Investigation of the Evolution Behavior of Light Tar During Bituminous Coal Pyrolysis in a

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第43卷第1期2024年1月硅㊀酸㊀盐㊀通㊀报BULLETIN OF THE CHINESE CERAMIC SOCIETY Vol.43㊀No.1January,2024负载S-g-C 3N 4/MgAl-CLDH 光催化砂浆的去污及水化性能研究林淑瑾1,罗盛洋2,熊晓立2(1.福州市建设工程质量监督站,福州㊀350007;2.福州大学土木工程学院,福州㊀350108)摘要:本研究合成了硫掺杂氮化碳/煅烧镁铝水滑石(S-g-C 3N 4/MgAl-CLDH)新型光催化复合材料,通过内掺的方式将其负载在水泥砂浆上,并测试了光催化砂浆的氮氧化物(NO x )降解性能和水化性能㊂结果表明,当光催化剂掺量小于5%(质量分数)时,S-g-C 3N 4/MgAl-CLDH 掺量与砂浆的NO x 降解率成正比㊂当光催化剂掺量超过5%时,砂浆的NO x 降解性能开始下降㊂适量的S-g-C 3N 4/MgAl-CLDH 使水泥早期(1d)水化程度显著提升,过量的S-g-C 3N 4/MgAl-CLDH 使水泥后期水化程度下降㊂当光催化剂掺量为7%时,水泥砂浆的28d 强度较对照组砂浆显著下降㊂此外,适量(3%)S-g-C 3N 4/MgAl-CLDH 能够改善砂浆的28d 强度㊂关键词:光催化砂浆;g-C 3N 4;MgAl-CLDH;氮氧化物降解;抗压强度;水泥水化中图分类号:O643.3㊀㊀文献标志码:A ㊀㊀文章编号:1001-1625(2024)01-0044-08Decontamination and Hydration Performance of Photocatalytic Mortar Loaded with S-g-C 3N 4/MgAl-CLDHLIN Shujin 1,LUO Shengyang 2,XIONG Xiaoli 2(1.Fuzhou Construction Engineering Quality Supervision Station,Fuzhou 350007,China;2.College of Civil Engineering,Fuzhou University,Fuzhou 350108,China)Abstract :In this study,a new type of photocatalytic composite material sulfur-doped carbon nitride /calcined magnesium aluminum hydrotalcite (S-g-C 3N 4/MgAl-CLDH) was synthesized and loaded on cement mortar through internal doping.The nitrogen oxide (NO x )degradation and hydration performance of photocatalytic mortar were tested.The results show that when the photocatalyst dosage is less than 5%(mass fraction),the S-g-C 3N 4/MgAl-CLDH content is directly proportional to the NO x degradation rate of mortar.When the photocatalyst dosage exceeds 5%,the NO x degradation performance of mortar begins to decrease due to agglomeration.In addition,due to the nucleation effect of nanomaterials,the incorporation of an appropriate amount of S-g-C 3N 4/MgAl-CLDH significantly improves the early (1d)hydration degree of cement.However,due to its water absorption and agglomeration phenomenon,excess S-g-C 3N 4/MgAl-CLDH reduces the later hydration degree of cement.When the photocatalyst dosage is 7%,the 28d strength of cement mortar significantly decreases compared with the control mortar.In addition,an appropriate amount of S-g-C 3N 4/MgAl-CLDH (3%)can improve 28d strength of mortar due to its micro-filling effect.Key words :photocatalytic mortar;g-C 3N 4;MgAl-CLDH;nitrogen oxide degradation;compressive strength;cement hydration收稿日期:2023-07-11;修订日期:2023-09-14作者简介:林淑瑾(1975 ),女,高级工程师㊂主要从事水泥混凝土材料研究和建筑工程质量监督管理㊂E-mail:770900765@ 0㊀引㊀言氮氧化物(NO x ,主要包括NO 和NO 2)是一种对人类健康危害极高的空气污染物[1]㊂长时间暴露在NO x环境下会对人类的呼吸道㊁心血管㊁免疫系统造成影响㊂近年来,石墨相氮化碳(g-C 3N 4)作为一种新型半导体光催化材料,由于稳定㊁无毒㊁平价等优点成为了环境污染治理领域的研究热点[2]㊂但是,g-C 3N 4光生电子-空穴对复合率较高,对可见光响应范围较窄[3]㊂针对这些问题,目前有研究者提出对g-C 3N 4进行改性处第1期林淑瑾等:负载S-g-C3N4/MgAl-CLDH光催化砂浆的去污及水化性能研究45㊀理㊂翟苓帆等[4]通过水热法,成功将g-C3N4和镁铝水滑石(MgAl-LDH)复合,合成了g-C3N4/MgAl-LDH复合异质结材料,异质结光生载流子的迁移和分离提供了更多高速通道,使g-C3N4/MgAl-LDH与其前驱体相比具有更高的光催化性能㊂陈璞等[5]通过机械研磨制备出了In2S3/g-C3N4复合光催化剂,结果表明,在氙灯下复合光催化剂的光降解表观速率常数是g-C3N4的1.6倍,在自然光下光降解表观速率常数是g-C3N4的1.4倍㊂Jiang等[6]通过掺杂碱金属离子(Li+㊁Na㊁和K+)对g-C3N4进行了改性,g-C3N4经改性后呈现出更大的比表面积㊁更窄的带隙,以及更高效的电荷载流子转移㊂这显著增强了改性g-C3N4在可见光照射下进行光催化制氢的性能㊂Liu等[7]通过三聚氰胺缩聚,制备得到了氯离子掺杂的g-C3N4样品(Cl-g-C3N4),与g-C3N4相比,Cl-g-C3N4的光催化活性显著提升,其对RhB的降解效率约为g-C3N4的12.9倍㊂水泥基材料是世界上应用最广的建筑材料之一[8],具有作为光催化材料载体的潜力[9]㊂Xu等[10]将纳米光催化材料TiO2@CoAl-LDH应用在水泥净浆中发现,纳米光催化材料的引入可以显著提高水泥的早期水化速率,这主要是由于纳米光催化材料为水化产物提供了额外的成核点㊂Li等[11]将g-C3N4应用在水泥砂浆中,发现适量g-C3N4能均匀分散在水泥砂浆中,水泥砂浆中没有出现明显的缺陷㊂这说明在水泥水化产物的胶结作用下,光催化砂浆具有良好的整体性㊂Yang等[12]用g-C3N4制备了水泥净浆,他们发现,添加0.5%(文中掺量㊁含量均为质量分数)g-C3N4的水泥净浆的水化程度比空白对照组提高了10.8%,但是过高的g-C3N4掺量会使水泥水化程度下降㊂Duan等[13]将MgAl-LDH掺入水泥基材料,并探究了其掺量对水泥基材料碳化深度的影响,结果表明,碳化深度随着MgAl-LDH掺量增大而减小,这表明水滑石材料对水泥基材料抗碳化性能有提升作用㊂基于此,本研究将硫掺杂氮化碳(S-g-C3N4)与煅烧镁铝水滑石(MgAl-CLDH)复合,得到了一种高催化活性的复合材料S-g-C3N4/MgAl-CLDH,并以内掺的方式制备了光催化水泥砂浆,研究了S-g-C3N4/MgAl-CLDH掺量对水泥砂浆抗压强度和NO x降解性能的影响㊂此外,通过等温量热法(isothermal calorimetry)㊁X射线衍射(X-ray diffraction,XRD)㊁热重分析(thermal gravimetric analysis,TGA)和扫描电子显微镜(scanning electron microscopy,SEM)等微观测试手段,阐明纳米S-g-C3N4/MgAl-CLDH对水泥砂浆水化过程的作用及影响机理㊂1㊀实㊀验1.1㊀原材料试验所用化学试剂均为分析纯,包括:硫脲(CH4N2S)㊁三聚氰胺(C3H6N6)㊁无水乙醇(C2H6O)㊁镁铝水滑石(Mg6Al2(OH)16CO3㊃4H2O)㊂试验所用细骨料为标准砂,符合‘水泥胶砂强度检验方法(ISO法)“(GB/T17671 2021)的要求㊂试验所用普通硅酸盐水泥(ordinary Portland cement,OPC)符合‘通用硅酸盐水泥“(GB175 2007)中P㊃O42.5的要求,其烧矢量(loss on ignition,LOI)为1.08%㊂通过X射线荧光光谱法得到了水泥的主要化学成分,其中CaO占64.21%,SiO2占20.83%,Al2O3占6.22%,SO3占1.82%㊂1.2㊀试验方法1.2.1㊀样品的制备将称量好的三聚氰胺(5g)和硫脲(5g)放入研钵中研磨后于60ħ烘箱烘干,再将其放置于马弗炉中煅烧(550ħ,2h),得到S-g-C3N4㊂称取MgAl-LDH(3g),将其放入马弗炉中煅烧(500ħ,3h),得到MgAl-CLDH㊂然后,将S-g-C3N4和MgAl-CLDH按如下步骤进行静电自组装:将0.2g S-g-C3N4加入装有20mL无水乙醇溶液的烧杯中,并超声分散,得到S-g-C3N4悬浮液;将0.5g MgAl-CLDH粉末加入装有50mL无水乙醇溶液的烧杯中,并超声分散;接着,将两种悬浮液混合,并置于80ħ油浴锅中,密封搅拌12h;随后,在油浴锅中开口搅拌,直至搅干,即得到S-g-C3N4/MgAl-CLDH光催化复合材料㊂1.2.2㊀物理化学表征采用MiniFlex600X射线多晶衍射仪对光催化材料进行了晶相分析,结果如图1(a)所示㊂可以看出, S-g-C3N4具有比g-C3N4更低的衍射峰((100)和(002)),这说明S掺杂导致g-C3N4结晶度降低㊂此外, S-g-C3N4/MgAl-CLDH中既有S-g-C3N4的衍射峰,又有MgAl-CLDH的衍射峰((111)㊁(200)㊁(220)),这表46㊀水泥混凝土硅酸盐通报㊀㊀㊀㊀㊀㊀第43卷明S-g-C3N4/MgAl-CLDH被成功合成㊂采用F-7000荧光分光光度计对光催化材料进行了光致发光谱(photoluminescence spectroscopy,PL)分析,考察了光生电子和空穴对复合情况,结果如图1(b)所示㊂可以看到,与S-g-C3N4相比,S-g-C3N4/MgAl-CLDH的PL发射峰出现蓝移(从465nm到442nm),此外,峰的强度明显降低㊂这是由于MgAl-CLDH中的MgO掺杂到了S-g-C3N4上,使得MgAl-CLDH与S-g-C3N4之间的有效电荷转移增加,从而抑制了光生电子和空穴对的复合㊂图1㊀S-g-C3N4㊁MgAl-CLDH及S-g-C3N4/MgAl-CLDH的表征Fig.1㊀Characterization of S-g-C3N4,MgAl-CLDH and S-g-C3N4/MgAl-CLDH采用SEM3100扫描电子显微镜观察了光催化材料的微观形貌,结果如图2所示㊂与S-g-C3N4相比, S-g-C3N4/MgAl-CLDH疏松多孔,具有更高的比表面积㊂此外,采用TECNAI G2F20透射电子显微镜考察了光催化材料晶体间异质结构建情况,结果如图3所示㊂可以看出,MgAl-CLDH为不规则的二维纳米片,表面粗糙㊂而S-g-C3N4为非晶态的二维纳米片结构,表面较为光滑㊂通过静电自组装法,MgAl-CLDH被搭载到了S-g-C3N4上,而灰度值的交界区域即为异质结(如图3(b)所示)㊂图2㊀S-g-C3N4和S-g-C3N4/MgAl-CLDH的SEM照片Fig.2㊀SEM images of S-g-C3N4and S-g-C3N4/MgAl-CLDH图3㊀S-g-C3N4/MgAl-CLDH的TEM照片Fig.3㊀TEM images of S-g-C3N4/MgAl-CLDH第1期林淑瑾等:负载S-g-C 3N 4/MgAl-CLDH 光催化砂浆的去污及水化性能研究47㊀1.2.3㊀光催化砂浆和净浆的制备与性能测试根据前期预实验筛选出光催化净浆与砂浆的配合比,如表1所示㊂光催化剂S-g-C 3N 4/MgAl-CLDH 的掺量分别为水泥的0%㊁3%㊁5%和7%㊂表1㊀光催化净浆与砂浆的配合比Table 1㊀Mix proportion of photocatalytic paste and mortarSample No.Mix proportion /g Photocatalyst OPC Sand Water CP00150052.5CP3 4.5150052.5CP57.5150052.5CP710.5150052.5CM004501350270CM313.54501350270CM522.54501350270CM731.54501350270根据表1称量所需材料,砂浆和净浆的制备过程如下:在拌合过程中,首先分别将称好的S-g-C 3N 4/MgAl-CLDH 与一半的水进行混合并快速搅拌60min,得到稳定的悬浮液;然后,将分别称量好的普通硅酸盐水泥和标准砂放入搅拌机内并慢速搅拌60s,待干料混合均匀后,在30s 内匀速倒入悬浮液;接着再将另一半的水倒入并慢速搅拌,整个过程持续90s;最后再快速搅拌90s,得到均匀的拌合物㊂将新拌净浆注入50mL 的离心管中充分振捣并用瓶盖密封;将新拌砂浆注入尺寸为40mm ˑ40mm ˑ40mm 的立方体模具中充分振捣,并贴上塑料薄膜㊂待1d 后脱模,放入(20ʃ2)ħ和相对温度95%的标准养护室中继续养护㊂达到选定龄期后,将试块取出进行测试㊂砂浆的1㊁3㊁7和28d 抗压强度测试按照‘水泥胶砂强度检验方法(ISO 法)“(GB /T 17671 2021)进行㊂光催化净浆的XRD 分析采用MiniFlex 600X 射线多晶衍射仪进行,测试电压为40kV,测试电流为40mA [14],测试样品为烘干粉末㊂TGA 采用STA449F5热重分析仪,Ar 环境,测试温度为30~1000ħ[15],测试样品为烘干粉末㊂扫描电镜图像采用SEM 3100扫描电子显微镜拍摄,样品测试前进行表面喷金处理㊂此外,参考文献[16]的方法,对新拌净浆进行水化热测试,测试仪器为TAM-AIR 等温量热仪㊂测试时将10g 新拌净浆用胶头滴管挤于安瓿瓶底部,然后,立即将安瓿瓶放入等温量热仪中进行测试㊂1.2.4㊀光催化砂浆的NO x降解性能测试图4㊀NO x 光催化降解试验流程图Fig.4㊀Flow chart of NO x photocatalytic degradation test参照文献[17]搭建了自制光催化NO x 降解装置㊂试验装置主要由气源(NO x 气体㊁合成空气)㊁氙灯光源(CEL-PF300-T8E,50W)㊁流量控制器(D07-7B)㊁圆柱反应箱(ϕ15cm ˑ15cm )㊁NO x 分析仪(GASTiger6000)组成㊂反应箱材质为紫外可见光透过性能优良的石英玻璃㊂此外,为减小外界光源对试验的影响,在光催化反应箱四周覆盖锡箔纸㊂图4展示了NO x 降解试验的过程:先将光催化砂浆试块放置于垫板上,打开NO x 气源,待样品达到吸附平衡后,打开氙灯㊂将NO x 气体流速调节至恒定0.5L /min,持续60min㊂反应系统中NO x 的降解率R 计算公式如式(1)所示㊂R =(NO x [0]-NO x [i ])NO x [0]ˑ100%(1)式中:NO x [0]为初始氮氧化物浓度,ppm(1ppm =10-6);NO x [i ]为反应i min 后的氮氧化物浓度,ppm㊂48㊀水泥混凝土硅酸盐通报㊀㊀㊀㊀㊀㊀第43卷2㊀结果与讨论2.1㊀光催化砂浆的NO x 降解性能图5(a)是不同光催化剂掺量下水泥砂浆的NO x 降解曲线㊂由图可知,当试验开始时,各组放有光催化砂浆的反应箱中的NO x 浓度开始直线下降,且各光催化砂浆降解NO x 的速率都较为稳定(在2~60min 出现了平台期)㊂有趣的是,光催化剂掺量为0%的CM0的反应箱的NO x 浓度也略微下降,这是因为虽然CM0本身不具备去污能力,但砂浆表面存在部分孔隙,起到了可吸附部分NO x 的作用㊂此外,根据图5(a)的数据,通过式(1)计算得到不同掺量光催化水泥砂浆在3min 时的NO x 的降解率,结果如图5(b)所示㊂如图5(b)所示,光催化砂浆的NO x 降解性能随着S-g-C 3N 4/MgAl-CLDH 掺量的增加而呈现出先上升再下降的趋势㊂具体而言,当S-g-C 3N 4/MgAl-CLDH 掺量从0%增加到5%时,NO x 降解率从7.2%上升到48.2%㊂这主要是因为随着S-g-C 3N 4/MgAl-CLDH 掺量的增加,砂浆与气体接触的活性位点增加,其光催化降解NO x 能力逐渐提升㊂但值得注意的是,当S-g-C 3N 4/MgAl-CLDH 掺量从5%增加到7%时,NO x 降解率从48.2%下降到37.8%㊂这可能是因为当S-g-C 3N 4/MgAl-CLDH 掺量过大时,由于微粒间的相互作用力,产生了团聚现象,使得去污效果下降㊂图6展示了CM7的28d SEM 照片,可以看到大片S-g-C 3N 4/MgAl-CLDH 团聚在一起,形成了絮凝体,这使得砂浆的NO x 降解率下降㊂图5㊀不同光催化剂掺量下砂浆的NO x 降解能力Fig.5㊀NO x degradation abilities of mortars with different photocatalyst dosages2.2㊀光催化砂浆的力学性能及水化过程2.2.1㊀力学性能图7为光催化砂浆的1㊁3㊁7和28d 的抗压强度测试结果㊂由图可知,随着S-g-C 3N 4/MgAl-CLDH 掺量的增加,光催化水泥砂浆的早期(1d)抗压强度呈上升趋势㊂当掺量从0%增加到7%时,1d 抗压强度从㊀㊀㊀㊀㊀图6㊀CM7的28d SEM 照片Fig.6㊀SEM images of CM7at 28d㊀图7㊀不同光催化剂掺量下砂浆的抗压强度Fig.7㊀Compressive strength of mortars with different photocatalyst dosages第1期林淑瑾等:负载S-g-C 3N 4/MgAl-CLDH 光催化砂浆的去污及水化性能研究49㊀15.3MPa 上升到18.3MPa㊂但光催化水泥砂浆的中期和后期(3㊁7和28d )强度随着S-g-C 3N 4/MgAl-CLDH 掺量增加呈先上升后下降的趋势㊂当掺量从3%增加到7%时,砂浆的28d 抗压强度从49.0MPa 下降到40.7MPa㊂此外,CM3的3㊁7和28d 抗压强度都是最高的,与对照组CM0相比,CM3的3㊁7和28d 强度分别提高了18.2%㊁11.3%和6.5%㊂这说明掺入适量(3%)S-g-C 3N 4/MgAl-CLDH 对砂浆的抗压强度有积极作用㊂2.2.2㊀水化过程为了探究S-g-C 3N 4/MgAl-CLDH 对砂浆水化过程的影响,进行了一系列微观测试㊂图8展示了不同光催化剂掺量下净浆的早期放热过程㊂如图8(a)所示,在12h 左右出现的第二个放热峰代表了水泥中的活性成分C 3S 等的水化㊂可以明显看出,随着S-g-C 3N 4/MgAl-CLDH 掺量的增加,第二放热峰的高度呈先上升后下降的趋势,其中CP5的第二放热峰最高㊂图8(b)展示了72h 内光催化净浆的累计放热量㊂CP5的放热量最大,达到了307.9J /g,是空白对照组CP0的1.18倍㊂虽然S-g-C 3N 4/MgAl-CLDH 本身没有水化活性,但其具有晶核作用,为水泥的水化产物提供了附着点,因此加速了水泥的水化㊂但当光催化剂掺量超过5%后,累计放热量开始下降㊂具体而言,与CP5相比,CP7的放热量下降了5.4%㊂这主要是因为,S-g-C 3N 4/MgAl-CLDH 细度高且疏松多孔(见图2(b)),其需水量较高,过多S-g-C 3N 4/MgAl-CLDH 的掺入降低了实际水灰比,因此对水泥的水化产生了不利影响,使得砂浆3d 抗压强度降低㊂图8㊀不同光催化剂掺量下净浆的早期放热过程Fig.8㊀Early exothermic process of pastes with different photocatalystdosages 图9㊀不同光催化剂掺量下净浆在28d 的XRD 谱Fig.9㊀XRD patterns of pastes with different photocatalyst dosages at 28d图9为不同光催化剂掺量下净浆在28d 的XRD谱㊂如图所示,光催化砂浆的水化产物和普通砂浆相似,包括AFt㊁AFm㊁氢氧化钙(CH)㊁碳酸钙(calcite)㊂这证明了S-g-C 3N 4/MgAl-CLDH 并未参与水化反应,因此S-g-C 3N 4/MgAl-CLDH 的掺入不会对水化产物类型造成影响㊂此外,可以明显看出,虽然CP3中CH 峰的强度与CP0相似,但随着掺量的升高,CH 峰的强度开始单调下降㊂这表明过多S-g-C 3N 4/MgAl-CLDH 会抑制水泥的后期水化,导致CH 产量下降㊂为量化光催化砂浆的水化程度,进行了TGA 测试㊂图10(a)和(b)分别为不同光催化剂掺量下净浆在28d 的DTG 和TG 曲线㊂其中,100~210ħ㊁400~500ħ㊁600~700ħ的质量损失分别与水合硅酸钙(C-S-H)凝胶㊁CH㊁碳酸钙的脱水有关[18]㊂各光催化净浆的这三个峰的强度均低于CP0㊂此外,根据式(2)[19]可以计算出光催化净浆的水化程度,结果如图11所示㊂W =m 30-m 850m 30-LOI 1-LOI ˑ100%(2)50㊀水泥混凝土硅酸盐通报㊀㊀㊀㊀㊀㊀第43卷式中:W 为水化程度,%;m 50和m 850分别为50和850ħ时试样的质量,mg;LOI 为水泥的烧矢量(1.08),%㊂图10㊀不同光催化剂掺量下净浆在28d 的DTG 和TG 曲线Fig.10㊀DTG and TG curves of pastes with different photocatalyst dosages at 28d 图11㊀不同光催化剂掺量下净浆在28d 的水化程度Fig.11㊀Hydration degree of pastes with different photocatalyst dosages at 28d 可以看出,随着S-g-C 3N 4/MgAl-CLDH 掺量的增加,光催化净浆的后期水化程度呈单调下降的趋势㊂特别是CP7,其水化程度只占CP0的89%㊂这说明过量的S-g-C 3N 4/MgAl-CLDH 团聚产生絮凝体,抑制了水泥的后期水化,导致高掺量光催化砂浆的后期强度下降㊂图12是不同光催化剂掺量下净浆在28d 的SEM照片㊂可以明显看出,与CP3(见图12(a))相比,CP7(见图12(b))表面出现了成片的絮凝体,使得内部更加疏松多孔㊂这是因为当掺量较多时,S-g-C 3N 4/MgAl-CLDH 在水泥中的团聚现象较为严重,导致砂浆内部结构分布不均匀,产生大量孔隙㊂此外,较高的S-g-C 3N 4/MgAl-CLDH 掺量会影响水泥的水化,减少水化产物的产量,降低基体的密实度,从而使光催化砂浆的后期强度(28d)下降㊂但是,少量纳米材料的掺入(3%)对水泥砂浆的孔隙也能起到一定的物理填充效果[20],这抵消了其对水泥水化产生的不利影响,从而使砂浆的后期强度得到提高(见图7)㊂图12㊀不同光催化剂掺量下净浆在28d 的SEM 照片Fig.12㊀SEM images of pastes with different photocatalyst dosages at 28d 3㊀结㊀论1)与S-g-C 3N 4相比,S-g-C 3N 4/MgAl-CLDH 的光生电子-空穴对复合率显著降低,这有利于提升其光催化活性㊂此外,砂浆的光催化降解NO x 性能随着S-g-C 3N 4/MgAl-CLDH 掺量的增加先提高后降低,当光催化第1期林淑瑾等:负载S-g-C3N4/MgAl-CLDH光催化砂浆的去污及水化性能研究51㊀剂掺量从5%增加到7%时,砂浆的NO x降解率从48.2%下降到37.8%2)由于晶核作用,S-g-C3N4/MgAl-CLDH的掺入使得水泥的水化速度和早期强度(1d)明显提升,当掺量从0%增加到7%时,1d抗压强度从15.3MPa上升到18.3MPa㊂此外,由于S-g-C3N4/MgAl-CLDH的需水率较高,过量掺入S-g-C3N4/MgAl-CLDH使得基体的实际水胶比降低,导致水泥放热量和砂浆3d强度下降㊂3)随着S-g-C3N4/MgAl-CLDH掺量的增加,水泥28d的水化程度呈下降趋势㊂此外,在适当掺量(3%)下,S-g-C3N4/MgAl-CLDH的掺入对水泥砂浆的孔隙也起到一定的微填充效果,这抵消了其对水泥水化产生的不利影响,从而使CM3后期强度得到提高㊂与对照组CM0相比,CM3的3㊁7和28d强度分别提高了18.2%㊁11.3%和6.5%㊂参考文献[1]㊀BONINGARI T,SMIRNIOTIS P G.Impact of nitrogen oxides on the environment and human health:Mn-based materials for the NO x abatement[J].Current Opinion in Chemical Engineering,2016,13:133-141.[2]㊀秦泽敏.石墨相氮化碳基材料光催化还原除铀研究进展[J].硅酸盐通报,2022,41(12):4458-4468.QIN Z M.Research progress on photocatalytic reduction of uranium by g-C3N4based materials[J].Bulletin of the Chinese Ceramic Society, 2022,41(12):4458-4468(in Chinese).[3]㊀FU J W,YU J G,JIANG C J,et al.G-C3N4-based heterostructured photocatalysts[J].Advanced Energy 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聚集态结构热模拟演化特征HRTEM分析——以内蒙古伊敏煤为例

