Biodiesel production from waste oil feedstocks by solid acid catalysis

Biodiesel is a non-toxic and biodegradable substitute for petroleum-based diesel. However, it is impractical to use refined edible oils to produce biodiesel due to its high cost and priority for food products, especially in China, while waste oils with high free fatty acids (FFAs) can be considered as the raw materials. In the present work, a solid acid catalyst comprising SO₄²⁻/TiO₂–SiO₂ was prepared, characterized and studied for its activity for the production of biodiesel from several low cost feedstocks with high FFAs. The solid acid catalyst can be recycled, easily removed and can simultaneously catalyze esterification and transesterification. The influence of reaction parameters was studied, and the optimized reaction parameters are reaction temperature 200 °C, molar ratio of methanol to oil 9:1 and catalyst concentration 3 wt.%. The catalyst showed good stability. A continuous process for biodiesel production from cheap raw feedstocks was proposed, and a 10,000-tonnes/year biodiesel production demonstration plant has been built.     

Optimization of novel pyrazolium ionic liquid catalysts for transesterification of bitter apple oil

In the present study, 4 different functionalized pyrazoliums based on sulfoalkyl-pyrazolium hydrogensulfate and alkylsulfo-alakylpyrazolium hydrogensulfate were explored to catalyze biodiesel production from bitter apple oil (BAO). The results demonstrated that a longer chains catalyst of 2-(4-sulfobutyl) pyrazolium hydrogensulfate (SBPHSO₄) exhibited the highest catalytic activity, which is attributed to its strong acidity. The highest yield of esters was up to 89.5% when the reaction was carried out under the conditions of 5.2 wt% of SBPHSO₄, molar ratio of methanol to BAO of 15:1, 170 °C, and 800 rpm for 6 h. These results demonstrated that ionic liquids offer a promising new type of pyrazolium catalyst for biodiesel production. The use of clean ionic liquids in preparing clean biodiesel could solve the drawbacks associated with using the old conventional catalysts and might be employed as an efficient catalyst for such relevance.     

Sucrose-derived catalytic biodiesel synthesis from low cost palm fatty acid distillate

The current homogeneous acid catalyst for biodiesel product however, would lead to formation of many undesirable by-products that make the post treatment of the biodiesel to be difficult and costly. Thus, sucrose-derived solid acid catalyst was developed in the present study which aims to improve the esterification process and reduce the generation of waste. The physicochemical properties of the synthesized catalysts were studied by various techniques such as, BET surface area, X-ray diffraction (XRD), temperature programmed desorption of NH₃ (TPD-NH₃), scanning electron microscopy (SEM). Response surface methodology (RSM) with central composite design (CCD) is used to determine the optimum parameters for the catalytic reaction. The experimental results showed that the catalyst exhibited good catalytic activity in the transesterification of PFAD, providing maximum biodiesel yield of 94% at optimum parameters. The better catalytic activity of the aforementioned catalyst in the biodiesel reaction could be attributed to the presence of optimal number of catalytically active acid site density on its surface.     

A summary of the available technologies for biodiesel production based on a comparison of different feedstock's properties

Biodiesel production is mainly done by carrying on the transesterification reaction while using refined oil, methanol and a homogeneous base catalyst. When using refined oil, a competition between oil for food and oil for fuel is then presented. Even more, the conventional technology has the disadvantage that the raw material has to be very pure, with no traces of other impurities. Otherwise, undesirable products will be produced decreasing the productivity of the process and making a large amount of waste treatment.Because of this, other technologies appear as possible sources for biodiesel production, mainly from refined oil, but also allowing less pure raw material to be used, such as waste oil, frying oil, soapstocks, and animal fats.In this work, a comparison of all these different raw materials, their physicochemical properties and how they can have an influence, and the magnitude of this phenomenon, in the biodiesel production will be presented and compared. Based on the previous analysis, a short summary of the technological possibilities to produce good quality biodiesel from low price raw material will be discussed with the aim of showing their advantages and disadvantages when using different feedstocks.     

