煤焦油的改质研究

以煤焦油为原料，通过在300℃空气氧化120min-480min和在430℃氮气热缩聚50min-270min，制备了一系列具有相近软化点的煤焦油沥青。原料煤焦油和改质沥青的化学结构通过了NMR、FT－IR、元素分析、软化点、族组成和偏光光学进行分析。在1．6MPa、480℃下将改质煤焦油沥青进行焦化，考察了焦收率和光学组织结构变化。结果表明空气氧化和氮气热缩聚可提高煤焦油沥青软化点、甲苯不溶物含量和焦收率，与氮气热缩聚沥青相比，相近软化点的空气氧化沥青具有较高的焦收率和O／C原子比。空气氧化煤焦油沥青成焦后各向异性光学结构单元尺寸随空气氧化时间增加而逐渐减小，而氮气热缩聚沥青成焦后均生成各向异性广域光学结构。     

平朔气煤DF_5的组成特性及煤液体统计平均结构参数的相似性

烟煤煤焦油、沥青和煤萃取物的表观特性的相似性已受到人们广泛关注[1]。早在1956年Ｏｒｉｎｇ等人[2]已用红外光谱研究了高真空短途径热解煤焦油和原煤的组成。研究表明,煤焦油中存在和原煤相同或相似的物质。80年代Ｌａｄｎｅｒ[3]指出,煤的萃取物结构特征反映了煤中的部分原始结构单元,所以根据萃取物的结构特征去推测煤的结构是合理的。研究也指出[1],煤萃取馏分的平均分子量和部分沥青馏分的平均分子量非常相近。因此煤中在强溶剂中能溶解的部分(萃取馏分)和煤焦油、沥青之间的相似性已被作为一个煤焦油中的部分高分子化合物代表煤中部…     

辽河稠油减渣深度戊烷脱沥青的研究

以戊烷为溶剂,在脱沥青实验装置上对辽河稠油减渣进行梯级分离,得到轻脱油、重脱油和脱油沥青。在温度155℃~170℃、压力为4.0 MPa~7.0 MPa,考察了温度、压力变化对脱沥青油收率及性质的影响。用超临界萃取分馏的实验结果关联了脱沥青油残炭、N元素、Ni元素的脱除率。结果表明,压力升高、温度降低,脱沥青油收率增加,轻、重脱油的残炭值及S、N、Ni、V等元素含量升高,脱沥青油性质变差。在脱沥青油收率最高为74.23%时,Ca、Ni元素的脱除率分别为92.75%、74.50%;残炭的脱除率为62.13%;N、S元素的脱除率分别为40.17%、24.10%。超临界萃取馏分油的杂质脱除率与脱沥青油的杂质脱除率有较好的相关性。     

中温热解焦油重馏分悬浮床加氢裂化的研究

以中温热解煤焦油为原料,对其性质进行了分析,其中,350℃重质馏分中胶质含量30.88%,沥青质含量37.27%,四氢呋喃不溶物3.36%,属于常规固定床加氢裂化难以直接处理的馏分。合成了一种Mo系超分散催化剂,采用FT-IR、XPS、XRD、SEM和TEM等对催化剂进行了表征,催化剂中含有Mo=O和Mo-S特征结构,活性金属的硫化率为84.34%,在体系中具有优良的分散性,在反应体系内原位分解为超分散MoS_2颗粒;在0.25 t/d连续装置上进行了热解重油悬浮床加氢裂化实验研究,考察了反应条件对产物分布情况和结焦率的影响,得出适宜的反应条件为19 MPa,440℃,催化剂的添加量为300 mg/kg;此条件下石脑油收率24.47%,柴油馏分收率49.71%,结焦率1.32%。     

减压渣油掺炼工业供氢剂缓和热转化的基础研究

以FCC油浆及其窄馏分作为工业供氢剂,首先测定其受热供氢能力,然后在此基础上考察了掺炼工业供氢剂对减压渣油缓和热转化生产燃料油和部分轻质油的改进效果及其化学原因.在实验室热反应装置上对减压渣油(VR)为原料掺炼FCC油浆(DO)及其窄馏分段(DO3)热转化实验结果表明,在400 ℃、100 min反应条件下随着供氢剂掺炼比增大,小于180 ℃馏分的收率减少,180 ℃～350 ℃馏分收率增加,大于180 ℃燃料油的100 ℃黏度减小、安定性增加;当掺炼比达15%时,燃料油的安定性合格.减压渣油掺炼相对供氢能力较大的工业供氢剂进行缓和热转化,有利于在提高轻油收率的同时使得燃料油黏度较低、安定性合格;但是燃料油四组分含量的变化与安定性关系不大.进一步研究表明,工业供氢剂对于减压渣油缓和热转化所得燃料油具有较好安定性的化学原因在于,工业供氢剂可同时抑制前沥青质的生成和沥青质分子缔合指数的增加.     

