Characteristics of oil shale pyrolysis in a two-stage fluidized bed

Rapid pyrolysis of oil shale coupled with in-situ upgrading of pyrolysis volatiles over oil shale char was studied in a laboratory two-stage fluidized bed(TSFB) to clarify the shale oil yield and quality and their variations with operating conditions. Rapid pyrolysis of oil shale in fluidized bed(FB) obtained shale oil yield higher than the Fischer Assay oil yield at temperatures of 500-600 ℃. The highest yield was 12.7 wt% at 500 ℃ and was about1.3 times of the Fischer Assay oil yield. The heavy fraction(boiling point 350 ℃) in shale oil at all temperatures from rapid pyrolysis was above 50%. Adding an upper FB of secondary cracking over oil shale char caused the loss of shale oil but improved its quality. Heavy fraction yield decreased significantly and almost disappeared at temperatures above 550 ℃, while the corresponding light fraction(boiling point 350 ℃) yield dramatically increased. In terms of achieving high light fraction yield, the optimal pyrolysis and also secondary cracking temperatures in TSFB were 600 ℃, at which the shale oil yield decreased by 17.74% but its light fraction yield of 7.07 wt% increased by 86.11% in comparison with FB pyrolysis. The light fraction yield was higher than that of Fischer Assay at all cases in TSFB. Thus, a rapid pyrolysis of oil shale combined with volatile upgrading was important for producing high-quality shale oil with high yield as well.     

生物油中乙酸和乙醇共裂化获取汽油产物的研究简

Abstract Acetic acid was selected as the model compound representing the carboxylic acids present in bio-oil. This work focuses the co-cracking of acetic acid with ethanol for bio-gasoline production. The influences of reaction temperature and pressure on the conversion of reactants as well as the selectivity and Conaposition of the crudegasoline phase were investigated. It was found that increasing reaction temperature benefited the conversion of reactants and pressurized cracking produced a higher crude gasoline yield. At 400 ℃ and 1 MPa, the conversion of the reactants reached over 99% and the selectivity of the gasoline phase reached 42.79% （by mass）. The gasoline phase shows outstanding quality, with a hydrocarbon content of 100%.     

Preparation of Hydrogen through Catalytic Steam Reforming of Bio-oil

Hydrogen was prepared via catalytic steam reforming of bio-oil which was obtained from fast pyrolysis of biomass in a fluidized bed reactor. Influential factors including temperature, weight hourly space velocity (WHSV) of bio-oil, mass ratio of steam to bio-oil (S/B) as well as catalyst type on hydrogen selectivity and other desirable gas products were investigated. Based on hydrogen in stoichiometric potential and carbon balance in gaseous phase and feed, hydrogen yield and carbon selectivity were examined. The experimental results show that higher temperature favors the hydrogen selectivity by H2 mole fraction in gaseous products stream and it plays an important role in hydrogen yield and carbon selectivity. Higher hydrogen selectivity and yield, and carbon selectivity were obtained at lower bio-oil WHSV. In catalytic steam reforming system a maximum steam concentration value exists, at which hydrogen selectivity and yield, and carbon selectivity keep constant. Through experiments, preferential operation conditions were obtained as follows: temperature 800~850℃, bio-oil WHSV below 3.0 h-1, and mass ratio of steam to bio-oil 10~12. The performance tests indicate that Ni-based catalysts are optional, especially Ni/a-Al2O3 effective in the steam reforming process.     

Characterization of pyrolytic lignins with different activities obtained from bio-oil