FAN Jing,LI Meifen,ZENG Fangui,et al. High resolution TEM image analysis of the aggregate structural character
istics under heat treatment:A case study of Yimin coal[ J]. Journal of China Coal Society,2021,46 ( 6) : 1978-
热解过程中气态产物的生成密切相关;384-456 阶段,1x1芳香层片增多，而较大尺寸的芳香层片减少，弯曲度为1.0-1.2的芳香层片增多，较大弯曲度的芳香层片减少，有序性变好，这些现象均与芳香结构内竣基或其他含氧杂环裂解有关，与此同时芳香层片层间距减小，堆垛高度增加；
456-528七阶段,体系内芳香甲基或芳香甲基瞇键断裂生成甲烷，新形成的芳香结构聚合，导致lx 1芳香层片减少，较大尺寸芳香层片增多，弯曲度为1.0-1.2的芳香层片减少，较大弯曲度的芳香
组在加热过程中其芳香层片的变化特征。这些工作使我们对热处理过程中煤聚集态结构的变化有了一定的认识,但是对聚集态结构中芳香层片的弯曲度、方向性等在加热过程中的变化特征鲜见报道。因此, 笔者以伊敏煤为研究对象，利用HRTEM详细分析加热过程中聚集态结构变化特征,期望为煤高效洁净利用提供新的依据。
Abstract:The aggregate structural characteristics of Yimin lignite under heat treatment at 384,456,528 and 600 弋 were examined by High-Resolution Transmission Electron Microscopy ( HRTEM) technique in this paper. Thermo gravimetry coupled with mass spectrometry ( TG-MS) was employed to measure the gaseous evolution characteristics from 30 °C to 900 °C. The results indicated that the length, crooked degree, orientation distribution, layer spacing and

热解过程煤焦微观结构变化的XRD和Raman表征

热解过程煤焦微观结构变化的XRD和Raman表征刘冬冬;高继慧;吴少华;秦裕琨【摘要】To deeply understand the changes of char microstructure, the pyrolysis experiments of Huolinghe lignite ( HLH) , Jixi bituminouscoal( JX) , Datong bituminous coal ( DT) and Jincheng anthracite ( JC) were carried out at 25~1 600 ℃. The microstructure information of char was obtained by X-ray diffraction ( XRD ) and Raman spectroscopy ( Raman ) ,of which the relationship was studied. The result demonstrates that the microstructure changes of char have obvious threestages:depolymerization and liquidity, thermal condensation and aromatization, and graphitization. When La < 3 nm, ID1/IG and ID4/IG increase with the increase of La;When La > 3 nm, ID1/IG and ID4/IG decrease with the increase of La, indicating that the mode of connection and the number of defects are relate to the change of the size of aromatic layers at different scales. Lc is inversely proportional to ID3/IG and thetotal integrated area of Raman, indicating that the amorphous sp2 carbon atoms exist in the interlayer of the aromatic layer, which is related to the activity of the aromatic structure.%为深入了解煤焦微观结构在热解过程的变化规律，对霍林河褐煤（ HLH）、大同烟煤（ DT）、鸡西烟煤（ JX）和晋城无烟煤（JC）进行热解实验（25～1600℃），采用X射线衍射（XRD）和拉曼光谱（Raman）获取煤焦微观结构信息，并对两者数据的关联性进行分析．结果表明，热解过程煤焦微观结构的变化存在明显的3个阶段，分别对应解聚与流动、热缩聚与芳构化、石墨化．当La ＜3 nm，ID1／IG和ID4／IG随La的增大而增加；当La ＞3 nm，ID1／IG和ID4／IG随La的增大而减小，表明层片在不同尺寸内发生改变，其相互连接方式和缺陷数量也不相同．Lc 分别与ID3／IG 和Raman谱峰总积分面积成反比，表明无定形sp2碳原子多存在于芳香片层的夹层间，且与芳香结构活性有关．【期刊名称】《哈尔滨工业大学学报》【年(卷),期】2016(048)007【总页数】7页(P39-45)【关键词】煤热解;微观结构;X射线衍射;拉曼光谱;相关性【作者】刘冬冬;高继慧;吴少华;秦裕琨【作者单位】哈尔滨工业大学能源科学与工程学院，哈尔滨150001;哈尔滨工业大学能源科学与工程学院，哈尔滨150001;哈尔滨工业大学能源科学与工程学院，哈尔滨150001;哈尔滨工业大学能源科学与工程学院，哈尔滨150001【正文语种】中文【中图分类】TQ530.2热解是煤燃烧、气化、活化前必经的热化学过程[1]．从晶体结构角度,煤焦内发生了芳香结构的解聚和缩合、芳香层片的移动和交联等[2]．从不同振动形式的碳结构角度,发生了晶体sp2杂化碳、孤立sp2杂化碳、无定形sp2和sp3杂化碳之间的相互转化[3]．X射线衍射(XRD)主要对晶体结构较敏感,拉曼光谱(Raman)对不同形式碳结构提供较好的表征[4]．由于煤燃烧、气化和活化的目的不同,对热解后煤焦结构要求也不同．如要合理地控制煤热解过程,制备出满足后续不同反应需求的煤焦结构,则需要建立XRD与Raman之间的关联,以深入认识热解过程煤焦微观结构的变化．Tuinstra等[5]和Yamauchi等[6]提出Raman特征峰的强度比ID1/IG与XRD得到的晶粒尺寸(La)呈负相关．Kinight等[7]研究得出ID1/IG与La的经验公式,但Cancado等[8]研究认为其具有局限性．同时Zickler等[9]研究表明,ID1/IG与La是存在正相关关系的．目前,关于建立XRD与Raman相互关联的研究还未得出较为一致的结论．分析认为,这与XRD与Raman各自所得参数间的差异有关．以往研究者分别使用XRD探究热解过程煤焦微晶结构参数变化[10-13]以及使用Raman探究热解过程煤焦内不同形式碳结构演变[6,14-16],结果表明,在相同温度区间内,不同样品的Raman 或XRD各自参数相比,其变化趋势有较大差异,并无较为一致的演变规律．分析认为,一方面,这与煤中灰分干扰有关．首先,热解过程煤不同种类(碱金属、碱土金属、高岭土等)和不同含量的灰分均会对煤焦结构的变化产生不同影响[17-20];其次,原料中高含量矿物质会对拉曼光谱产生荧光效应[21],干扰测试结果．另一方面,Zickler等[9]认为分峰拟合峰数量不同,会对结果产生重要影响,同时相对窄的热解温度区间也不利于全面认识煤焦微观结构的变化．本文选用4种煤为原料,使用HCl/HF对原煤进行脱灰处理,排除灰分干扰．在不同温度下(25～1 600 ℃)进行热解制焦实验,首先分别采用XRD和Raman表征焦炭微观结构,并通过多种分峰方法找到最佳拟合方式．然后通过分析Raman与XRD数据间存在的关联,获得关于热解过程煤焦微观结构变化的一些新发现及认识,进而指导煤的高效清洁利用．1.1 煤样及其处理方式实验选用霍林河褐煤、大同烟煤、鸡西烟煤和晋城无烟煤为原料．使用玛瑙研钵将原料煤研磨并筛分至150～180 μm．按照文献[22]对4种样品(分别记为HLH、JX、DT和JC)进行HCl/HF脱灰处理,其元素分析和工业分析结果如表1所示(其中氧元素由差减法获得)．经酸洗后4种煤灰分质量分数均低于1%．实验中所用盐酸、氢氟酸等均为国产分析纯．1.2 实验条件采用水平管式炉对样品进行热解实验．每次实验均使用3 g样品装入石英管反应器中,用600 mL/min高纯N2进行吹扫．以8 ℃/min从室温升至1 600 ℃后结束,并分阶段进行取样．当管式炉达到指定温度后,迅速取出石英管反应器,在高纯N2气氛下降至室温获得煤焦样品．1.3 测试分析方法对不同热解温度下所得煤焦样品进行相关分析测试．采用日本理学D/max 220型X射线衍射仪 (60 kV, 200 mA, Cu-Kα),扫描速度为3°/min,扫描范围为5°～80°．采用英国雷尼绍inVia显微拉曼光谱仪,激光波长532 nm,光谱分辨率选择为4 cm-1,扫描范围为500～4 000 cm-1．Raman测试中采用多点检测并取平均值,以保证数据准确性．2.1 煤焦XRD分析用XRD粉末衍射法考察4种酸洗煤及其焦炭晶体结构信息,XRD图谱见图1．不同热解温度下所得煤焦都具有两个特征峰,即002峰(19°～24°)和100峰(42°～45°)．002峰越窄且越高,说明芳香层片的定向程度越好;100峰越窄且越高,说明芳香层片的尺寸越大[23]．为进一步分析煤焦碳微晶结构的变化规律,参考Zhang等[17]的分峰拟合方法,使用Origin 9.1将XRD数据进行平滑,扣除背景,并分峰拟合处理,获得002峰和100峰的峰位和半峰宽．以HLH为例,分峰拟合结果见图2,衍射峰拟合度>0.996．在(a)中002峰左侧的γ(20 °)峰为微晶边缘连接的脂肪侧链等结构,造成002峰的不对称[24]．由Bragg定律和Scherrer[18]公式计算煤焦微晶结构参数,具体结果见图3,其中La表示层片直径,Lc表示层片堆叠高度,La/Lc为层片直径与堆叠高度比,A20/A24为γ峰与002峰面积比．由图1和3可看出,煤热解过程煤焦微观结构的变化具有明显阶段性．对于HLH、JX和DT,在热解初期(≤300 ℃),002峰较宽,参数Lc和A20/A24增大,La减小．可能由于煤有机质大分子结构发生解聚,使内部更多的脂肪族侧链得到释放所致．当热解温度继续升高至500 ℃,002峰变窄,参数A20/A24和La减小,Lc增加．这可能与烟煤的热塑性有关[25]．烟煤热解生成的小分子物质在芳香层间起到润滑剂作用,使其沿片层方向发生相对滑动,加速微晶结构的纵向堆叠和片层数增加[26]．由于解聚和流动作用,HLH、JX和DT的芳香结构单元呈横向断裂,纵向增厚的发展趋势(La/Lc减小)．由于煤种特性JC无流动物质生成,其在此阶段只表现出解聚特性．在800～1 000 ℃,4种煤焦的002峰变宽,100峰明显突出,La和A20/A24增加,Lc减小．这是由于煤焦内部发生缩聚反应,氢化芳香族的脱氢作用以及杂环的高温裂解等生成更多的芳环结构所致．而在纵向堆叠高度上的迅速减小是由于较薄的片层结构更易于移动,有利于后续高温形成堆叠规则的石墨结构[27-28]．因此,由于热缩聚等作用,4种煤焦的芳香结构单元均呈横向增长,纵向减薄的发展趋势(La/Lc 增大)．热解温度较高(1 200～1 600 ℃)时,4种煤焦的002峰和100峰越来越高而窄．A20/A24显著减小,La和Lc增加．可能是芳香结构单元纵向上相邻片层间夹层缺陷开始消失,使纵向上发生接合和缩聚．芳香结构单元的扩张生长是石墨化开始的标志[29]．因此,石墨化开始阶段4种煤焦的芳香结构单元纵向接合作用更为明显(La/Lc减小)．2.2 煤焦Raman分析图4表明不同热解温度下所制煤焦Raman光谱都有两个明显的特征峰,即D峰(～1 350 cm-1)和G峰(～ 1 580 cm-1)．观察可知,随着热解温度的升高,两个特征峰发生了明显变化,说明在这个过程中煤焦内不同碳结构间发生了相互转化．由于原始图谱是多个峰重叠的结果,因此需要通过进一步的分峰拟合以提取出不同碳结构的定量参数信息．对于不同波长的拉曼光谱所采用的拟合峰数量也不相同,通常对于波长为514 nm或532 nm的拉曼光谱采用2～5个子峰来拟合[16,30-31]．而对于1 064 nm近红外激光的光谱通常采用10个子峰进行拟合[17,32]．因此本文分别采用2～5个子峰(D1～D4和G)进行分峰拟合处理．不同特征的含义如下[3]: D1峰属于较大的芳环系统(≥6个),其与孤立sp2杂化键面内振动导致边缘或其他缺陷(如边缘碳原子或杂原子)相关．G峰与晶体sp2碳原子有关,表示高度有序的石墨层片碳网平面．D2峰(1 620 cm-1)一般都随D1峰一并出现,其与表面的石墨层E2g振动有关．D3(1 520 cm-1)峰表示煤焦芳香结构单元中较小的芳环系统(3～5个),属于sp2-sp3混合杂化的无定形碳结构．D4(1 200 cm-1)通常表示交联结构,其与sp3杂化轨道碳原子有关．图5所示,以 HLH 煤的拟合为例,首先对图谱进行归一化处理,然后进行不同数目的子峰拟合,得到相关系数(R2)．可以看出,采用5峰拟合其拟合度最高,可以获得全面的碳结构信息．由文献[21]可知,拉曼谱峰总面积大小与煤焦活性结构数量有关．由图6(a)可看出,在热解初期(≤500 ℃),活性结构数量先增多后降低．这与煤大分子结构的解聚和有机组分大量释放有关．而此阶段JC的谱峰总面积一直减小．在500～1 000 ℃煤焦活性结构数量增多,这与热缩聚反应生成大量芳香单元有关,随着石墨化进程的开始(≥1 200 ℃)芳香结构逐渐扩张,造成了谱峰总面积减小．图6(b)表示煤焦缺陷碳结构的相对含量,图6(c)表示煤焦无定形碳结构的相对含量．当热解温度≤500 ℃时,ID1/IG和ID3/IG增加．这是由于大分子结构发生解聚,形成的小分子物质在煤焦表面会发生沉积现象所致．由于JC煤种特性,此阶段以解聚为主,故ID1/IG和ID3/IG一直减小．当热解温度为500～1 000 ℃,ID1/IG显著增加,ID3/IG先增加后减小．芳香结构发生缩合和杂环断裂反应,产生了孤立的sp2碳原子和无定形的sp2碳原子．当热解温度继续增加,由于缩聚反应导致小芳环系统向大芳环系统转变[3]．当热解温度≥1 200 ℃时,ID1/IG和ID3/IG 显著减小,表明无定形碳结构和缺陷结构开始向有序晶体sp2碳原子进行转变,即发生石墨化转变．4种煤焦的ID4/IG(即交联结构)随热解温度变化见图6(d),在低于500 ℃时,ID4/IG 逐渐减小,这是由于芳香结构的解聚和移动,导致相邻碳晶体之间的交联结构断裂．在500～1 000 ℃,ID4/IG明显增大说明由交联键构成的新芳香结构大量生成．在高温下(≥1 200 ℃),ID4/IG逐渐减小说明芳香结构间交联键断裂,导致大幅合并和石墨化．2.3 XRD与Raman关联分析根据2.1和2.2结果,由于JC煤种特性与其他3者差别较大,本节只分析HLH、JX 和DT的XRD和Raman参数的相关性,如图7所示．图7(a)为La与ID1/IG的相关性,当La<3 nm时, ID1/IG随La的增大而增加．当La>3 nm时,ID1/IG随La 的增大而减小．图7(b)为La与ID4/IG的相关性,当La<3 nm时, ID4/IG随La的增大而增加．当La>3 nm时,ID4/IG随La的增大而减小．分析认为,当芳香片层较小时(<3 nm),其层片增大是由交联键相互连接所致,同时导致边缘缺陷增多．当芳香片层较大时(>3 nm),其片层增大是由于交联键断裂层片间相互合并所致,而导致边缘缺陷减少．图7(c)为La/Lc与ID4/IG的相关性,当La/Lc<2时,ID4/IG随La/Lc的增大而增加．当La/Lc>2时,ID4/IG随La/Lc的增大而减小．这说明芳香结构的形状与交联键有密切关系．图7(d)为Lc与谱峰总积分面积的相关性,随着Lc的增加,谱峰总积分面积逐渐减小．说明芳香层片在纵向上的接合、缩聚和生长导致芳香结构单元边缘活性降低．图7(e)为Lc与ID3/IG的相关性,随着Lc的增加,ID3/IG逐渐减小．表明无定形的sp2碳原子多存在于芳香层片的夹层间．1)XRD和Raman数据表明,热解过程煤焦微观结构的变化具有明显3个阶段．当热解温度低于500 ℃时,芳香结构主要以解聚反应为主,促进了微晶层片的移动．在500～1 000 ℃,热缩聚反应会导致更多由交联键连接的芳环结构生成．当热解温度高于1 200 ℃时,煤焦石墨化特征逐渐增强,交联键断裂及单元结构扩张．由于JC 煤种特性差异,当温度低于500 ℃时以解聚为主,其后微观结构变化与另外3种煤相似．2)XRD和Raman相关性表明,当La<3 nm, ID1/IG和ID4/IG随La的增大而增加,层片间以交联键连接为主,导致缺陷增多．当La>3 nm,ID1/IG和ID4/IG随La的增大而减小,层片间以相互合并为主,导致交联键和缺陷减少．当La/Lc<2,ID4/IG 随La/Lc的增大而增加．当La/Lc>2,ID4/IG随La/Lc的增大而减小．Lc与ID3/IG和谱峰总积分面积成反比,表明无定形sp2碳原子多存在于芳香片层间,而片层在纵向的变化与芳香结构活性有关．。

