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2019年 第21卷 第3期    刊出日期:2019-09-30
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2019, 21(3):  0-1. 
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 Content of this issue
Scientific Research
氧化铝负载金属氧化物脱除NOx及碱吸附
杨雪 孙敏 刘博 林伟
2019, 21(3):  1-9. 
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在NO氧化脱除的过程中,NO的氧化过程至关重要。本工作中,氧化铝负载不同金属作为NO氧化催化剂,氧化产物进行碱液吸收以脱除NOx被仔细的研究。氧化催化剂的活性规律为V<< Ce < Ni < Fe < Co < Mn。NO氧化过程包括金属氧化物晶格得到O和吸附的NO被晶格中的O氧化,由于Mn具有合适的氧化还原电势,对晶格得到O和NO 的氧化过程均有利,因此具有最高的氧化活性。对于所有的M-Al2O3催化剂,NO转化率随反应温度变化均存在峰值,催化剂活性越高,达到最高转化率的反应温度越低。这说明,NO氧化过程是低温动力学控制,高温热力学限制的过程。NOx的脱除率随着NO2/NO比值的增加而增加,当NO2/NO高于3时,脱除率最高达到80%,这也说明NO的完全氧化是不需要的。
Effects of microwave torrefaction with Mg(OH)2 on characteristics of bio-oil from co-pyrolysis of straw stalk and soapstock
王允圃 温平威
2019, 21(3):  10-16. 
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This study investigated the effects of torrefaction with Mg(OH)2 on the bio-oil properties obtained from the microwave-assisted catalytic fast co-pyrolysis of straw stalk and soapstock. The effects of torrefaction temperature and residence time on bio-oil yield and composition were discussed. Results showed that torrefaction temperature and residence time remarkably influenced the yield and composition of bio-oil. With increases in temperature and time, the bio-oil yield and the proportion of oxygen-containing compounds decreased while the proportion of aromatic compounds increased. With 20 min of torrefaction reaction at 260 °C, the proportion of oxygen-containing compounds decreased from 29.89 wt% to 16.49 wt%. Meanwhile, Mg(OH)2 could render the deoxidization of torrefaction increasingly noticeable. The proportion of oxygen-containing compounds was minimum (14.41 wt%) when the biomass-to-Mg(OH)2 ratio was 1:1.
Effects of added HY zeolite on the catalytic behavior of Pt/OMC-HY in the hydrogenation of naphthalene
吴冰峰 杨丽娜 李剑 杨肖荣 白金 黄一峰
2019, 21(3):  17-28. 
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In this work, HY zeolites were embedded in the ordered mesoporous carbon (OMC) to prepare a support for a noble metal catalyst Pt/OMC-HY, and the hydrogenation of naphthalene to decalin was carried out over the catalyst. The results showed Pt/OMC-HY-0.14 (mess ratio of HY to phenolic resin oligomer is 0.14) possessed much better catalyst performance than Pt/OMC, which were related to its proper surface acidity, hierarchical pore structure, metal dispersion and the interaction between metal and support. Furthermore, Pt/OMC-HY-0.14 had better sulfur tolerance than Pt/OMC as well. According to the XPS results, it can be concluded that the channels of catalysts were blocked by adsorbed DBTs may be another main cause of deactivation, and the improved sulfur tolerance of Pt/OMC-HY-0.14 was ascribed to its acidity and the shape selectivity of hierarchical pore structure.
Process Research
酸性聚醚离子液体中异丁烷和异丁烯的烷基化反应
于凤丽 谷昱龙 刘其春 解从霞
2019, 21(3):  29-35. 