孤岛减压渣油窄馏分的热反应动力学：——反应级数的计算

用超临界流体萃取精密分馏技术将孤岛减压渣油分成１５个窄馏分，选取其中８个在热重装置上进行了反应动力学研究。所得数据用（经本文作者改进）Ｚｓａｋｏ法进行动力学处理，计算了各窄馏分的热反应级数。结果发现，升温速率的改变对各窄馏分在同一转化率范围的反应级数影响不大，而在每一升温速率下，反应级数随反应温度和转化深度不同而改变。同时，不同升温速率下，随着转化深度的增加，各窄馏分的表观活化能升高。     

大港减压渣油的多层次分离与组成结构研究

采用超临界戊烷萃取分馏技术，分离了大港减压渣油，得到16个窄馏分和1个萃余残渣，对其组成和结构进行了表征；对超临界萃取分离窄馏分进行了四组分分离，研究了饱和分、芳香分、胶质和沥青质等亚组分的元素组成、相对分子质量分布和平均分子结构。结果表明，由窄馏分得到的四组分（SARA）性质结构差别很大，饱和分的平均分子结构最简单，芳香分的平均相对分子质量最小，胶质中的硫、氮含量最多，从萃余残渣中得到的沥青质相对分子质量分布范围最宽（200~40000）。     

白术挥发性成分的超临界流体萃取及其分析

采用超临界流体萃取白术挥发油成分,对萃取条件进行优化,并用气相色谱、气相色谱－质谱分析鉴定出超临界流体萃了的挥发油中22个化合物。最佳的超临界流体萃取条件为压力22.0MPa,温度60℃,0.5mL乙醇作改性,先静态萃取10min(CO2用量2.0mL),再动态萃取40min(CO2流速为0.3mL/min)。将超临界流体萃取与水蒸气蒸馏进行对比,水蒸气蒸馏5h的油收率仅为超临界流体萃取1h油收率的10.32%,证明超临界流体萃取替代传统萃取的必要性。     

超临界水中煤焦油沥青轻质化的实验研究

采用间歇超临界水（supercritical water, SCW）反应器,考察了反应温度（400℃~480℃）、停留时间(1 min~80 min)和反应压力（25 MPa~40 MPa）对煤焦油沥青轻质化的影响。与常压N2热解相比,煤焦油沥青在SCW中反应后产物中的轻油质量分数高,残焦质量分数低,表明SCW可以促进煤焦油沥青的轻质化反应进行并抑制缩合反应。沥青质是煤焦油沥青在SCW中发生反应的主要组分。在440 ℃和34 MPa时反应20 min,产物中轻油的质量分数可达原料的两倍,说明煤焦油沥青在SCW中可以发生明显轻质化反应。与温度相比,压力和停留时间的影响相对较小。     

煤焦油酚的高效液相色谱分析

煤衍生产物中酚类化合物是重要的化工原料,对其组成的分析具有实际意义。近几年,用GC和GC/MS以及HPLC研究煤液化油中和高温煤焦油中的酸性萃取物已有些报道,在以正相和反相HPLC法研究烷基酚的分离方面,亦做了不少工作,而此类研究在国内实属少见,本工作目的在于确定一种分析高温煤焦油中酚类化合物,既简单迅速、又准确方便的高效液相色谱法。     

Optimization of the extraction and fractionation of corn bran oil using analytical supercritical fluid instrumentation

