CHARACTERIZATION AND STABILITY PROPERTIES OF POLAR EXTRACTS DERIVED FROM A RECENT SHALE LIQUID

A shale fuel of marginal stability has been used as a source of nitrogen-rich polar extracts. Polar compounds were isolated by mild acid extraction followed by silica gel adsorption and were identified by GC/HS. Alkyl substituted pyridines were the prevalent class of compounds present in most extracts. The effects of adding these shale derived fractions as dopants to a stable shale diesel fuel (0-11) were examined in terms of sediment formation and peroxide number under accelerated storage stability test conditions. The activities of the extracts in inducing fuel instability were correlated with their composition.     

FUEL INSTABILITY STUDIES: REACTION OF POLAR NITROGEN HETEROCYCLES DERIVED FROM A STABLE SHALE FUEL

Abstract

The degradation of middle distillate fuels with increasing time in storage is a continuing problem. Model systems have defined both the scope and the chemical types of molecules that are Implicated in fuel deterioration. To gain insight into a real fuel system, nitrogen-rich extracts have been isolated from a marginally stable shale derived middle distillate fuel and added as a dopant to a stable base fuel in order to induce instability reactions. Alkyl substituted pyridines, tetrahydro-quinolines, quinolines, and indoles were the prevalent classes of compounds present in the extract. The effects of this added extract were examined in terms of sediment formation and peroxide number under accelerated storage stability test conditions. The activity of the extract in inducing fuel instability was correlated with its nitrogen heterocylic composition.     

FUEL INSTABILITY STUDIES: REACTION OF POLAR NITROGEN HETEROCYCLES DERIVED FROM A STABLE SHALE FUEL

The degradation of middle distillate fuels with increasing time in storage is a continuing problem. Model systems have defined both the scope and the chemical types of molecules that are Implicated in fuel deterioration. To gain insight into a real fuel system, nitrogen-rich extracts have been isolated from a marginally stable shale derived middle distillate fuel and added as a dopant to a stable base fuel in order to induce instability reactions. Alkyl substituted pyridines, tetrahydro-quinolines, quinolines, and indoles were the prevalent classes of compounds present in the extract. The effects of this added extract were examined in terms of sediment formation and peroxide number under accelerated storage stability test conditions. The activity of the extract in inducing fuel instability was correlated with its nitrogen heterocylic composition.     

泥页岩构成及泥页岩井壁表面和岩屑表面特征对井壁稳定性的影响--文献综述

泥页岩的构成及泥页岩井壁表面和岩屑表面的特征对井壁稳定性的影响 ,是防塌技术研究领域值得不断深入研究的课题 ,是客观全面地研究防塌机理和方法的基础。本文综述了有关这方面的研究文献 ,希望能为拓宽防塌技术研究的思路提供一些有益的启示     

酯基功能化离子液体的合成、表征及性质

采用两步法合成了含酯基官能团的功能化离子液体1-乙酸乙酯基-3-甲基咪唑四氟硼酸盐,用核磁共振、红外光谱、元素分析对其进行了结构表征,研究了离子液体的密度、酸值、黏温性、吸湿性、溶解性、玻璃化转变温度及热稳定性能。结果表明:制备的离子液体与预期结构一致,且纯度较高,证明了该功能化离子液体的制备和提纯方法的可靠性;与含有相同烷基的1-丁基-3-甲基咪唑四氟硼酸盐离子液体相比,功能化离子液体具有较高的密度、黏度、玻璃化转变温度和较低的酸值、吸水性及热稳定性,表明酯基官能团的引入,使烷基离子液体展现出不同的特性;另外,制备的2种离子液体均可以与极性大的溶剂混溶,而不溶于非极性或极性小的溶剂。     

基于水热处理的介孔钛硅分子筛的合成及表征

 摘要：采用高温水蒸气处理商品HZSM-5分子筛，调变其孔结构，得到含有部分介孔的HZSM-5分子筛，脱铝生成羟基窝的同时引入更多的结构缺陷。采用TiCl4气-固相同晶取代法将高温水热处理后的HZSM-5分子筛进行涂钛反应，制备了介孔钛硅分子筛。采用XRD、IR和UV-Vis技术对合成的钛硅分子筛进行了表征。结果表明，钛被成功地引入了水热处理后的HZSM-5分子筛的孔壁中，并且水热处理后的分子筛比处理前有更大的载钛能力。     

