煤中各族组分FTIR解析

采用全组分分离法将徐州夹河气煤(JHM)、河南平顶山煤(PDSM)、徐州庞庄煤(XZM)和山西介休焦煤(JXM)分离成萃余煤组分、沥青质组分、精煤组分和轻质组分四大族组分,通过FTIR比对研究各族组分的官能团结构特征。结果表明:酚、醇、醚等含氧化合物主要富集于精煤组分,沥青质组分中也有一定含量;脂肪族物质主要富集于沥青质组分;而芳香族物质与矿物质主要富集于萃余煤组分;轻质组分中含有很少量酚、醇和醚类物质。回收NMP溶剂可促进酚、醇类物质的溶解。脂肪族物质更易于在二级萃取中溶出。     

煤的族组分基本特性研究

以徐州庞庄煤、河南平顶山煤和山西介休煤为研究对象,利用CS_2/NMP混合溶剂和反萃取剂将煤全组分分离成萃余煤组分、沥青质组分、精煤组分和轻质组分四大族组分。通过SEM、FTIR探讨族组分微观形态,同时测定族组分的工业分析指标、粘结指数、収热量以及真密度,对比研究各族组分的基本特性。结果表明,同一煤样不同族组分之间的组成结极差异很大,而不同煤样的同一族组分之间存在枀高的统一性。精煤组分为褐色絮团状颗粒,疏松质轻,微观上呈现出一种蜂窝状或巢状结极分布,孔隙収达,以含氧基团较多的酚、醇、醌酮等芳香族化合物为主;沥青质组分为深黑色,表面晶莹透亮,有直形或弧形边界均一块体,富含脂肪族化合物,微观上是大小均一且高度堆积黏连的灰白色小球体,迚入反萃取剂时小球体经历了融幵长大的过程。二者为煤中靠溶剂的浮沉作用悬浮到溶剂中的中型分子,比萃余煤组分有较多的侧链和官能团,挥収分产率较高,灰分少而密度小,粘结能力尤其以沥青质组分较强。萃余煤组分是不被溶剂溶解的大分子基底,结极致密,芳香族成分多,密度最大,灰分含量最高,挥収分与収热量低,基本无粘结能力。     

精煤组分与沥青质组分性质研究

以徐州夹河气煤、河南平顶山肥煤为研究对象,利用CS2/NMP混合溶剂和反萃取剂在温和条件下将煤全组分分离成萃余煤组分、沥青质组分、精煤组分和轻质组分四大族组分。通过扫描电镜(SEM)探讨精煤组分和沥青质组分微观形态,并针对精煤组分与沥青质组分可能的加工利用方向,分别测定沥青质组分的软化点、QI含量、N和S含量;精煤组分颗粒粒度分布、油煤浆流变特性等。结果表明,精煤组分是孔隙高度发达且呈蜂窝状的质轻疏松体,制备的精细油煤浆具有明显的剪切稀化流变特性,经溶胀煤浆黏度增大,通过升高浆体温度降低黏度,成浆性、流动性和稳定性优良。沥青质组分为400nm左右高度聚集的大小均匀小球体,QI含量(0.22%)极低,灰分产率低,软化点150℃,是制备碳纤维的优良原料。     

煤的族组分形成机理研究

采用CS2/NMP混合溶剂和反萃取剂,将徐州夹河煤在常温常压下分离为萃余煤组分、沥青质组分、精煤组分和轻质组分四大族组分,通过扫描电镜(SEM)对混合溶剂萃取、反萃取过程进行了追踪研究,主要探讨了族组分中精煤组分和沥青质组分形成的微观机理.结果表明,精煤组分和沥青质组分均是以微纳米颗粒形式从煤大分子基质悬浮到萃取液中,两种颗粒在后续反萃取过程中均发生融并现象.以深灰色呈现的精煤组分颗粒在加入反萃取剂后,融并为网孔状或表层均一的块体;以灰白色(或亮白色)呈现的沥青质组分颗粒在加入反萃取剂前后由分散聚集变为高度聚集,进一步融并成表面极为光滑均一的块体,最后经历了合并和长大的过程,于少量NMP中重新分散成大小均匀的小球体.     

