New path in the thermal cracking of triacylglycerols (canola and soybean oil)

Triacylglycerols (TGs) are naturally occurring oils abundant in many crops. A series of batch uncatalyzed thermal decomposition experiments were performed using canola and soybean oils to explore pathways of TG cracking. A detailed gas chromatographic protocol based on mass spectrometric identification and flame ionization quantification was applied to the organic liquid product generated upon cracking. Reaction conditions were identified that resulted in a novel organic liquid product (OLP) composition compared to previously reported work. Under these conditions (temperatures within a 420-440 °C range) a new route for TG thermolysis was discovered in which cracking reactions of original TG-bound fatty acids were nearly complete and led to the formation of 15-25 wt.% C₂-C₁₀ linear saturated monocarboxylic acids and ca. 30% linear alkanes. Less than 2 wt.% C₁₆-C₁₈ fatty acids which were originally present in the feedstocks as glycerol triesters were found in the OLP. These reactions appear to be kinetically controlled due to abundant hydrogen formation. This route provides a significant enrichment of low-MW compounds in the OLP (65-70 wt.% being <C₁₁) and thus may be considered as a new option for the production of replacement products for petroleum-based fuels and chemicals.     

Effects of oil type on products obtained by cracking of oils and fats

This paper deals with cracking of vegetable oils and animals fats in the presence of zeolite catalysts, the objective being preparation of liquid products similar in their properties to fossil diesel. The effects of oil/fat type on the liquid condensate yields and parameters were monitored. The tests were carried out with rapeseed, sunflower, soybean and jatropha oils as well as with used frying oils. Liquid condensates with yields of 85 to 90% relative to the input oil were obtained at temperatures of 350 to 440 °C applied for the period of 20 to 30 min in the presence of zeolite catalysts NaY and clinoptilolite. The input oil types had no significant effect on the yields and characteristics of the treated condensate. In this respect, used frying oils (UFO) as a feed material match other types of fresh oils and fats. Treated condensates blended with fossil diesel (5-7% of the condensate by volume) are compliant with the EN 590 standard and can thus be used as a component of diesel fuels.     

The effect of phytosterol concentration on oxidative stability and thermal polymerization of heated oils

This study determined the effect of adding mixed phytosterols, at various concentrations, on the thermal polymerization and oxidative stability index (OSI) of soybean and high‐oleic sunflower oils. The indigenous tocopherols and phytosterols were removed from the oils by molecular distillation. Pure phytosterols were added back to these stripped oils at concentrations of 0.25, 0.5, 1, and 2.5 wt‐%. These oils were heated at 180 °C, and triacylglycerol dimers and polymers, fatty acid composition, and residual phytosterols were determined. Added phytosterols at 1 and 2.5% significantly decreased thermal polymerization of stripped soybean oil over 8 h. Phytosterols at 2.5% significantly increased polymerization of stripped high‐oleic sunflower oil over 12 h. Added phytosterols did not affect the loss of polyunsaturated fatty acids in either oil. The decomposition of the added phytosterols was followed in both oils during the heating study. The loss of phytosterols in soybean oil ranged from 7 to 13%, while loss in stripped high‐oleic sunflower oil ranged from 13 to 20%. Phytosterols added at 1 and 2.5% significantly decreased the OSI for stripped high‐oleic sunflower oil. This research shows that added phytosterols, especially at higher concentrations, will have an impact on the thermal and oxidative stability of oils.     

Effect of phytosterol structure on thermal polymerization of heated soybean oil

This study determined the effect of phytosterol structure, including the degree of unsaturation and the presence of an ethylidene group in the side chain, on the thermal polymerization of heated soybean oil. Indigenous tocopherols and phytosterols were removed from soybean oil by molecular distillation. Pure phytosterols were added back to the stripped soybean oil at concentrations of 0.5, 1.0, and 5 mg/g oil (0.05, 0.1, and 0.5 wt-%). These oils were heated at 180 °C over a period of 8 h, and triacylglycerol dimers and polymers, fatty acid composition, and residual phytosterol content were determined. None of the phytosterols prevented triacylglycerol dimer and polymer formation when used at 0.5 mg/g; however, phytosterols with two or more double bonds, regardless of the presence of an ethylidene group in the side chain, provided slight protection when added at 1 mg/g. Ergosterol addition at 5 mg/g reduced polymer formation by 16–20% compared to the control oil, but at this level none of the other phytosterols provided protection of any practical significance. Thus, under the conditions used for this heating study, the degree of phytosterol unsaturation was more important for its anti-polymerization activity than the presence of an ethylidene group.     