Pyrolytic lignin, the water-insoluble fraction in bio-oil, often shows a high content and has strong intermolecular interactions with other compounds in bio-oil. In order to obtain pure pyrolytic lignin and facilitate the utilization of aqueous phase obtained from water extraction of bio-oil, methanol–water extraction method was employed to further separate the bio-oil water-insoluble phase in this paper. Different technologies, including Fourier transform infrared spectroscopy, gel permeation chromatography, and nuclear magnetic resonance, were adopted to characterize the structures of pyrolytic lignins with different activities obtained through this method. Both the heating value and the polymerization degree of high-molecular-weight pyrolytic lignin were higher than those of low-molecular-weight pyrolytic lignin. The molecular weight distribution of high-molecular-weight pyrolytic lignin was relatively wider, among which the contents of dimers to pentamers all accounted for 12% –18%,while the low-molecular-weight pyrolytic lignin mainly consisted of trimers(75.38%). The pyrolytic lignins had similar basic structures, both of which contained syringyl and guaiacyl units, whereas the low-molecular-weight pyrolytic lignin had more abundant syringyl units, reactive carbonyl groups and hydroxyl groups. Meanwhile,thermogravimetric study revealed that the final char residue yield of low-molecular-weight pyrolytic lignin was lower than that of high-molecular-weight pyrolytic lignin.     

Bromine content of lipids of marine organisms

Lipids were extracted from a number of organisms taken in the northern Pacific ocean and the bromine content measured by neutron activation analysis. The lipids of each species studied were found to contain bromine with concentrations ranging from ten to several hundred μg/g. The major portion of the bromine was associated with the fatty acids in Chromatographic separations; however, the presence of a number of different brominated compounds was indicated. When the fatty acids were prepared from the crude lipids by acid hydrolysis, partitioned into base, and then esterified, 60% of the initial bromine was recovered in the ester fraction. This would indicate the presence of brominated acids in marine lipids.     

Production of Indigo by Immobilization of E. coli BL21 （DE3） Cells in Calcium-Alginate Gel Capsules

The ability of catalyzing indole into indigo of gene engineering strain expressing P450 BM3 immobilized by entrapment in calcium-alginate gel capsules was examined,and various characteristics of immobilized cells were assessed.Optimum conditions for cells activity were not affected after immobilization,and pH and tempera- ture for both free and immobilized cells were found to be pH 7.5 and 35℃,respectively.The immobilized cells exhibited a markedly improved thermal stability than free cells.After five repeated experiments,the yield of indigo with the immobilized cells retained over 94%of their original activity,which indicated that the operational stability for recycling in batch processes was improved.     

Understanding the influence of microwave on the relative volatility used in the pyrolysis of Indonesia oil sands

In this paper, pyrolysis of Indonesian oil sands(IOS) was investigated by two different heating methods to develop a better understanding of the microwave-assisted pyrolysis. Thermogravimetric analysis was conducted to study the thermal decomposition behaviors of IOS, showing that 550 °C might be the pyrolysis final temperature. A explanation of the heat–mass transfer process was presented to demonstrate the influence of microwave-assisted pyrolysis on the liquid product distribution. The heat–mass transfer model was also useful to explain the increase of liquid product yield and heavy component content at the same heating rate by two different heating methods. Experiments were carried out using a fixed bed reactor with and without the microwave irradiation. The results showed that liquid product yield was increased during microwave induced pyrolysis,while the formation of gas and solid residue was reduced in comparison with the conventional pyrolysis. Moreover, the liquid product characterization by elemental analysis and GC–MS indicated the significant effect on the liquid chemical composition by microwave irradiation. High polarity substances(ε N 10 at 25 °C), such as oxyorganics were increased, while relatively low polarity substances(ε b 2 at 25 °C), such as aliphatic hydrocarbons were decreased, suggesting that microwave enhanced the relative volatility of high polarity substances. The yield improvement and compositional variations in the liquid product promoted by the microwave-assisted pyrolysis deserve the further exploitation in the future.     

海澡酸钙胶囊化重组E.coli BL21(DE3)生产靛蓝(英文)

The ability of catalyzing indole into indigo of gene engineering strain expressing P450 BM3 immobi- lized by entrapment in calcium-alginate gel capsules was examined,and various characteristics of immobilized cells were assessed.Optimum conditions for cells activity were not affected after immobilization,and pH and tempera- ture for both free and immobilized cells were found to be pH 7.5 and 35℃,respectively.The immobilized cells ex- hibited a markedly improved thermal stability than free cells.After five repeated experiments,the yield of indigo with the immobilized cells retained over 94%of their original activity,which indicated that the operational stability for recycling in batch processes was improved.     