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The Br?nsted-acidic polyether ionic liquids (ILs) with different polymerization degrees (n value) were prepared via the reaction of tetramethylguanidine and epoxy ethane, followed by successive reactions with 1,3-propane sultone and trifluoromethanesulfonic acid (TfOH). The prepared ILs were characterized by infrared spectroscopy and 1H nuclear magnetic resonance spectroscopy, and their thermal stability was determined by thermal gravimetry. The synthesized polyether ILs coupled with TfOH were used to catalyze the alkylation reaction of isobutane and isobutene for the preparation of alkylate gasoline. The polyether ILs could improve the substrate dissolution and promote the separation of the catalyst from the products. The ideal IL (n = 94) was determined. The optimized alkylation reaction conditions covered: a VTfOH / VIL ratio of 0.35, a reaction temperature of 40 °C, a reaction time of 50 min, and a stirring speed of 800 r/min. The conversion of isobutene was 92.4% and the selectivity for the C8-product was 81.6%. Under optimal conditions, the catalyst life was determined and TfOH showed improved cyclic performance in the polyether ILs. After 8 operating cycles, the catalytic activity of the catalyst showed negligible decline.
Enhanced pervaporative separation of thiophene/n-heptane Using Metal Loaded PEBAX/PAN membrane
韩健健 王艺东 胡勇杰 刘琨 Yaseen Muhammad 胡敏专
2019, 21(3):  36-45. 
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[Bmim]Br/FeCl3离子液体脱除页岩油柴油中的氮化物
刘洁 刘进博 李文深
2019, 21(3):  46-52. 
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合成了低粘度的离子液体[Bmim]Br/FeCl3,采用红外光谱对其结构进行表征,并考察其对高氮含量的抚顺页岩油柴油馏分中氮化物的脱除效果。结果表明:[Bmim]Br/FeCl3离子液体具有良好的脱氮性能,在萃取温度30 ℃、剂油质量比1:1、萃取时间30 min、静置时间2h的条件下,[Bmim]Br/FeCl3对柴油馏分中碱氮和总氮的脱除率分别为95.29%和89.76%,对应的柴油馏分中的碱氮和总氮含量分别由5454μg/g,9832μg/g降低到257μg/g,1006μg/g。且该离子液体经回收重复使用4次后,在剂油质量比1:7的条件下,碱氮脱除率仍能达到60%。
Study on Reaction of Thiophene Compounds and Olefins for Deep Desulfurization of Gasoline
许昀
2019, 21(3):  53-60. 
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The HY, Hβ, HZSM-5, and SAPO-11 zeolites were investigated in the alkylation reaction of thiophene and olefins. As a result, some sulfur-containing impurities could be converted to higher molecular weight components with their boiling point being in the range of diesel fraction. HZSM-5 had the highest activity and selectivity of desulfurization. At the same time, extensive oligomerization of olefins was not found and coke yield was very low, which could lead to high yield of gasoline products. The main reaction mechanism verifies that the second order alkylation reaction can be carried out on the outer surface and / or pores of the catalyst. . The catalytic performance of the HZSM-5 catalyst which is poisoned by 2,4-dimethyl quinoline during alkylation to form larger molecules of sulfur compounds is obviously weakened due to the decrease of the acid sites on the outer surface and at the mouth of pores.
萃取法脱除模拟富硫油中的噻吩
沈喜洲 李志强 方柳亚 宋浩 甘锋 沈陟
2019, 21(3):  61-67. 
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中国已全面执行国V汽油标准,硫含量不大于10μg/g。传统加氢脱硫方法存在氢耗大、能耗高、噻吩不能有效利用等弊端。萃取脱硫技术因反应条件温和已成为研究热点。萃取脱硫的研究对象主要是催化汽油或模拟汽油,而对于萃取后回收富硫油萃取脱硫的研究在文献中尚未见报道。本文以模拟富硫油为原料,考察了单剂、复配剂、温度及剂油比对脱硫率、油损失率、剂损失率和选择性的影响。实验结果表明:(1)二甲基亚砜(DMSO)和环丁砜(SF)的单级脱硫率分别为53.51%和47.36%,但SF选择性高于DMSO,分别为1.13和1.04。(2)复配剂DMSO+10%MEA一级萃取脱硫率能达到49.59%,选择性系数为1.40,均高于SF,较之DMSO,脱硫率有小幅度的下降,但选择性系数从1.04增加到1.40,增加了25.71%。(3)复配剂50%SF+50%DMSO选择性系数为1.37,此时脱硫率可达50.92%,均高于SF的脱硫率和选择性系数,较DMSO,尽管脱硫率有小幅度的下降,但选择性系数从1.04增加到1.37,增加了31.73%。(4)在1.5:1的最佳溶剂油比下,DMSO+10%MEA的选择性系数和脱硫率略高于50%SF+50%DMSO。
Environmental Protection
快速驯化产甲烷颗粒污泥形成自养短程反硝化颗粒污泥过程研究
刘春爽 李雪晨 白雪 王永兴 赵朝成
2019, 21(3):  68-73. 