浸渍液pH值对V-Mo/Ti脱硝催化剂性能的影响研究

为提升V-Mo/Ti催化剂的脱硝性能,在催化剂制备过程中调节浸渍工艺参数,制备了一系列不同浸渍液pH值的催化剂,采用XRD、N2-吸附脱附、拉曼光谱、UV-Vis、H2-TPR、NH3-TPD等手段对催化剂进行表征,考察了pH值的变化对催化剂物理化学性能的影响,采用固定床微型反应器对催化剂的脱硝性能进行评价。结果表明,降低浸渍液pH值,可以抑制催化剂上VOx物种的聚合,提升催化剂的还原性能,有利于提升催化剂的脱硝效率,降低脱硝反应过程中N2O生成量。同时,浸渍液pH值的变化,也会影响催化剂的酸性性能。当浸渍液pH值低于3.64时,催化剂酸性性能显著降低,造成催化剂脱硝性能降低;当浸渍液pH值控制在3.64时,催化剂的还原性能和酸性性能匹配较好,从而显示了较高的脱硝性能。     

石油化工催化剂生产过程中的职业病防治及应急处理

石化企业使用了大量的催化剂,催化剂开发、生产过程复杂,有许多原料和生产工艺,存在许多潜在的安全隐患和职业病危害因素。为预防催化剂生产过程中的事故,通过分析催化剂生产过程中的职业病危害分析,提出了相应的职业病防范及应急处置措施,加强催化剂生产过程中的职业病防治和应急处置能力,创造良好的经济、生态和社会效益,有效防止催化剂生产过程中发生安全事故和职业病。     

Feasibility of honeycomb monolith supported sugar catalyst to produce biodiesel from palm fatty acid distillate (PFAD)

Carbon coated monolith was prepared by sucrose solution 65 wt.% via dip-coating method. Sulfonation of incomplete carbonized carbon coated monolith was carried out in order to synthesize solid acid catalyst. The textural structure characteristics of the solid acid catalyst demonstrated a low surface area and pore volume. Palm fatty acid distillate (PFAD), a by-product of palm oil refineries, was utilized as oil source in biodiesel production. The esterification reaction subjected to different reaction conditions was performed by using the sulfonated carbon coated monolith as heterogeneous catalyst. The sulfonation process had been performed by using vapour of concentrated H₂SO₄ that was much easier and efficient than liquid phase sulfonation. Total acidity value of carbon coated monolith was measured for unsulfonated sample (0.5 mmol/g) and sulfonated sample (4.2 mmol/g). The effect of methanol/oil ratio, catalyst amount and reaction time were examined. The maximum methyl ester content was 89% at the optimum condition, i.e. methanol/oil molar ratio (15:1), catalyst amount (2.5 wt.% with respect to PFAD), reaction time (240 min) and temperature 80 °C. The sugar catalyst supported on the honeycomb monolith showed comparable reactivity compared with the sugar catalyst powder. However, the catalyst reusability studies showed decrease in FFA% conversion from 95.3% to 68.8% after four cycles as well as the total acidity of catalyst dropped from the value 4.2 to 3.1 mmol/g during these cycles. This might be likely due to the leaching out of SO₃H group from the sulfonated carbon coated monolith surface. The leaching of active species reached a plateau state after fourth cycle.     

Influence of Feedstock and Process Chemistry on Biodiesel Quality

Biodiesel production in the United States is anticipated to double by 2010. Biodiesel's characteristics and performance as a fuel vary depending on its composition, and the fuel composition has to be stringently monitored to avoid adverse impacts on the environment and engines. The final biodiesel composition depends on the initial feedstock, as well as on the reaction conversions and process separation efficiencies. The thermo-physical properties depend upon factors such as chain length, branching, and degree of saturation. Impurities in biodiesel, either due to side-reactions, unreacted feedstock, or non-fatty acid constituents, may increase pollutants. This paper focuses on chemical composition of commonly used feedstocks for biodiesel manufacturing and provides an overview of the process chemistry.     