库拜煤田拜城县顺发煤矿A3煤层煤岩煤质特征及其清洁利用方法研究

104能源是国民经济和社会发展的基础，我国能源状况是富煤缺油少气[1]，煤炭在能源消费结构中占三分之二。

随着国家生态文明建设的不断推进及“双碳”政策的实施，对煤炭进行清洁高效利用已成为我国煤炭工业绿色发展的必由之路[2]。

煤气化、液化是煤炭清洁利用的重要方式，而煤岩、煤质特征是研究煤炭清洁利用方式的重要依据[3-4]。

通过对顺发煤矿A3煤层煤岩煤质的系统分析，对顺发煤矿煤炭的资源分布、煤的分类以及选取清洁利用方法具有指导意义。

1 工程概况顺发煤矿呈现近南西-北东向的条带状，东部和北部以铁列克河为界，南部和西部为人为边界。

井田东西长约3.99km，南北宽0.86km，面积3.4381Km 2。

主要含煤地层为侏罗系下统塔里奇克组下段（J 1t 1）A 1、A 2、A 3号煤层，目前主要研究A3煤层，煤层总厚5.80~6.20m，煤层平均总厚5.99m，全区可采，煤层稳定，煤层对比可靠。

2 A3煤层特征A3煤层位于含煤地层侏罗系下统塔里奇克组下段（J 1t 1），A2煤层之上，从区域上来讲，该煤层是唯一的较厚煤层，厚度特征明显，并且以光泽暗淡，丝炭组分体积分数高为独有的煤岩特征。

全区分布、厚度变化不大，3.60~7.95m，平均厚度6.10m，结构简单，夹矸0~1层，煤层厚度变异系数2.90%，属于稳定型煤层。

3 A3煤层的煤岩特征3.1 煤的物理性质及煤岩特性煤的颜色为黑色，条痕色为棕色-褐色，半玻璃-油脂光泽，断口阶梯状，具有条带状结构，层状构造，内生裂隙不发育，煤芯大多呈现碎块状、粉末状。

视相对密度值1.27~1.50t/m 3。

3.1.1 宏观煤岩特征A3煤层主要以暗煤、亮煤为主，夹有少量丝炭，煤岩类型为半暗煤。

3.1.2 显微煤岩组分A3煤层显微组分[5]鉴定结果：有机质组分占73.02%~89.74%，平均81.47%，无机质组分占9.99%~26.79%，平均18.24%。

有机组成以镜质组和惰质组为主，含少量半镜质组，壳质组为零，镜质组体积分数一般在2.2%~89.4%之间，平均49.37%；惰质组体积分数在10.3%~97.8%之间，平均48.66%；半镜质组体积分数在0%~11.5%，平均1.95%。

acs.energyfuels.6b00503外文

1. INTRODUCTION Zhundong coal is a new choice for energy production in China, owing to its large reserve of 3.9 × 1011 tons, high reaction activity, and easy burn-out.1 Given that the mass fraction of Na2O in ash (usually above 2%, even over 10% in some mine districts) is above that in other power coals in China, its utilization is dramatically limited by the severe fouling and slagging caused by the high-alkali coal in actual engineering projects.2−5 Since fouling and slagging during combustion cannot be eliminated eﬀectively, the technology of circulating ﬂuidized bed gasiﬁcation (CFBG) could be a choice to process the high-alkali Zhundong coal. The behavior of alkali metals (mainly sodium) during highalkali coal thermal conversion has been investigated extensively.2−17 Generally, sodium in coal can be classiﬁed as watersoluble, acid-soluble, ammonium-acetate (NH4Ac)-soluble, and insoluble sodium.2,7,8,18,19 Among the main mineral matter in coal, sodium (except the insoluble form) is strongly prone to sublimation, which will lead to a series of serious ash-related problems. As reported, water-soluble and organic alkali species can accelerate ash deposition.19 The majority of sodium in coal will be released in the form of NaCl at 800 °C.6,8 Hence, exploring the transformation and migration of alkali metals in high-alkali coal is rather important before application. Compared with other types of coal, alkali vapor from Zhundong coal will condense to form the stickier inner layer on the bare tube surfaces and the stickier coating surface of particles, which will enhance ash deposition.2 Wang et al.5 presented a temperaturedependent ash deposition mechanism from ash evaporation to condensation for Zhundong coal, and indicated that sulfate condensed at about 850 °C played an important role in ash deposition. According to the research results of Zhou et al.,3

煤焦油沥青制备中间相_英文_

1 1 2 2
Abstract : Mesophase pitch ( MP) was produced by heating coal tar pitch in a microautoclave furnace at various temperatures
terize MP , indicating that the coal tar pitch was transformed into MP through dehydrogenative condensation reactions . The opti2 mum yield was found at 400 ℃ and 7 h . and residence times under nitrogen atmosphere . FTIR , Polarized Light Microscopy , XRD and S EM were employed to charac2
Keywords : Coal tar pitch ; Mesophase CLC number : TQ 522. 65 Document code : A
1 Introduction
Mesophase pitch is one of the most important pre 2 cursors , making high technology products , among which pitch2based carbon fibers are a new of high performance materials . Among precursor materials for carbon fibers [1 ] such as synthetic polyvinyl chloride , polyacryloni2 [2 ] [3 ] [4 ] triles , naphthene , coal tar pitch and petroleum [5 ,6 ,7 ] pitch . The coal tar and petroleum pitches are the cheapest raw materials . [8 ] As proposed by L . S . Singer , “pitch ”is black material ( between tar and mesophase ) consisting of complex mixture of many aromatic hydrocarbons . Brook [9] and Taylor have found that although pitch is consid 2 ered to be isotropic in nature , it produces anisotropic liq2 uid crystalline phase ( mesophase ) ; when it is heated to above 350 ℃ . The composition of pitch depends upon the source of material , from which it has been derived and also up 2 on the method , by which low molecular weight compo 2 nents have been removed . Coal tar , petroleum and natu2 rally occurring pitches have been used by H . H . Lowery [10 ,11 ] [12 ] and Diefendforf . J . B . Barr et al investigated that by heating the pitches above 350 ℃, the molecules un2 derwent a succession of dehydrogenation condensation reactions with activation energy of 40 to 50 kcalΠ mol , wherein the isotropic pitches are converted into liquid crystalline phase . [13 ] C . Y. Wang et al also investigated the petroleum2 based mesophase pitch , prepared by two stage thermal condensation at a temperature of 430 ℃for 3 h under ni2 trogen flow , and at 410 ℃ for 5 h under vacuum . The properties of isotropic and anisotropic pitch were ana 2

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＠
２０１５Ｓｃｉ．Ｔｅｃｈ．Ｅｎｇｒｇ．
矿冶技术
煤层气钻探无固相聚合物钻井液的研制与性能评价
王胜郭凯彬袁超鹏陈礼仪张川
（成都理工大学地质灾害防治与地质环境保护国家重点实验室，成都６１００５９）
上，制作标准岩样，通过线性膨胀试验对钻井液的防塌性能进行评价。最后，评价了处理剂的添加方法对钻井液性能的影响。
结果表明，研制的无固相聚合物钻井液优化配方流变性能好，防塌性能强，配方简单，配制方便，适于煤层气钻探。
关键词
煤层气钻探无固相聚合物钻井液流变性中图法分类号ＴＤ１６６；文献标志码Ａ
１．３试验方法１．３．１流变性评价方法
地质灾害防治与地质环境保护国家重点实验室自由
探索课题（ｓＫＬＧＰ２０ｌ２Ｏ７）和地调子题（１２１２０１１３０１７３００）资助第一作者简介：王胜（１９８２一），副教授，博士。研究方向：钻井液。
防塌性
处理剂添加方法
煤层气是煤炭的共、伴生气体资源，俗称 “ 瓦斯” ¨ 。在煤层气钻探施工过程中，钻井液是首先与煤层气储层接触的流体，其优劣对煤层气开发具有重要的影响。煤系地层水敏性强，毛细效应突出，容易吸附水，含煤岩系中的黏土、泥岩等遇水后极易产生吸水膨胀、垮塌、埋钻等事故ｊ。