Supercritical fluid extraction (SFE) is combined with supercritical fluid chromatography (SFC) in an analytical mode to develop a system for fractionating and enriching high value ferulate-phytosterol esters (FPE) contained in corn bran oil. Corn bran is initially extracted with neat supercritical carbon dioxide (SC-CO2) at various pressures (13.8, 34.5, and 69 MPa) and temperatures (40, 60, and 80 degrees C) to see if the FPE can be enriched in the extracts. These initial studies show the greatest percentage of FPE could be extracted under two sets of conditions: 69 MPa at 80 degrees C and 34.5 MPa at 40 degrees C. Both sets of parameters yield an extract containing approximately 1.25% FPE. A stock supply of corn bran oil is then produced by scaled-up SFE at 34.5 MPa and 40 degrees C for subsequent chromatographic fractionation. The SFE-obtained corn bran oil is then applied to the head of a minichromatographic column containing an amino-propyl sorbent. SFC is than commenced using neat SC-CO2 at 69 MPa and 80 degrees C to remove the majority of the triglyceride-based oil. Pressure and temperature are then lowered to 34.5 MPa and 40 degrees C, respectively, and ethanol is added as a modifier. The modifier is added in an increasing stepwise gradient program, and fractions are collected at equal volume intervals. The resultant fractions are analyzed by analytical high-performance liquid chromatography with evaporative light-scattering detection and show that FPE could be enriched to a 14.5% (w) level.     

Extraction of flavonoids from Rhodiola sachlinesis A. Bor by UPE and the antioxidant activity of its extract

Rhodiola sachlinesis, A. Bor is one of the most popular traditional Chinese medicines and has been proved to have many effective compounds, such as flavonoids, anthraglycosides, essential oil with cinnamic aldehyde and citral and organic acids. In this article, a new method of ultrahigh pressure extraction (UPE) was used to extract flavonoids from R. sachlinesis. Uniform Design was employed to get the optimum extraction conditions. The optimum UPE conditions were as follows: pressure was 500 MPa; ethanol concentration was 40%; solid/liquid ratio (g mL(-1)) was 1 : 70. The optimum extraction yield of flavonoids was 52.33 mg g(-1). The antioxidant activity of the crude extract was tested with DPPH assay. It showed a higher activity, compared with tertiary butyhydroquinone (TBHQ) at the same concentration (1 mg mL(-1)).     

中温煤焦油沥青的超临界溶剂抽提和分离

用超临界溶剂在半连续装置上对中温煤焦油沥青（ＭＣＴＰ）进行了抽提和分离，考察了抽提段的实验条件对灰分和吡啶不溶物（ＰＩ组分）脱除率的影响；在分离段使用升温和／或降压法、精馏法调节ＭＣＴＰ族组成分布，并用分步抽提法调节ＭＣＴＰ的族组成。实验表明：用甲苯为超临界溶剂抽提可脱除全部灰分，ＰＩ组分也可在较低的压力下选择性地脱除；采用升温和／或降压法对抽出物可进行一定程度的分离，但对庚烷可溶物（ＨＳ组分）分离的选择性不高；采用精馏法可选择性地脱除ＨＳ组分，但尚需改进设备进一步提高分离效率；采用分步抽提法用石油醚作一次抽提溶剂可高选择性地脱除ＨＳ组分，其选择性在９５％以上。     

超临界二氧化碳萃取秋水仙碱（英文）

 利用超临界二氧化碳对秋水仙块根（经粉碎）中的秋水仙碱进行了萃取,采用高效液相色谱法对萃取出的秋水仙碱的质量分数进行了测定。实验选择40℃20～40MPa作为超临界苹取的操作条件,采用体积分数为95％的乙醇在索氏提取器中对样品进行了对比苹取实验。结果表明:不加浸泡剂进行浸泡处理的样品中的秋水仙碱很难被超临界二氧化碳萃取,在40℃,35MPa条件下,消耗1．28mol的二氧化碳只得到3％的萃取率。加入极少量的有机溶剂浸泡处理样品15min后再进行超临界萃取,可以极大程度地提高秋水仙碱的萃取率。     

克拉玛依减渣热转化前后的溶解度参数研究

对克拉玛依减渣进行适度热转化,确定了其裂解深度最大且不结焦的条件。利用超临界萃取分馏技术,将克拉玛依减渣及其热转化残渣油分离成一系列窄馏分和萃余残渣,对窄馏分及萃余残渣的性质（相对分子质量、密度、残炭、C、H、N、S元素和金属元素等）进行了表征。用改进的方法测定了萃余残渣的溶解度参数,并根据性质计算了各个窄馏分的溶解度参数,克拉玛依减渣及其热转化残渣油萃余残渣的溶解度参数分别为18.27 MPa1/2和19.79 MPa1/2;从溶解度参数的角度解释了渣油加工过程中的分相、结焦等问题。     

