胜利褐煤超临界醇解反应行为研究

对胜利褐煤在甲醇、碱体系中的超临界反应行为进行了研究,考察了反应温度、反应时间和碱的种类分别对胜利褐煤转化率、产物收率和分布规律的影响.结果表明,反应温度显著影响褐煤的转化率和产物收率,产物主要为四氢呋喃可溶组分(占67%～85%)和甲苯可溶组分(占8%～22%);300℃时,胜利褐煤在甲醇-NaOH体系中转化率和收率最高(99%左右);反应时间显著影响褐煤的转化率和产物收率,80 min后褐煤的转化率和产物收率分别为99%和100%;反应过程中四氢呋喃可溶组分可转化为甲苯可溶组分、正己烷可溶组分和水溶性组分;碱的种类对褐煤超临界醇解转化率和产物收率有显著影响.     

煤直接液化油渣萃余物组成、性质分析及应用场景探讨

煤直接液化油渣用洗油萃取后再经离心分离、常减压闪蒸等工艺处理,分离沥青质后可得到不同等级的沥青产品以及萃余物,将萃余物大规模利用,可以大大提高企业的经济效益。分析了萃余物的族组成、性质,在此基础上讨论了萃余物应用于配煤气化、循环流化床锅炉掺烧、炭灰分离的可行性。分析认为：萃余物更适合通过配入原料煤应用于干粉煤气化。     

煤焦油石油醚萃余物族组分分离与分析

煤焦油石油醚萃余物组成成分里包含许多类型的酚类,所以其分离的价值十分高,但是利用的基础是组分的分离与分析.开展对煤焦油石油醚萃余物的研究,对煤焦油的分离过程和分离结果进行了阐述和分析,4种洗脱物TS、EAS、MAS、THFS收率按高低顺序分别为1.41％、1.70％、18.97％、33.22％,相加的和值仅为55.30...     

从紫皮大蒜萃余物中提取SOD

通过对紫皮大蒜中优先提取SOD与超临界CO2萃取蒜油后提取SOD的对比研究,实验结果表明,从紫皮大蒜萃余物中提取的SOD相对于优先从新鲜紫皮大蒜中提取的SOD活力相差不到10%。说明紫皮大蒜萃余物仍有很大的利用价值。     

从大蒜萃余物中提取超氧化物歧化酶研究

通过对大蒜中优先提取超氧化物歧化酶(SOD)与超临界CO2萃取蒜油后提取SOD的对比实验,结果表明,从大蒜萃余物中提取的SOD相对于优先从新鲜大蒜中提取的SOD活力相差不到10%。说明萃余物仍有很大的利用价值。     

两种萃余煤的温和氧化产物的组成分析

分别用二硫化碳 ( CS2 ) /四氢呋喃 (体积比 1∶ 2 )混合溶剂和环己酮对义马煤和美国Pocahontas No.3( P3)标准煤样进行了彻底萃取 ,在 60℃下用 30 %双氧水溶液分别氧化了所得的两种萃余煤 ,用 GC/MS对反应混合物中的水溶液的苯可溶物和水不溶物的 CS2 可溶物进行了分析 .结果表明 :在所得水溶液的苯可溶物中都检测出苯酚 ;在由义马萃余煤氧化所得的水不溶物的CS2 可溶物中检测出多种含氧有机化合物和长链烷烃 ,而在 P3萃余煤氧化所得的水不溶物的 CS2可溶物中只检测到一系列长链烷烃 .     

碳酸钾催化竹材在超临界甲醇中醇解

以K2CO3为催化剂,甲醇为溶剂,在不锈钢高压反应釜内进行了竹材的超临界条件下的醇解反应,用气相色谱-质谱联用仪(GC-MS)定性分析了醇解产物的成分.分别考察了反应温度、反应时间和催化剂用量对竹材醇解转化率的影响.结果表明,当达到甲醇超临界状态时,不论是否添加催化剂,竹材的醇解转化率都有一个明显的突跃;添加K2CO3催化剂后,超临界醇解转化率明显升高,K2CO3催化剂有利于溶解木素,并生成苯酚和酚类化合物,而且减少了氧杂环的生成,醇解液体产物中没有半纤维素和纤维素醇解的主要产物糠醛,甲酯类等有机小分子的含量变化较大,乙酸甲酯、丙酸甲酯和丁酸甲酯等含量均有大幅度提高.     