童亭煤族组分的溶剂萃取及萃取物分析

采用正己烷、甲醇、丙酮和氯仿4种溶剂对童亭煤经CS2/NMP混合溶剂萃取和反萃取所分离的3个族组分(沥青质组分、精煤和萃余煤组分)进行索氏分级分次萃取,以FTIR和GC为分析测试手段,研究各组分萃取物的结构特征和其中小分子的赋存规律。结果表明:各族组分在不同溶剂中溶解能力差异显著,沥青质组分在正己烷中有很高的萃取率,而精煤则在丙酮中有大量物质被溶出,萃余煤在氯仿中表现出较高的可溶性;各族组分可溶物在溶出行为和组成结构上既有相似性又存在一定的差别;各族组分可溶物中均有小分子化合物存在,且这些GC可检测的小分子主要集中于一定的保留时间区域内;不同族组分中的小分子的赋存形态具有相似性,且这种赋存形态是影响小分子溶出行为的决定性因素。     

两种亮煤用CS2-NMP溶剂抽提后的结果分析

研究了童亭亮煤和洼里亮煤在CS2 - NMP混合溶剂中的可溶性,重点考察了原煤,萃取物,萃余物在工业分析、真密度和黏结指数方面的联系;同时运用红外光谱( FTIR)现代分析技术对原煤及其萃取物和萃余物的组成和结构特征进行了对比分析,在此基础上提出了煤中主要存在两种组分即“致黏组分”和“不黏组分”的概念,并据此对胶质体液相的来源作了初步解释.最后得出了萃取物中主要是煤中富含脂肪族和酚,醇,醚结构的组分,而萃余物中主要是富含缩合芳环的组分.     

神华煤直接液化用煤检测项目关联性及回归分析研究

以神华鄂尔多斯煤制油分公司用作煤直接液化原料的原煤、精煤检测数据为依据,通过统计分析手段,建立了灰分、挥发分与发热量二元回归方程、煤的发热量与元素分析结果的回归方程,分析了煤质指标中灰分、挥发分与煤岩组分中镜质组+壳质组含量、惰质组含量、矿物质含量间的相关性。     

褐煤弱氧化产物的成分分析

利用石油醚、氯仿对褐煤进行分级萃取,将萃余煤进行碱性弱氧化.GC/MS对褐煤和氧化产物的萃取液进行成份分析,并采用面积归一化法确定各成份的相对含量.实验表明:原煤石油醚萃取液中鉴定了46种组分,主要以烃类(80.2%)和酯类(14.3%)为主;萃余氧化煤的石油醚萃取液中鉴定了44种为氧化产物,与原煤组分相比,其中烃类(43.3%)相对含量减少,酯类(18.9%),醇类(15%),芳香烃(6.5%),酚类(6.1%),烯烃(4.6%),酸类(2.2%)相对含量增加.这表明在该氧化条件下可以使分子结构发生变化从而得到其它有机化学品.     

炼焦中煤解离精煤的炼焦性能与煤岩学分析

选取重介中煤为研究对象,将其破碎、研磨,并按密度分离后得到解离精煤,将解离精煤与重介精煤进行对比,通过工业分析、元素分析、胶质层指数和黏结指数测定等分析方法,探讨解离精煤与重介精煤在炼焦性能和煤岩学特征上的差异。结果表明:解离精煤和重介精煤的工业分析和元素分析各项指标均非常接近,然而解离精煤的胶质层指数和黏结指数显著低于重介精煤的胶质层指数和黏结指数,发现解离精煤并不适用于炼焦。解离精煤相比重介精煤,其镜质组含量降低了16.0%,惰质组含量增加了17.7%。解离精煤镜质组含量降低主要是因为碎屑镜质体的减少,惰质组含量增加主要是因为半丝质体和碎屑惰质体的增加,解离精煤和重介精煤的煤岩组分差异是导致两种精煤胶质层指数和黏结指数差异显著的主要原因。因此,将重介中煤破碎解离再选后获得的精煤用于炼焦用煤的可行性及其意义需要充分论证和研究。     

