富马酸十六醇酯-苯乙烯二元共聚物柴油低温流动改进剂的合成、表征及性能评价(英文)

以富马酸和十六醇为原料、对甲苯磺酸为催化剂、对苯二酚为阻聚剂、甲苯为溶剂,采用直接酯化法制备了富马酸十六醇酯单体（DHF）;以富马酸十六醇酯和苯乙烯为聚合单体、过氧化苯甲酰为引发剂,通过自由基聚合制备了富马酸十六醇酯-苯乙烯二元共聚物（FOS）。用IR、¹H-NMR对DHF单体及FOS共聚物进行了表征,分析了张家港0# 柴油和胜利海科5# 柴油的正构烷烃分布,考察了共聚物的降滤效果,讨论了降滤作用机理。结果表明,当添加剂量为0.1%时,FOS能使张家港0# 柴油冷滤点降低6℃,胜利海科柴油5# 柴油冷滤点降低3℃;FOS对不同柴油表现出了不同的感受性;与2种商业降凝剂复配后,表现出良好的协同效应,作为商业降凝剂的优良助剂,FOS具有一定的应用前景。     

柴油低温流动性改进剂的研制及性能评价 Ⅰ. 低温流动性改进剂对柴油的感受性

在分析胜利石化总厂 0 #柴油和齐鲁石化 0 #柴油的烃族组成、蜡碳分布的基础上 ,进行分子设计 ,研制出一种柴油低温流动性改进剂。它主要由具有一定粘度的三元共聚物组成。实验结果表明 ,这种柴油低温流动性改进剂能十分有效地提高胜利石化总厂 0 #柴油的低温使用性能 ,而胜利石化 0 #柴油对目前国内外其它低温流动性改进剂的感受性较差。     

Application of Plasma Fuel Reformer to an On-Board Diesel Burner

A conventional diesel burner has arisen several shortcomings, such a large supply of air for a stoichiometric combustion, and a long heat-up time to reach the light-off temperature of catalyst in a diesel after-treatment system. This study shows a promising potential of using a plasma reformer for staged diesel combustion with minimized air and fuel consumption, and increased the flame stability with low NOx emission. A working principle of a plasma fuel reformer for staged combustion is explained in detail by both visualizing the plasma-assisted flame and analyzing the gas products. The concentrations of H₂, CO, NOx and the unburned total hydrocarbons were measured by gas chromatography and a commercial gas analyzer. Considering the operating condition of diesel exhaust gas is too harsh to maintain a stable diesel flame with a conventional diesel burner, plasma fuel reformer has distinctive advantages in stable flame anchoring under the condition of low oxygen concentration and fast flow speed. The re-ignition and stable flame anchoring by entrapment of oxygen in exhaust gas is mainly attributed to the low ignition energy and high diffusion velocity of hydrogen molecule. From an economic point of view, plasma reformer is also the only technology which can use only 1/3–1/8 of the air required for the stoichiometric burning of a conventional diesel burner. A conventional burner was simulated and analyzed to consume up to 30 % more fuel compared to the plasma reformer with the staged combustion to get the same level of temperature elevation in a real diesel engine scale.     

Melting Properties of Butter Fat and The Consistency of Butter. Effect of modification of cream ripening and fatty acid composition

The cold unspreadable consistency of butter after taking it out of the refrigerator is a rightful objection on behalf of consumers. The possibilities to improve the cold spreadability of butter are: the enrichment with low melting point triglycerides and the application of a good cream-ripening method. In our investigations milk fat fractions of different low melting points and plant oils of low melting points obtained by cold pressing and extraction have been used to change the original fatty acid composition of milk fat. The cream-ripening, the traditional method and the heat-step ripening method, which seemed to be the most effective to our earlier research, have been applied. The consistency of butter was examined by penetration measurements and its thermal characteristics by differential scanning calorimetric (DSC) method. The cold unspreadable consistency of butter can only be improved by the combination of the heat-step cream ripening and enrichment with low melting point triglycerides to get stable consistency at room temperature. The milk fat fraction of melting point below 5°C made the spreadability better but the spreadable consistency of margarine still cannot be attained. Plant oils with melting point below 0°C improved the cold spreadability of butter to a significantly higher degree than the former did. In the case of the same melting point the plant oil obtained by a cold method (pressing) was more effective. There is a close relationship between the consistency of butter and its product characteristics. From DSC curves the cold spreadability and room temperature stability of butter can be directly concluded. This revised version was published online in July 2006 with corrections to the Cover Date.     

