Biofuels from waste fish oil pyrolysis: Continuous production in a pilot plant

Fast pyrolysis of waste fish oil was performed in a continuous pyrolysis pilot plant. The experiment was carried out under steady-state conditions in which 10 kg of biomass was added at a feed rate of 3.2 kg h⁻¹. A bio-oil yield of 72-73% was obtained with a controlled reaction temperature of 525 °C. The bio-oil was distilled to obtain purified products with boiling ranges corresponding to light bio-oil and heavy bio-oil. These biofuels were characterized according to their physico-chemical properties, and compared with the Brazilian-fuel specifications for conventional gasoline and diesel fuels. The results show that the fast pyrolysis process represents an alternative technique for the production of biofuels from waste fish oil with characteristics similar to petroleum fuels.     

厨余垃圾水热液化制取生物燃料

以厨余垃圾为原料进行水热液化,考察了反应温度和料液比对产物分布的影响。温度320℃、料液比1:15时,生物油产率最高为16.7%,继续升高温度或降低料液比将促进气体产物生成。与重质原油、常减压渣油相比,生物油氧、氮元素含量较高,热值为32.33~34.82 MJ·kg^-1,其中汽油和煤柴油馏分超过50%。利用GC-MS、FT-IR和FT-ICR MS对生物油化学组成、官能团和杂原子组成进行了表征。生物油是一种复杂混合物体系,已检测出烃类、酸类、醛类、酮类、酯类、胺类、酚类、醇类和含氮杂环类等多种物质,对其酸性组分进一步分析显示,含氧组分主要是O₂、O₃类化合物,含氮组分主要是N₁O₂、N₁O₃和N₁O₄类化合物。     

稻壳快速热裂解生物油的特性研究

Physicochemical properties of bio-oil obtained from fast pyrolysis of rice husk were studied in the present work.Molecular distillation was used to separate the crude bio-oil into three fractions viz.light fraction,middle fraction and heavy fraction.Their chemical composition was analyzed by gas chromatograph and mass spectrometer(GC-MS).The thermal behavior,including evaporation and decomposition,was investigated using thermogravimetric analyzer coupled with Fourier transform infrared spectrometer(TG-FTIR).The product distribution was significantly affected by contents of cellulose,hemicellulose and lignin.The bio-oil yield was 46.36%(by mass) and the yield of gaseous products was 27%(by mass).The chemicals in the bio-oil included acids,aldehydes,ketones,alcohols,phenols,sugars,etc.The light fraction was mainly composed of acids and compounds with lower boiling point temperature,the middle and heavy fractions were consisted of phenols and levoglucosan.The thermal stability of the bio-oil was determined by the interactions and intersolubility of compounds.It was found that the thermal stability of bio-oil was better than the light fraction,but worse than the middle and heavy fractions.     

The viscosity reduction of nano-keggin-K3PMo12O40 in catalytic aquathermolysis of heavy oil

Nano-keggin-K₃PMo₁₂O₄₀ was synthesized, characterized by FT-IR, XRD and TEM, and then used in catalytic aquathermolysis of extra-heavy oil for the first time. The results evidently showed a viscosity reduction by 92.3% for the extra-heavy oil Zhen 411 at 280 °C, and by 80% and 90% in viscosity reduction for the extra-heavy oil G540 at 200 °C and 280 °C, with 9.25% and 11.69% in conversions of heavy to light content, respectively. To evaluate the performance, the structure and group composition of the heavy oil before and after the reaction were tested and analyzed by TLC-FID, FT-IR, GC-FID, ¹H NMR, EL and GC-MS. It was found that changes in oxygen-containing groups mainly happen during the catalytic aquathermolysis.     