族组分对原煤流动性的影响及其作用机制

为了研究煤族组分含量及热解特性与原煤热解流动性的关系,将炼焦煤全组分分离后各族组分收率Y_(DMC)、Y_(LMC)、Y_(HC)、Y_(LC)和疏中质组奥阿膨胀度(a+b)_(LMC)对lg F_(wa)进行多元线性回归,采用逐步回归分析法解释变量的筛选,并从族组分组成结构角度解释了不同族组分对原煤流动性的作用机制。结果显示:重质组在原煤中起到"骨架"作用,是阻碍原煤流动性的主要组分,其含量是影响煤流动性的决定性因素;密中质组虽然是促进煤流动性的主要组分,但其含量对原煤流动性只起到辅助作用。对原煤流动性来说,只需要适当的密中质组产生胶质体液相起到"润滑"作用即可;密中质组与重质组间存在一定的协同作用共同决定了原煤流动性,而轻质组含量、疏中质组含量及其性质(膨胀性)对原煤流动性没有显著影响。     

低温煤焦油沥青质和胶质的分离与表征

对沥青质和胶质的分离与表征是低温煤焦油科学开发和综合利用的重要突破口之一。笔者借鉴原油三组分分离法将样品分离为沥青质、胶质和轻质组分3个组分,前两者的质量分数为53％～63％。由^1H—NMR谱图信息计算获得的结构参数可知,沥青质芳香度较高,芳香环缩合度较低,环烷烃含量较高,链烃含量较少;胶质芳香度较低,芳香环缩合度较高,环烷烃含量较少,链烃含量较高,碳链较长。     

中温煤焦油加氢原料的杂质处理

针对目前国内煤焦油加工工艺的阐述,尤其是煤焦油加氢轻质化的预处理方面,天元化工通过延迟焦化的工艺原理,通过处理前后的结果分析对比,得知煤焦油中的沥青质、胶质、残炭及重金属极大的得到降低,且很好的改善了下游加氢原料的品质,同时降低了原料中的硫、氮含量。生产结果表明:预处理后的油品为后续的全馏分加氢提供了长周期运行的条件。     

渣油中沥青质的存在形态及其加氢转化反应

沥青质是渣油的重要组成部分,是渣油加氢反应过程中的转化难点。文章在叙述沥青质化学结构表征方法的基础上,讨论了沥青质的结构组成及其在渣油中的存在形态,并对渣油加氢转化反应过程中沥青质的转化行为和反应机理进行了论述。     

基于柱色谱分离的阿曼减压渣油结构表征与溶解度参数测定

采用液-固色谱分离方法将阿曼减压渣油分离成饱和分、轻芳烃、中芳烃、重芳烃、轻胶质、中胶质、重胶质和沥青质8个组分,对各组分烃类组成和分子结构进行表征;同时采用基团贡献法计算各组分溶解度参数并与各组分性质进行关联。结果表明,芳香分和胶质组分中S分布相对均匀,绝大部分N（85.05%）、残炭（91.95%）和镍钒金属（99.85%）分布在重芳烃、胶质和沥青质中,金属和残炭脱除率分别在流出组分累计收率为53.8%和43.8%时存在明显下降拐点,对溶剂脱沥青工艺操作有重要指导意义;从饱和分到沥青质,各组分的密度ρ_i、摩尔体积V_i和溶解度参数δ_i依次增加;阿曼减压渣油的溶解度参数δ_VR为17.29MPa^1/2,介于轻芳烃和中芳烃之间。相对于S、N、残炭值、H/C比和芳香度f_A,溶解度参数δ与密度、总环数R_T和分子量关联性较好,尤其与对数lnM呈现良好线性关系,可以近似看成分子量的单值函数δ=4.7282lnM-14.639。     

Some factors influencing the rheological properties of concentrated brown coal—oil suspensions on storage

Rheological properties of coal—oil suspensions are strongly dependent on the characteristics of coal and the medium of suspension. The variations in the rheological properties of brown coal—KC220 oil suspensions with storage time were strongly influenced by the moisture content in the coal, coal concentration, medium of suspension, and to a lesser degree, by the extent of mechanical agitation. The increase of both plastic viscosity and yield stress of the brown coal—KC220 oil suspension with storage time was due to an overall reduction of free oil in the suspension, particle aggregation, solvation and swelling. The increase of relative viscosity due to ageing in moist coal—KC220 oil suspensions could be an order of magnitude higher than a suspension of similar concentration, but containing only dry coal.     