Evaluation of a completely automated cold fiber device using compounds with varying volatility and polarity

A fully automated cold fiber solid phase microextraction device has been developed by coupling to a GERSTEL multipurpose (MPS 2) autosampler and applied to the analysis of volatiles and semi-volatiles in aqueous and solid matrices. The proposed device was thoroughly evaluated for its extraction performance, robustness, reproducibility and reliability by gas chromatograph/mass spectrometer (GC/MS). With the use of a septumless head injector, the entire automated setup was capable of analyzing over 200 samples without any GC injector leakages. Evaluation of the automated cold fiber device was carried out using a group of compounds characterized by different volatilities and polarities. Extraction efficiency as well as analytical figures of merit was compared to commercial solid phase microextraction fibers. The automated cold fiber device showed significantly improved extraction efficiency compared to the commercial polydimethylsiloxane (PDMS) and cold fiber without cooling for the analysis of aqueous standard samples due to the low temperature of the coating. Comparing results obtained from cold fiber and commercial divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber temperature profile demonstrated that the temperature gap between the sample matrix and the coating improved the distribution coefficient and therefore the extraction amount. The linear dynamic range of the cold fiber device was 0.5 ng mL⁻¹ to 100 ng mL⁻¹ with a linear regression coefficient ≥0.9963 for all compounds. The limit of detection for all analytes ranged from 1.0 ng mL⁻¹ to 9.4 ng mL⁻¹. The newly automated cold fiber device presents a platform for headspace analysis of volatiles and semi-volatiles for large number of samples with improved throughput and sensitivity.     

Sustainable Diesel from Pyrolysis of Unsaturated Fatty Acid Basic Soaps: The Effect of Temperature on Yield and Product Composition

The production of sustainable diesel without hydrogen addition remains a challenge for low-cost fuel production. In this work, the pyrolysis of unsaturated fatty acid (UFA) basic soaps was studied for the production sustainable diesel (bio-hydrocarbons). UFAs were obtained from palm fatty acids distillate (PFAD), which was purified by the fractional crystallization method. Metal hydroxides were used to make basic soap composed of a Ca, Mg, and Zn mixture with particular composition. The pyrolysis reactions were carried out in a batch reactor at atmospheric pressure and various temperatures from 375 to 475 °C. The liquid products were obtained with the best yield (58.35%) at 425 °C and yield of diesel fraction 53.4%. The fatty acids were not detected in the pyrolysis liquid product. The gas product consisted of carbon dioxide and methane. The liquid products were a mixture of hydrocarbon with carbon chains in the range of C₇ and C₂₀ containing n-alkane, alkene, and iso-alkane.     

Utilization of α-olefins obtained by pyrolysis of waste high density polyethylene to synthesize α-olefin-succinic-anhydride based cold flow improvers

A new route of utilization of α-olefin rich hydrocarbon fractions obtained by waste polymer pyrolysis was investigated. α-olefin-succinic-anhydride intermediate-based pour point depressant additives for diesel fuel were synthesized, in which reactions needed α-olefins were obtained by pyrolysis of waste high-density polyethylene (HDPE). Fraction of α-olefins was produced by the de-polymerization of plastic waste in a tube reactor at 500℃ in the absence of catalysts and air. C17～22 range of mixtures of olefins and paraffins were separated for synthesis and then, these hydrocarbons were reacted with maleic-anhydride (MA) for formation of α-olefin-succinic-anhydride intermediates. The olefin-rich hydrocarbon fraction contained approximately 60% of olefins, including 90%～95% α-olefins. Other intermediates were produced in the same way by using commercial C20 α-olefin instead of C17～22 olefin mixture. The two different experimental intermediates with number average molecular weights of 1850g/mol and 1760g/mol were reacted with different alcohols: 1-butanol, 1-hexanol, 1-octanol, i-butanol, and c-hexanol to produce their ester derivatives. The synthesized ten experimental pour point depressants were added in different concentrations to conventional diesel fuel, which had no other additive content before. The structure and efficiency of experimental additives were followed by different standardized and non-standardized methods. Results showed that the experimental additives on the basis of the product of waste pyrolysis were able to decrease not only the pour but also the cloud point and cold filter plugging point (CFPP) of diesel fuel, whose effects could be observed even if the concentration of additives was low. Furthermore, all additives had anti-wear and anti-friction effects in diesel fuel.     

