Heat treatment of mesocarbon microbeads under high pressure

Mesophase spherules separated from pitches and asphalt by quinoline (mesocarbon microbeads) were heat-treated under a pressure of 5 kbar at 1300–2000°C for 1 hr. The as-separated microbeads gave a bulk density of 1.8–1.9 g/cm³ after heat treatments at high temperatures. The pre-heated microbeads gave high bulk density above 2.0 g/cm³ after high temperature heat treatment. The mesocarbon microbeads were found to have low graphitizability under pressure. The as-separated microbeads showed a heterogeneous process of graphitization, but the maximum amount of the graphitic component was only 60% even after 2000°C-treatment under 5 kbar. On the pre-heated microbeads, almost no graphitization was observed. The spherical shape of the as-separated microbeads was lost even after the heat treatments at low temperatures under 5 kbar. However, the pre-heated microbeads showed the tendency to keep the original spherical shape even after heat treatment at 1900°C.     

由脱晶蒽油制备沥青树脂的研究

以脱晶蒽油为原料,苯甲醛为交联剂,在浓硫酸的催化作用下合成了沥青树脂.采用FT-IR和TCA分析手段研究了缩聚反应机理和热失重行为.试验过程中考察了合成条件对沥青树脂的结焦值、恩氏黏度和黏结强度等性能的影响.结果表明,脱晶蒽油与苯甲醛发生了阳离子聚合反应,与原料相比,沥青树脂的残炭值提高了24％,最大失重速率时的温度相对升高了143℃.改变合成工艺条件能调控沥青树脂的性能指标.     

Heat transfer in the cooling of thermoplastic melts under pressure

The dimensionless equations describing the cooling with solidification of polymer melts under pressure are solved numerically for partially crystalline and glassy polymers. The proposed finite-difference solution assumes constant, but different, average properties for each of the amorphous and crystalline phases. Natural convection is ignored (Grashof Number <10?8), and internal flow as a result of pressure gradients and the effect of pressure anisotropy on temperature profiles have been neglected. Numerical predictions of temperature profiles, pressure, and the position of the freezing front in a long, cylindrical mold are in good agreement with experimental data.     

压力瞬态下超临界压力CO2的传热特性

在均匀加热条件下,开展超临界压力二氧化碳在压力瞬态下的传热特性实验研究。实验段内径为10.0mm,实验参数范围：压力P=7.58~9.97MPa,热流密度q _w=64~256kW/m²,质量流速G=660~893kg/(m²·s)。分析了正常传热和传热恶化条件下,瞬间泄压过程对传热的影响规律。实验结果表明,正常传热工况下,壁温随着压力的减小有降低的趋势,传热系数明显增大;传热恶化发生后壁温迅速上升,对应的传热系数减小传热恶化更加严重,且恶化壁温峰值点向着入口方向移动。最后对实验现象进行了解释,正常传热下壁温降低是由于压力的降低增大了比热容,从而改善了传热。传热恶化发生后,压力的降低减小了拟临界焓值i _pc,从而增大了超临界沸腾数SBO,更大的SBO表明膨胀动量力占主导,靠近壁面低密度的vapor-like fluid在不断向外膨胀,从而使得低密度层流体的厚度增加,从而加大了传热热阻,这时壁温升高或者出现更大的恶化。     

Pyrolysis oil upgrading by high pressure thermal treatment

High pressure thermal treatment (HPTT) is a new process developed by BTG and University of Twente with the potential to economically reduce the oxygen and water content of oil obtained by fast pyrolysis (pyrolysis oil), properties that currently complicate its co-processing in standard refineries. During the HPTT process, pyrolysis oil undergoes a phase split yielding a gas phase, an aqueous phase and an oil phase. In this study, HPTT experiments were carried out at different operating conditions in a continuous tubular reactor. Experimental results showed that, with increasing temperature and residence time, the release of gases (mainly CO₂) and the production of water increased, reducing the oxygen content of the oil phase and hence increasing the energy content (from 14.1 to 28.4 MJ/kg) having the temperature a larger effect when compared to the residence time. Using gel permeation chromatography (GPC), an increase of the molecular weight of the oil phase, probably due to polymerisation of the sugars present in pyrolysis oil, was observed. When water was added as solvent to dilute the feed oil, a decrease of the molecular weight of the resulting oil phase was observed. This indicated that the concentration of organic components had a direct effect on the formation of high molecular weight components. In conclusion, during HPTT an oil with lower oxygen and water content with higher energy value was produced, but adverse formation of high molecular weight components was also detected.     