不同晶型铁氧化物Fenton和UV-Fenton降解橙Ⅱ的催化性能

选取了磁铁矿、赤铁矿和针铁矿3种不同晶型的铁氧化物,用XRD和BET进行了表征。将3种铁氧化物作为催化剂用于Fenton和UV-Fenton(254 nm UVC)降解偶氮染料橙II,测定了染料降解过程中溶液中铁离子浓度的变化规律,用于分析3种铁氧化物的催化过程。用单位比表面积反应速率常数(k/Ssur)评价了3种铁氧化物UV-Fenton催化降解橙Ⅱ的能力,以揭示UV-Fenton体系中铁氧化物晶型与催化性能的关系。结果表明,Fenton体系中,磁铁矿能通过表面固有的2价铁催化产生羟基自由基降解橙Ⅱ,其催化能力高于针铁矿和赤铁矿;UV-Fenton体系中,磁铁矿、赤铁矿和针铁矿催化降解橙Ⅱ的单位比表面积反应速率常数分别为0.048 8 g/(m2·min)、0.023 4 g/(m2·min)和0.001 0 g/(m2·min),可见磁铁矿的催化能力明显高于针铁矿和赤铁矿;UV-Fenton体系中,磁铁矿以多相反应为主,针铁矿以均相反应为主,而赤铁矿则是两者共同作用。研究表明,磁铁矿是多相铁氧化物UV-Fenton催化剂的理想晶型,同时也是合成新型多相光助-芬顿催化剂理想的活性组分。     

Integration of safety instrumented system with automated HAZOP analysis: An application for continuous biodiesel production

Integration of a human-machine interface (HMI) with hazard and operability (HAZOP) analysis is proposed in this work. This concept can potentially lead to the identification of some unexpected deviations, and radically decreases the time necessary for hazard identification. A continuous biodiesel production was simulated. This can be divided into two cases, covering both conventional and reactive distillation. Soybean oil (trioleic, trilinoleic and tripalmitic) at 1000 kg/h as raw material is converted to 99 wt% pure biodiesel. The HMI was designed to improve these processes by combining automatic HAZOP analysis. With this approach, users can receive sufficient information from the simulation to analyze the optimum operation and safety. Severity levels are also provided to classify the actions in the process. Severity levels 1 and 2 are concerned with operating conditions, which are 58-64 °C, and 50-150 kPa. If the analysis shows severity level 3, the safety instrumented system (SIS) will automatically manage the operation in order to reduce/restrain the amount of damage at this level. This proposed system could minimize the damage and also improve the overall quality of the process.     

仿酶型Fe_3O_4/焦炭非均相降解P-NP研究

采用原位氧化沉淀法制备出仿酶型Fe_3O_4/焦炭,并将其作为非均相类Fenton催化剂用于对硝基苯酚(P-NP)废水的降解;采用扫描电子显微镜(SEM)、X射线衍射(XRD)和红外光谱(FTIR)对样品进行表征。表征结果表明,Fe_3O_4牢固地负载在焦炭上,并有利于Fe_3O_4的分散及粒径的减小。实验结果表明,催化剂降解P-NP的最佳条件为:催化剂投加量1.2 g/L,[H2O2]=30 mmol/L,p H=3.0,温度30℃,P-NP的去除率达到99%。Fe_3O_4/焦炭结构稳定,可再生使用。     

Optimization of biodiesel production from the waste cooking oil using response surface methodology

In this research, transesterification of the waste cooking oil has been studied. Response surface methodology (RSM) based on Box–Behnken design was used to investigate the effects of the main operating parameters, including the methanol to oil molar ratio, catalyst concentration, and reaction temperature, on the biodiesel yield. The results revealed that the catalyst concentration is the most important parameter. The maximum biodiesel yield under the optimized conditions was 99.38 wt.%. Thermogravimetric analysis (TGA) was used for the determination of biodiesel conversion and the results were compared with that of gas chromatography (GC) analysis, showing a very small difference. Furthermore, an empirical quadratic equation has been presented to show the relation between biodiesel conversion and product viscosity.     

