Preparation of silica aerogel from oil shale ash by fluidized bed drying

The silica aerogel with high specific surface area and large pore volume was successfully synthesized using oil shale ash (OSA) via ambient pressure drying. The oil shale ash was burned and leached by sulfuric acid solution, and then was extracted using sodium hydroxide solution to produce a sodium silicate solution. The solution was neutralized with sulfuric acid solution to form a silica gel. After washing with water, the solvent exchange with n-hexane, and the surface modification with hexamethyldisilazane (HMDZ), the aged gel was dried by fluidization technique and also using a furnace to yield silica aerogels. The physical and textural properties of the resultant silica aerogels were investigated and discussed. The results have been compared with silica aerogel powders dried in a furnace. From the results, it is clear that the properties of silica powders obtained in fluidized bed are superior to that of powders dried in the furnace. Using fluidization technique, it could produce silica aerogel powders with low tapping density of 0.0775 g/cm³, high specific surface area (789 m²/g) and cumulative pore volume of 2.77 cm³/g.     

油页岩灰渣碱法制取白炭黑的工艺研究

以广东省茂名市油页岩灰渣为原料,采用碱溶法制备白炭黑,考察了碱溶条件对白炭黑产率的影响。结果表明,碱溶法制取白炭黑的碱溶最佳工艺为：c（氢氧化钠）=4 mol/L, n（氢氧化钠）/n（二氧化硅）=5∶1,碱溶温度为110 ℃, 碱溶时间为4 h,焙烧温度为750 ℃,焙烧时间为2.5 h。在最佳条件下制备的产品,白炭黑的产率为81.49%、白度为98.1%。对白炭黑进行了FT-IR表征及性能测试,所制白炭黑符合化工行业标准（HG/T 3061—2009）的要求。     

Synthesis of Na-A and -X zeolites from oil shale ash

The solid by-product of oil shale processing (PETROBRAS-Brazil) was used as a raw material to synthesize Na-A and -X zeolites. Two preparation methods using the same starting material composition were carried out. In Method (1), alkaline fusion was used to prepare a glass, which was then hydrated by refluxing. The largest amount of crystallinity was reached with 2 h 30 min of refluxing. In Method (2), alkaline fusion was followed by hydrothermal treatment. The most crystalline sample was obtained after 12 h of heat treatment, and after 96 h hydroxysodalite zeolite was formed. In both procedures, the synthesis products were mainly composed of Na-X zeolite, whose content was influenced by the crystallization time, and of Na-A zeolite, with a practically constant content.     

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.     

Experimental and numerical analysis of oil shale drying in fluidized bed

The main objective of this work was to experimentally and numerically investigate the Liu Shu River oil shale drying by the means of flue gas in a fluidized bed dryer. Several experiments were performed under different temperatures conditions. The moisture content of oil shale was measured during the experiments. The two-stage drying model was incorporated in computational fluid dynamics (CFD) package FLUENT via user-defined functions (UDF) and utilized for simulation of heat and mass transfer of oil shale drying in the fluidized bed dryer. The simulation results for solid moisture content agreed well with experimental data. The effects of the temperature and velocity of flue gas, initial bed height, and the particle size on the drying characteristics were predicted and analyzed. It is shown that the gas temperature and velocity are the important parameters in the whole drying process. The particle size has more obvious influence in the falling drying period than the constant drying period. The temperatures of gas and solid phases were monitored. It is shown that the so-called “near gas distributor zone” is the most effective heat transfer zone, which agrees well with the calculated value. The system quickly reached thermal equilibrium, characterizing a nearly isothermal bed. The developed model provides a very good demonstration to describe the oil shale drying in the fluidized bed dryer, and may provide important information for design, optimization of operation conditions.     

Synthesis and characterization of calcium–alumino-silicate hydrates from oil shale ash – Towards industrial applications

The influence of the alkaline medium on the hydrothermal activation of the oil shale fly ash with NaOH and KOH was studied using SEM/EDX, XRD, ²⁹Si and ²⁷Al high-resolution MAS-NMR spectra. In the presence of NaOH the silicon in the original fly ash was completely converted into calcium–aluminum–silicate–hydrates, mainly into 1.1 nm tobermorite structure during 24-h treatment at 160 °C. At similar reaction conditions, the activation with KOH resulted only to the formation of amorphous calcium–silica-hydrate gel on the surface of ash particles at temperature. The results obtained in this study indicate that the oil shale fly ash can be used for production of Al-substituted tobermorites when strongly alkaline media (NaOH) is applied. The synthesized product was used in a catalytic d-lactose isomerization reaction.     