Frying stability of soybean and canola oils with modified fatty acid compositions

Pilot plant-processed samples of soybean and canola (lowerucic acid rapeseed) oil with fatty acid compositions modified by mutation breeding and/or hydrogenation were evaluated for frying stability. Linolenic acid contents were 6.2% for standard soybean oil, 3.7% for low-linolenic soybean oil and 0.4% for the hydrogenated low-linolenic soybean oil. The linolenic acid contents were 10.1% for standard canola oil, 1.7% for canola modified by breeding and 0.8% and 0.6% for oils modified by breeding and hydrogenation. All modified oils had significantly (P<0.05) less room odor intensity after initial heating tests at 190°C than the standard oils, as judged by a sensory panel. Panelists also judged standard oils to have significantly higher intensities for fishy, burnt, rubbery, smoky and acrid odors than the modified oils. Free fatty acids, polar compounds and foam heights during frying were significantly (P<0.05) less in the low-linolenic soy and canola oils than the corresponding unmodified oils after 5 h of frying. The flavor quality of french-fried potatoes was significantly (P<0.05) better for potatoes fried in modified oils than those fried in standard oils. The potatoes fried in standard canola oil were described by the sensory panel as fishy.     

Kinetics of asphaltene thermal cracking and catalytic hydrocracking

A pentane-insoluble asphaltene was processed by thermal cracking and catalytic hydrocracking over NiMo/γ-Al₂O₃ in a microbatch reactor at 430 °C. Kinetic analysis shows that the first-order kinetics fits the data of conversion in reaction times ≤ 30 min approximately, but deviates from the data of times over 30 min significantly; whereas the second-order kinetics fits the data of the reaction times up to 60 min adequately, to give the apparent rate constants of 1.704 × 10⁻² and 9.360 × 10⁻² wt frac⁻¹min⁻¹ for the two cracking processes. Furthermore, a three-lump kinetic model is proposed to include parallel reactions of asphaltenes to produce liquid oil (k₁) and gas + coke (k₃), and consecutive reaction from liquid to gas + coke (k₂). The evaluated value of k₁ is 1.697 × 10⁻² and 9.355 × 10⁻² wt frac⁻¹min⁻¹, k₂ is 3.605 × 10⁻² and 6.347 × 10⁻³ min⁻¹ , and k₃ is 6.934 × 10⁻⁵ and 4.803 × 10⁻⁵ wt frac⁻¹min⁻¹ for asphaltenes thermal cracking and catalytic hydrocracking, respectively. Selectivity analysis shows that the catalytic hydrocracking process promotes liquid production and inhibits coke formation effectively.     

Conversion of Calotropis procera biocrude to liquid fuels using thermal and catalytic cracking

With the fast depletion of petroleum reserves, renewable resources like biomass are acquiring great significance. Calotropis procera, a laticiferous arid plant is identified as a potential petrocrop. The dried biomass of C. procera was subjected to non-polar (n-heptane) solvent extraction. Biocrude so obtained is a rich source of tri terpenoid type of hydrocarbons. The biocrude was upgraded to useful liquid fuels using different conversion processes such as thermal and catalytic cracking (fluid catalytic cracking, FCC). The temperature, pressure and reaction time maintained during thermal conversions were 430 and 460 °C; 1.2 and 0.2 MPa; and 15 and 30 min, respectively. Catalytic cracking was carried out in continuous mode micro reactor varying the catalyst to feed ratio (3-7.03) and temperature (460-520 °C) aiming at maximization of lighter fractions (up to diesel range). High conversions (up to 92%) were obtained using FCC as compared to thermal process (57.7%). The HPLC analysis of the liquid fuels indicated that thermal cracking yielded a better quality fuel compared to FCC. The fuel obtained by FCC was found to contain large proportions of aromatics and poly-aromatic hydrocarbons (PAH).     

植物油脂裂解催化剂的合成及其催化性能研究

选用典型的高含油光皮树果实,采用等体积浸渍法制备固体碱催化剂KF/CaO催化裂解制备生物燃料油,并通过FTIR、XRD、SEM、CO2-TPD等对催化剂进行表征。对催化裂解后气相产率、液体油产率和固相产率的变化来验证催化剂的催化性能,考察催化剂用量、裂解反应时间和裂解反应温度对产物产率的影响。实验结果表明,在催化剂用量1.2%、反应温度500℃、反应时间为45min的条件下,实测生物燃料油产率可以达到82.56%。     

Highly accurate photopyroelectric measurement of thermal diffusivity of vegetable oils

