(xiàn)質(zhì)譜耦合測得的氣體釋放順序為CO2、COC2H、CH4和H2,所對應的初釋溫度分別為155、178、146、174、354℃。結合核磁和紅外對不同溫度段液固產(chǎn)物的化學(xué)結構進(jìn)行分析,發(fā)現350℃前主要是油砂中輕質(zhì)油脫附,還包括羧基和烷基側鏈的斷裂,輕質(zhì)油品中芳碳率達792%;350~520℃之間為油砂的主要熱解階段,油砂油結構中芳碳率為23.51%。據 Coats- Redfern法計算得到油砂低溫熱解和主要熱解段的活化能分別為27.63和90.30kJ·mol',說(shuō)明開(kāi)環(huán)與裂解反應所需活化能大于油砂油脫附、羧基分解和弱鍵斷裂反應的活化能,揭示了分段熱解機理。關(guān)鍵詞:油砂;熱重分析:氣體逸岀順序;核磁和紅外分析;熱解機理DOI:10.11949/isn.0438-115720150493中圖分類(lèi)號文獻標志碼:A文章編號:0438-1157(2015)11-4626-08Segmenting pyrolysis mechanism of Tuoli oil sand in XinjiangBAI Xiang, MA Fengyun, LIU Jingmei, ZHONG MeiCollege of Chemical and Engineering, Xinjiang University, Urumqi 830046, Xinjiang, China)Abstract: The pyrolysis characteristics of oil sand at different heating rate was investigated by using athermogravimetric analyzer. The results showed that the mass loss of oil sand sample contained four processesdesorption, low temperature pyrolysis, main pyrolysis and char condensation. The evolution order of CO2, COC2H6, CHa and H2 was determined via the micro fixed bed reactor coupled with mass spectra analyzer, and thecorresponding initial releasing temperature were 155, 178, 146, 174 and 354C, respectively. The composition andchemical structure parameters of liquid and solid products in different temperature ranges were studied by nmrspectroscopy and IR spectrometry. The results showed that the principle reaction before 350C was desorption oflight oil, in which the aromatic carbon ratio amounted to 7.92% including the breaking of carboxylic and alkylside chains. The oil sand pyrolysis process mainly occurred in the temperature range of 350--520C. The aromaticcarbon ratio of the obtained pyrolysis oil was 23.51%. By using Coats-Redfern method, the correspondingactivation energy of low temperature pyrolysis and main pyrolysis process were 27.63 and 90.30 kJ molrespectively, indicating that the activation energy of ring-opening and cracking reaction was higher than that ofdesorption of oil sand, decomposition of carboxyl and breaking of the weak bondsKey words: oil sand; pyrolysis; gas evolution order; NMR and IR analysis; pyrolysis mechanism2015-04-17收到初稿,2015-08-10收到修改稿。