Strong and chemically inert sinter crystallised glass ceramics based on Estonian oil shale ash

Abstract

In heat and power production, oil shale combustion forms substantial amounts of solid waste, including fly ash. The present paper is dedicated to the manufacturing of frit derived glass ceramics from melting high amounts of this waste (65–67 wt-%) combined with inexpensive minerals, such as rhyolite (33–35 wt-%). Owing to a surface mechanism of crystallisation, fine powders led to glass ceramics with high strength and reliability, even for rapid treatments (fast heating, at a rate of 40°C min^?1, followed by 30 min holding stage). To minimise the presence of pressing and demoulding induced defects, the tiles were prepared by incorporating binders, i.e. polyethylene glycol or kaolin, to the frit mixtures. Finally, the stabilising effect of recycled borosilicate glass powders, mixed with waste derived glass powders, was also investigated with promising results for the production of a chemically stable material.     

燃烧过程对页岩灰孔隙结构的影响

页岩灰为油页岩及其半焦的燃烧产物,可作为建筑原材料、化工填料和吸附剂等,具有一定的工程应用价值。采用氮气等温吸附/脱附法对油页岩燃烧生成的页岩灰的孔隙结构进行了测量,并对不同升温速率和不同终温所得到的页岩灰的孔隙结构进行了比较,结果表明：如果油页岩在快速升温条件下燃烧所放出的热量能够被周围环境吸收而使得油页岩颗粒温度始终低于其灰熔点温度,所得到的页岩灰的孔容积和孔比表面积较大,适宜工业应用。     

Copper and zinc sorption by treated oil shale ash

Jordanian oil shale ash was used as an adsorbent for the removal of copper and zinc from aqueous solution. This ash was treated with either hydrochloric, nitric, sulfuric or phosphoric acids followed by washing and/or neutralization with sodium hydroxide in order to enhance its adsorption capacity. The sample that was treated with nitric acid showed the highest cation exchange capacity (CEC) of 146 meq/100 g, while the one that was treated with sulfuric acid showed a value of 32 meq/100 g. Different adsorption isotherm data for both copper and zinc were obtained using the nitric acid-treated sample at different pH values. Freundlich and BET models were used to fit the experimental data, which showed that BET best-fitted these data. The separation factor for these isotherms shows unfavorable adsorption type at lower pH value.     

油页岩灰渣制备聚氯化铝的工艺研究

以广东省茂名市油页岩灰渣为原料,用碱法制备聚氯化铝(PAC),考察了酸溶条件对产品的铝浸出率与盐基度的影响。结果表明,以油页岩灰渣制备聚氯化铝的最佳酸溶条件为:酸的质量分数为12%,酸量比n(HCl)∶n(Al2O3)=10,酸溶温度为110℃,酸溶时间为3 h。此条件下,铝浸出率为62.92%,聚合氯化铝的盐基度为82.25%。     

油页岩灰渣综合利用技术研究进展

介绍了我国油页岩资源的开发与利用概况。针对油页岩开发中产生的大量灰渣,认为采用填埋和堆积的处理方式,不仅造成资源的浪费,且占用大量的土地资源、破坏周边生态环境。参考国内外对油页岩灰渣的处理工艺,总结了油页岩灰渣制作水泥、轻质砖材、白炭黑、微晶泡沫玻璃,烧制陶粒以及提取氧化铝等综合利用的方法,并对油页岩灰渣综合利用提出了建议。     

Preparation and characterization of glass-ceramics via co-sintering of coal fly ash and oil shale ash-derived amorphous slag