农作物秸秆快速热解液化与超临界醇解方法分析对比

农作物秸秆是生物质能源的重要组成部分,其开发和利用备受关注。对采用快速热解液化和超临界醇解两种技术降解农作物秸秆进行阐述,并对这两种技术做了比较。结果表明:较于快速热解液化,超临界醇解反应条件温和,一次反应所得产物含有长链脂肪酸甲酯和大量的酚类及其衍生物,可通过分离提取用于生产高品质的生物柴油和化学品。     

煤液化残渣萃余物与煤共气化的灰渣特性

与煤共气化是实现煤直接液化残渣萃余物(ER)资源化利用,提升煤直接液化工程整体经济性的重要途径。气化过程灰渣的流动性是影响气化操作条件的重要参数,利用灰熔点仪、高温旋转黏度计、XRD及SEM等测试手段考察了ER与煤共气化的灰渣熔融特性、黏温特性及晶体特性,并结合壳牌气化装置入炉煤配比和操作条件,从灰化学角度确定ER的最佳掺混比例及气化操作窗口。结果表明：ER属于高灰、高铁、高钙、高硫物质,且其灰成分偏碱性,随煤中ER添加量增大,掺混后的灰分、铁含量和硅铝比逐渐增大。当萃余物质量分数超8%,全液相温度T_liq降低,但萃余物添加量超20%时,熔渣类型从玻璃渣转变为结晶渣。XRD与SEM分析结果表明钙长石的析出造成熔渣类型改变,钙长石的析出主要是因为萃余物的添加使熔渣黏度降低,熔渣中团簇的扩散能力增强,有利于结晶行为。结合Shell气化炉的操作条件及对煤灰中铁含量的要求,当萃余物添加量为10%时,共气化熔渣适合气化炉排渣,对应的排渣窗口为1 335～1 557℃。该研究结果为ER与煤共气化提供指导,提高煤直接液化流程的经济性。     

煤阶对煤-甲醇超临界醇解反应体系的影响

对3种典型煤种在甲醇-碱体系中的超临界反应行为进行了研究,主要考察了典型煤种煤阶(煤化程度)对煤炭在煤-甲醇超临界体系中醇解转化率及醇解产物分布的影响.结果表明,低碳、高氢、高氧、变质程度较低的煤种较易发生醇解转化反应,煤炭的醇解转化率随着煤阶的增加而呈下降趋势.     

Effect of mineral matter on product yield in supercritical water extraction of lignite at different temperatures

The effect of demineralization on conversion of Soma Lignite in supercritical water extraction was studied using a batch autoclave operated at 400, 450 and 500 °C under nitrogen atmosphere. The experiments were carried out to investigate the effect of mineral matter and temperature on gaseous, liquid, residue yield and composition of gaseous products. According to the results, main product in gaseous state is CO₂. Temperature is key factor affecting product distribution when compared the effect of minerals in lignite. As temperature was increased, yield of gas and solid residue increased, while yields of liquid decreased for raw and demineralized lignite samples. The removal of mineral matter caused to decrease the conversion for all lignite samples and to increase the carbon content of solid residue in supercritical water extraction.     

Phase transition at subcritical and supercritical conditions of triglycerides methanolysis

The analysis of phase equilibrium between methanol and glycerides during methyl esters of fatty acids (FAME or biodiesel) synthesis at high pressure and temperature is very important for describing the kinetic and process design. It was studied at pressure between 1.1 and 28.0 MPa and temperature from 150 to 270 °C. The transition of phases and composition of identified phases was calculated using RK-Aspen EOS and obtained values were also compared to experimentally determined data at subcritical condition (1.1-4.5 MPa and 150-210 °C).Results of experimental investigation, as well as performed simulation of some specified composition of reaction mixture, showed that system of triglycerides and methanol, at the beginning of reaction (at all analysed conditions except for supercritical state of mixture) is in equilibrium between two liquid phases. During the methanolysis of triglycerides, the phase's distribution was changed accordingly and it highly depends on actual composition of reaction mixture, temperature and pressure. Calculated and measured values indicated that distribution of methanol between the oil phase, the methyl esters, and the glycerol rich phase exists and depends of working condition. As a consequence of fact, that the methanolysis of triglycerides (oil) is mainly realized in the oil-rich phase, at the end of reaction, after all triglycerides are converted into FAME and glycerol, the oil phase disappears. Furthermore, according to the results of phase composition calculation, it was shown that from the beginning to the end of reaction one phase only exists, for methanolysis performed at 270 °C and 20.0 MPa.     

褐煤的溶剂萃取研究进展

介绍了褐煤的溶剂萃取研究状况,包括褐煤的组成特征,萃取剂的选取原则,不同萃取溶剂和不同溶剂萃取方式等得到的褐煤萃取效果,并对褐煤溶剂萃取研究进行了总结,指出目前褐煤溶剂萃取研究还停留在实验室研究阶段,距离工业应用还有很大距离。     

Product analysis of catalytic multi-stage hydropyrolysis of lignite

A lignite added with 0.2% MoS₂ as catalyst was pyrolyzed under H₂ using multi-stage heating method (MHyPy) which means holding a suitable time near the peak temperature. The product distribution and detailed analysis of products were performed. The results show that the tar yield increased to 63.9% during MHyPy compared with that of 51.8% in traditional hydropyrolysis (HyPy), while the gas yield decreased to a half. This suggests the effective utilization of hydrogen during MHyPy. The light aromatics in the tar from MHyPy increased remarkably 42, 37.8 and 115.4% for BTX, PCX and naphthalenes, respectively. Biphenyls were also observed in the tar from MHyPy, which indicated the effective hydrogenation occurs during catalytic MHyPy. The rich pore structure of the char from MHyPy hints its high reactivity in the subsequent conversion process such as gasification and combustion.     