Ga－Al－Si－ZSM－5 的合成、表征与催化性能

利用廉价的水玻璃作硅源、正丁胺作导向剂合成出Ｇａ－Ａｌ－Ｓｉ－ＺＳＭ－５泡沸石分子筛。ＸＲＤ、ＩＲ、ＤＳＣ、ＸＰＳ等测试结果表明，Ｇａ已进入分子筛的骨架，并以高价氧化态存在，呈体相富集。对酸催化的甲醇芳构化反应，Ｇａ－Ｓｉ－ＺＳＭ－５比Ａｌ－Ｓｉ－ＺＳＭ－５有更好的产物选择性，芳烃收率高，裂解产物Ｃ１、Ｃ２烃的收率较低。     

ZSM—5沸石的合成及表征

在吸附态模板剂作用下的Ｎａ２Ｏ－ＳｉＯ２－Ａｌ２Ｏ３－ＮａＦ－ＥＤＡ（乙二胺）干粉体系中合成了ＺＳＭ－５沸石。采用ＸＲＤ、ＳＥＭ及ＩＲ等技术对其物化性能进行了表征。结果表明，与水热体系相比，干粉体系合成的ＺＳＭ－５沸石的晶胞略有收缩；红外骨架振动有向高波数移动的趋势。在合成气制备低碳烯烃反应中，ＣＯ转化率为７５．６％，Ｃ２￣Ｃ４烯烃选择性达４６．６％。     

ZSM—5沸石分子筛的微波辐射法合成与表征

以工业硅溶胶作硅源,用廉价的乙醇作模板剂,用微波辐射的方法合成了ＺＳＭ－５分子筛,探讨了微波晶化时间,微波反应釜压力等合成影响因素,确定了合适的配比范围及合成条件。利用ＸＲＤ,ＳＥＭ等方法对ＺＳＭ－５分子筛的物相和晶貌作了表征。微波辐射法合成的样品粒度小且均匀,并且大大地缩短了反应时间,降低了能耗。     

离子液体Cl复合盐酸改性木质素的结构及热稳定性研究

为了增加木质素分子中羟基的含量,采用3mL 0.2mol/L的盐酸和3mL[BMIm]Cl离子液体混合溶剂对木质素进行改性得到再生木质素。利用FT-IR、SEM和TGA对制备的再生木质素进行表征分析。FTIR表征分析结果表明:木质素上烷基取代的苯环转变为带有孤对电子基团取代的苯环,且木质素上的羧基含量减少,而羟基含量增加;SEM表征分析结果表明:木质素的形貌发生变化,由无规则、非晶体型转变为规则的、块状晶体型结构;TGA表征分析结果表明:在氯离子液体中,经盐酸改性的木质素的热稳定性明显降低,并且增加了再生木质素的亲水性。     

芳烃抽提返洗液常压芳构化研究

以扬子石化公司芳烃抽提返洗液为原料,以改性ZSM-5分子筛为催化剂,在200 mL气固相催化反应装置上进行常压芳构化研究,考察反应温度、进料空速对芳构化反应的影响以及催化剂的稳定性及再生情况。结果表明,在常压、体积空速为4.0h-1、反应温度为450℃时,芳构化效果最佳,此时催化剂单程寿命约为12 h;再生多次的催化剂具有与原始催化剂同样的催化性能;芳烃抽提返洗液常压芳构化可同时降低返洗液中的烯烃和环烷烃含量,增加目标产物芳烃含量。     