Catalytic cracking of 1-butene to propylene by Ag modified HZSM-5

Silver modified HZSM-5 (AgHZ) zeolite catalysts were prepared by ion exchange method and their catalytic properties in the 1-butene cracking reaction were measured. The catalysts were characterized by infrared spec-troscopy with pyridine adsorption (Py-IR), N2 adsorption and X-ray diffraction (XRD). The effects of Ag loading and steaming treatment on catalytic performances were studied. It is found that the activity of HZSM-5 (HZ) cat-alyst significantly decreases with the steaming time, whereas AgHZ catalysts show stable activity in the steaming time of 24–48 h and their activities increase with the Ag loading. When the steaming time is 24–48 h, the yield of propylene over HZ catalyst significantly decreases, whereas it is stable over AgHZ catalysts. The AgHZ catalysts with Ag loadings of 0.28%–0.43%(by mass) show similar propylene yields (~30%), which are higher than that over the AgHZ catalyst with a Ag loading of 0.55%(by mass). These results indicate that the steam-treated AgHZ catalysts with optimum Ag loadings have higher yield of propylene and are more stable than the steam-treated HZ catalyst. The regeneration stability measurement in butene cracking also shows that the AgHZ catalyst steam-treated under a suitable condition has better stability than the HZ catalyst.     

Mild oxidative degradation of spent auricularia auricular substrate and molecular composition of carboxylic acids in the resulting soluble portion

Spent auricularia auricular substrate(SAAS) was oxidatively degraded with aqueous hydrogen peroxide(AHPO)/acetic anhydride(AAH) to produce carboxylic acids(CAs) under mild conditions. The results show that up to 53.6% of the organic matter in SAAS was converted to the soluble species(SSs). In total 122 CAs were detected in the SSs by the analysis with a gas chromatograph/mass spectrometer, which can be classified into 29 group components, mainly being aliphatic acids and along with small amount of aromatic acids. Among the aliphatic acids, normal alkanedioic acids are the most abundant. The detected aromatic acids include benzoic acids,phthalic acids, trimellitic acids, pyromellitic acids, and their derivatives. The synergistic oxidation and the released ·OH, CH_3COO·, and HOO· induced by AHPO/AAH play crucial roles in oxidatively degrading SAAS.     

Determination of polar compounds in Rundle shale oil

The acidic and basic components of three distillate fractions (light, middle and heavy) of shale oil from the Rundle (Queensland, Australia) deposit were selectively extracted. Capillary gas chromatography/mass spectrometry was used to identify individual polar components. The major nitrogen-containing polar compounds in the light fraction were alkyl-substituted pyridines, and substituted quinolines were more abundant in the middle and heavy fractions. Significant quantities of pyrrole derivatives were also identified. Small quantities of anilines and benzoquinolines made up the remainder of the bases. The oxygen-containing compounds were mainly phenolic in nature; alkyl-substituted phenols were the major components, but significant quantities of naphthols and traces of fluorenols were identified.     

厨余垃圾水热液化制取生物燃料

以厨余垃圾为原料进行水热液化,考察了反应温度和料液比对产物分布的影响。温度320℃、料液比1:15时,生物油产率最高为16.7%,继续升高温度或降低料液比将促进气体产物生成。与重质原油、常减压渣油相比,生物油氧、氮元素含量较高,热值为32.33~34.82 MJ·kg^-1,其中汽油和煤柴油馏分超过50%。利用GC-MS、FT-IR和FT-ICR MS对生物油化学组成、官能团和杂原子组成进行了表征。生物油是一种复杂混合物体系,已检测出烃类、酸类、醛类、酮类、酯类、胺类、酚类、醇类和含氮杂环类等多种物质,对其酸性组分进一步分析显示,含氧组分主要是O₂、O₃类化合物,含氮组分主要是N₁O₂、N₁O₃和N₁O₄类化合物。     