A multi-criteria approach to screening alternatives for converting sewage sludge to biodiesel

The search for cheaper feedstock for use in the production of biofuels such as biodiesel has turned attention to various forms of waste products including animal fats, waste oils and now lipids in sludge. With the potential of obtaining sludge at a reduced cost, free, or possibly with incentives, sewage sludge is being investigated as a potential feedstock for biofuel production. For the extraction of oils from the sewage sludge and the subsequent processing, there are various alternatives that should be designed, analyzed, and screened. In developing and screening these alternatives, it is necessary to have a consistent basis for comparing alternatives based on key criteria. While most of the design studies focus on techno-economic criteria, it is also important to include safety metrics in the multi-criteria analysis. In this work, a detailed economic analysis and a safety evaluation are performed on a process involving extraction of triglycerides and fatty acids, pre-treatment of fatty acids (direct conversion to biodiesel), and transesterification of triglycerides to biodiesel. Four solvents, toluene, hexane, methanol and ethanol, are individually used in the extraction process. The resulting triglycerides and fatty acids from each extraction are modeled in the pre-treatment process. ASPEN Plus software is used to simulate the detailed process. Economic analysis is performed using ASPEN ICARUS, and scale-up of a previously analyzed process is used to estimate the cost of the biodiesel portion of the process. A new safety metric (referred to as the Safety Index “SI”) is introduced to enable comparison of the various solvent extraction processes. The SI is based on solvent criteria as well as process conditions. A case study is presented to demonstrate the insights and usefulness of the developed approach. The results of the techno-economic analysis reveal that of the four solvents used for the initial extraction, hexane and toluene were least costly (2.89 and 2.79 $/gal, respectively). Conversely, the safety analysis utilizing the SI reveals that methanol and ethanol are the safer solvent options. The issue of cost/safety tradeoffs is also discussed.     

Flash point of biodiesel/glycerol/alcohol mixtures for safe processing and storage

Mixtures of biodiesel, glycerol, and ethanol/methanol are commonly processed and stored in biodiesel production. In this work, non-ideal models are used to calculate the Flash Points (FPs) of binary and ternary mixtures, using data available from different feedstocks. Despite the fact that biodiesel is considered safer than common diesel fuels, results show a synergistic effect of biodiesel/methanol and biodiesel/ethanol mixtures, resulting in a reduction of the flash point of mixtures to values lower than the ones of pure compounds. Most soluble ternary mixtures were found flammable, the only exception being mixtures with a relatively lower alcohol content (45% mol. ethanol or 42% methanol) at temperature lower than 303 K. Accidental increase in temperature can cause domino effect, due to the higher solubility and the formation of new flammable ternary mixtures.     

Cu-Ag/海泡石催化还原NO的研究

以天然海泡石为原料,对其进行酸改性并与活性氧化铝混合后作为催化剂载体,采用浸渍法制备了用于CO还原NO的Cu-Ag复合金属催化剂.对不同Ag负载量催化剂催化还原NO的活性进行了评价,考察了载体对催化剂催化活性的影响,用BET、XRD、SEM等对催化剂进行了表征.结果表明,当Ag负载量不超过5%时,复合金属催化剂性能好于单一金属催化剂;Ag负载量为2%时催化剂性能最好;采用海泡石-氧化铝混合物为载体的催化剂的孔径分布得到改善,对NO催化还原反应有更高的活性.     