Fuels by pyrolysis of waste plastics from agricultural and packaging sectors in a pilot scale reactor

The pyrolysis of waste plastics (so called chemical recycling) is one perspective way of their utilizations, but the end product properties are a key point of the industrial leading of processes. In this paper a pilot scale pyrolysis process has been investigated. Waste plastics were decomposed in a tube reactor at 520 °C, using hourly feed rate of 9.0 kg. Raw materials were selectively collected wastes from agricultural and packaging industry. For supporting the more intensive cracking of CC bonds of main polymer structure a commercial ZSM-5 catalyst was tested in concentration of 5.0%. Products were separated into gases, gasoline, light and heavy oil by distillation. Plastic wastes could be converted into gasoline and light oil with yields of 20–48% and 17–36% depending on the used parameters. The gas and liquid products had significant content of unsaturated hydrocarbons, principally olefins. In the presence of ZSM-5 catalyst the yields of lighter fractions (especially gasoline) could be considerably increased and the average molecular weight of each fraction has decreased. Gasoline had C₅–C₁₅ hydrocarbons, while light oil had C₁₂–C₂₈. The used catalyst has promoted the formation of i-butane in gases and affected the composition of both gasoline and light oil. Properties of products are advantageous for fuel-like applications, and they are able to increase the productivity of refinery. On the other hand the possibility for further utilization of products from pyrolysis basically was affected by the source and the properties of raw materials. Waste polyethylene from agricultural consisted of some elements from fertilizers (N, S, P and Ca), which could not be removed from the surfaces of raw materials by pre-treatment (e.g. washing). In that case significant concentration of N, S, P and Ca can be measured in all products, but the catalyst has decreased the concentration of impurities. Gasoline, light oil and heavy oil were nitrogen free and sulphur content was below 12 mg/kg in hydrocarbons obtained by the pyrolysis of polypropylene waste from packaging.     

Performance and emission study of waste anchovy fish biodiesel in a diesel engine

Waste anchovy fish oils transesterification was studied with the purpose of achieving the conditions for biodiesel usage in a single cylinder, direct injection compression ignition. With this purpose, the pure biodiesel produced from anchovy fish oil, biodiesel-diesel fuel blends of 25%:75% biodiesel-diesel (B25), 50%:50% biodiesel-diesel (B50), 75%:25% biodiesel-diesel (B75) and petroleum diesel fuels were used in the engine to specify how the engine performance and exhaust emission parameters changed. The fuel properties of test fuels were analyzed. Tests were performed at full load engine operation with variable speeds of 1000, 1500, 2000 and 2500 rpm engine speeds. As results of investigations on comparison of fuels with each other, there has been a decrease with 4.14% in fish oil methyl ester (FOME) and its blends' engine torque, averagely 5.16% reduction in engine power, while 4.96% increase in specific fuel consumption have been observed. On one hand there has been average reduction as 4.576%, 21.3%, 33.42% in CO₂, CO, HC, respectively; on the other hand, there has been increase as 9.63%, 29.37% and 7.54% in O₂, NO_x and exhaust gas temperature has been observed. It was also found that biodiesel from anchovy fish oil contains 37.93 wt.% saturated fatty acids which helps to improve cetane number and lower NO_x emissions. Besides, for biodiesel and its blends, average smoke opacity was reduces about 16% in comparison to D2. It can be concluded that waste anchovy fish obtained from biodiesel can be used as a substitute for petroleum diesel in diesel engines.     

Synthesis of mycolic acid biosurfactants and their physical and surface-active properties