正庚烷和正辛烷在无黏结剂5A分子筛上的吸附动力学特性

采用重量法研究正庚烷和正辛烷在无黏结剂和有黏结剂5A分子筛上的吸附动力学,采用简化的扩散模型计算扩散系数,并估算扩散活化能。结果表明,正构烷烃在无黏结剂5A分子筛颗粒上的扩散时间常数大于有黏结剂的5A分子筛,黏结剂的存在降低了正构烷烃在5A分子筛上的扩散速率。在300～480 K,正庚烷和正辛烷在无黏结剂5A分子筛上的微孔扩散系数分别为(20.84~85.77)×10-14、(3.80～23.44)×10-14 cm2/s,在有黏结剂5A分子筛上的大孔扩散系数分别为(4.87～38.58)×10-7、(4.28～14.65)×10-7 cm2/s。正庚烷和正辛烷在无黏结剂5A分子筛上的扩散活化能分别为10.74、12.71 kJ/mol,在有黏结剂分子筛上的扩散活化能分别为14.16、16.35 kJ/mol。     

5A和ZSM-5分子筛吸附分离石脑油中烷烃组分的研究

为了提高石脑油生产乙烯和芳烃的利用效率，采用5A分子筛和ZSM-5分子筛对石脑油进行连续吸附分离研究，分别得到脱正构烷烃吸余油（简称脱正构油）和脱单甲基异构吸余油（简称脱烷烃油）；采用氮气对分子筛进行脱附得到富含烷烃组分油（简称脱附油）。试验结果表明：脱烷烃油中正构烷烃质量分数为0.1%，单甲基异构烷烃质量分数为3.8%，芳烃潜含量为53.4%，可作为优质的催化重整原料；脱附油的烷烃质量分数可达到84%以上，可作为裂解制乙烯的优质原料。     

MECHANISMS OF SYNFUEL DEGRADATION. I. EFFECTS OF ORGANIC NITROGEN COMPOUNDS ON THE STABILITY OF A SHALE DERIVED DIESEL FUEL

ABSTRACT

A reliable accelerated fuel stability teat regimen has been developed and applied to the study of the storage stability of a shale derived diesel fuel marine (DFM). The results of a survey of nitrogen compounds as dopants in a stable shale DFM base fuel indicate that 3ome pyrroles and indoles may play significant roles in storage stability. A complete stability test matrix has been developed for the temperatures of 43, 65 and 80°C, for time periods between A and 179 days, and for a ten-fold concentration range of a model dopant, 2,5-dimethylpyrrole (DMP). Stability was defined by the amount of total insoluble material (filterable sediment and adherent gum) produced after stress, and also by the amount of titratable peroxide present in the filtrates of stressed fuel samples. A very regular pattern for insolubles formation was found within the test matrix. Deposit formation rates exhibited a first-order dependence on DMP concentration, with an apparent activation energy of 11-12 kcal/mol. The sediment was found to contain 12% nitrogen and 18-20% oxygen irrespective of the stress conditions employed.     

ZSM—5沸石催化剂的失活历程和活性稳定性

研究了ZSM－5分子筛催化剂上苯／乙烯烷基化制乙苯反应体系的结焦失活历程,结果表明,失活历程经历了搞水平活性稳定期,活性衰退期和低水平活性稳定期3个阶段,通过考察失活催化剂的孔结构及酸性质,分析了失活机理,认为采用降低强酸活性位和晶粒表面活性位这两种手段来改性催化剂,都有利于改善催化剂的活性稳定性。     

5A和ZSM-5分子筛吸附分离石脑油中烷烃组分的研究

为了提高石脑油生产乙烯和芳烃的利用效率,采用5A分子筛和ZSM-5分子筛对石脑油进行连续吸附分离研究,分别得到脱正构烷烃吸余油（简称脱正构油）和脱单甲基异构吸余油（简称脱烷烃油）;采用氮气对分子筛进行脱附得到富含烷烃组分油（简称脱附油）。试验结果表明：脱烷烃油中正构烷烃质量分数为0.1%,单甲基异构烷烃质量分数为3.8%,芳烃潜含量为53.4%,可作为优质的催化重整原料;脱附油的烷烃质量分数可达到84%以上,可作为裂解制乙烯的优质原料。     