由蒽油制备COPNA树脂

以煤焦油中提取的蒽油为单体,苯甲醛为交联剂,在对甲苯磺酸的催化作用下合成缩合多核芳烃(COPNA)树脂。采用FT-IR研究其反应机理;热重分析仪研究该COPNA树脂的热行为;环球法测定了该树脂的软化点;以及元素分析仪分析其元素组成。结果表明,蒽油能够与苯甲醛合成COPNA树脂,其反应机理为酸催化下的阳离子型缩聚反应;COPNA树脂具有较好的耐热性和炭收率。     

蒽油加工及分离技术研究进展

简述了国内外煤焦油和蒽油的加工情况,系统地总结了溶剂法、结晶法、精馏法、化学分离法等新工艺以及超临界流体萃取、膜分离、区域熔融法等多种分离新技术在蒽油组分分离上的开发与研究。提出了要在深入研究蒽油中各组分之间相互作用的基础上,将传统工艺与先进的分离技术有机地结合,可望在简化工艺流程、节能减排和消除环境污染的前提下,显著改善蒽油的分离效果和工艺条件。     

Analysis of the volatile fraction from sunflower oil extracted under pressure

This study concerns the analysis of volatile components that may contribute to the formation of the flavor of the oil extracted from sunflower seeds. The compounds were trapped on a charcoal cartridge, then desorbed and analyzed by gas chromatography/mass spectrometry. The principal compounds were terpenes (about 225 mg/L) consisting of α-pinene (80%), limonene (5%), sabinene (3.3%), β-pinene (1.8%), 1,2,6,6-tetramethyl-1,3-cyclohexadiene (1.5%), and camphene (1.2%). There were also a small amount of hexanal (1.3%) and traces (<1%) of unidentified compounds, which probably correspond to other terpenic hydrocarbons and to terpenic alcohols and/or aldehydes.     

蒽油馏分深加工工艺现状及研究进展

介绍了蒽油馏分深加工的2种工艺、蒽油精制分离提取精蒽、菲、咔唑工艺的现状及研究进展,阐述了蒽油馏分加氢生产轻质燃料油工艺研究进展、工艺原理、工艺流程等。对山西焦化集团有限公司未来建设蒽油深加工项目提出了建议。     

Influence of tall oil and ultrasound treatment on pitch production from semicoking tar or the anthracene fraction

The properties of coal pitch obtained from blends of tall oil and semicoking tar or the anthracene fraction are investigated. Small additions of tall oil to semicoking tar (in the ratio 1: 6) increase the yield of pitch on thermal oxidation and its softening temperature but decrease the coke residue. On ultrasound treatment, chemical transformations of the molecules under the action of cavitation change the characteristics of the pitch produced on thermal oxidation. Primarily, however, the ultrasound permits reduction in the benzo[a]pyrene concentration in the mixture by almost half. On thermal oxidation, the benzo[a]pyrene concentration is further reduced, but most of its mass is concentrated in the pitch.     

Heat treatment of 6H-SiC under different gaseous environments

Silicon carbide is a useful material for the reactors in chemical processes. In recent years, microreactors have gained significant attentions due to the high demand for process miniaturization. As heat and mass-transfer are highly improved inside the gas flow channels in microreactors, any change on the surface of inner channels under heating becomes critical to the performance of microreactors. To investigate the surface changes of silicon carbide during the heat treatment, 6H-SiC coupons were processed in five different gases—Ar, N₂, air, 0.9% O₂ in Ar and 50% H₂O in air—that are commonly encountered in high temperature chemical processes. While the formation of oxide film was found to be dependent on the partial pressure of oxidizing gas, surface decomposition was found from the treatment in nitrogen environment. Characterization of the SiC surface by Raman spectroscopy and SEM–EDX revealed that a graphitic layer has formed at the oxide film/SiC interface. Crystallinity of graphitic layer at the interface seemed to be dependent on the partial pressure of oxidizing gas, which was revealed by the relationship between G peak position and R(I_D/I_G). The intensity ratio of FTO(0)/FTO(2/6) bands showed that stacking faults on the surface of SiC coupons were reduced after heat treatment.     