A novel preparation method of glass-ceramics from coal fly ash (CFA) and oil shale ash-derived amorphous slag (OSAS) was developed in this study. Effects of important factors such as OSAS/CFA ratio and sintering temperature on the crystalline phase compositions, microstructure, mechanical-chemical properties, heavy metals leaching characteristics, and potential ecological risk assessment of glass-ceramics were investigated. The results showed that the properties of glass-ceramics increased with increasing OSAS/CFA ratio and sintering temperature, and S4 glass-ceramics (100% OSAS) showed the most superior product performances, followed by the S3 (80%OSAS-20%CFA), S2 (60%OSAS-40%CFA), and S1 (100% CFA). As for the products from the mixed sources, the best product properties of S2 glass-ceramics (density, 2.00 ± 0.04 g/cm³; water absorption, 3.11 ± 0.22%; and compressive strength, 106.67 ± 28.42 MPa) were achieved at 1085 °C. S3 glass-ceramics showed the highest density of 2.16 ± 0.04 g/cm³, and lowest water absorption of 0.22 ± 0.01%, and highest compressive strength of 195.99 ± 23.85 MPa at 1085 °C. Specially, the overall energy consumption for preparing S2 and S3 glass-ceramics was estimated to be reduced 23.66–27.00% and 11.67–13.50%, respectively, compared to that of S4 glass-ceramics. In addition, the good chemical stability, low heavy metals leaching concentrations and low potential ecological risk of OSAS-CFA-derived glass-ceramics further confirmed its potential and feasibility as building material in engineering application.     

Modeling calcium dissolution from oil shale ash: Part 1. Ca dissolution during ash washing in a batch reactor

Batch dissolution experiments were carried out to investigate Ca leachability from oil shale ashes formed in boilers operating with different combustion technologies. The main characteristics of Ca dissolution equilibrium and dynamics, including Ca internal mass transfer through effective diffusion coefficients inside the ash particle were evaluated. Based on the collected data, models allowing simulation of the Ca dissolution process from oil shale ashes during ash washing in a batch reactor were developed. The models are a set of differential equations that describe the changes in Ca content in the solid and liquid phase of the ash-water suspension.     

油页岩灰渣酸法制备纳米白炭黑碱浸工艺研究

以茂名油页岩灰渣为原料,采用酸法制备白炭黑,考察了碱浸条件对二氧化硅产率的影响。实验得到制取白炭黑的最佳碱浸工艺：碱浓度为3 mol/L、碱用量（氢氧化钠与二氧化硅的物质的量比）为4∶1、碱浸时间为4.0 h、碱浸温度为90 ℃。在最佳条件下,白炭黑的产率为63.79%,粒径为54 nm。制得的白炭黑符合HG/T 3061—1999《橡胶配合剂 沉淀水合二氧化硅技术条件》的要求。     

An advanced ash fusion study on the melting behaviour of coal,oil shale and blends under gasification conditions using picture analysis andgraphing method

This study investigates the potential of solid fuel blending as an effective approach to manipulate ash melting behaviour to alleviate ash-related problems during gasification, thus improving design, operabil-ity and safety. The ash fusion characteristics of Qinghai bituminous coal together with Fushun, Xinghua and Laoheishan oil shales (and their respective blends) were quantified using a novel picture analysis and graphing method, which incorporates conventional ash fusion study, dilatometry and sintering strength test, in a CO/CO2 atmosphere. This image-based characterisation method was used to monitor and quan-tify the complete melting behaviour of ash samples from room temperature to 1520 ℃. The impacts of blending on compositional changes during heating were determined experimentally via X-ray diffraction and validated computationally using FactSage. Results showed that the melting point of Qinghai coal ash to be the lowest at 1116 ℃, but would increase up to 1208 ℃, 1161 ℃ and 1160 ℃ with the addition of 30％–50％ of Laoheishan, Fushun, and Xinghua oil shales, respectively. The formation of high-melting anorthite and mullite structures inhibits the formation of low-melting hercynite. However, the sintering point of Qinghai coal ash was seen to decrease from 1005 ℃ to 855 ℃, 834 ℃, and 819 ℃ in the same blends due to the formation of low-melting aluminosilicate. Results also showed that blending directly influences the sintering strength during the various stages of melting. The key finding from this study is that it is possible to mitigate against the severe ash slagging and fouling issue arising from high calcium and iron coals by co-gasification with a high silica-alumina oil shale. Moreover, blending coals with oil shales can also modify the ash melting behaviour of fuels to create the optimal ash chemistry that meets the design specification of the gasifier, without adversely affecting thermal performance.     