Scale-up study of supercritical fluid extraction process for clove and sugarcane residue

Many scale-up criteria for supercritical fluid extraction (SFE) can be found in literature. However, the studies are often divergent and inconclusive; therefore, more studies on this field are needed. The objective of the present work was to study the scale-up of SFE process focusing application to Brazilian raw materials. A laboratory scale equipment (290 mL extraction vessel) and a pilot scale equipment (5.15 L extraction vessel) were used to study scale-up of SFE for clove and sugarcane residue. The scale-up criterion adopted consisted in maintaining solvent mass to feed mass ratio constant. The criterion was successfully used for a 15-fold scale-up of overall extraction curves for both raw materials studied; yields in pilot scale were slightly higher than in laboratory scale. The criterion studied allows a rapid and simple scale-up procedure, which can be very useful for the purpose of developing SFE technology at industrial scale in developing countries where such technology is still not available at industrial level.     

Recovery of triglycerides from used frying oil by extraction with liquid and supercritical ethane

The extraction of triglycerides from used frying oil with liquid and supercritical ethane has been studied in a semibatch system at different temperatures (25-80 °C) and pressures (150-250 kg/cm²). It has been found that isobaric decreases of temperature and isothermal increases of pressure lead to both increasing extraction yields and decreasing separation efficiencies. Lipid fractions recovered in the high density region had acceptable concentrations of polar compounds.Results with ethane have been compared to those reported for CO₂ in earlier works. At similar reduced densities of the solvents, oil solubility in ethane was higher than in CO₂, being the separation efficiency of polar fractions slightly better when using ethane.The extraction process was further analyzed in a packed countercurrent column. At optimum conditions (250 kg/cm², 25 °C, and solvent-to-oil ratio 45 g:g) about 85% of the triglycerides were recovered, being 11.2% the polar content of the triglyceride fraction recovered.     

Bio-oil production from Glycyrrhiza glabra through supercritical fluid extraction

Glycyrrhiza glabra was liquefied by ethanol and acetone in an autoclave under high pressure using potassium hydroxide or sodium carbonate as the catalyst, as well as without catalyst at various temperatures (250, 270 and 290 °C) for producing bio-oil. The experimental results show that the yield of the main liquefaction product (bio-oil) was influenced significantly by liquefaction parameters such as solvent type, and catalyst type and temperature. The results showed that the maximum bio-oil yield was obtained in acetone (79%) at 290 °C without catalyst. The products of liquefaction (bio-oil) were analysed and characterized using various methods including elemental analysis, Fourier transform infrared spectroscopy and gas chromatography–mass spectrometry. GC–MS identified 131 and 147 different compounds in the bio-oils obtained at 270 and 290 °C, respectively.     

Continuous extraction of glycerol acetates from their mixture using supercritical carbon dioxide

Supercritical carbon dioxide was used for partially selective extraction of triacetin from a mixture of triacetin, diacetin, and monoacetin with a molar ratio of 1:2:1. The extraction was carried out in two stages. In the first stage, a central composite design was used to optimize the four variables of pressure, temperature, liquid CO₂ flow rate, and extraction time at three levels using a semi-continuous, supercritical carbon dioxide extraction setup. The composition of the extract under the predicted optimum conditions (i.e., 109 bar, 56 °C, 0.86 mL min⁻¹, and 61 min) was about 69% triacetin accompanied by only 30% diacetin and no detectable monoacetin. In the second stage, the effect of the two factors, pressure (100, 109, and 140 bar) and liquid CO₂ flow rates of 0.86 and 1.5 mL min⁻¹ measured at average laboratory temperature (27 °C) and pressure (0.89 bar), were studied using a continuous, supercritical carbon dioxide fractionation setup equipped with a glass-bead packed column kept under a thermal gradient of 56-70 °C. The experimental design was organized as a 3 × 2 general factorial design. Under the best conditions (i.e., 140 bar and 1.5 mL min⁻¹), the extraction yield of triacetin and diacetin were 41.8 and 3.0%, respectively, without any detectable monoacetin as verified by GC-FID.     

ATP技术用于褐煤热解提质的技术经济分析

介绍了ATP(A lberta-Taciuk Processor)技术的发展历程及应用领域,提出利用ATP技术加工处理内蒙古褐煤的设想,并进行了技术经济分析,得出利用ATP技术处理褐煤的可行性结论。