煤液化沥青烯的荧光光谱表征及缔合结构研究

王知彩，崔雪萍，恒福，水王祖山，雷智平，康士刚
安徽工业大学化学与化工学院，安徽省煤洁净转化与利用重点实验室，安徽马鞍山２３０４０２
摘要通过分子荧光光谱和紫外可见吸收光谱表征、究了煤液化沥青烯结构及缔合行为。研结果发现：煤液化沥青烯属于萘环结构为主的芳香化合物混合体系，具有强的荧光效应；剂与沥青烯分子能够形成激溶态复合物，导致沥青烯荧光峰红移和荧光猝灭；沥青烯分子问存在非共价键缔合作用，高温液化沥青烯芳香度高，缔合作用强；沥青烯分子间缔合属于逐步缔合过程，不存在“ 临界缔合浓度 ” 其表观荧光强度随浓度，
１２荧光光谱分析。
光发色体。ｏｈ等口］Ｇｈｓ通过荧光光谱研究了不同溶剂中煤焦油沥青烯缔合行为，测定了沥青烯起始缔合浓度。本文研究了神府煤液化沥青烯的分子荧光光谱及其缔合结构特征。
样品的荧光光谱分析测定在Ｈｉｃｉ－６０型荧光光谱ｔｈ４０ａＦ分析仪上完成。使用１０Ｗ氙弧灯为激发光源，Ｐ５ＭＴ电压：
ＭＰ，液化时间３ｎａ０ｍｉ。液化产液化产物经索氏抽提，截取甲苯可溶正己烷不溶物作为试验沥青烯。不同温度下液化ＡＳ的元素分析列于表１。ＡＳ首先溶解于一定溶剂，超声处
研究沥青烯结构特点不仅有利于探索提高煤液化效率的有效
措施，且有助于深入认识复杂的煤分子结构。虽然”Ｃ核而
第３卷，６０第期
２０１０年６月
光
谱
学
与
光
谱
分
析

南非规范解读

•
பைடு நூலகம்
3. METHODOLOGY
• The study was conducted through a detailed assessment of the content, quality and relevance of each guideline.
•
•
Involved the preparation of a template that was used in interviews with specific industry players. Organizations and forums that were approached include: - Roads Coordinating Committee (RCC) and its relevant sub-committees - South African Bitumen and Tar Association (SABITA) - CSIR - Provincial Roads Authorities - Road Pavements Forum - SANRAL - Cement and Concrete Institute (C&CI) - SATCC TU
COTO TMH DOCUMENTS • DRAFTS - TMH 3: Traffic Axle Load Surveys for Pavement Design. - TMH 6: Special Methods for Testing Roads. - TMH 8: Verkeerstellings Presedures vir Buitestedelike Paaie. - TMH 12: Pavement Management Systems: Standard Visual Assessment Manual for Unsealed Roads, Version 1.

Tar sand(油砂介绍)