Comparative analysis of the oil and supercritical CO(2) extract of Cymbopogon citratus Stapf

Dried and ground leaves of lemon grass (Cymbopogon citratus Stapf.) were used as a matrix for supercritical extraction of essential oil with CO(2). The objective of this study was to analyze the influence of pressure on the supercritical extraction. A series of experiments were carried out, for 360 min, at 50 degrees C and at different pressures: 90, 100, 110 and 120 bar. Extraction conditions were chosen to maximize citral content in the extract oil. The collected extracts were analysed by GC-MS and their composition was compared with that of the essential oil isolated by hydrodistillation and by steam distillation. At higher solvent density the extract aspect changes passing from a characteristic yellow essential oil to yellowish semi-solid mass because of the extraction of high molecular mass compounds. The optimum conditions for citral extraction were 90 bar and 50 degrees C, at these conditions citral represent more than 68% of the essential oil and the extraction yield was 0.65% while the yield obtained from hydrodistillation was 0.43% with a content of citral of 73%.     

Supercritical fluid extraction of cynaropicrin and 20-hydroxyecdysone from Leuzea carthamoides DC

Leuzea carthamoides is an adaptogenic plant containing biologically active compounds as ecdysteroids and guaianolide-type sesquiterpene lactones, conventionally extracted from the plant with ethanol. It may be a potential source of the mentioned natural compounds. Ethanol-modified near-critical CO(2) was used as selective solvent with the aim to increase the level of 20-hydroxyecdysone in the extract from L. carthamoides roots and to remove selectively cynaropicrin, a sesquiterpene lactone of bitter taste, from the leaves. The extraction conditions were varied (pressure 20-28 MPa, temperature 40-60 degrees C, ethanol concentration in the solvent 0-7.1%) and the extraction yield and extract composition were compared with the results of ethanolic extraction. The supercritical fluid extraction (SFE) from finely powdered plant was controlled by phase equilibrium. Cynaropicrin was quantitatively removed from the leaves where 89% of 20-hydroxyecdysone was retained. The extraction yield of 20-hydroxyecdysone from roots with ethanol-modified CO(2 )was lower by 30% than with ethanol but its concentration in the extract was higher by 67%.     

FCC油浆抽提分离产物结构组成分析

以切尾FCC油浆为原料，采用DMF和反抽提剂的复配溶剂进行抽提分离，对FCC油浆及其抽提产物的物性和组成进行了分析表征。结果表明，复配溶剂可以较好地将FCC油浆分离成以芳香烃为主的抽出相和以饱和结构为主的抽余相，在抽出油收率为58.5%时，抽出油芳香分含量80.5%，芳碳率为73.82%，所含芳烃以二环、三环和四环为主，可以作为橡胶填充油和增塑剂等的原料；抽余油饱和分含量高达90%以上，芳碳率只有2.38%，基本不含杂原子，可以作为优良的催化裂化原料。溶剂抽提可以使低附加值的FCC油浆得到较好的利用。     

Supercritical fluid extraction of grape seed oil and subsequent separation of free fatty acids by high-speed counter-current chromatography

Supercritical fluid extraction (SFE) of grape seed oil was performed to study the effect of various parameters such as pressure, temperature and the particle size of the sample on the yield and composition of oil using an analytical-scale SFE system. Then the extraction was scaled up by 125 times using a preparative SFE system under the optimized conditions of high pressure (30-40 MPa) and low temperature (35-40 degrees C) with medium particle size (20-40 mesh). The maximum yield of the oil can reach 6.2% with pure supercritical CO2 and 4.0% more oil can be obtained by adding 10% of ethanol as modifier. The unsaturated fatty acids (UFSs) make up about 70% in the oil on the basis of free fatty acids. The grape seed oil was then subjected to separation and purification for free fatty acids after saponification by high-speed counter-current chromatography coupled with evaporative light scattering detection (ELSD). The separation of 1.0 g of oil can yield about 430 mg pure linoleic acid at 99% purity. The fatty acids were analyzed by HPLC-ELSD.