High‐accuracy photopyroelectric measurements, in the thermal‐wave‐resonator‐cavity configuration, were performed in order to measure the thermal diffusivity of some vegetable oils. The high resolution (relative error ±0.5%) of the above method allows for the detection of small changes in the values of this dynamic thermal parameter. The accuracy of the results is mainly due to the possibility to precisely control the variation (30‐nm step) of sample thickness, a proper selection of the range of the thickness scan (2 µ_m < L_m < 4 µ_m ? 5 µ_m), and an iterative procedure of data analysis. A correlation between thermal diffusivity and the fatty acid composition (obtained via gas chromatography) is suggested for some fresh (sunflower, hemp, flax, and soybean) oils and for hemp oil exposed to a microwave field: Thermal diffusivity appears to be determined by the overall content of polyunsaturated fatty acids.     

Towards synthesis of an optimal thermal cracking reactor

To develop new reactor options for thermal cracking of ethane or other light hydrocarbons to lower olefins a fundamental process synthesis approach is taken. Firstly, an optimal reaction path and conditions are targeted, starting from a mechanistic reaction network. Secondly, to implement the optimal reaction path the reactor geometry and equipment are designed. This contribution focuses on the development of a targeting approach, for which a new distributive reaction-mixing synthesis model is formulated and applied. The mixing kernel in the model provides freedom to redistribute the reaction mixture along a continuous reaction coordinate to optimize product yield. The model was validated for two applications. It reproduces the results for the Van de Vusse reaction network as obtained by the attainable region theory. When applied to a small reaction network for the conversion of ethane into ethylene, it reconfirms the existing result that for this network the plug flow mode at maximum temperature and minimum pressure gives the optimal olefin yield.     

Analysis of hydroformylated vegetable oils and their methyl esters for rhodium

Two procedures for the determination of fatsolubilized rhodium were investigated. Analysis in aqueous media involves a sulfuric acid digestion which previously was carried out in 20–30 hr. Digestion now takes only 1 to 2 hr. The acid concentration in samples and standards is very critical. For analysis in nonaqueous media the sample is weighed, dissolved in methyl isobutyl ketone containing hydrogen chloride, and analyzed directly by atomic absorption spectrophotometry. Absorbance in both procedures follows Beer’ s law. Results varied when hydrogen chloride was omitted or replaced with phosphoric acid. The results agreed closely with results obtained by published colorimetric procedures.     

脂肪酸甲酯加氢脱氧和蒸汽裂解两步法制备生物烯烃

脂肪酸甲酯经生物烷烃制备轻质烯烃,有望缓解低原油价格导致的生物柴油产业发展困境。采用浸渍法制备了NiMo/Al₂O₃催化剂,首先考察其催化脂肪酸甲酯加氢脱氧制备生物烷烃的性能,然后进一步分析生物烷烃蒸汽裂解制烯烃的转化规律。结果表明,预硫化的NiMo/Al₂O₃能够高选择性地催化饱和脂肪酸甲酯加氢制备生物烷烃,并且催化剂的结构在反应1000 h后无明显改变。以上述烷烃为原料,在裂解炉出口温度为810℃,出口压力为0.10 MPa,物料停留时间为0.23 s和水油质量比为0.75的反应条件下进行蒸汽裂解,产物中乙烯、丙烯和丁二烯的收率分别达到36.30%、18.14%和7.46%,显著高于同等条件下石脑油原料得到的27.45%、14.74%和5.31%,表明源于脂肪酸甲酯的生物烷烃可以作为生产轻质烯烃的原料补充。     

Flow and crystallization of saturated fatty acid methyl esters and their binary mixtures

Demand for biodiesel has increased due to being a more environmentally-friendly fuel. Cold weather operation of biodiesel is challenging due to fatty acid methyl ester (FAME) content in biodiesel. Saturated FAMEs crystallize at relatively high temperatures, increase the viscosity of biodiesel, and can clog fuel lines. Here, several factors altered crystallization temperature (CT) of FAMEs, including composition, shear rate, and cooling rate. The crystallization of pure and binary mixtures of methyl palmitate, methyl myristate, and methyl stearate were studied under shear flow and static conditions. Static phase CTs of pure methyl palmitate, methyl myristate, and methyl stearate were 26, 14, and 35°C, respectively. In binary mixtures, CTs were depressed up to 7°C, which agreed with freezing point depression theory. Increasing shear rate up to 100 s⁻¹ decreased CT by 2°C compared to static conditions. Decreasing cooling rate from 1 to 0.1°C/min increased CT less than 2°C. Overall, FAME composition altered CT more than shear flow or cooling rate for pure and binary mixtures of three FAMEs.     