Synthesis of Renewable Diesel through Hydrodeoxygenation Using Pd/zeolite Catalysts

Hydrodeoxygenation of oleic acid as model compound of vegetable oils over Pd/zeolite catalysts was investigated under conditions of 375−400 °C and 15 bar in a semi batch stirred autoclave reactor. Pd/zeolite-1 and Pd/zeolite-2 catalysts were prepared using microwave polyol method with different treatment conditions. The liquid hydrocarbon products named Renewable Diesel have suitable density and viscosity, and quite high cetane index in accordance with standard commercial diesel and ASTM D-975. The IR spectrum of Renewable Diesel products have similarities with commercial diesel. The oxygenation removal pathway of oleic acid over Pd/zeolite 1 catalyst was primarily compiled through decarboxylation at 375 °C.     

Comparison of the Fuel Properties of Nitromethane Emulsions in Diesel and Biodiesel Assisted by Microwave Irradiation and Magnetic Stirring

Microwaves are high-frequency electromagnetic waves that assist in the formation of emulsions by enhancing the transfer of both mass and heat between the dispersed and continuous phases of the emulsion. Nitromethane has been used to improve combustion, but it is not miscible with petroleum-derived liquid fuels. In this study, the fuel properties of two-phase emulsions of nitromethane droplets dispersed in a mixture of diesel and biodiesel prepared by microwave irradiation were analyzed and compared with those of emulsions prepared by magnetic stirring. The emulsions were composed of various mass compositions of nitromethane, diesel, and biodiesel. The experimental results show that the emulsions formed by microwave irradiation had superior fuel properties, including a higher kinematic viscosity, higher flash point, lower cold filter plugging point, and less carbon residue than the emulsions prepared by magnetic stirring. Microwave irradiation is a more effective method for the preparation of more stable emulsions containing a uniform distribution of smaller dispersed droplets. In addition, the flash point, heat of combustion, cold filter plugging point, and carbon residue decreased while the kinematic viscosity increased with the increase in the weight fraction of nitromethane in the two-phase emulsions.     

Trace Element Determination in Diesel Particulates by Total-Reflection X-Ray Fluorescence Analysis

 Particulate matter of Diesel emissions collected from diluted exhaust during standard test runs with two Diesel fuels of different sulfur content was analysed by total-reflection X-ray fluorescence (TXRF). The trace elements determined were S, Ca, Cr, Mn, Fe, Ni, Cu, Zn and Pb. Additionally, some filter materials were tested with respect to their applicability for sample collection. Quartz fibre filters were found to be most suitable, both from a technical and a chemical point of view. A clear reduction of total particulate emissions during the whole test was observed when the fuel with very low sulfur content was used. In addition, it was found that the wear metal content of particulate matter emitted by a cold engine was higher than that observed during normal engine working temperature. Received September 10, 1998. Revision March 2, 1999     

含芳香基团的梳状聚合物型降凝剂与沥青质协同改善合成蜡油的流变性

采用流变学实验、 差示扫描量热(DSC)分析、 显微观察及沥青质沉淀实验研究了聚丙烯酸十八酯-马来酸酐(POM)、 聚丙烯酸十八酯-马来酸酐-苯胺(POMA)及聚丙烯酸十八酯-马来酸酐-萘胺(POMN)梳状聚合物对合成蜡油的流变性能的影响规律. 实验结果表明, 这3种梳状聚合物降凝剂均能在一定程度上改善不含沥青质合成蜡油(MO-1)的低温流变性, 其中POM对MO-1蜡油的流变性改善效果最佳. 添加500 mg/kg POM后, MO-1的凝点从29 ℃降至23 ℃, 屈服值从627.20 Pa降至83.35 Pa. 而POM, POMA和POMN可以显著改善含0.3%(质量分数)沥青质的合成蜡油(MO-2)的低温流变性, 且添加500 mg/kg POMA后MO-2蜡油的流变改善效果最佳: 凝点降至3 ℃, 屈服值降至1.27 Pa. 可见, 本文制备的梳状聚合物降凝剂均能与沥青质协同改善MO-2蜡油的流变性, 并且向POM中引入芳香基团能进一步促进沥青质与降凝剂分子的相互作用, 进而增强梳状聚合物降凝剂与沥青质的协同作用.     