Received date: 2015-04-17聯(lián)系人:鐘梅。第一作者:白翔(1988—),男,碩士研究生。CorrespondingauthorpRof.ZhoNgMei,zhongmei0504@126.com基金項目:新疆維吾爾自治區高?？蒲谢痦椖? XJEDU2014003Foundation itethe University Scientific ResearchFoundation of Xinjian中國煤化工20141003CNMHG第11期白翔等:新疆托里油砂分段熱解機理4627能,驗證了油砂熱解斷鍵的難易程度,從而為油砂低溫熱解技術(shù)提供基礎參數。中國能源結構為“富煤、貧油、少氣”,2014年原油對外依存度已達596%。故此,國家對非常規油1實(shí)驗部分氣資源的開(kāi)發(fā)愈來(lái)愈重視。油砂因其儲量豐富、分布1.1樣品集中等特點(diǎn)成為石油資源的有益補充。油砂資源的油砂樣取自中國新疆托里二區油砂礦,其工業(yè)分開(kāi)發(fā)利用,將對中國能源戰略安全起到積極的作用。砂的提油工藝包括水熱洗法叮、溶劑萃取法24析和元素分析分別采用國標GB/T212-2001和元素和低溫熱解法η等。與前兩種方法相比,低溫熱解分析儀測定( Thermo Flash ea-1112, Thermo finnigan節水、節能和減排 Corporation),結果如表1所示。油砂樣品中有機質(zhì)等特點(diǎn)。王擎等考察了不同干餾終溫下印尼油砂熱含量(干基)為914%(質(zhì)量)。其中,干燥無(wú)灰基解產(chǎn)物,在150℃氣體產(chǎn)率達0.52%,通過(guò)核磁分析固定碳含量?jì)H為21.2%(質(zhì)量)。該樣品中HC高了油砂熱解油,發(fā)現隨溫度的升高,芳碳率變化較小,達1.99,說(shuō)明熱解產(chǎn)物中油產(chǎn)率較高。實(shí)驗所用的芳碳和環(huán)烷碳含量減少。孫楠等研究了扎賚特旗油油砂樣磨至粒徑≤74m,在105℃下干燥2h除去砂,當反應溫度高于540℃時(shí),油砂二次裂解反應加水分,密封干燥保存待用劇,縮合成焦炭,裂解成小分子。Meng等對圖牧1.2實(shí)驗儀器與方法吉油砂熱解特性及熱解干餾提油法進(jìn)行了系統研究,實(shí)驗采用的主要儀器有SDTQ600熱重分析儀發(fā)現350~550℃范圍內油砂的失重量最大,520℃時(shí)(美國TA公司)、LCDl00m在線(xiàn)質(zhì)譜(美國油砂熱解液體產(chǎn)率達到最大為80.4%(mass,daf),AMETEK公司)、GC-4000A氣相色譜(東西電子研究表明,在較低溫度下聚合物之間的-CH2-CH2、有限公司)、 Varian Inova-400超導核磁共振譜儀(美CH2-O、-O等橋鍵,受熱易裂解生成自國Mman公司)、 EQUINOX-55傅里葉變換紅外光由基“碎片”,脂肪側鏈裂解生成CH4、CH6和CH譜儀(德國 Bruker)等氣態(tài)烴!3Ma等開(kāi)展了印尼布頓島油砂的熱油砂的程序升溫熱解實(shí)驗在熱重分析儀上進(jìn)解動(dòng)力學(xué)研究,從350℃升至50℃時(shí)油砂熱解轉化行。操作過(guò)程如下:取樣品(65±03)mg置于氧率達到95%,相應的活化能從13kJ·mor增至85化鋁坩堝內,高純氮[999體積)]作為載氣,kJ·mo1 Al-Otoom等用熱重分析儀考察了升溫氣體流速20 mI . min,先吹掃30min,排盡空氣,速率對約旦油砂熱解性能的影響,當升溫速率由隨后以一定的升溫速率(5、10、20、40、60、70、1℃∴mim1升至50℃·mim1時(shí),相應的活化能由80、100℃·min)升至105并保持20mm,繼3212kJ·mol增至42.93kJ·moll。續升溫至600℃并保持60min。綜上所述,研究者們大多針對油砂熱解氣體和熱解實(shí)驗在微型固定床反應裝置中進(jìn)行反應焦油進(jìn)行分析,而對各個(gè)不同溫度段油砂熱解剩余(圖1)。實(shí)驗升溫速率為10℃·min,以高純殘渣的變化及氣體的釋出規律卻未做出相應描述為載氣,油砂熱解產(chǎn)物測定分兩步進(jìn)行:①由室溫本實(shí)驗采用熱重分析儀研究油砂的失重特征,通過(guò)升至350℃并保持30min后,在N2氣氛下冷卻至微型固定床與在線(xiàn)質(zhì)譜耦合,揭示了相應溫度段各室溫;②繼上述步驟再從室溫升至520℃并保持30氣體的釋放特征,通過(guò)核磁和紅外對樣品及其液相min。分別收集各段氣液產(chǎn)物,主要氣體組分H2產(chǎn)物和殘渣進(jìn)行了分析,得出油砂熱解過(guò)程中液固CO、CH4、CO2和C2H6的逸出規律由在線(xiàn)質(zhì)譜分析。產(chǎn)物變化規律,推測熱解過(guò)程中不同溫度段熱解機檢測各氣體體積分數,計算氣體產(chǎn)率。