Effect of demineralization of El-lajjun Jordanian oil shale on oil yield

The effect of demineralization on oil yield and mineral composition of Jordanian oil shale was investigated. A standard digestion procedure using a range of inorganic and organic acids including HCl, HNO₃, HF, and CH₃COOH was used to enhance the oil recovery of oil shale samples collected from the El-lajjun area. The total yield of the digested samples, as determined by Fischer Assay, has shown a maximum value (two folds the untreated sample) obtained when using CH₃COOH. The kaolin in the treated oil shale with a high concentration of CH₃COOH is believed to have transformed to illite as found in the XRD analysis. The treatment of oil shale using HCl has shown an increased ratio of oil to gas as a result of the digestion of calcite in the oil shale. At higher concentrations of HNO₃, the acid is believed to react with the kerogen in the oil shale resulting in high levels of low molecular weight compounds. Therefore, the amount of non-condensable gases produced by Fischer assay after treatment with a high concentration of HNO₃ is relatively high. HF is believed to drive off water from the oil shale by dissolving the clay minerals leading to increased oil to gas ratio.     

The chemistry and mineralogy of the Negev oil shale ashes

The characteristic feature of the oil shale ashes produced by fluidized bed combustion (700-800 °C) in PAMA's demonstration power plant is the large amount of amorphous phases, Ca-Al-silicates and Al-silicates, together with anhydrite and lime. Practically all the S and heavy metals in the oil shales are retained in the ash, which, from an ecological point of view, is important. Two kinds of ashes were examined: industrial ashes produced at PAMA's demonstration plant and ashes produced in laboratory experiments. Three different types of ash are produced at the demonstration plant. Ash Cooler (AC), which is comparable to bottom ash in coal power plants. This ash is produced from oil shale subjected to the lowest temperatures and is the most coarse-grained. It contains relatively larger quantities of unaltered minerals (calcite, clays, apatite, etc.) than the other two. The two other ashes Boiler Bank (BB) and Fly Ash (FAS) are not much different from each other and both may be compared to fly ash in coal power plants. Both BB and FAS ashes contain more authigenic (formed in the boiler) phases than AC. The results of the laboratory experiments show that the main factor in the raw material controlling the mineralogy and chemistry of the oil shale ashes is the Al₂O₃ concentration (clay content), and not the organic matter concentration.     

大庆油页岩及干馏产物的利用途径分析

大庆油页岩的舍油率大部分都在10%以上,具有很好的经济开发价值.对大庆油页岩及其干馏产物性质的实验研究表明,油页岩的机械强度较低,应选择粉末、颗粒干馏炉进行加工处理;页岩油主要由柴油馏分和重油馏分组成,分别可加工成成品油和直接用作燃料油;热解干馏气热值约为17MJ/m3,可以在除作自身干馏所需的热量燃料外,用作城市煤气或工业锅炉的燃料;半焦着火点低,热值约为23 MJ/kg,可作为清洁燃料用于发电或民用;页岩灰的主要组分是氧化钙争氧化硅,可用于生产建筑材料.     

Investigation on pyrolysis of Moroccan oil shale/plastic mixtures by thermogravimetric analysis

Thermal degradation processes for a series of mixtures of oil shale/plastic were investigated using thermogravimetric analysis (TGA) at four heating rates of 2, 10, 20 and 50 K min^− 1 from ambient temperature to 1273 K. High density polyethylene (HDPE), low density polyethylene (LDPE) and polypropylene (PP) were selected as plastic samples. Based on the results obtained, three thermal stages were identified during the thermal degradation. The first is attributed to the drying of absorbed water; the second was dominated by the overlapping of organic matter and plastic pyrolysis, while the third was linked to the mineral matter pyrolysis, which occurred at much higher temperatures. Discrepancies between the experimental and calculated TG/DTG profiles were considered as a measurement of the extent of interactions occurring on co-pyrolysis. The maximum degradation temperatures of each component in the mixture were higher than those of the individual components; thus an increase in thermal stability was expected. In addition, a kinetic analysis was performed to fit thermogravimetric data. A reasonable fit to the experimental data was obtained for all materials and their mixtures.