蒽油加氢装置酸性水酸性气综合治理新技术应用

介绍了蒽油加氢装置产生的酸性水、酸性气综合治理新技术,酸性水采用加压汽提制液氨,汽提塔顶富H2S酸性气及加氢装置酸性尾气采用专利技术生产硫氢化钠。工业应用表明,酸性水汽提处理后氨氮质量比小于100 mg/kg,硫化物质量比小于50 mg/kg,满足一般工业废水处理装置入口技术指标,酸性气经净化处理后H2S质量浓度小于10 mg/m3。副产品液氨满足GB 536—88《液体无水氨》质量标准,液体硫氢化钠满足GB 23937—2009《工业硫氢化钠》质量标准,该技术能有效回收中小型石化加氢装置产生的酸性污水中的NH3、H2S等有毒气体。     

河北新启元蒽油加氢机械密封改造

通过对河北新启元能源技术开发股份有限公司蒽油加氢机械密封进行改造,实现了高温热油泵密封的长周期安全运行,取得了较好的经济效益.     

原子吸收光谱法测定蒽油中金属含量

研究了原子吸收光谱法测定蒽油中铁、钾、镁、钠、钙、铜等金属含量。先将蒽油试样经过灼烧灰化后,用盐酸溶解,采用火焰原子吸收光谱法测定其中的铁、钾、镁、钠、钙、铜等金属含量。实验表明,铁和铜含量在0~5mg/L范围内,钾和镁含量在0~0.4mg/L范围内,钠含量在0~0.8mg/L范围内,钙含量在0~8mg/L范围内均显现良好的线性关系,相关系数均为r=0.999,铁、钾、镁、钠、钙、铜加标回收率均在95%~105%内。     

蒽油加氢尾气回收技术改造研究

蒽油加氢尾气回收装置无法对低压硫化氢进行回收,因此需要对尾气回收装置进行改造。通过对尾气回收装置中的水洗塔、硫氢化钠反应器进行改造,使尾气全部回收,减少硫化氢气体排放,并提高硫氢化钠产量,取得良好的社会及经济效益。     

Carbonization of an anthracene oil extract of Akabira (Japan) coal

The carbonization of a non-hydrogenated extract (STC) from a low-rank coal (C, 83 wt%) of high fluidity was studied as single carbonizations and as co-carbonizations with additives, an objective being the production of needle-coke. The coke from STC had an optical texture of fine-grained mozaics; however, fractionation followed by co-carbonizations were effective in modifying carbonization properties. The lighter fraction of STC could give a coke with flow texture but in reduced yield. The addition of hydrogenated Ashland A240 pitch (HA240) in a quantity as low as 20% could effectively modify the carbonization properties of STC. A novel co-carbonization, in which an additive such as dihydroanthracene is recovered at the latter stage of the carbonization in the dehydrogenated form, was found to be effective also, although a relatively large amount of the additive was required. Among the non-hydrogenated additives, Ashland A240 pitch was the most effective in modifying the STC. The cocarbonization of fractionated STC reduced the quantity of additive required while maintaining a reasonable coke yield. Some practical aspects for the production of needle-coke from STC are discussed.     

Production of coal pitch by the oxidation of coal extracts in anthracene oil

If anthracene oil is used to produce extracts from 2B, D, 2G, GZh coal, coal pitch may be produced by oxidation of the extracts using atmospheric oxygen. The resulting pitch is characterized by higher yield and by a greater coke residue than is observed in pitch produced from anthracene oil without added coal in analogous conditions. Ultrasound treatment for 3 h on an IL10-0.63 unit ensures complete solution of the coal (4–9%) in the anthracene oil. The mineral component of the coal also enters the solution and is then concentrated in the pitch formed. To reduce the ash content of the pitch, ash must preliminarily be removed from the initial coal. For the example of 2B and D coal, it is found that reducing the ash content of the coal to ~1% and subsequent solution in the anthracene oil to a coal concentration of 5–8% yields a coal extract such that pitch with no more than 0.4% ash and up to 41% coke residue is formed on oxidation by atmospheric oxygen.