液體產(chǎn)物經(jīng)理。根據〔oats- Redfern法計算了各溫度段的活化深度冷凝后用脫脂棉擦拭,由差重法計算其產(chǎn)率。表1油砂樣品的工業(yè)分析和元素分析Table 1 Proximate and ultimate analysis of oil sand sampleProximate analysis/%Ultimate analysis1.3177.73H中國煤化工CNMHG化工學(xué)報第66卷10距lnAR計算E和ABE2結果與討論2.1油砂的TG程序升溫熱解過(guò)程分析圖2為不同升溫速率下油砂的TG與DTG曲圖1固定床耦合在線(xiàn)質(zhì)譜流程線(xiàn)。圖2(a)曲線(xiàn)A~H的升溫速率分別為5、10、Fig 1 Schematic diagram of micro fixed bed reactor coupled20、40、60、70、80、100℃·min。由圖2可知,retry油砂熱解過(guò)程可分為4個(gè)階段,以10℃·min1的I--argon; 2--mass flow meter; 3--thermocouple; 4--electric furnace升溫速率為例:第1段為干燥脫氣段,溫度范圍為5 fixed bed.6 cooling units;7 gas washing bottle;: gas flow meter30~120℃,該階段失重量約占總失重量的1.98%9U type dry pipe: 10--online mass spectrometry; 1l--air trap可能是油砂樣中微量水分和吸附氣體的脫除;第2將不同溫度段液體產(chǎn)物進(jìn)行油水分離,油樣的測試段溫度區間為120~350℃,是油砂的低溫熱解段,全部在核磁共振譜儀上進(jìn)行,溶劑為CDCl3。樣品其失重量占總失重量的3843%,主要是油砂中輕質(zhì)和不同溫度段殘渣采用FTR進(jìn)行分析。油的脫附,還包括羧基分解生成CO2、吸附氣體脫1.3動(dòng)力學(xué)分析方法附及弱鍵斷裂;第3段為350~520℃,是油砂的主油砂熱解速率y如式(1)所示要熱解階段,有機質(zhì)發(fā)生強烈熱解反應:①有機dxkf(x)(1)質(zhì)→重油+殘炭+氣;②重油→輕油+殘炭+氣,其失重量為總失重量的54.53%;第4段是520~600℃,其中,模型函數f(x)可由式(2)描述為半焦縮聚段,該階段TG曲線(xiàn)變得平緩,其失重f(x)=(1-x)100由 Arrhenius方程可得將式(2)和式(3)代入式(1)中求得E100200300式(1)~式(3)中,x為t時(shí)刻的總熱解轉化temperature/C率;m為樣品初始質(zhì)量;m是t時(shí)刻樣品的質(zhì)量m為熱解終溫時(shí)的樣品質(zhì)量:k為溫度T下的反應速率常數;n為熱解反應級數,通常認為油砂熱解n=1;A為指前因子;E為活化能;R為普適氣D′體常數。對于非等溫熱解過(guò)程,引入升溫速率尸=dT/d,整理后得到 Coats- Redfern方程1719,當n=1時(shí)aRTE10020000400500temperature/℃式中二約為0.1,故此1-二可認為是1,圖2不同升溫速率時(shí)油砂的失重率與失重速率曲線(xiàn)EFig 2 TG and dTG curves of oil sand at different以ln對作圖,通過(guò)直線(xiàn)斜率-和截heating ratesA, B, C, D, E.中國煤化工)℃·minCNMHG第11期白翔等:新疆托里油砂分段熱解機理4629·表2氣體釋放的特征溫度Table 2 Gas release characteristic temperaturePeak 1(25-120℃)eak2(120350℃)Peak3(350520℃)Peak4(520600℃)TiinitialT155178Ha354585量占總失重量的505%當升溫速率由5℃·min增至100℃·minl時(shí),油砂的失重曲線(xiàn)向高溫方向移動(dòng)圖2(a)1,。0ysma cO從350℃升至520℃時(shí),熱解特征溫度7(T為失00Co14008重速率最大時(shí)對應的溫度)由433℃升至489℃[圖CH13002(b)升溫速率對熱解反應的影響可從兩方面闡喜述:①升溫速率增加,樣品顆粒表面快速達到熱解所需溫度優(yōu)先發(fā)生熱解;②產(chǎn)生傳熱滯后效應,導致顆粒內外溫差變大,當內部顆粒開(kāi)始熱解時(shí),表01000200030004000500060007000面顆粒的溫度繼續上升,故與低升溫速率相比,T向高溫方向移動(dòng)。