Biofuels from waste fish oil pyrolysis: Chemical composition

In a previous study, waste fish oil was converted into bio-oil by a fast pyrolysis process at 525 °C in a continuous pilot plant reactor with 72-73% yield. The bio-oil was distilled to obtain light bio-oil and heavy bio-oil and these biofuels were characterized in terms of their physico-chemical properties. In this study, the chemical composition of light bio-oil and heavy bio-oil was determined using GC-FID, GC-MS, ¹H and ¹³C NMR techniques. The GC-MS analysis of waste fish oil showed the main composition of fatty acids to be the following: C_16:0 (15.87%), C_18:2 (20.96%), C_18:1 (17.29%), C_20:5 (5.11%), C_20:1 (7.59%), C_22:6 (4.53%), C_22:1 (10.42%) and others. The GC-FID analysis of the light bio-oil showed 482 compounds that were PIONA classified as paraffins (4.48%), iso-paraffins (8.31%), olefins (26.56%), naphthenes (6.07%) and aromatics (16.86%). The heavy bio-oil had a similar chromatographic profile as diesel oil, with a high content of carboxylic acids and olefins. These results are in good agreement with those for the gasoline and diesel oil fractions of petroleum.     

生物质热解气分级冷凝对生物油特性的影响

利用分级冷凝手段对成分复杂的生物质热解气在不同冷凝温度下的分离特性进行研究,将成分复杂的混合物依据自身露点的不同,通过控制冷凝温度,实现生物油的分组富集。对热解气在不同冷凝温度(300℃、100℃、0℃和-20℃)下生成的各级液体产物的物理特性和化学成分进行系统分析。生物质热解气经过分级冷凝处理后得到4组生物油样品,其中0℃时得到的生物油产率最大,超过液体总量的50%;其次是100℃时的冷凝产物,为分子量80~200的有机物,以杂酚类物质为主;300℃冷凝得到的产物为沥青类物质,不含水分,状似固体碳,没有流动性。分级冷凝能够很好地将水分和有机酸成分从生物油中分离出来,几乎所有的有机酸和超过80%的水分都富集在0℃和-20℃冷凝组分中。结合各组分GC-MS的分析结果,对乙酸、苯酚、愈创木酚和多环芳烃等生物油中典型有机组分的分布特性进行分析总结,得到各类物质在分级冷凝过程中的富集规律。     

Fast pyrolysis of heavy metal contaminated willow: Influence of the plant part

Fast pyrolysis of heavy metal contaminated willow, with high concentrations of Cd, Cu, Pb and Zn, resulting from phytoremediation, is investigated. The distribution of the heavy metals depends on the plant part (leaves and branches). Nevertheless, their individual pyrolysis fractions (at an operational temperature of 623 K), i.e., bio-oil/tar and gas, are both heavy metal free. Some small differences in the kind and amounts of the organic compounds are found in the bio-oil and gaseous fraction. In view of practical considerations leaves and branches should nevertheless be pyrolysed simultaneously. The use of hyphenated thermal analytical techniques allows obtaining more detailed information on the compositional features of the pyrolysis fraction.     

Effects of particle size on the fast pyrolysis of oil mallee woody biomass

This study aims to investigate the effects of biomass particle size (0.18-5.6 mm) on the yield and composition of bio-oil from the pyrolysis of Australian oil mallee woody biomass in a fluidised-bed reactor at 500 °C. The yield of bio-oil decreased as the average biomass particle size was increased from 0.3 to about 1.5 mm. Further increases in biomass particle size did not result in any further decreases in the bio-oil yield. These results are mainly due to the impact of particle size in the production of lignin-derived compounds. Possible inter-particle interactions between bio-oil vapour and char particles or homogeneous reactions in vapour phases were not responsible for the decreases in the bio-oil yield. The bio-oil samples were characterised with thermogravimetric analysis, UV-fluorescence spectroscopy, Karl-Fischer titration as well as precipitation in cold water. It was found that the yields of light bio-oil fractions increased and those of heavy bio-oil fractions decreased with increasing biomass particle size. The formation of pyrolytic water at low temperatures (<500 °C) is not greatly affected by temperature or particle size. It is believed that decreased heating rates experienced by large particles are a major factor responsible for the lower bio-oil yields from large particles and for the changes in the overall composition of resulting oils. Changes in biomass cell structure during grinding may also influence the yield and composition of bio-oil.     