Five mycolic acids [2-alkyl-3-hydroxy FA: R₁C^*(OH)C^*HR₂COOH] were synthesized using acyl chlorides with alkyl chains of different lengths (total carbon numbers of mycolic acids, 12, 16, 20, 24, 36). The relationship between the chemical structures of the mycolic acids and their surface-active properties was determined. The acids were synthesized in three steps: (i) dimerization of acyl chloride into alkyl ketene dimer, (ii) selective reduction of C=C to C-C by hydrogenation, and (iii) β-lactone ring cleavage under alkaline conditions. The yields of C₁₂-, C₁₆-, C₂₀-, C₂₄-, and C₃₆-mycolic acid were 72, 73, 73, 73, and 73%, respectively. The critical micelle concentrations (CMC) of C₁₂-, C₁₆-, and C₂₀-mycolic acid were 2.2×10⁻⁴, 1.36×10⁻⁴, and 7.4×10⁻⁵ M, respectively. As the carbon number increased, the surface tension at the CMC value was also lower; the values for C₁₂-, C₁₆- and C₂₀-mycolic acid were 46.54, 43.59, and 41.57 dyn/cm, respectively. The emulsifying activities of mycolic acids were determined for n-tetradecane, n-hexadecane, cyclohexane, and diesel oil. The results showed that C₁₂-mycolic acid was the best emulsifier for diesel oil, C₁₆-mycolic acid was the best emulsifier for n-tetradecane and n-hexadecane, and C₂₀-mycolic acid was the best emulsifier for cyclohexane. This study showed that mycolic acids having, surface-active properties can be chemically synthesized for potential applications in the detergent/cleaning material industries, for example, in oil spill cleanup, oil recovery, textiles, pharmaceuticals, and cosmetics.     

丙胺溶液水热液化海藻残渣及产物生物油分析

使用丙胺溶液对裙带菜孢子叶残渣进行水热液化,分析了水热液化后生物油、水溶性物质和固体残渣的成分。在丙胺浓度1.5 mol·L^-1、反应温度240℃、料液比1：10的条件下得到生物油的最大产率为39.81%（质量）。生物油通过GC-MS和FT-IR进行分析,结果表明成分包含醇类、烷类、酯类、酸类、酚类和酰胺类等,并存在C=C、C=O、O-H等化合键。水溶性物质通过HPLC和GC-MS进行分析,结果表明主要产物为酸类物质。固体残渣通过XRD进行分析,结果表明水热液化后纤维素的结晶度降低。最后对丙胺进行回收,在温度100℃条件下回收率达到92.56%。     

环烷基瓦斯油催化裂解反应规律及产品性质

利用提升管催化裂解实验装置研究了加拿大合成原油瓦斯油HGO和LGO的催化裂解反应规律和裂解产品性质。发现总低碳烯烃（乙烯、丙烯和丁烯）产率随反应温度和剂油比的增大存在最大值,随反应时间的延长而减小,随水油比的增大而升高。实验确定了HGO催化裂解的优化反应条件：反应温度620～640℃、剂油比16、反应时间2 s、水油比0.5左右。在此反应条件下,乙烯、丙烯和总低碳烯烃产率分别可达9.0%（质量）,15.8%（质量）和32.6%（质量）。催化裂解汽油馏分、柴油馏分和重油馏分含有大量的芳香烃,其中催化裂解汽油馏分总芳香烃含量在80%（质量）以上,主要是甲苯和C₈芳香烃;催化裂解柴油馏分总芳香烃含量在60%（质量）以上,主要是单环和双环芳香烃;催化裂解重油馏分总芳香烃含量在70%（质量）以上,主要是多环芳香烃。     

Characterization of chilean hazelnut (Gevuina avellana mol) seed oil

The fatty acid composition, tocopherol and tocotrienol content, and oxidative stability of petroleum benzene-extracted Gevuina avellana Mol (Proteaceae) seed oil were determined. Positional isomers of monounsaturated fatty acids were elucidated by gas chromatography-electron impact mass spectrometry after 2-alkenyl-4,4-dimethyloxazoline derivatization. This stable oil (Rancimat induction period at 110°C: 20 h) is composed of more than 85% monounsaturated fatty acids and about equal amounts (6%) of saturated and polyunsaturated (principally linoleic) fatty acids. Unusual positional isomers of monounsaturated fatty acids, i.e., C_16:1 Δ¹¹, C_18:1 Δ¹², C_20:1 Δ¹¹, C_20:1 Δ¹⁵, C_22:1 Δ¹⁷, and presumably C_22:1 Δ¹⁹ were identified. The C_18:1 Δ¹² and C_22:1 Δ¹⁹ fatty acids are described for the first time in G. avellana seed oil. While only minute quantities of α-, γ-tocopherols and β-, γ- and δ-tocotrienols were found, the oil contained a substantial amount of α-tocotrienol (130 mg/kg). The potential nutritional value of G. avellana seed oil is discussed on the basis of its composition.     