圖3油砂熱解氣體的釋放規律22油砂熱解主要氣相產(chǎn)物釋放規律Fig 3 Evolution characteristics of major volatile gases為解析熱重圖中各階段揮發(fā)分的析出特性,在微型固定床反應器中采用10℃·min的升溫速率00610×10升至終溫600℃,考察溫度對氣體析出規律的影響0100020003000CO(圖3)。由圖可知,各氣體的逸出曲線(xiàn)出現了峰的至oCH6疊加。為揭示圖3中氣體在不同溫度段的逸出特性CH41300003于120、350和520℃分別保持20、30和30min(圖4)。由圖可知,C2H6和CH4氣體在25~520℃溫度0.01范圍內均有釋出,其中在25~120℃溫度區間為少量C2H6和CH4氣體的脫附:120~350℃溫度段內二者的逸出溫度和峰溫分別約為146、74℃和177312℃(表2),可歸屬于油砂樣品的低溫熱解和吸圖4不同溫度段油砂熱解氣體的釋放規律附氣體的高溫脫附;在350~520℃溫度范圍,兩種Fig 4 Gas release law at different temperature ranges氣體的逸出峰溫分別為425和438℃(表2);在CO3釋出峰,可歸屬為碳酸鹽的分解,與賈春霞2520~600℃溫度區間,幾乎沒(méi)有ClH生成,說(shuō)明其的結論一致。CO的析出曲線(xiàn)較為平緩,無(wú)明顯峰在主要熱解段已釋放完全,CH4的峰溫為573℃值,說(shuō)明該油砂樣有機質(zhì)中羰基和醚鍵官能團數量可能是由重油的二次裂解與長(cháng)碳鏈的氣態(tài)烴裂解產(chǎn)較少生。H2的初釋溫度高于其他氣體,約為354℃,其表3為油砂熱解產(chǎn)物的分布情況。由表可知,釋出曲線(xiàn)有兩個(gè)逸出峰,峰溫分別為423和585℃,在50~350℃溫度區間,CO2產(chǎn)率達0.41%,約占該在520~600℃溫度段內H2主要來(lái)源于芳香結構的溫度段氣體總產(chǎn)率的9678%,說(shuō)明溫度低于350℃縮聚。CO2于155℃左右開(kāi)始釋出,在120~520℃時(shí),主要發(fā)生羧基分解反應,少量的CH4和C2H6溫度區間有兩個(gè)明顯的逸出峰,峰溫分別為321為油砂中吸附氣體的脫附及輕烴類(lèi)物質(zhì)的斷鍵。此和408℃,在520~600℃區間仍有一個(gè)較弱的溫度范圍內TYHa中國煤化工2.12%,意味CNMHG化工學(xué)報第66卷表3油砂熱解產(chǎn)物分布Table 3 Results of oil sand pyrolysis products distribution600℃25-350℃350-520℃H2著(zhù)低熱穩定性的羧基含量高于高熱穩定性的羧基含量。在350~520℃溫度區間,CO2、CH4、C2HH2產(chǎn)率分別為0.25%、0.32%、0.056%和0.18%結合圖4可知,H2、CH4和C2lH6的生成曲線(xiàn)峰面積較大,說(shuō)明上述3種氣體在該溫度段內集中釋放。0002000H的生成源于該油砂樣中芳香族結構縮聚脫氫wavenumber/cmCH4和C2H6主要由連有烷烴側鏈的一CH3和C2H圖5油砂與反應后樣品FTIR分析官能團直接裂解及含亞甲基的脂鏈或脂環(huán)斷裂 Fig 5 FT-IR spectra of oil sand and products after pyrolysis產(chǎn)生at different temperature從表3可以看出,在50~350℃與350~520℃結論相吻合,即350℃之前羧基和部分弱鍵斷裂,溫度區間,油砂熱解氣產(chǎn)率與液體產(chǎn)率之和分別為同時(shí)油砂油發(fā)生高溫脫附反應。一OH的振動(dòng)峰無(wú)4.28%和6.10%,采用熱重分析儀測得數據分別為明顯變化,這源于熱穩定性-OH>CO>-COOH441%和6.18%(圖2),二者測量值相符程度達>-OCH3圖5(c)與圖5(b)相比較可得,在96.94%和9871%,說(shuō)明實(shí)驗數據可靠520℃殘渣樣品中-OH、脂肪區、較弱烯烴-CH23油砂及殘渣的紅外分析芳環(huán)CH的振動(dòng)峰幾乎完全消失,說(shuō)明當溫度從油砂及殘焦的紅外光譜分析如圖5所示。圖5350℃升至520℃時(shí),油砂有機質(zhì)中大部分官能團發(fā)(a)油砂樣品具有復雜的吸收峰,其中3695cm1生斷裂,重新組合生成新的化合物。圖5(d)為的峰形較尖銳,由一OH伸縮振動(dòng)引起,醇羥基、600℃時(shí)油砂殘渣的紅外圖譜,與圖5(c)相比較酚羥基等寬化了一OH的吸收帶出現在3620cm。沒(méi)有明顯差別,進(jìn)一步證明羰基、活性的醚鍵和連3020~2790cm1處的峰為油砂中脂肪類(lèi)物質(zhì)的吸接在脂鏈或脂環(huán)烷烴側鏈的_C2H5官能團在520℃收振動(dòng)峰,2925和2856cm的峰分別歸屬為脂肪之前完全斷裂。族-CH3的反對稱(chēng)和對稱(chēng)伸縮振動(dòng)峰。