Kirk-Othmer Encyclopedia of Chemical Technology.Copyright c John Wiley&Sons,Inc.All rights reserved.TAR SANDSIn addition to conventional petroleum(qv)and heavy crude oil,there remains another subclass of petroleum, one that offers to provide some relief to potential shortfalls in the future supply of liquid fuels and other products.This subclass is the bitumen found in tar sand deposits(1,2).Tar sands,also known as oil sands and bituminous sands,are sand deposits impregnated with dense,viscous petroleum.Tar sands are found throughout the world,often in the same geographical areas as conventional petroleum.Petroleum,and the equivalent term crude oil,cover a vast assortment of materials consisting of gaseous, liquid,and solid hydrocarbon-type chemical compounds that occur in sedimentary deposits throughout the world(3).When petroleum occurs in a reservoir that allows the crude material to be recovered by pumping operations as a free-ﬂowing dark-to light-colored liquid,it is often referred to as conventional petroleum.Heavy oil is another type of petroleum,different from conventional petroleum insofar as theﬂow properties are reduced.A heavy oil is much more difﬁcult to recover from the subsurface reservoir.These materials havea high viscosity and low API gravity relative to the viscosity and API gravity of conventional petroleum(Fig.1)(3,4),and recovery of heavy oil usually requires thermal stimulation of the reservoir.The deﬁnition of heavy oil is usually based on API gravity or viscosity,but the deﬁnition is quite arbitrary. Although there have been attempts to rationalize the deﬁnition based on viscosity,API gravity,and density(2, 3),such deﬁnitions,based on physical properties,are inadequate,and a more precise deﬁnition would involve some reference to the recovery method.In a general sense,however,the term heavy oil is often applied to a petroleum that has a gravity <20◦API.The term heavy oil has also been arbitrarily used to describe both the heavy oil that requires thermal stimulation for recovery from the reservoir and the bitumen in bituminous sand(also known as tar sand or oil sand)formations,from which the heavy bituminous material is recovered by a mining operation. Extra heavy oil is the subcategory of petroleum that occurs in the near-solid state and is incapable of freeﬂow under ambient conditions.The bitumen from tar sand deposits is often classiﬁed as an extra heavy oil.Tar sand,also variously called oil sand(in Canada)or bituminous sand,is the term commonly used to describe a sandstone reservoir that is impregnated with a heavy,viscous black extra heavy crude oil,referred to as bitumen(or,incorrectly,as native asphalt).Tar sand is a mixture of sand,water,and bitumen,but many of the tar sand deposits in the United States lack the water layer that is believed to cover the Athabasca sand in Alberta,Canada,thereby facilitating the hot-water recovery process from the latter deposit.The heavy asphaltic organic material has a high viscosity under reservoir conditions and cannot be retrieved through a well by conventional production techniques.It is incorrect to refer to bitumen as tar or pitch.Although the word tar is somewhat descriptive of the black bituminous material,it is best to avoid its use in referring to natural materials.More correctly,the name tar is usually applied to the heavy product remaining af.ter the destructive distillation of coal(qv)or other organic matter.Pitch is the distillation residue of the various types of tar(see Tar and pitch).Physical methods of fractionation of tar sand bitumen usually indicate high proportions of nonvolatile asphaltenes and resins,even in amounts up to50%wt/wt(or higher)of the bitumen.In addition,the presence of12TAR SANDSFig.1.Relative viscosity data for conventional petroleum,heavy oil,and bitumen.ash-forming metallic constituents,including such organometallic compounds as those of vanadium and nickel, is also a distinguishing feature of bitumen.Asphalt(qv)is prepared from petroleum and often resembles bitumen.When asphalt is produced sim-ply by distillation of an asphaltic crude,the product can be referred to as residual asphalt or straight-run petroleum asphalt.If the asphalt is prepared by solvent extraction of residua or by light hydrocarbon(propane) precipitation,or if blown or otherwise treated,the term should be modiﬁed accordingly to qualify the product, eg,propane asphalt.1.Origin of BitumenThere are several general theories regarding the origin of the bitumen.One theory is that the oil was formed locally and has neither migrated a great distance nor been subjected to large overburden pressures.Because un-der these conditions the oil cannot have been subjected to any thermal effects with the resulting decomposition or molecular changes,it is geologically young and therefore dense and viscous.Another theory promotes the concept of a remote origin for the bitumen,or,more likely,the bitumen pre-cursor,both geographically and in geological time.The bitumen precursor,originally resembling a conventional crude oil,is assumed to have migrated into the sand deposit,which may originally have beenﬁlled with water. After the oil migrated,the overburden pressures were relieved,and the light portions of the crude evaporated, leaving behind a dense,viscous residue.TAR SANDS3 Table1.Bitumen vs Conventional Petroleum PropertiesProperty Bitumen Conventionalgravity,API8.625–37distillation Vol%IBP a,◦C5221102933043750543viscosity,suspensionat38◦C35,000<30at99◦C513pour point,◦C10≤0elemental analysis,wt%carbon83.186hydrogen10.613.5sulfur 4.80.1–2.0nitrogen0.40.2oxygen 1.1hydrocarbon type,wt%asphaltenes19≤5resins32oils49metals,ppmvanadium250≤100nickel100iron75copper5ash,wt%0.750Conradson carbon,wt%13.51–2net heating value,kJ/g b40.68ca45.33a IBP=initial boiling point.b To convert kJ/g to btu/lb,multiply by430.2.Included in the remote origin theory is the postulate that the light hydrocarbons were destroyed by bacteria carried into the petroleum reservoirs in oxygenated,meteoric waters.The remote origin theory would explain the water layer surrounding sand grains in the Athabasca deposit.However,because the metals and porphyrin contents of bitumen are similar to those of some conventional Alberta crude oils of Lower Cretaceous age and because Athabasca bitumen has a relatively low coking temperature,the bitumen may be of Lower Cretaceous age.This is the age of the McMurray formation(Canada),which is geologically young.This evidence supports the theory that the oil was formed in situ and is a precursor,rather than a residue of some other oil. The issue remains unresolved as of this writing(ca1997).2.OccurrenceMany of the reserves of bitumen in tar sand formations are available only with some difﬁculty,and optional reﬁnery methods are necessary for future conversion of these materials to liquid products,because of the substantial differences in character between conventional petroleum(qv)and bitumen(Table1).Because of the diversity of available information and the continuing attempts to delineate the various world oil sands deposits,it is virtually impossible to reﬂect the extent of the reserves in terms of barrel units with4TAR SANDSFig. 2.Principal tar sand deposits of the world,where•represents>2,385,000m3(>15×106bbl)bitumen; ,probably <159,000m3(<1×106bbl)bitumen;and ,reported occurrence information limited.Table2.Tar Sand Deposits and Mode of Entrapment aNumber Deposit Location1.stratigraphic trap:structure of littleimportance;short-distance migrationassumedSunnyside,P.R.Springs,Santa Cruz2.structural/stratigraphic trap:folding/faulting and unconformity equallyimportant Oﬁcina–Temblador tar,Bemolanga, Asphalt Ridge,Melville Island, Guanoco,Kentucky deposits3.structural trap:structure important;long-distance migration assumed;unconformity may be absentWhiterocks,La Brea4.intermediate between1and2Athabasca,Edna,Sisquoc,Santa Rosa5.intermediate between2and3Selenizza,Dernaa See Fig.3.a great degree of accuracy.The potential reserves of hydrocarbon liquids that occur in tar sand deposits have, however,variously been estimated on a world basis to be in excess of477×109m3(3×1012bbl).Reserves that have been estimated for the United States are believed to be in excess of795×104m3(50×106bbl),although estimates vary.Bitumen reserves throughout the world can compare favorably with reserves of conventional crude oil.Tar sand deposits are widely distributed throughout the world(Fig.2)(5,6)and the various deposits have been described as belonging to two types:stratigraphic traps and structural traps(Table2;Fig.3)(7). However,there are the inevitable gradations and combinations of these two types of deposits,and thus a broad pattern of deposit entrapment is believed to exist.In general terms,the entrapment character of the very large tar sand deposits involves a combination of both stratigraphic and structural traps.TAR SANDS5Fig.3.Types of traps for tar sand deposits,where represents a stratigraphic trap,×,an intermediate between stratigraphic and structural/stratigraphic traps; ,a structural/stratigraphic trap;•,an intermediate between struc-tural/stratigraphic and structural traps;and ,a structural trap.The largest tar sand deposits are in Alberta,Canada,and in Venezuela.Smaller tar sand deposits occur in the United States(mainly in Utah),Peru,Trinidad,Madagascar,the former Soviet Union,Balkan states, and the Philippines.Tar sand deposits in northwestern China(Xinjiang Autonomous Region)also are large;at some locations,the bitumen appears on the land surface around Karamay,China.The largest deposits are in the Athabasca area in the province of Alberta,Canada,and in the Orinoco region of east central Venezuela.The Athabasca deposit,along with the neighboring Wabasca,Peace River,and Cold Lake heavy oil deposits,have together been estimated to contain1.86×1011m3(>1.17×1012bbl)of bitumen.The Venezue-lan deposits may at least contain>1.60×1011m3(1.0×1012bbl)bitumen(2).Deposits of tar sand,each containing>3×106m3(20×106bbl)of bitumen,have also been located in the United States,Albania,Italy,Madagascar,Peru,Romania,Trinidad,Zaire,and the former Soviet Union,comprising a total of ca 450×109m3(2.8×1012bbl).The Alberta(Athabasca)tar sand deposits are located in the northeast part of that Canadian province (Fig.4).These are the only mineable tar sand deposits undergoing large-scale commercial exploitation as of this writing(ca1997).The Athabasca deposits have been known since the early1800s.Theﬁrst scientiﬁc interest in tar sands was taken by the Canadian government in1890,and in1897–1898,the sands wereﬁrst drilled at Pelican Rapids on the Athabasca River.Up until1960,many small-scale commercial enterprises were attempted but not sustained.Between1957and1967,three extensive pilot-plant operations were conducted in the Athabasca region,each leading to a proposal for a commercial venture,eg,Suncor and Syncrude.The Venezuelan tar sands are located in a50–100-km belt extending east to west for>700km,imme-diately north of the Orinoco River.The precise limits of the deposit are not well deﬁned because exploration efforts in the past concentrated on light and medium crude accumulations.The geological setting of the Orinoco deposit is complex,having evolved through three cycles of sedimenta-tion.The oil is contained by both structural and stratigraphic traps,depending on location,age of sediment,and6TAR SANDSFig.4.Tar sand and heavy oil deposits in Alberta,Canada.degree of faulting.The tar sands are located along the southernﬂanks of the eastern Venezuelan basin,where three distinct zones are apparent from north to south:a zone of tertiary sedimentation,a central platform with transgressive overlapping sediments,and a zone of erosional remnants covered by sediments.The deposit also contains three systems of faulting.All the faults are normal and many are concurrent with deposition.Tar sands in the United States are contained in a variety of separate deposits in various states(Fig.5) but because many of these deposits are small,information on most is limited(8).Attempts at development of the deposits have occurred primarily in Utah.3.PropertiesTar sand has been deﬁned as sand saturated with a highly viscous crude hydrocarbon material not recoverable in its natural state through a well by ordinary production methods(2–8).Technically the material shouldTAR SANDS7 perhaps be called bituminous sand rather than tar sand because the hydrocarbon is bitumen,ie,a carbon disulﬁde-soluble oil.The data available are generally for the Athabasca materials,although workers at the University of Utah (Salt Lake City)have carried out an intensive program to determine the processibility of Utah bitumen and considerable data have become available.Bulk properties of samples from several locations(Table3)(9)show that there is a wide range of properties.Substantial differences exist between the tar sands in Canada and those in the United States;a difference often cited is that the former is water-wet and the latter,oil-wet(10).Canada United Statessand is water-wet,thus disengagement of bitumen isefﬁcient using hot-water process( caustic=sodium hydroxide; bitumen recovery>98%)sand is oil-wet,thus efﬁcient dis-engagement of bitumen requires high shear rates( caustic=sodium carbonate; bitumen recovery∼95%)formations usually unconsolidated formations usually consolidated tosemiconsolidated by mineralcementationfew deposits have been identiﬁed (Alberta contains ca0.4m3 bitumen)numerous deposits identiﬁed(33 major deposits=12m3bitumen; 20minor deposits=12m3bitu-men);total resource=6.5m3 bitumen(2.6m3measured and 3.8m3billion speculative)problems exist in settling and removal of clay from tar sand deposits and process streams little is known about the nature and effect on processing of claysbitumen properties fairly uniform (sulfur=4.5−5.5wt%,nitrogen= 0.1–0.5wt%;H/C ratio∼1.5;API gravity from6to12◦)bitumen properties diverse(sul-fur=0.5−10wt%,nitrogen0.1–1.3wt%;H/C ratio=1.3−1.6; API gravity from−2to14◦)bitumen deposits large with uniform quality;recovery and upgrading plants on-stream since 1970s bitumen deposits small and not of uniform quality;recovery and upgrading methods need to be site-speciﬁcThe sand component is predominantly quartz in the form of rounded or angular particles(11),each of which is wet with aﬁlm of water.Surrounding the wetted sand grains and somewhatﬁlling the void among them is aﬁlm of bitumen.The balance of the void volume in the Canadian sands isﬁlled with connate water plus,sometimes,a small volume of ually the gas is air but methane has been reported from some test borings in the Athabasca deposit.Some commercial gas deposits were developed in the late1980s.The sand grains are packed to a void volume of ca35%,corresponding to a mixture of ca83wt%sand;the remainder is bitumen and water which constitute ca17wt%of the tar sands.3.1.BitumenThere are wide variations both in the bitumen saturation of tar sand(0–18wt%bitumen),even within a particular deposit,and the viscosity.Of particular note is the variation of density of Athabasca bitumen with temperature,and the maximum density difference between bitumen and water(70–80◦C(160–175◦F));hence the choice of the operating temperature of the hot-water bitumen-extraction process.8TAR SANDSTable3.Bulk Properties of Tar SandsProperty Alberta Asphalt Ridge a