High efficient mesoporous HZSM-5 nanocatalyst development through desilication with mixed alkaline solution for methanol to olefin reaction

Methanol to olefin (MTO) process is a non-oil route for the light olefins production. We report the mesoporous and high siliceous HZSM-5 nanocatalyst development through the new desilication process including the mixed alkaline solution. The properties of nanocatalysts were characterized using TGA/DTA, XRD, ICP, FE-SEM, BET, FT-IR, and NH₃-TPD techniques. FE-SEM images represent the spherical morphology of parent nanocatalyst including smooth surface. The XRD analysis confirms that applied desilication does not change the typical MFI-type structure of ZSM-5 nanocatalysts. The BET and NH₃-TPD results show that mixed alkaline solution including 40 wt% TPAOH results in the best adjustment of textural (299.7 m²/g) and acidity (strong/weak ratio of 0.21) properties, respectively. The PHZ-NaTP0.4 nanocatalyst represents the highest methanol conversion (99.2%), propylene selectivity (48.3%), C₃ ⁼/C₂ ⁼ molar ratio (7.4) as well as lowest selectivity to C₁–C₄ alkanes (4.6%) for long time on stream (170 h). The low selectivity of light alkanes (C₁–C₄) and high total light olefins (ca. 75%) confirm the stable performance of nanocatalyst. Consequently, the developed PHZ-NaTP0.4 nanocatalyst is a high efficient MTO catalyst and can be candidate for commercial scale up.     

Combustion characteristics of fatty acid methyl esters derived from recycled cooking oil

The goal of this study is to find out the exhaust emissions differences produced by different kinds of fatty acid methyl esters (FAME) derived from used cooking oils and animal fats, as well as the importance of the purification step in exhaust emissions production. A total of 120 L of waste vegetable oil and 30 L of waste frying oil were collected and converted into three batches of FAME. There were two batches of FAME produced from waste vegetable oil (B01 and B02), and one batch of FAME produced by mixing 2% of waste frying oil with waste vegetable oil (B03). The FAMEs used in this study had higher density, kinematic viscosity, and flash point, but a lower gross heating value, when compared to the premium diesel. The B01 engine produced higher CO formation and the diesel-fuelled engine produced higher CO than the B02 and B03 did for engine speeds higher than 1400 rpm. Most of the FAME fuels produced higher CO₂ than the diesel fuel did. The FAME fuels emitted higher NO_x and PM, but lower SO₂, than the diesel fuel. C_nH_2n+2, diphenyl sulfone (C₁₂H₁₀O₂S), and diethyl phthalate (C₁₂H₁₄O₄) can be selected as the character index for the combustion of FAME.     

Steam pyrolysis of an industrial waste for bio-oil production

Potato skin, a food industry waste, was pyrolysed under three different atmospheres namely static, nitrogen, and steam to produce bio-oil and its derivatives. The oil yield obtained at 550 °C was 24.77% in static atmosphere, whereas it reached to 27.11% in nitrogen atmosphere. Moreover, the use of steam caused a sharp increase of oil yields up to 41.09% with a steam velocity of 1.3 cm s^− 1. TG-DTA analyses were applied on the raw material to investigate the thermal degradation. Liquid products obtained under the most suitable conditions were characterized by elemental analyses, FT-IR and ¹H NMR. In addition, column chromatography was employed to separate the bio-oil into its derivatives. Asphaltene fraction of bio-oil is decreased under steam atmosphere. Gas chromatography was also used to investigate the C distributions. The characterization has shown that the bio-oil obtained under steam atmosphere was more beneficial than those obtained under both static and inert atmospheres. Further comparison of H/C ratios of pyrolysis oils with conventional fuels indicates that the H/C ratios of the oils obtained in this study lie between those of light and heavy petroleum products. It can be concluded that potato skin could be evaluated as a promising biomass candidate of bio-oil production.     