反应时间对加氢沥青质结构变化的影响

在高压反应釜中对煤焦油进行催化加氢反应,利用XPS和元素分析对不同加氢反应时间下提取的煤焦油沥青质进行表征,系统分析加氢油品四组分变化、沥青质转化率、化学组成和杂原子赋存形态的变化。结果表明,随着反应时间的延长,加氢油品中饱和分和芳香分收率增大,胶质和沥青质收率减小。加氢后沥青质转化率逐渐增大,分子量先减小后增大,沥青质中氧原子主要以羰基氧和碳氧单键形式存在,氮原子主要以吡咯氮、吡啶氮和质子化吡啶形式存在。     

Depolymerization of Illinois no. 6 coal by quinoline diffusion into the coal matrix

The range of temperatures at which depolymerization reactions of coal in quinoline start, the change of conversion into soluble material with respect to time and temperature, and the nature of resistances opposing the progress of coal—quinoline interactions were investigated. A mechanically stirred stainless-steel autoclave and a set of identical pressure-resistant pyrex glass ampoules were used throughout the investigation. The ratio of solvent to coal was 20:1 in all experiments. Differential thermal analysis of the coal—quinoline system showed that endothermic reactions occurred within the range 325–360°C during the solvent—coal interaction. The difference in weights of the dried residue and the starting coal was used to calculate conversion to extractable material. Maximal yields of primary solubles of 90 and 30 percent occurred at about 1 and 20 minutes in the autoclave and glass ampoule experiments, respectively, at 350°C. During the course of reactions in experiments done in the autoclave the presence of colloidal material was indicated by microfiltration. At extended reaction times the colloidal material was converted into residual precipitated matter. It was found that the resistance to diffusion of quinoline through the coal particle itself controlled the rate of reaction during most of the reaction time for the production of primary solubles.     

Comparative reactivities of coal asphaltenes during hydropyrolysis

Comparisons have been drawn in the relative reactivities of three coal asphaltenes during hydropyrolysis. All were derived from hydrogen donor-solvent extracts of bituminous coal, but had different hydrotreatment histories and different carbon contents (87.1, 91.9 and 90.8 wt% for asphaltenes 1, 2 and 3, respectively). The hydropyrolyses were carried out in the presence of CoO–MoO₃ catalyst and gaseous hydrogen at 8.7 MPa. For two of the asphaltenes (1 and 2) systematic comparisons were made for different reaction times at 425°C; for all three asphaltenes comparisons were made for l h of hydropyrolysis at 425°C. The general pattern of asphaltenes conversion indicated that more pentane-soluble product was produced from asphaltene isolated from straight coal extract (asphaltene 1). For the asphaltenes isolated from hydrotreated extracts, the extent of conversion to liquids was limited when the carbon content was high (asphaltene 2) although the pattern of conversion was similar in the other hydrotreated asphaltene (asphaltene 3). The aliphatic content of the liquid products formed was low, and the distribution of hydrogenated species in the highly aromatic liquid products indicated that complete hydrogenation of the polyaromatics produced in pyrolysis is difficult. Altogether the aliphatics made up ≈ 10 wt% of the asphaltene 1 hydropyrolysate. Aromatic hydrocarbons made up 90% of the liquid product. Phenanthrene, pyrene and anthracene were prominent, and the largest component in the mixture was phenanthrene which, together with other polyaromatics such as fluoroanthene, dominated the liquid product.     

轮古稠油悬浮床加氢裂化工艺的中型试验研究

通过悬浮床加氢裂化工艺对高硫、高残碳、高金属、高密度、高黏度、高沥青质含量的塔里木轮古稠油进行中试改质研究。通过分析反应产物性质和分布规律,确定了比较适合轮古稠油悬浮床加氢的反应条件。