P.R.Springs a Sunnyside a Tar SandTriangle a Texas Alabamabulk density,g/cm31.75–2.19 1.83–2.50porosity,vol%27–5616–276–3316–289–32326–25permeability, m2×10−16b 99–5,9004,905–5,950553–14,9025,265–7,4022,043–7,77731589.9–6,316speciﬁc heat,J/(g·◦C)c1.46–2.09 thermalconductivity,J/( s·◦C·cm)c 0.0071–0.0015a Deposit in Utah.b To convert m2to millidarcies,multiply by1.013×1012.c To convert J to cal,divide by4.184.Fig.5.Tar sand deposits in the United States.The API gravity of tar sand bitumen varies from5to ca10◦API,depending on the deposit,and the viscosity is very high.Whereas conventional crude oils may have a high(>100MPa·s(=cP))viscosity at40◦C, tar sand bitumen has a viscosity on the order of10−100kPa·s(105−106P)at formation temperature(ca0–10◦C),depending on the season.This offers a formidable obstacle to bitumen recovery and,as a result of the high viscosity,bitumen is relatively nonvolatile under conditions of standard distillation(Table4)(12,13), which inﬂuences choice of the upgrading process.TAR SANDS9 Table4.Distillation Data for Various BitumensCut point,◦C Athabasca,wt%distilled aNW Asphalt Ridge,wt%distilled aP.R.Springs,wt%distilled aTar Sand Triangle,wt%distilled a200 3.0 2.30.7 1.7225 4.6 3.3 1.4 2.9250 6.5 4.4 2.4 4.42758.9 5.8 3.8 5.930014.07.5 4.98.432525.98.8 6.812.435018.111.78.015.237522.413.810.118.640026.216.812.522.442529.119.516.026.945033.123.720.028.947537.028.422.532.350040.034.025.035.152542.940.027.338.553844.644.228.040.0538+55.455.872.060.9a Cumulative.3.2.MineralsUsually>99%of the tar sand mineral is composed of quartz sand and clays(qv).In the remaining1%,more than30minerals have been identiﬁed,mostly calciferous or iron-based(14).Particle sizes range from large grains(99.9%ﬁner than1000µm)to44µm(325mesh),the smallest size that can be determined by dry screening.The size between44and2µm is referred to as silt;sizes<2µm(equivalent spherical diameter)are clay.Clays(qv)are aluminosilicate minerals,some of which have deﬁnite chemical compositions.In regard to tar sands,however,clay is only a size classiﬁcation and is usually determined by a sedimentation method. According to the previous deﬁnition ofﬁnes,theﬁnes fraction equals the sum of the silt and clay fractions.The clay fraction over a wide range ofﬁnes contents is a relatively constant30%of theﬁnes.The Canadian deposits are largely unconsolidated sands having a porosity ranging up to45%and good intrinsic permeability.However,the deposits in Utah range from predominantly low porosity,low permeability consolidated sand to,in some instances,unconsolidated sands.In addition,the bitumen properties are not conducive toﬂuidﬂow under normal reservoir conditions in either Canadian or U.S.deposits.Nevertheless, where the general nature of the deposits prohibits the application of a mining technique,as in many of the U.S. deposits,a nonmining technique may be the only feasible bitumen recovery option(6).4.RecoveryOil prices and operating costs are the key to economic development of tar sand deposits.However,two technical conditions of vital concern for economic development are the concentration of the resource(percent bitumen saturation)and its accessibility,usually measured by the overburden thickness.The remoteness of the U.S.tar sands is often cited as a deterrent to development but topography of the site,overburden-to-ore body ratio,and richness of the ore body are also important.In the1990s context of mining tar sand deposits in the United States,the Utah deposits(Tar Sand Triangle,P.R.Springs,Sunnyside, and Hill Creek)generally have an overburden-to-net pay zone ratio above the0.4–1.0range,with a lean oil10TAR SANDSFig.6.Recovery processes.content.On the other hand,the Asphalt Ridge deposit is loosely consolidated and could be mined using aripper/front-end loader(without drilling and blasting)at the near-surface location of the deposit.Recovery methods are based either on mining combined with some further processing or operation onthe oil sands in situ(Fig.6).The mining methods are applicable to shallow deposits,characterized by anoverburden ratio(ie,overburden depth-to-thickness of tar sand deposit)of ca1.0.Because Athabasca tar sandshave a maximum thickness of ca90m and average ca45m,there are indications that no more than10%ofthe in-place deposit is mineable within1990s concepts of the economics and technology of open-pit mining.The bitumen in the Athabasca deposit,which has a gravity on the API scale of8◦,is heavier than waterand very viscous.Tar sand is a dense,solid material,but it can be readily dug in the summer months;duringthe winter months when the temperatures plunge to−45◦C,tar sand assumes the consistency of concrete.To maintain acceptable digging rates in winter,mining must proceed faster than the rate of frost penetration;ifnot,supplemental measures such as blasting are required.4.1.Nonmining MethodsNonmining(in situ)processes depend on injecting a heating-and-driver substance into the ground throughinjection wells and recovering bitumen through production wells.Such processes need a relatively thick layerof overburden to contain the driver substance within the formation between injection and production wells(2).In principle,the nonmining recovery of bitumen from tar sand deposits is an enhanced oil recoverytechnique and requires the injection of aﬂuid into the formation through an injection well.This leads to the insitu displacement of the bitumen from the reservoir and bitumen production at the surface through an egress(production)well.There are,however,several serious constraints that are particularly important and relateto the bulk properties of the tar sand and the bitumen.In fact,both recovery byﬂuid injection and the seriousconstraints on it must be considered in toto in the context of bitumen recovery by nonmining techniques(seePetroleum,enhanced oil recovery).Another general constraint to bitumen recovery by nonmining methods is the relatively low injectivityof tar sand formations.It is usually necessary to inject displacement/recoveryﬂuids at a pressure such thatfracturing(parting)is achieved.Such a technique,therefore,changes the reservoir proﬁle and introduces aseries of channels through whichﬂuids canﬂow from the injection well to the production well.On the otherTAR SANDS11 hand,the technique may be disadvantageous insofar as the fracture occurs along the path of least resistance, giving undesirable or inefﬁcientﬂow characteristics within the reservoir between the injection and production wells,which leave a part of the reservoir relatively untouched by the displacement or recoveryﬂuids.In steam stimulation,heat and drive energy are supplied in the form of steam injected through wells into the tar sand formation.In most instances,the injection pressure must exceed the formation fracture pressure in order to force the steam into the tar sands and into contact with the oil.When sufﬁcient heating has been achieved,the injection wells are closed for a soak period of variable length and then allowed to produce,ﬁrst applying the pressure created by the injection and then using pumps as the wells cool and production declines.Steam can also be injected into one or more wells,with production coming from other wells(steam drive). This technique is effective in heavy oil formations but has found little success during application to tar sand deposits because of the difﬁculty in connecting injection and production wells.However,once theﬂow path has been heated,the steam pressure is cycled,alternately moving steam up into the oil zone,then allowing oil to drain down into the heatedﬂow channel to be swept to the production wells.If the viscous bitumen in a tar sand formation can be made mobile by an admixture of either a hydrocarbon diluent or an emulsifyingﬂuid,a relatively low temperature secondary recovery process is possible(emulsion steam drive).If the formation is impermeable,communication problems exist between injection and production wells.However,it is possible to apply a solution or dilution process along a narrow fracture plane between injection and production wells.To date(ca1997),steam methods have been applied almost exclusively in relatively thick reservoirs containing viscous crude oils.In the case of heavy oilﬁelds and tar sand deposits,the cyclic steam injection technique has been employed with some success.The technique involves the injection of steam at greater than fracturing pressure,usually in the10.3–11.0MPa(1500–1600psi)range,followed by a soak period,after which production is commenced(15).Variations include the use of steam and the means of reducing interfacial tension by the use of various solvents.The solvent extraction approach has had some success when applied to bitumen recovery from mined tar sand but when applied to unmined material,losses of solvent and bitumen are always an obstacle.This approach should not be rejected out of hand because a novel concept may arise that guarantees minimal acceptable losses of bitumen and solvent.Combustion has also been effective for recovery of viscous oils in moderately thick reservoirs where reservoir dip and continuity promote effective gravity drainage,or where several other operational factors permit close well spacing.During in situ combustion orﬁreﬂooding,energy is generated in the formation by igniting bitumen in the formation and sustaining it in a state of combustion or partial combustion.The high temperatures generated decrease the viscosity of the oil and make it more mobile.Some cracking of the bitumen also occurs,and theﬂuid recovered from the production wells is an upgraded product rather than bitumen itself.The recovery processes using combustion of the bitumen are termed forward combustion or reverse combustion,depending on whether the combustion front moves with or counter to the direction of airﬂow. In either case,burning occurs at the interface where air contacts hot,unburned oil or,more likely,coke. Thus,if theﬂame front is ignited near the injection well,it propagates toward the production well(forward combustion).However,if the front is ignited near the production well,it moves in the opposite direction(reverse combustion).In forward combustion,the hydrocarbon products released from the zone of combustion move into a relatively cold portion of the formation.Thus,there is a deﬁnite upper limit of the viscosity of the liquids that can be recovered by a forward combustion process.On the other hand,because the air passes through the hot formation before reaching the combustion zone,burning is complete;the formation is left completely cleaned of hydrocarbons.In reverse combustion,some hydrocarbons are left in the formation.The theoretical advantage of reverse combustion is that the combustion products move into a heated portion of the formation and therefore are not subject to a strict viscosity limitation.However,most attempts to implement reverse12TAR SANDScombustion inﬁeld pilot installations have been unsuccessful.In many cases,the failure resulted from the onset of secondary combustion at the production well.Using combustion to stimulate bitumen production is attractive for deep reservoirs and in contrast to steam injection usually involves no loss of heat.The duration of the combustion may be short(days)depending on requirements.In addition,backﬂow of oil through the hot zone must be prevented or excessive coking occurs(15,16).Another variation of the combustion process involves use of a heat-up phase,then a blow-down (production)phase,followed by a displacement phase using aﬁre–waterﬂood(COFCAW process).4.2.Mining MethodsThe alternative to in situ processing is to mine the tar sands,transport them to a processing plant,extract the bitumen value,and dispose of the waste sand(17,18).Such a procedure is often referred to as oil mining.This is the term applied to the surface or subsurface excavation of petroleum-bearing formations for subsequent removal of the oil by washing,ﬂotation,or retorting treatments.Oil mining also includes recovery of oil by drainage from reservoir beds to mine shafts or other openings driven into the oil rock,or by drainage from the reservoir rock into mine openings driven outside the oil sand but connected with it by bore holes or mine wells.On a commercial basis,tar sand is recovered by mining,after which it is transported to a processing plant, where the bitumen is extracted and the sand discharged.For tar sands of10%wt/wt bitumen saturation,12.5 metric tons of tar sand must be processed to recover1m3(6.3bbl)of bitumen.If the sand contains only5% wt/wt bitumen,twice the amount of ore must be processed to recover this amount.Thus,it is clear that below a certain bitumen concentration,tar sands cannot be processed economically(19).The Athabasca tar sands deposit in Canada is the site of the only commercial tar sands mining operations. The Suncor operation(near Fort McMurray,Alberta),started production in1967.The Syncrude Canada project, located8km away,started production in1978.In both projects,about half of the terrain is covered with muskeg, an organic soil resembling peat moss,which ranges from a few centimeters to7m in depth.The primary part of the overburden,however,consists of Pleistocene glacial drift and Clearwater Formation sand and shale.The total overburden varies from7to40m in thickness,and the underlying tar sand strata averages about45m, although typically5–10m must be discarded because of a bitumen content below the economic cut-off grade of ca6%wt/wt.Mining of the Athabasca tar sands presents two principal issues:in-place tar sand requires very large cutting forces and is extremely abrasive to cutting edges,and both the equipment and pit layouts must be designed to operate during the long Canadian winters at temperatures as low as−40◦C.There are two approaches to open-pit mining of tar sands.Theﬁrst uses a few mining units of custom design,which are necessarily expensive,eg,bucket-wheel excavators and large drag lines in conjunction with belt conveyors.In the second approach,a multiplicity of smaller mining units of conventional design is employed at relatively much lower unit costs.Scrapers and truck-and-shovel operations have been considered. Each method has advantages and risks.Theﬁrst approach was originally adopted by Suncor and Syncrude Canada,Ltd.,with Suncor converting to large-scale truck and shovel technology in1993.In the Suncor pit design,the ore body is divided into two layers(benches),each nominally23m high. The pitﬂoor and the dividing plane between the upper and lower bench are roughly horizontal,and7300-t/h bucket-wheel excavators are employed as the primary mining equipment(Fig.7).Tar sands loosened from the face of each bench by the bucket-wheels are discharged onto a series of conveyors.The overburden is stripped by an electric shovel that discharges to trucks for removal of the overburden material.Syncrude utilizes a single-bench design with four60-m3capacity draglines as the primary mining equipment(Fig.8).The draglines pile tar sands in windrows along the edge of the pit;four60,000-t/h bucket-wheels transfer the tar sands to a system of trunk conveyor belts that move the material to the extraction plant.The mining operations at the two plants differ by choice of the primary mining equipment;the bucket-wheel excavators sit on benches, whereas the draglines sit on the surface.。