醛羰基CO2.4油砂兩段熱解液相產(chǎn)物核磁分析伸縮振動(dòng)發(fā)生在1730~1630cm1,羧酸根-COOH表4為油砂油HNMR譜的化學(xué)位移歸屬及積伸縮振動(dòng)位于1620~1540cm2,100-1020cm1分計算結果。由表可知,在1為02~4,2區間,低包含了直鏈C-C、C=C、C-OH的伸縮,油砂無(wú)溫熱解段和主要熱解段油砂油芳環(huán)上α、β和γ位的機組分中90%以上是SO2,頻率1100cm1和880CH、一CH2及一CH3三者之和,分別占總H量的780cm為SOSi的強伸縮振動(dòng),950-90092.52%和9286%,即油砂油富含側鏈,其中H和cm較弱的吸收峰可歸屬為烯烴CH2面外搖擺,H之和占三者之和的93.20%和8904%,說(shuō)明側鏈700cm1左右的峰則由芳環(huán)上的=CH面內彎曲中以長(cháng)鏈為主;兩溫度段中H2僅占三者之和的68%引發(fā)和10.96%,意味著(zhù)側鏈中支鏈較少,油砂油結構支對不同溫度段所產(chǎn)生的殘渣進(jìn)行紅外分析,發(fā)鏈化程度較低現與原油砂相比,350℃殘渣的脂肪區和羧酸峰位的表5為油砂油CNMR譜的化學(xué)位移歸屬及積吸收振動(dòng)峰減弱Ⅸ圖5(a)],與圖4和表3所述的分計算結果TYH影作第11期白翔等:新疆托里油砂分段熱解機理463l·表4HNMR中各類(lèi)H的歸屬Table 4 Assignment of hydrogen types in H NMRRelative contentType of hydrogeChemical shift25-350℃350-520℃H, methyl hydrogen y or further from aromd=0.2-1.02aliphatic hydrogen B or further from aromatic rin50.14H6=2.04.2HoIphenolic hydrogen4.972.12aromatic hydrogen6=6.09.0表51CNMR測得油砂兩段熱解油結構參數Table 5 Structural parameters of two-stage pyrolysis oil-sand oil inC NMRRelative content/%Type of carbons350℃520℃terminal methyl in alkyl chains3.73naphthenic methyl, methyl to aromatic rings16-2522831944methylene, methane, -CH2 to saturated hydrocarbonquaternary carbon, a-CH3 to aromatic ringsftertiary carbon, proton aromatic carbon13.11aromatic carbon tocarbon129150methyl, carboxyl group, aromatic carbon to phenolic hydroxyl150-188faliphatic carbon weight ratioaromatic carbon weight ratioll5-1523,517.92%和23.51%,說(shuō)明油砂油芳香度較低,油品較圖(圖6),并求算出相關(guān)的動(dòng)力學(xué)參數(表6)。由輕。f1與f1(25~36)峰的強度之比分別為0178表可知,方程線(xiàn)性相關(guān)系數R2均大于0.9,表明和0.104,均大于θ.1③3,表明油砂油結構中脂肪鏈Coas- Redfern法適用于不同熱解段活化能的計算長(cháng)鏈的平均長(cháng)度小于10個(gè)碳鏈;6為16~25之間當升溫速率從5℃·min升至100℃·min時(shí),低的含量分別為22.83%和19.44%,表明短程烷基側溫熱解階段的活化能與指前因子分別從22.65鏈含量較多,結合表4油砂油側鏈支鏈化程度較低,kJ·mol和2.45s-增至31.22kJ·mol和112.30說(shuō)明短程烷基側鏈大多與環(huán)烷和芳環(huán)直接相連。s',主要熱解階段的活化能與指前因子則分別從∥和/B在低溫熱解段中分別為309%和4.82%,84.8kJ·mo和146×10°s增至9723kJ·mo而在主要熱解段中兩者值較高,分別為13119和和,16×10。從兩段活化能的大小佐證了油砂10.40%,這是因為在350℃之前熱解程度較低,而分段劃分的合理性與熱解機理推測的可行性從350c升至520時(shí)油砂低溫熱解殘渣發(fā)生了環(huán)3結論烷烴脫氫芳構化反應,導致兩者值較高,此過(guò)程還伴隨著(zhù)烴類(lèi)和氫氣的析出。