Uneven Dielectric Barrier Discharge Reactors for Diesel Particulate Matter Removal

Uneven dielectric barrier discharge (DBD) reactors driven by positive–negative pulse plasma discharges were investigated for particulate matter (PM) removal from a diesel engine. Two kinds of uneven alumina plates and three kinds of uneven stainless steel plates were used to assemble six kinds of uneven DBD reactors of discharge gaps 0.4–1.0 mm. The experimental results show that PM from diesel engines can be removed using the uneven DBD reactors. The maximum PM removal was 67% at 300 W energy injections using the DBD reactor of 0.4 mm gap distance. PM removal increased with decreasing gap distance. The energy efficiency using the uneven DBD reactor of a shorter gap distance was higher than that using the uneven DBD reactor of a longer gap distance as the uneven DBD reactor of a shorter gap distance has a higher PM deposition rate. The energy efficiency was typically in a range of 3–10.6 g/kWh at an energy density of 2–16 J/L. A comparison of this study with reports given by other research groups is given.     

Utilization of α-olefins obtained by pyrolysis of waste high density polyethylene to synthesize α-olefin-succinic-anhydride based cold flow improvers

A new route of utilization of α-olefin rich hydrocarbon fractions obtained by waste polymer pyrolysis was investigated. α-olefin-succinic-anhydride intermediate-based pour point depressant additives for diesel fuel were synthesized, in which reactions needed α-olefins were obtained by pyrolysis of waste high-density polyethylene (HDPE). Fraction of α-olefins was produced by the de-polymerization of plastic waste in a tube reactor at 500℃ in the absence of catalysts and air. C_17~22 range of mixtures of olefins and paraffins were separated for synthesis and then, these hydrocarbons were reacted with maleic-anhydride (MA) for formation of α-olefin-succinic-anhydride intermediates. The olefin-rich hydrocarbon fraction contained approximately 60% of olefins, including 90%~95% α-olefins. Other intermediates were produced in the same way by using commercial C₂₀ α-olefin instead of C_17~22 olefin mixture. The two different experimental intermediates with number average molecular weights of 1850g/mol and 1760g/mol were reacted with different alcohols: 1-butanol, 1-hexanol, 1-octanol, i-butanol, and c-hexanol to produce their ester derivatives. The synthesized ten experimental pour point depressants were added in different concentrations to conventional diesel fuel, which had no other additive content before. The structure and efficiency of experimental additives were followed by different standardized and non-standardized methods. Results showed that the experimental additives on the basis of the product of waste pyrolysis were able to decrease not only the pour but also the cloud point and cold filter plugging point (CFPP) of diesel fuel, whose effects could be observed even if the concentration of additives was low. Furthermore, all additives had anti-wear and anti-friction effects in diesel fuel.     

大豆油生物柴油低温流动性能影响的研究

以大豆油为原料采用碱催化酯交换法合成生物柴油,测定了其酸值、游离甘油、总甘油、灰分、黏度和磷含量等指标。实验表明,共存的甲醇、水分和甘油酯对生物柴油的低温流动性能影响极少,饱和脂肪酸甲酯的同时析出对生物柴油低温流动性能起关键作用。考察了5种柴油降凝剂、0号和20号柴油以及乙醇对生物柴油低温流动性能的影响。0号柴油有效地改善生物柴油黏度,但对其低温流动性能影响不大。20号柴油和乙醇能显著降低生物柴油的凝点、倾点、冷滤点和黏度。其中3种降凝剂有效降低生物柴油的凝点和倾点,1种降凝剂能小幅度改善冷滤点,5种降凝剂都能使生物柴油的黏度小幅上升。     

小波变换-分段直接校正法用于近红外光谱模型传递研究

提出了一种新的传递算法(WT-PDS)———小波变换-分段直接校正法,并详细讨论了模型传递参数和传递结果。首先利用小波变换对光谱进行压缩处理,采用PDS算法消除不同仪器之间压缩数据的差异,最后利用经校正的压缩数据进行分析,实现模型传递。本方法能够扣除不同仪器之间的大部分差异,大幅度改善分析精度。传递后模型分析精度与源机模型稳健性紧密相关。如果源机模型稳健性强,则能够实现不同仪器之间的共享。本方法能够实现源机的0#轻柴十六烷值、凝点、馏出温度;-10#轻柴十六烷值、凝点以及-10#军柴凝点和馏出温度共10个模型在5台仪器之间共享,简化了建模的成本。与传统的PDS相比,WT-PDS方法具有传递和建模变量少、速度快、光谱校正性能高等优点,而其模型分析精度与传统PDS基本一致。     

Relation between Molecular Structure and Low Temperature Behavior of Diesel Oil

Recently years, it has been developed that near infrared spectroscopy to analyze the quality indexes of fuel and it has been a study stress on researching the relation between molecular structure of petroleum product and its performances. In this paper, authors have analyzed the methyl and methylene of diesel oil by using NIR and have researched the relation between these structural groups and the solid point of diesel oil. Study result has shown that effect of methyl and methylene of diesel oil on the low temperature behavior is consistent with the theory study.     