Catalytic Cracking of Heavy Olefins into Propylene, Ethylene and Other Light Olefins

Hybrid catalysts developed for the thermo-catalytic cracking of liquid hydrocarbons were found to be capable of cracking C₄ ⁺ olefins into light olefins with very high combined yields of product ethylene and propylene (more than 60 wt%) and C₂–C₄ olefins (more than 80 wt%) at 610–640 °C, and also with a propylene/ethylene weight ratio being much higher than 2.4. The olefins tested were heavier than butenes such as 1-hexene, C₁₀ ⁺ linear alpha-olefins (LAO) or a mixture of LAO. The hydrogen spillover effect promoted by the Ni bearing co-catalyst, contributed to significantly enhancing the product yield of light olefins and the on-stream stability of the hybrid catalyst.     

Catalytic cracking reaction of used lubricating oil to liquid fuels catalyzed by sulfated zirconia

The conversion of used lubricating oil to transport fuel by direct cracking is a suitable way to dispose of waste oil. The aim of this research was to study the catalytic cracking of used lubricating oil, and thus change its classification from a waste produce to a liquid fuel as a new alternative for the replacement of petroleum fuels. The experiments were carried out in a 70-cm³ batch microreactor at a temperature of 648-698 K, initial hydrogen pressure of 1-4 MPa, and reaction time of 10-90 min over sulfated zirconia as a catalyst. The conditions that gave the highest conversion of naphtha (~20.60%) were a temperature of 698 K, a hydrogen pressure of 2 MPa, and a reaction time of 60 min, whereas, under the same conditions, kerosene, light gas oil, gas oil, long residues, hydrocarbon gases, and a small amounts of solids were present (~9.04%, 15.61%, 5.00%, 23.30%, 25.58%, and 0.87%, respectively). The liquid product consisted of C₇-C₁₅ of n-paraffins, C₇-C₉ of branched chain paraffin and aromatic compounds such as toluene, ethylbenzene and xylene. The kinetic study reveals that the catalytic cracking of waste lubricating oil follows a second order reaction, and the kinetic model is defined as k(s⁻¹)=2.88×10⁴exp[−(103.68 kJmol⁻¹)/(RT)].     

Alpha olefin sulfonates from a commercial SO3-Air reactor

Alpha olefin sulfonate (AOS) can be made by SO₃-air sulfonation of straight chain alpha olefins followed by saponification of the neutralized product. The sulfonation step forms unsaturated sulfonic acids, sultones and sultone sulfonic acids. Hydrolysis of the various sultones yields a mixture of unsaturated and hydroxy sulfonates. Sulfonation of commercial mixtures of straight chain alpha olefins in a large-scale SO₃ falling film unit has given AOS of 1.5–3.0% oil based on active content and tristimulus color of about 40% saturation (2% solution) which is readily bleachable with 1–3% NaOCl to about 10–15% saturation. Performance of AOS made from C₁₅−C₁₈ alpha olefin is comparable to that of the high-foaming C₁₁−C₁₄ LAS in both detergency and dishwashing foam. It is superior to similar products made from internal straight chain olefins. The product shows a low order of toxicity and biodegrad-ability slightly better than that of LAS. A C₁₅−C₁₆ AOS blend is especially attractive in liquid detergent formulations. Presented at the AOCS Meeting, Los Angeles, April 1966.     

Evaluation of solvent dearomatization effect in heavy feedstock thermal cracking to light olefin: An optimization study

Response surface method was used to study the effect of aromatic extraction of heavy feedstock in thermal cracking. N-methylpyrrolidone as the solvent performing dearomatization of feedstock was at different temperature and molar solvent to oil ratios. Temperature, flow rate and steam-to-hydrocarbon ratio were in the range of 1,053–1,143 K, 1–2 g/g, and 0.75–1.2 g/min, respectively. From the CCD studies, the effects of flow rate and coil outlet temperature were the key factors influencing the yield of light olefins. Ethylene and propylene yields increased more than 10% by dearomatization. C ₅ ⁺ decreased by 13% on average. Finally, we obtained the single maximum yield of ethylene, propylene, and simultaneous maximum yields for untreated and raffinate.     