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ＬＩ　Ｃｈａｏ　，ＦＡＮＧ　Ｍｅｎｇｘｉａｎｇ　，ＸＩＡＯ　Ｐｉｎｇ。，ＳＨＩ　Ｚｈｅｎｇｈａｉ。，ＣＥＮ　Ｊｉａｎｍｅｎｇ　，　

ＹＡＮ　Ｑｉｋｅ　，ＷＡＮＧ　Ｑｉｎｈｕｉ　ａｎｄ　ＬＵＯ　Ｚｈｏｎｇｙａｎｇ　Ｊ．ＳｔａｔｅＫｅｙＬａｂｏｒａｔｏｒｙ　ｏｆＣｌｅａｎＥｎｅｒｇｙ　Ｕｔｉｌｉｚａｔｉｏｎ，　ＺｈｅｆｉａｎｇＵｎｉｖｅｒｓｉｔｙ，Ｈａｎｇｚｈｏｕ　３１００２７，　Ｒ．Ｃｈｉｎａ，＂　２．Ｈｕａｎｅｎｇ　ＰｏｗｅｒＩｎｔｅｒｎａｔｉｏｎａｌ　Ｉｎｃ．，ＢｅＯｉｎｇ　１０００３１，　Ｒ．Ｃｈｉｎａ　

Ａｂｓｔｒａｃｔ　Ｔｈｅ　ｅｖｏｌｕｔｉｏｎ　ｂｅｈａｖｉｏｒ　ｏｆ　ｔｈｅ　ｌｉｇｈｔ　ｔａｒ　ｆｒａｃｔｉｏｎ　ｏｆ　ｔａｒ　ｄｕｒｉｎｇ　ｌａｒｇｅ　ｂｉｔｕｍｉｎｏｕｓ　ｃｏａｌ　ｐａｒｔｉｃｌｅ　ｐｙｒｏｌｙｓｉｓ　ｉｎ　ａ　ｆｌｕｉｄｉｚｅｄ　ｂｅｄ　ｒｅａｃｔｏｒ　ａｔ　５００－－９００。Ｃ　ｗａｓ　ｉｎｖｅｓｔｉｇａｔｅｄ　ｔｏ　ｏｐｔｉｍｉｚｅ　ｔｈｅ　ｉｎｄｕｓｔｒｉａ１　ｐｒｏｃｅｓｓ．Ｔｌｌｅ　ｃｏａ１　ｒｅｓｉｄｅｎｃｅ　ｔｉｍｅ　ｗａｓ　ｖａｒｉｅｄ　ｆｒｏｍ　３０　ｓ　ｔｏ　ｌ　５０　ｓ．Ｔｈｅ　ｃｒｕｄｅ　ｔａｒ　ｏｂｔａｉｎｅｄ　ｗａｓ　ｄｉｓｔｉｌｌｅｄ　ａｎｄ　ｓｅｐａｒａｔｅｄ　ｉｎｔｏ　ｔｈｅ　ｌｉｇｈｔ　ｆｒａｃｔｉｏｎ　ａｎｄ　ｔｈｅ　ｈｅａｖｖ　ｆｒａｃｔｉｏｎ　ｔｈｒｏｕｇｈ　ａｎ　ｅｖａｐｏｒａｔｏｒ　ｕｎｄｅｒ　ｃｏｎｄｉｔｉｏｎｓ　ｏｆ２８０。Ｃ　ａｎｄ　１０　Ｐａ．Ｔｈｅ　ｌｉｇｈｔ　ｔａｒ　ｗａｓ　ｓｕＮｅｃｔｅｄ　ｔｏ　ＧＣ．ＭＳ　ａｎａｌｙｓｉｓ　ａｎｄ　ｔｈｅ　３００　ｍａｉｎ　ｓｐｅｃｉｅｓ　ｉｎ　ｅａｃｈ　ｓｐｅｃｔｒｕｍ　ｗｅｒｅ　ｄｅｔｅｒｍｉｎｅｄ　ａｎｄ　ａｎａｌｙｚｅｄ．Ｔｈｅ　ｅｘｐｅｒｉｍｅｎｔａｌ　ｒｅｓｕｌｔｓ　ｓｈｏｗｅｄ　ｔｈａｔ　ｔｈｅ　ｅｖｏｌｕｔｉｏｎ　ｂｅｈａｖｉｏｒ　ｏｆ　ｔｈｅ　１ｉｇｈｔ　ｔａｒ　ｆｒａｃｔｉｏｎ　ａｎｄ　ｔｈｅ　ｈｅａｖｙ　ｔａｒ　ｆｒａｃｔｉｏｎ　ｐｒｅｓｅｎｔｅｄ　ｓｐｅｃｔａｃｕｌａｒｌｙ　ｄｉｆｆｅｒｅｎｔ　ｖａｒｉａｔｉｏｎ　ｔｒｅｎｄｓ　ｗｉｔｈ　ｐｙｒｏｌｙｓｉｓ　ｔｅｍｐｅｒａｔｕｒｅ　ａｎｄ　ｃｏａｌ　ｒｅｓｉｄｅｎｃｅ　ｔｉｍｅ．Ｔｈｅ　ｍｏｌｅｃｕｌａｒ　ｗｅｉｇｈｔ　ａｎｄ　ｎｕｍｂｅｒ　ｏｆ　ｒｉｎｇｓ　ｐｅｒ　ａｒｏｍａｔｉｃ　ｃｏｍ－　ｐｏｕｎｄ　ｍｏｌｅｃｕｌｅ　ｃｏｎｔａｉｎｅｄ　ｉｎ　ｔｈｅ　ｌｉｇｈｔ　ｔａｒ　ｆｒａｃｔｉｏｎ　ｉｎｃｒｅａｓｅｄ　ｗｉｍ　ｉｎｃｒｅａｓｉｎｇ　ｐｙｒｏｌｙｓｉｓ　ｔｅｍｐｅｒａｔｕｒｅ　ｂｅｃａｕｓｅ　ｏｆ　ｐｏｌｙ—　ｍｅｒｉｚａｔｉｏｎ．Ｉｔ　ｗａｓ　ａｌｓｏ　ｏｂｓｅｒｖｅｄ　ｔｈａｔ　ｔｈｅ　ａｍｏｕｎｔ　ｏｆ　ｍｅｔｈｙ１　ｓｕｂｓｔｉｔｕｅｎｔｓ　ｄｅｃｒｅａｓｅｄ　ｗｉｔｈ　ａｎ　ｉｎｃｒｅａｓｉｎｇ　ｎｕｍｂｅｒ　ｏｆ　ｒｉｎｇｓ　ｐｅｒ　ｍｏｌｅｃｕｌｅ　ｏｆ　ｐｏｌｙ—ａｒｏｍａｔｉｃ　ｒｉｎｇ　ｃｏｍｐｏｕｎｄｓ　Ｔｈｅ　ｃｈａｉｎ　ａｌｉｐｈａｔｉｃ　ｃｏｍｐｏｕｎｄ　ｅｖｏｌｕｔｉｏｎ　ｗａｓ　ｓｕｐｐｒｅｓｓｅｄ　ａｎｄ　ｕｎｄｅｒ・　ｗｅｎｔ　ｈｅｔｅｒｏｃｙｃｌｉｚａｔｉｏｎ州ｍ　ｉｎｃｒｅａｓｉｎｇ　ｔｅｍｐｅｒａｔｕｒｅ．　Ｋｅｙｗｏｒｄｓ　Ｂｉｔｕｍｉｎｏｕｓ　ｃｏａｌ；Ｆｌａｓｈ　ｐｙｒｏｌｙｓｉｓ；Ｌｉｇｈｔ　ｔａｒ　ｅｖｏｌｕｔｉｏｎ　