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短程反硝化颗粒污泥快速形成对于废水处理过程中的升流式厌氧污泥反应器(UASB)的快速启动具有实际意义。本研究证明产甲烷颗粒污泥能够在一天内快速驯化为短程反硝化颗粒污泥,所得颗粒污泥能够将2.7 kg-S/(m3?d)硫化物的82%转化为单质硫,0.9 kg-N/(m3?d)硝酸盐的97%转化为亚硝酸盐,为厌氧氨氧化过程提供了有力的底物保障。实验证实菌株Arcobacter sp.对于单质硫的累积至关重要。高负荷条件下,菌株Arcobacter sp.丰度降低, unclassified_p_Firmicutes丰度增加使得自养短程反硝化工艺崩溃,但运行效能可通过降低进水负荷恢复。
CuO/Al2O3催化臭氧氧化实际含酚废水的条件优化
马睿 刘广民 冯思慧 邱晓雨 张琰清 夏淑梅 薛建良
2019, 21(3):  74-80. 
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非均相催化臭氧氧化是一种很有潜力的高级氧化技术。本文使用浸渍沉淀法制备高效的CuO/Al2O3催化剂催化臭氧氧化实际含酚污水。通过考察CuO/Al2O3催化剂投加量,臭氧流量,初始pH等因素,确定最佳反应条件。当催化剂投加量为30g/L,臭氧流量为0.3m3/h,pH为8.80(污水初始pH值)时,反应15分钟后,酚的去除率达到98%,得到最佳的处理效果。文中也考察了污水水质因素(例如盐度、硬度、氨氮浓度等)对含酚污水降解的影响。此外还探讨了不同反应体系对含酚污水的降解效果以及对含酚污水的矿化度。与单独臭氧氧化体系相比,CuO/Al2O3催化臭氧氧化体系的矿化度高15%左右。实验结果表明CuO/Al2O3催化剂的引入可以有效提高实际含酚污水在臭氧氧化体系中的降解效果。
Fenton预氧化后微生物降解去除污染土壤中的原油
高春阳 张羽 宋权威 陈昌照 陈宏坤 郑瑾 韩占涛
2019, 21(3):  81-89. 
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Through the Fenton pre-oxidation followed by microbial degradation, this study gave full play to its advantages while avoiding its shortcomings for the remediation of crude oil contaminated soil. The Fenton reagent coupled with different volumes of H2O2 was applied to the oil contaminated soil and then the microbial agents were introduced to biodegrade the residual oil for 15 days. The correlation between the characteristics of residual oil in soil, the changes in soil physical-chemical property after the Fenton pre-oxidation, and the biodegradation rate was analyzed in this paper. The results show that the above factors are strongly correlated with the subsequent biodegradation rate, and the order of correlation is as follows: the ratio of TOC to NH4+-N (R2 = 0.9513) > the ratio of light oil components to the heavy oil components (R2 = 0.9095) > the proportion of hydrocarbons with carbon chain number of less than C23 (R2 = 0.8259) > the crude oil content (R2 = 0.7603) > the soil pH (R2 = 0.7492) > the number of microorganisms (R2 = 0.6506). During the biodegradation and pre-oxidation reactions of heavy oil components, an appropriate C:N ratio turns out to be the most critical factor in this study.
Simulation and Optimization
采用氙气的鼓泡床流体力学特性研究
唐晓津
2019, 21(3):  90-93. 