Development of calibration equations to predict oil content and fatty acid composition in brassicaceae germplasm by near-infrared reflectance spectroscopy

The use of nondestructive analytical methods is critical for the evaluation of very small seed samples such as those from germplasm collections. The objective of this study was to evaluate the potential of near-infrared reflectance spectroscopy (NIRS) for the simultaneous analysis of seed oil content and concentration of major fatty acids in intact-seed samples of the family Brassicaceae. A total of 495 samples from 56 genera and 128 species were analyzed by NIRS. The fatty acid composition of the seed oil was determined in all the samples by gas-liquid chromatography (GLC). The total seed oil content was determined by solvent extraction in 129 samples from 22 genera. Calibration equations for oil content (n=97) and individual fatty acids (n=410) were developed and tested through external validation with the samples not included in the calibration sets. The calibration equations for oil content (r ²=0.97 in validation) and concentrations of C_18:1 (r ²=0.93), C_18:3 (r ²=0.95), and C_22:1 (r ²=0.94) showed very good performance and provided reliable estimations of these traits in the samples of the validation set. The calibration equations for C_16:0, C_18:0, and C_18:2 content were less reliable, with r ² from 0.67 to 0.73. There was practically no response of NIRS to differences in C_20:1 (r ²=0.31). These results demonstrated that the oil content and concentrations of C_18:1, C_18:3, and C_22:1 can be estimated reliably within the family Brassicaceae by using NIRS calibration equations integrating broad taxonomic variability.     

Biodegradation of diesel oil in a baffled roller bioreactor

BACKGROUND: Ex situ bioremediation is a feasible and economical way to remove petroleum pollutants from contaminated soil or water. A baffled roller bioreactor was shown to be effective for biodegradation of diesel oil as a model petroleum pollutant. Microorganisms enriched from an industrially contaminated soil with heavy hydrocarbons were shown to be the best inoculum source for diesel biodegradation. RESULTS: The baffled roller bioreactor demonstrated better performance than control (roller bioreactor without baffles) or bead mill roller (control bioreactor filled partially with spherical beads) bioreactors. Biodegradation consisted of both fast and slow stages for degradation of light and heavy compounds, respectively. Among the tested temperatures ranging from 15 to 35 °C, room temperature (23 °C) was found to be the optimum temperature for biodegradation. The values of maximum specific growth rate and substrate yield (µ_max and Y_XS) for the indigenous microorganisms in the baffled roller bioreactor at room temperature were found to be 0.72 ± 0.08 h^?1 and (7.0 ± 1.0) × 10⁷ cells mg^?1 diesel, respectively. Biodegradation of diesel concentrations up to 200 g L^?1 was achieved with the highest biodegradation rate of 266 mg L^?1 h^?1 at the highest rotation rate of 45 rpm in the baffled roller bioreactor. CONCLUSION: Using indigenous bacteria enriched from industrial contaminated soil at room temperature, a baffled roller bioreactor is able to biodegrade high diesel oil concentrations at high biodegradation rates. Copyright © 2008 Society of Chemical Industry     

生物质快速热解制油试验及流程模拟

使用自主研发的流化床热解反应器对生物质热解制油进行实验研究,通过对不同实验温度450、500、525、550、580、610℃下得到的目标产物进行分析,得到了反应温度对生物油产率的影响规律。实验表明：550℃时,最大液体产率为42.5%（质量）;实验得到的不可冷凝气体的组分以CO、CO₂、CH₄和H₂为主,气相产物产率约为37.7%（质量）。在实验基础上,利用Aspen Plus流程模拟软件,建立了生物质热解制油工艺模拟流程,模拟分析了热解温度对生物油产率的影响,结果表明该模型能准确模拟实际热解过程,具有较好的适用性和可靠性。