生物质与废轮胎共热解催化热解油蒸发过程及其动力学研究

采用热重微商(TG-DTG)法考察生物质稻壳与废轮胎共热解经催化与非催化热解油的热失重行为，并同0#柴油的热失重行为进行了比较；同时采用Achar微分法和Coats-Redfern积分法对热解油热失重蒸发过程的蒸发热进行了计算，并结合Satava和Bagchi法确定了热失重蒸发过程的机理函数， 建立了0#柴油和在催化与非催化条件下得到的热解油蒸发过程的动力学方程，得出了在催化与非催化条件下热解油热失重过程的机理函数，其动力学方程为dα/dt=Ae-△vapH/RT(1-TBX〗α)2；而0#柴油的热失重蒸发过程动力学方程为dα/dt=1.5Ae-△vapH/RT(1-α)2/3\[1-(1-α)1/3\]-1。蒸发热的顺序由大到小依次为,柴油＞非催化热解油＞SBA-15热解油＞MCM-41热解油。结果表明，通过建立的模型函数得到的蒸发热与实验值非常接近。催化剂SBA-15和MCM-41的存在对降低高沸点馏分的物质具有一定作用，而SBA-15催化作用强于MCM-41。     

近红外光谱法快速测定生物柴油调和比及理化指标

通过比较偏最小二乘法(PLS)处理调和生物柴油近红外光谱图与标准方法测定调和生物柴油所获得的基础数据,确立了调和生物柴油的调和比、密度、运动黏度、热值、闭口闪点及冷凝点之间的相互关系。结果表明:经优化后,在OPUS光谱分析软件推荐维数(Rank)下,各指标模型的预测值与标准测定值之间线性相关关系均显著。在用于测定未知调和生物柴油样品的上述指标方面具有测定快速简便、误差小、成本低等优点,并用马氏距离限制异常项,每份生物柴油各指标的马氏距离都处于允许范围内。对于新类型生物柴油,可向模型添加10个以上调配样本,扩充模型后即可用于测定这类型调和生物柴油相关理化指标,可成为测定调和生物柴油相关理化指标新方法。在此基础上,可进一步开发出生物柴油近红外光学理化指标测定仪,实现低成本与快速测定。     

大庆蜡油催化裂化过程中的质子化裂化反应

在小型固定流化床装置上采用酸性催化剂进行了多系列不同反应深度的催化裂化实验,对大庆VGO催化裂化过程中发生的质子化裂化反应进行了初步的研究。在重质油的催化裂化过程中会出现二次质子化裂化反应。二次质子化裂化反应主要是由于汽油中烷烃重新在酸性催化剂上形成五配位正碳离子随后分解所造成,其产生的原因主要是由于反应后期催化剂对反应中间产物的选择性吸附改变所致。二次质子化裂化反应对温度不敏感。大庆VGO在500℃下反应时二次质子化裂化反应约占整个质子化裂化反应的60%。     

Catalytic degradation of polyethylene and polypropylene to fuel oil

Thermal and catalytic degradation of plastic polymers, polyethylene and polypropylene to fuel oil were carried out in batch operations. The catalysts employed were acid silica-alumina (SA-1, SA-2) and zeolite ZSM-5, and non-acidic mesoporous silica FSM (folded sheet material). The yields of product gas, liquid and residues, recovery rate of liquid products, and boiling point ranges of liquid products due to degradation were compared with those of non-catalytic thermal degradation. Both the effect of catalytic contact mode and of catalyst type on the degradation were studied. In liquid-phase degradation of PP over SA-1, liquid hydrocarbon products were obtained in a yield of 69 wt.-% with a boiling point range 36-270°C, equivalent to the boiling point of normal paraffins C6 - C15. The liquid products from catalytic degradation have a carbon-number distribution very similar to commercial motor gasoline. In vapor-phase contact, the yield of liquid products was much lower (54%) and the rate of liquid recovery was much slower. With FSM, the initial rate of degradation of PP and PE to liquid products was as fast as that over acid catalyst SA-1, but the yield of liquid products was higher. The liquid products from catalytic degradation over FSM have a carbon-number distribution similar to kerosene and diesel oil. In repeated use, SA-1 deactivated very rapidly due to coke deposition on the catalyst, whereas FSM deactivated much more slowly. These findings suggest that mesopores surrounded by the silica sheet may act as reservoir for radical species, which accelerate the degradation of plastic melt.