ZSM-5分子筛酸性修饰及探针分子表征

采用柠檬酸、硫醚、苯胺、二苯胺、磷酸二氢铵及硅油作为改性试剂对二甲苯异构化专用HZSM-5分子筛进行液相浸渍改性,结合甲苯、邻二甲苯、间二甲苯、乙苯及间二异丙苯的脉冲反应表征,对各种改性手段的效果进行评估。各种改性方法对微孔体积和比表面积的影响很小,均减弱了酸性,对L酸的影响大于B酸。5种探针反应结果表明:柠檬酸改性强化了分子筛酸性,提高了歧化/异构化活性;磷酸二氢铵改性提高了歧化和脱乙基反应活性;苯胺、二苯胺、硫醚改性手段部分钝化了分子筛酸性,降低了歧化异构化活性;随着改性剂分子尺寸的增大,钝化外表面酸性越明显,从而改变分子筛孔内外的酸位分布,产生不同程度的择形效果;硅油改性充分地钝化了外表面酸性,形成最明显的择形效应。     

CHARACTERIZATION OF HEAVY RESIDUA BY APPLICATION OF A MODIFIED D 2007 AND ASPHALTENE SEPARATION: EFFECT OF SOLVENTS ON PHYSICAL AND CHEMICAL PROPERTIES OF FRACTIONS DERIVED FROM HONDO 850°F RESIDOOM

Hondo 850 ^°F residuum was separated into saturate, aromatic, resin, and asphaltene fractions by a modified D 2007 and asphaltene separation. Two different asphaltene precipitation solvents were used — isooctane and heptane — and differences in selected physical and chemical properties of the derived fractions were compared.

The principal difference in the use of the two solvents was weight recovery after the separation. Isooctane yielded good recovery, while heptane exhibited poor recovery. Isooctane precipitated substantially more asphaltenes, as predicted from the solubility parameters of the two solvents.

The metals concentrations in the fractions were comparable for each solvent — no metals in the saturate and aromatic fractions, approximately 300 and 1500 ppm Ni + V in the resin and asphaltene fractions respectively. The relative distribution was also similar for both solvents, with the highest percentage coming from the asphaltenes.     

埕东泡沫复合驱采出液油-水界面性质及乳状液稳定性研究

 以埕东泡沫复合驱采出液为研究对象, 配制一系列含不同浓度泡沫剂的模拟水和模拟油组成的体系,采用界面张力仪、表面黏弹性仪和Zeta电位仪测定了这些体系的油-水界面特性,考察了发泡剂浓度对这些界面特性及乳状液稳定性的影响。结果表明,由于泡沫复合驱采出水中含有固体悬浮物,使得过滤后采出水-原油模拟油体系的油-水界面张力和界面剪切粘度降低。模拟水中加入发泡剂后,模拟水-原油模拟油体系的油-水界面张力降低,界面剪切粘度增加,但变化幅度较小,而油滴表面的Zeta电位绝对值增大;原油与含发泡剂的模拟水所形成的W/O和O/W乳状液的稳定性随发泡剂浓度的增加而增强。     

气-固相法制备的 Ti-ZSM-5 的表征及其催化氧化性能--母体性质的影响

分别以B-ZSM-5和Al-ZSM-5沸石分子筛为母体，预处理后，在高温下与TiCl4进行气-固相反应合成钛硅沸石Ti-ZSM-5。以XRD、FT-IR、UV-Vis、XRF、ICP-AES、SEM等手段对催化剂进行了表征，并考察了母体性质对钛进入骨架及其存在形式的影响以及各样品的丙烯环氧化和苯酚羟基化性能。结果表明，母体本身的物化性能直接决定了所合成的Ti-ZSM-5分子筛中钛的含量及其存在形式。以脱硼ZSM-5分子筛为母体，所合成的Ti-ZSM-5中骨架钛含量高，非骨架钛含量低，催化性能最好。丙烯环氧化反应中，少量锐钛矿型非骨架钛的存在不会对过氧化氢的有效利用率产生太大影响，但当非骨架钛占据多数且为金红石型TiO2时，会使得过氧化氢的有效利用率急剧降低，同时由于反应活性中心少且被覆盖，催化活性降低；苯酚羟基化反应中，骨架钛含量的差异与催化剂晶粒的大小同时起着重要的作用，强酸中心的存在降低了样品的苯酚羟基化活性。