１　Ｉｎｔｒｏｄｕｃｔｉｏｎ　Ｃｈｉｎａ　ｗｉｌｌ　ｈａｖｅ　ａ　ｓｔｒｏｎｇ　ｄｅｍａｎｄ　ｆｏｒ　ｃｈｅｍｉｃａｌｓ　ａｎｄ　ｌｉｑｕｉｄ　ｆｕｅｌｓ　ｉｎ　ｔｈｅ　ｃｏｍｉｎｇ　ｄｅｃａｄｅｓ　ｗｉｔｈ　ｔｈｅ　ｇｒｏｗｔｈ　ｏｆｔｈｅ　ｅｃｏｎｏｍｙ．　Ｔｈｅ　ｅｆｆｅｃｔｉｖｅ　ｍｅｔｈｏｄｓ　ｔｈａｔ　Ｃａｌｌ　ｂｅ　ｄｅｐｌｏｙｅｄ　ｔｏ　ｐｒｏｄｕｃｅ　ｓｙｎ．　ｔｈｅｔｉｃ　ａｎｄ　ｌｉｑｕｉｄ　ｆｕｅｌｓ　ｆｒｏｍ　ｔｈｅ　ｅｘｔｅｎｓｉｖｅ　ｃｏａｌ　ｒｅｓｅｒｖｅｓ　ｉｎ　Ｃｈｉｎａ　ａｒｅ　ｂｅｉｎｇ　ｐａｉｄ　ｉｎｃｒｅａｓｉｎｇ　ａｔｔｅｎｔｉｏｎ　ｂｙ　ｒｅｓｅａｒｃｈｅｒｓ＿ｌ　Ｊｌ　Ｃｐａｌ　ｆｌａｓｈ　ｐｙｒｏｌｙｓｉｓ　ｉｓ　ａ　ｐｒｏｃｅｓｓ　ｂｙ　ｗｈｉｃｈ　ｃｏａｌ　ｉｓ　ｈｅａｔｅｄ　ａｔ　ａｈｉｇｈｈｅａｔｉｎｇ　ｒａｔｅｕｎｄｅｒ　ａｒｔｉｎｅｒｔ　ｏｒ　ｒｅｄｕｃｆｉｖｅ　ａｔｍｏｓｐｈｅｒｅｔｏ　ｐｒｏｄｕｃｅ　ｃｈａｒ，ｔａｒ　ａｎｄ　ｆｕｅｌ　ｇａｓ　Ｔｈｅ　ｔａｒ　ｎｏｔ　ｏｎｌｙ　ｉｓ　ｕｓｅｄ　ａｓ　ａ　ｆｅｅｄｓｔｏｃｋ　ｎｅｅｄｅｄ　ｂｙ　ｔｈｅ　ｃｈｅｍｉｃａｌ　ｉｎｄｕｓｔｒｙｔ　ｂｕｔ　ａｌｓｏ　ｉｓ　ｗｅｌｌ　ｓｕｉｔａｂｌｅ　ｆｏｒ　ｕｐｇｒａｄｉｎｇ　ｔｏ　ｄｉｅｓｅｌ　ａｎｄ　ｇａｓｏｌｉｎｅ　ｆｕｅｌｓｌｊ　Ｊｌ　Ｉｔ　ｉｓ　ｗｅｌｌ　ｋｎｏｗｎ　ｔｈａｔ　ｔａｒ　ｉｓ　ａ　ｃｏｍｐｌｉｃａｔｅｄ　ｍｉｘｔｕｒｅ　ｗｈｏｓｅ　ｃｏｍｐｏｎｅｎｔｓ　ａｒｅ　ｍａｉｎｌｙ　ｄｅｐｅｎｄｅｎｔ　ｏｎ　ｔｈｅ　ｃｏａｌ　ｐｙｒｏｌｙｓｉｓ　ｃｏｎｄｉｔｉｏｎｓ．Ｍａｎｙ　ｒｅ．　ｓｅａｒｃｈｅｒｓ　ｈａｖｅ　ｄｅｖｏｔｅｄ　ｅｆｆｏｒｔｓ　ｔｏ　ｅｘｐｌｏｒｅ　ｔｈｅ　ｔａｒ　ｅｖｏｌｕｔｉｏｎ　ｂｅ．　ｈａｖｉｏｒ　ｔｈｒｏｕｇｈ　ｖａｒｉｏｕｓ　ｒｅａｃｔｏｒｓ．　Ａ　ｓｅｒｉｅｓ　ｏｆ　ｒｅｓｅａｒｃｈ　ｈａｓ　ｂｅｅｎ　ｆｏｃｕｓｅｄ　ｏｎ　ｔｈｅ　ｆｌｕｉｄｉｚｅｄ　ｂｅｄ　ｒｅａｃｔｏｒ　ａｎｄ　ｔｈｅ　ｍａｘｉｍｕｍ　ｔａｒ　ｙｉｅｌｄ　ｗａｓ　ｏｂｔａｉｎｅｄ　ａｔ　ｔｅｍｐｅｒａ－　ｔｕｒｅｓ　ｏｆ　５５０　ｔｏ　６５０。Ｃ．　ｅ　ｄｅｒｉｖａｔｉｖｅｓ　ｏｆ　ｂｅｎｚｅｎｅ　ａｎｄ　ｎａｐｈ－　ｔｈａｌｅｎｅ　ｗｅｒｅ　ｔｈｅ　ｍａｉｎ　ｖｏｌａｔｉｌｅ　ｃｏｎｓｔｉｔｕｅｎｔｓ　ｏｆ　ｔｈｅ　ａｒｏｍａｔｉｃ　ｈｙｄｒｏｃａｒｂｏｎ　ｃｏｍｐｏｕｎｄｓ，ａｎｄｔｈｅ　ａｌｋａｎｅ　ａｎｄ　ａｌｋｅｎｅｆｒａｃｔｉｏｎｉｎ　ｔａｒ　ｃｏｎｓｉｓｔｅｄ　ｍａｉｎｌｙ　ｏｆ　ｓｔｒａｉｇｈｔ．ｃｈａｉｎ　ｈｙｄｒｏｃａｒｂｏｎｓ　ｆｒｏｍ　ＣＩＯ　ｔｏ　Ｃ３４ｔ　Ｔｈｅ　ｈｅａｖｙ　ｔａｒ　ｃｏｍｐｏｎｅｎｔｓ．ｓｕｃｈ　ａｓ　ａｓｐｈａｌｔｅｎｅｓ　ｏｒ　ｐｉｔｃｈ　

ｗｅｒｅ　ｍａｄｅ　ｕｐ　ｏｆ　ｓｍａｌｌ　１－ｏｒ　２－ｒｉｎｇ　ａｒｏｍａｔｉｃ　ｕｎｉｔｓ　ｐｒｏｂａｂｌｙ　

ｌｉｎｋｅｄ　ｂｙ　ｍｅｔｈｙｌｅｎｅ　ｃｈａｉｎｓ　ｂｏｎｄｅｄ　ｔｈｒｏｕｇｈ　ｉｎｔｅｒｍｅｄｉａｔｅ　ｆｕｎｃｔｉｏｎａｌ　ｇｒｏｕｐｓＤ，￣Ｊ．Ｙｉｅｌｄｓ　ｏｆ　ａｒｏｍａｔｉｃ　ｈｙｄｒｏｃａｒｂｏｎｓ　ｗｉｔｈｏｕｔ　

ｈｅｔｅｒｏａｔｏｍｓ　ｏｂｔａｉｎｅｄ　ｆｒｏｍ　ｄｉｆｆｅｒｅｎｔ　ｒｅａｃｔｏｒｓ　ｗｅｒｅ　ｓｉｍｐｌｙ　ｉｎ．　ｃｒｅａｓｅｄ　ｗｉｔｈ　ｉｎｃｒｅａｓｉｎｇ　ｐｒｉｍａｒｙ　ｐｙｒｏｌｙｓｉｓ　ｔｅｍｐｅｒａｔｕｒｅ【　．Ｔｌ１ｅ　ｔａｒｓ　ｃｏｎｔａｉｎｉｎｇ　ａ　ｌｏｗｅｒ　ｐｒｏｐｏｒｔｉｏｎ　ｏｆ　ｈｅｔｅｒｏａｔｏｍｓ　ｂｅｃａｍｅ　ｍｏｒｅ　ａｒｏｍａｔｉｃ　ａｎｄ　ｃｏｎｔａｉｎｅｄ　ｉｎｃｒｅａｓｉｎｇ　ｃｏｎｃｅｎｔｒａｔｉｏｎｓ　ｏｆ　ｃｏｎｄｅｎｓｅｄ　ｒｉｎｇ　ｓｌｒｕｃｔｕｒｅｓ　ａｔ　ｈｉｇｈｅｒ　ｐｙｒｏｌｙｓｉｓ　ｔｅｍｐｅｒａｔｕｒｅｓｔ　．Ｐｈｅｎｏｌｉｃ　

ｃｏｍｐｏｕｎｄｓ　ｗｅｒｅ　ｔｈｅ　ｍａｊｏｒ　ｃｏｍｐｏｓｉｔｉｏｎ　ｏｆｔｈｅ　ｖｏｌａｔｉｌｅ　ｆｒａｃｔｉｏｎ　ｏｆ　ｃｏａｌ　ｔａｒ　ｐｒｏｄｕｃｅｄ　ｂｙ　ｔｈｅ　ｆｉｘｅｄ　ｂｅｄ　ｒｅａｃｔｏｒｔ　１１ｌｅ　

ＰＣＸ（ｐｈｅｎｏｌ，ｃｒｅｓｏｌ　ａｎｄ　ｘｙｌｅｎｏ１）ｃｏｎｔｅｎｔ　ｓｔｅｅｐｌｙ　ｄｅｃｒｅａｓｅｄ　ａｆｔｅｒ　６５０。Ｃ，ａｎｄ　ｔｈｅ　ＢＴＸ（ｂｅｎｚｅｎｅ．ｔｏｌｕｅｎｅ　ａｎｄ　ｘｙｌｅｎｅ、ｃｏｎ—　ｔｅｎｔ．ａｓ　ｅｘｐｅｃｔｅｄ，ｉｎｃｒｅａｓｅｄ　ａｆｔｅｒ　５８０。Ｃ　ａｔ　ａ　ｌｏｗ　ｈｅａｔｉｎｇ　ｒａｔｅ．　Ｔｈｅｎａｐｈｔｈａｌｅｎｅ　ｃｏｎｔｅｎｔｓｉｎｃｒｅａｓｅｄｆｒｏｍ　５８０。Ｃａｎｄ　ｓｔａｂｉｌｉｚｅｄ　ａｔ　７８０。Ｃｔ１ｏｊ．Ｉｔ　ｗａｓ　ａ１ｓｏ　ｏｂｓｅｒｖｅｄ　ｔｈａｔ　ｔｈｅ　ｙｉｅｌｄ　ｏｆ　ｐｏｌｙｃｙｃｌｉｃ　

ａｒｏｍａｔｉｃ　ｃｏｍｐｏｕｎｄｓ　ｉｎｃｒｅａｓｅｄ　ｍｏｎｏｔｏｎｏｕｓｌｙ　ｗｉｔｈ　ｉｎｃｒｅａｓｉｎｇ　ｃｏａｌ　ｐｙｒｏｌｙｓｉｓ　ｔｅｍｐｅｒａｔｕｒｅｔＩｌ’　．　１ｅ　ｍｏｌｅｃｕｌａｒ　ｗｅｉｇｈｔ　ｄｉｓｔｒｉｂｕ．　

ｔｉｏｎｓ　ｏｆ　ｔａｒｓ　ｒｅｌｅａｓｅｄ　ｄｕｒｉｎｇ　ｒａｐｉｄ　ｐｙｒｏｌｙｓｉｓ　ｉｎ　ｔｈｅ　ｗｉｒｅ　ｍｅｓｈ　ｒｅａｃｔｏｒ　ｗｅｒｅ　ｉｎ　ｔｈｅ　ｒａｎｇｅ　ｏｆ　４００　ｔｏ　４０００．Ｔｈｅｒｅ　ｗａｓ　ａ　ｓｈｉｆｔ　ｔｏｗａｒｄｓ　ｈｉｇｈｅｒ　ｍｏｌｅｃｕｌａｒ　ｗｅｉｇｈｔｓ　ｗｉｔｈ　ｉｎｃｒｅａｓｉｎｇ　ｔｅｍｐｅｒａｔｕｒｅ　ｗｈｉｃｈ　ｗａｓ　ｃｏｎｓｉｓｔｅｎｔ　ｗｉｔｈ　ｔｈｅ　ｅｘｐｅｃｔｅｄ　ｉｎｃｒｅａｓｅ　ｉｎ　ｖａｐｏｒ　ｐｒｅｓ．　ｓｕｒｅ　ｏｆ　ｈｅａｖｙ　ｓｐｅｃｉｅｓ　ｗｉｔｈ　ｔｅｍｐｅｒａｔｕｒｅＬ　Ｔｈｅ　ｌｉｔｅｒａｔｕｒｅ　ｓｈｏｗｅｄｔｈａｔ　ａ　ｒｅａｃｔｉｏｎｔｉｍｅ　ｏｆ　３　ｍｉｎ　ｉｓ　ｓｕｆｆｉｃｉｅｎｔ　ｆｏｒｔｈｅ　ｅｖｏｌｕ．　ｔｉｏｎ　ｏｆｔａｒ　ｐｒｏｄｕｃｔｓｔ１４１．Ｔｈｅ　ｔａｒ　ｏｂｔａｉｎｅｄ　ｆｒｏｍ　ｃｏａｌ　ｐｙｒｏｌｙｓｉｓ　ａｔ　ａ　

ｈｉ　ｈｅａｔｉｎｇ　ｒａｔｅｗａｓｍｏｒｅｒｅａｃｔｉｖｅｔｈａｎｔｈａｔ　ｏｂｔａｉｎｅｄ　ａｔ　ａｌｏｗ　