铂载钴钼二元硫化物对H_2S电催化活性研究

为考察溶胶凝胶法制备的Co-Mo二元硫化物对H_2S气体的电催化活性,通过循环伏安法和Tafel曲线分析对铂载不同Co、Mo掺杂比的电催化剂进行表征.结果表明,不同阳极电催化剂交换电流密度J_0由大到小依次为,铂载n(Co):n(Mo)=2:3、铂载n(Co):n(Mo)=2:1、铂载n(Co):n(Mo)=1:1和铂,即铂载n(Co):n(Mo)=2:3阳极电催化剂具有较好的活性,这与循环伏安曲线测试结果一致.电解质溶液pH值为6～7时,随着温度的升高铂载n(co):n(Mo)=2:3阳极电催化剂活性呈现上升的趋势.优化后的Co、Mo掺杂原子比约为0.66,此类电催化剂在操作温度80℃下,交换电流密度为1.318mA/cm~2,表观活化焙值为616.6 kJ/mol .研究表明,铂载钴钼二元硫化物适合作为低温H_2S燃料电池阳极电催化剂,其中Co、Mo掺杂比对电催化活性影响较大.     

Optimization of biodiesel production by alkali-catalyzed transesterification of used frying oil

Biodiesel as an alternative fuel for fossil diesel has many benefits such as reducing regulated air pollutants emissions, reducing greenhouse gases emissions, being renewable, biodegradable and non-toxic. In this study, used frying oil was applied as a low cost feedstock for biodiesel production by alkali-catalyzed transesterification. The design of experiments was performed using a double 5-level-4-factor central composite design coupled with response surface methodology in order to study the effect of factors on the yield of biodiesel and optimizing the reaction conditions. The factors studied were: reaction temperature, molar ratio of methanol to oil, catalyst concentration, reaction time and catalyst type (NaOH and KOH). A quadratic model was suggested for the prediction of the ester yield. The p-value for the model fell below 0.01 (F-value of 27.55). Also, the R² value of the model was 0.8831 which indicates the acceptable accuracy of the model. The optimum conditions were obtained as follows: reaction temperature of 65 °C, methanol to oil molar ratio of 9, NaOH concentration of 0.72% w/w, reaction time of 45 min and NaOH as the more effective catalyst. In these conditions the predicted and observed ester yields were 93.56% and 92.05%, respectively, which experimentally verified the accuracy of the model. The fuel properties of the biodiesel produced under optimum conditions, including density, kinetic viscosity, flash point, cloud and pour points were measured according to ASTM standard methods and found to be within specifications of EN 14214 and ASTM 6751 biodiesel standards.     

[HPMo][OTAC]2/SiO2的制备及其催化柴油氧化脱硫的研究

采用溶胶-凝胶法制备不同负载量的[HPMo][OTAC]2/SiO2,通过红外光谱、比表面积和孔结构分析对[HPMo][OTAC]2/SiO2进行表征,考察负载量、催化剂用量、氧化剂用量、反应温度和反应时间对模拟柴油脱硫效果的影响。结果表明,掺杂后的催化剂保持了Keggin结构,[HPMo][OTAC]2/SiO2在最佳反应条件下,苯并噻吩的脱除率达到48.3%,二苯并噻吩的脱除率达到67.2%。     

Stable and eco-friendly solid acids as alternative to sulfuric acid in the liquid phase nitration of toluene

Liquid-phase nitration of toluene was carried out using a silica supported Cs salt of phosphomolybdic acid (Cs_2.5H_0.5PMoO₄₀) as catalyst with dilute nitric acid under mild conditions. The Cs_2.5H_0.5PMoO₄₀ particles with Keggin-type structure were well dispersed on the surface of silica, and the catalysts exhibited strong acidity, which may be responsible for the high catalytic nitration activity. The effects of various parameters on nitration were tested, which included reaction temperature, reaction time, catalyst amount and reactants ratio. Under suitable conditions, the nitrations gave high toluene conversion (99.6%) and good mono-nitration selectivity. Compared to the conventional process, there was no other organic solvent or sulfuric acid used in the reaction system, which made it more environment-friendly. Moreover, the supported catalyst was proven to have excellent stability in the nitration process.