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Xenon was used as gas phase to investigate the hydrodynamic characteristics in a bubble column. It was found that the flow pattern is mainly in the churn-turbulent flow regime by analysing the relationship between the slip velocity and gas holdup. The influences of operating conditions on the gas holdup and Sauter mean diameter were studied. The experimental results show that the Sauter mean diameter decreases with the increase of energy dissipation rate. A new correlation was developed to predict the Sauter mean diameter with an average error less 15%.
节能技术在三氯硅烷精馏提纯工艺中的应用
郄思远 庞伟伟 赵明 黄哲庆
2019, 21(3):  94-102. 
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The trichlorosilane (TCS) purification process consumes a significant amount of energy to achieve the high purity requirement for TCS quality (99.9999%). This work proposed a series of energy saving technology to enhance the TCS purification process, including the conventional process, the conventional process coupled with heat-pump (HP), the multi-effect distillation process, and the dividing-wall columns process. All proposed schemes have been conceptually constructed by Aspen Plus. The design and optimization of the processes have been performed by the sensitivity analysis and the response surface methodology. Moreover, the energy consumption and total annual cost (TAC) for these schemes were discussed. The simulation results show that the TAC of the conventional process coupled with the integrated heat pump can reduce 50.5% of energy consumption as compared with the conventional process; the double-effect and three-effect processes can save 15.6% and 33.8% of energy consumption, respectively; the dividing wall column process and that coupled with the heat pump process can reduce by 22.3% and 48.1% of energy consumption, respectively. It can be found that the operating cost can be saved by using the heat pump technology, while the capital cost increases due to the investment in the compressor, when the processes coupled with the heat pump are used. These results demonstrate that the conventional process coupled with the HP technology has advantages over other distillation schemes for TCS purification in terms of the energy saving and economic effects.
COSMO-SAC模型和密度泛函理论在萃取分离剂分子设计中的应用比较研究
方静 王一晶 张淑婷 郑雯雯 李浩 李春利
2019, 21(3):  103-111. 
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基于离子液体的结构可设计性,通过计算机辅助的方式可以设计出具有高萃取效果的离子液体萃取分离剂。通常使用的是COSMO-SC模型和密度泛函理论,两种方法均具有各自的优点。然而,本文发现对于同一待分离体系COSMO-SAC模型和密度泛函理论所预测的萃取效率排序存在不同。针对这一问题,本文以离子液体萃取脱硫为例通过COSMO-SAC模型筛选出具有高分离效率的六种离子液体,同时使用密度泛函理论在机理的角度上获得了六种离子液体的分离效率,发现两种方法的分离效率确实存在不一致。通过实验并利用高效液相色谱对分离后的含硫化合物进行浓度测定,实验结果表明,六种离子液体的分离效率与密度泛函理论的结果是一致的。最终,在计算原理的角度上说明了两种模型计算结果存在差异的原因。
Lubrication Research
Tribological Properties of Lubricating Oils with triethanolamine borate under Electromagnetic Field
王鑫 方建华 江泽琦 谷科城 刘坪
2019, 21(3):  112-118. 
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Tribological properties of 150SN mineral oil and lubricating oils containing triethanolamine borate (TBE) with and without electromagnetic field impact were evaluated on a modified four-ball tribo-tester. The characteristics of the worn surfaces were observed by scanning electronic microscopy (SEM), energy dispersive spectrometer (EDS) and X-ray photoelectron spectroscopy (XPS). Moreover, the tribological mechanisms are discussed from the viewpoint of physical effect and chemical effect. The results indicated that the friction coefficients and wear scar diameters (WSDs) lubricated by 150SN mineral oil under electromagnetic field were higher than those without electromagnetism impact. The WSDs of steel balls lubricated by TBE-doped oils under electromagnetic field were smaller than those obtained from non-electromagnetic field, but the friction coefficients were higher than those under non-electromagnetic field. A protective coating consists of wear particles could be formed on the frictional surface due to the physical effect of electromagnetic field on wear debris. The electromagnetic field could facilitate the interaction of elemental boron and nitrogen in TBE with metal interfaces, and contributes to forming tribo-chemical reaction film to reduce friction and wear.