采用TG非等溫法考察了升溫速率對油砂熱解2.5油砂熱解動(dòng)力學(xué)計算過(guò)程的影響,并研究了其熱解動(dòng)力學(xué),通過(guò)微型固圖6(a)、(b)為不同升溫速率下油砂在120定床耦合在線(xiàn)質(zhì)譜,揭示了氣體釋出特性,結合核350℃和350~520℃熱解過(guò)程動(dòng)力學(xué)擬合曲線(xiàn)。結磁與紅外分析了兩段油砂熱解液固產(chǎn)物,結論如下合圖2(b)、表3和圖4可以看出,120~350℃區(1)新疆托里油砂熱解過(guò)程可分為干燥脫氣間的熱失重歸因于油砂油的脫附,還包括較弱鍵斷(30~120℃)、低溫熱解(120~350℃)、主要熱解裂和脫羧反應。油砂熱解油氣大量的生成主要發(fā)生(3℃)和半焦縮聚(520~600℃)4個(gè)階段31c的TH史牌煤化工的主要區間化工學(xué)報第66卷13.813.05℃.m0℃,min1134。10℃.min-14.2▲20℃·min百-14.3-136440℃mn14.6701751.801.851901.952002052.102.151201251.301.351.401451.50b)圖6油砂在不同升溫速率下低溫熱解和主要熱解階段的 Arrhenius圖Fig 6 Arrhenius diagram of oil sand pyrolysis at different heating rates表6 Coats- Redfern積分法計算熱解段活化能結果Table 6 Coats-Redfern integral method to calculate thermal decomposition activation energyHeating rateLow -temperature pyrolysisHigh-temperature pyrolysis℃EkJ·molTran℃EkJ· mol- A×105s217—25722.652.4412-4640.999236-2765.44430-470241-282450-4900.999250-29035.800.999264-304460-50092.5026.400.99100270-310112.300.999468-50871.600.999(2)CO2、CO、CH4、C2H6、H2的初釋逸Contemporary Chemical Industr(當代化工),2008,29(1):242溫度分別約為155、178、174、146、354℃[3] Tang xiaodong(唐曉東), Li Jingjing(李晶晶), Qing Dayong(卿大詠), Zhang Yangyong(張洋勇), Deng Jieyi(鄧杰義). Experimental(3)油砂油在低溫熱解和主要熱解段的芳碳tudy on solvent extraction and separation of Karamay oil sands [j率分別為792%和23.51%,說(shuō)明油品均較輕。兩段Applied Chemical Industry(應用化工),2104,43(5)874876油砂油結構中富含側鏈,側鏈以小于10個(gè)碳鏈的長(cháng)[4] Ren sili(任嗣利). Research progress in water-based bitume鏈為主,側鏈中支鏈化程度較低,短程烷基側鏈大extraction from oil sands[ CESC Journa!(化工學(xué)報),2011,62(9):2406-2412多與環(huán)烷環(huán)和芳環(huán)直接相連[S] Xu Xiuqiang(許修強), Wang Hongyan(王紅巖), Zheng Dewen(鄭(4)當升溫速率由5℃·min增至100tef im). Research progress in application of the oil sands [J]. Liaoning℃·min1時(shí),低溫熱解段活化能與指前因子分別從Chemical Industr(遼寧化工),2008,37(4):268-271[6] Strausz O P, Jha K N, Montgomery D S Chemical composition of22.65kJ·mol和245s增至31.22kJ·mo和gases in Athabasca bitumen and in low-temperature thermolysis of oil112.30s-1,主要熱解段的活化能與指前因子分別sand, asphaltene and maltene []. Fuel, 1977, 56(2): 114-120從84.88kJ·mol和1.46×1053s1增至97,23] Wang Yimin(王益民, Cao zubin(曹祖賓), Shi junfeng(石俊峰)Liu Jingjie(劉井杰), Li Dandong(李丹東). 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