重质生物油理化性质及其热解特性研究

利用核磁共振波谱仪（NMR）与气相色谱/质谱联用仪（GC/MS）对重质生物油理化性质进行表征,并应用热重分析仪（ TG-DTG）与热裂解仪-气相色谱/质谱联用仪（Py-GC/MS）对重质生物油热解特性进行研究。结果表明：重质生物油主要由芳香族化合物和糖类物质组成。重质生物油在N₂氛围下热解主要分为三个阶段: 室温~300℃为蒸发段,300～520℃为热解段,520～800℃为成焦段。重质生物油经不同温度热解后,产物种类有明显差异：中温段（低于500℃）热解时,产物种类随温度的升高逐渐增加;高温段（高于500℃）热解时,随着热解温度的提高,产物种类逐渐趋于稳定。     

丙胺溶液水热液化海藻残渣及产物生物油分析

使用丙胺溶液对裙带菜孢子叶残渣进行水热液化,分析了水热液化后生物油、水溶性物质和固体残渣的成分。在丙胺浓度1.5 mol·L^-1、反应温度240℃、料液比1：10的条件下得到生物油的最大产率为39.81%（质量）。生物油通过GC-MS和FT-IR进行分析,结果表明成分包含醇类、烷类、酯类、酸类、酚类和酰胺类等,并存在C=C、C=O、O-H等化合键。水溶性物质通过HPLC和GC-MS进行分析,结果表明主要产物为酸类物质。固体残渣通过XRD进行分析,结果表明水热液化后纤维素的结晶度降低。最后对丙胺进行回收,在温度100℃条件下回收率达到92.56%。     

Catalytic Pyrolysis of Pine Wood Sawdust to Produce Bio-oil: Effect of Temperature and Catalyst Additives

In this work, non-catalytic pyrolysis of Turkish pine (Pinus brutia Ten.) wood sawdust was performed in a fixed-bed reactor at various temperatures to obtain the optimum conditions to achieve a maximum bio-oil yield. The highest yield of bio-oil was obtained about 46 wt% at 550°C for non-catalytic pyrolysis. At the optimum conditions, the effects of different catalyst types (KOH, ZnCl₂, and ZnO) and amount of catalyst (5, 10, 15, and 20 wt%) on the pyrolysis product yields and bio-oil properties were investigated. The presence of catalysts changed the product distribution considerably. Increasing the amount of catalyst led to a decrease in the yield of liquid product, while the gas and char yields increased compared to non-catalytic pyrolysis. The chemical compositions of bio-oil were determined with GC-MS analyses. It was determined that bio-oils contain a large variety of organic compounds, such as furans, aldehydes, ketones, phenols, acids, benzenes, alcohols, alkanes, and polycyclic aromatic hydrocarbons (PAHs). The catalysis by KOH significantly increased the levels of phenols, while it reduced the formation of acids and aldehydes. ZnCl₂ produced bio-oil with high percentages of aldehydes. Moreover, ZnO reduced the proportion of PAH in the bio-oil. These results demonstrated that bio-oils could improve with a catalyst. Therefore, catalyst selection for high bio-oil quality is crucial in industrial applications.     

餐厨废弃油脂合成的生物油磺酸盐与碱复配的界面性能

利用餐厨废弃油脂经磺化反应合成了生物油磺酸盐,并与碳酸钠进行复配,测定了复配体系的界面活性、动态界面张力、界面张力稳定性和分配性能。结果表明,生物油磺酸盐的平均分子量为393,属于水溶性;生物油磺酸盐与碳酸钠的复配体系具有较宽的界面活性范围和较好的界面张力稳定性。在碳酸钠质量分数为0.4%~0.8%范围内,能降低油水界面张力至10~(-3)m N/m。随着碳酸钠质量分数增加,复配体系与原油的最低界面张力呈现先减小后增大的趋势,碳酸钠最佳质量分数为0.6%。放置90 d后,最低界面张力基本上保持在10~(-3)m N/m。碳酸钠质量分数一定时,随着生物油磺酸盐质量分数增加,生物油磺酸盐在油水两相中的分配系数降低,当质量分数大于0.25%后,分配系数降幅变小。生物油磺酸盐质量分数一定时,随着碳酸钠质量分数增加,生物油磺酸盐在油水两相中的分配系数增大,增幅较小。