Formation of coke in thermal cracking of jet fuel under supercritical conditions

Continuous-flow reactor experiments were carried out to study coke formation from thermal cracking of home-made jet fuel RP-3 under supercritical conditions. The mechanism and precursor of coke forming were analyzed. The starting cracking temperature of RP-3 fuel was determined to be 471.8°C by differential scanning calorimetry (DSC). Temperature-programmed oxidation and scanning electron microscopy (SEM) characterizations of the stressed tubes showed that there are three different coke species including chemisorbed carbon, amorphous carbon and filamentous coke in the solid deposits. More than 90% of coke deposits are carried away by the supercritical fluid, which has strong capabilities of extraction for coke deposits and their precursors. There were 17.1 wt-% of iron and 11.1 wt-% of chromium found on the coke surface detected by energy dispersive spectroscopy (EDS) which suggests carburetionon alloy. RP-3 fuel and its cracking liquids were analyzed by GC-MS,which showed that the content of alkyl benzene and alkyl naphthalene increased evidently in cracking liquids. __________ Translated from Petrochemical Technology, 2006, 35(12): 1151–1155 [译自:石油化工]     

Recovery of solubilized rhodium from hydroformylated vegetable oils and their methyl esters

Procedures were developed to extract rhodium from hydroformylated vegetables oils and methyl esters. Among the numerous reagents surveyed, aqueous hydrogen cyanide with triethanolamine (TEA) was found to be most effective. The effects of time, temperature, and concentration of reagents were studied. Over 98% of the solubilized rhodium was removed from crude methyl formylstearate at 100 C for 1 hr with 0.5% hydrogen cyanide, 5% water, and 0.5% TEA. Over 98% of the solubilized rhodium was also extracted from hydroformylated soybean and safflower methyl esters; however, 1% hydrogen cyanide, 10% water, and 0.62% TEA had to be used. Only 90% of the rhodium was removed from hydroformylated soybean oil. The reagents used can be adpated to a continuous extraction procedure.     

从废弃油脂生物柴油中分离不饱和脂肪酸甲酯

以废弃油脂制生物柴油为原料,以95%醇为溶剂,采用尿素包合法提取不饱和脂肪酸甲酯,为生物柴油联产具有高附加值化工产品打下基础.重点考察了尿素用量、溶剂用量、包合时间和包合温度对不饱和脂肪酸甲酯分离效果的影响.结果表明,尿素包合法从生物柴油中分离不饱和脂肪酸甲酯的适宜工艺条件为:尿素,生物柴油质量比为1.4～1.7,溶剂/生物柴油质量比为4.6～6.0,包合温度为10℃,包合时间为18 h.在适宜条件下,不饱和脂肪酸甲酯含量可达93.5%,收率可达55.8%.     

Studies on thermal cracking behavior of residual feedstocks in a batch reactor

Thermal cracking of residual fractions has gained interest of refiners due to increasing demand of middle distillates and at the same time decline in demand of fuel oils. The present study is an attempt to gain deeper insight into the thermal cracking behavior of residual feedstocks in terms of certain key characteristics. Laboratory scale experiments on a 400 ml capacity stainless steel batch reactor were conducted with four residual feedstocks of Indian and Middle East origin—North Gujarat short residue (NGSR), Visbreaker feed from Mathura refinery (MVBF), Bombay High short residue (BHSR) and Asphalt from Haldia refinery (HRA), with asphaltene content varying in the range 1.85-10.15 wt%. The cracked products were separated by distillation up to 500 ^°C. The distillate (500 ^°C-) was analyzed by ASTM D2887 (SIMDIST) method and obtained data were classified into lumps, namely Gas (C₅-), Gasoline (IBP-150 ^°C), Light Gas Oil (150-350 ^°C) and Vacuum Gas Oil (350-500 ^°C) prior to detailed data analysis. The analysis of results reveals that the thermal cracking of petroleum residues follows first order kinetics. The rate constants and activation energies have also been estimated.     

碳氢燃料热裂解与引发裂解换热对比实验

通过流动管反应器对碳氢燃料RP-3在超临界条件下的热裂解及引发裂解进行了实验,对两种条件下的燃料吸热能力及传热特性进行了对比分析,并对裂解产物进行了采样分析。结果表明,引发裂解降低了燃料的裂解起始温度,在一定温度区间内提高了燃料的裂解率,从而有效提高了燃料热沉,在相同热通量条件下,降低了燃料温度,并降低了加热段壁面温度。对流换热受化学反应及物性变化的影响,燃料裂解吸热可增强换热,而大量气态产物的生成会降低换热,因此,裂解反应的增强不一定增强换热。