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。     

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.     

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.     

Evaluation of Eremurus spectabilis for production of bio-oils with supercritical solvents

Eremurus spectabilis samples were liquefied in organic solvents (methanol, ethanol and acetone) with (sodium hydroxide and ferric chloride) and without catalyst in a cylindrical reactor at temperatures of 270, 290 and 310 °C under supercritical conditions. The effects of liquefaction parameters such as temperature, catalyst and solvent on product yields were investigated. The liquid products were extracted with diethyl ether and benzene using an extraction procedure. The product yields in supercritical methanol, ethanol and acetone were found to as 41.6%, 53.8% and 64.3% in the non-catalytic runs at 310 °C, respectively. The highest conversion was obtained in supercritical acetone in the presence of ferric chloride (10%) at same temperature in the catalytic runs. The produced liquids in acetone were analyzed and characterized by elemental, Fourier transform infrared spectroscopy (FT-IR), gas chromatography–mass spectrometry (GC–MS). The liquid products (bio-oils) obtained with acetone contained various types of components including aromatics, nitrogenated and oxygenated compounds. As the bio-oils obtained exhibit high heat values, E. spectabilis is presented as a potential feedstock candidate for production of bio-fuels or valuable chemicals.     

改性生物质炭对电解锰废渣中Mn淋溶迁移的影响

利用有机酸(柠檬酸和EDTA)螯合载铁改性生物质炭,探究改性生物质炭对电解锰废渣中Mn淋溶迁移的影响。结果表明,改性生物质炭对电解锰废渣淋溶液中Mn的迁移有明显的效果。添加柠檬酸和EDTA改性的生物质炭处理后,电解锰废渣淋溶液中Mn含量减少百分率较未改性生物质炭平均增加了1.46倍、2.05倍,Mn质量浓度最大值分别为8.63,5.61 mg/L,且此时生物质炭对电解锰废渣中Mn迁移减少率分别达44.81%,64.08%。     

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.     

一种复合催化剂及其光催化降解煤矿瓦斯的性能研究

为提高催化剂光催化降解煤矿瓦斯效率,运用溶胶-凝胶浸渍过程将具有优异吸附性能的活性炭颗粒引入催化剂,制备了新型复合催化剂Ga2O3/AC。采用XRD、SEM、N2吸附等方法对新型复合催化剂的结构形貌及比表面积进行理化表征,验证了复合催化剂制备方法的可行性。同时以真空紫外灯为光源,进行光催化氧化降解瓦斯的模拟实验,对比考察Ga2O3、活性炭颗粒及复合催化剂的光催化活性。结果表明,相比单一Ga2O3,复合催化剂光照时间为180 min后对甲烷的降解率提高了13%,达到100%去除率。     

Influence evaluation of ionic liquids on the alteration of nitrification waste for thermal stability

Nitrification waste (NW) is the processed product of nitro compounds, flammable and explosive, and is prone to accidents due to thermal runaway. Ionic liquids (ILs) are widely used as flame retardants and have a good inhibitory effect. The effect of 1-butyl-3-methylimidazole hexafluorophosphate and 1-butyl-3-methylimidazole tetrafluoroborate as humectants on the thermal stability of NW was investigated in this paper. The microstructure and properties of the ionic liquid hybrid NW were first investigated using scanning electron microscopy. Secondly, thermogravimetric experiments were carried out on the ionic liquid mixed NW by thermogravimetric-infrared spectroscopy to analyze the decomposition law. Finally, six advanced linear regression thermokinetic models were used to calculate its apparent activation energy, pre-exponential factor, and other thermokinetic parameters, and the reaction model was simulated through multiple linear regression. The experimental research results in this paper can provide a reference for the storage and disposal of nitro compounds and their wastes.     

两种有机酸对茶园土微团聚体等温吸附锌的影响

为了明确茶园紫色土Zn容量及潜在污染状况,利用虹吸沉降和离心冻融法进行批量培养,研究区域土壤及不同粒径微团聚体等温吸附Zn~(2+)的水平,以及去除有机质和外源添加柠檬酸、乙二胺四乙酸(EDTA)对吸附的影响。结果表明:1)以专性吸附为主的多层吸附随Zn~(2+)质量浓度增至200 mg/L总体接近饱和,吸附量从大到小依次为0.002 mm、0.002~0.05 mm、原土、0.25~2 mm、0.05~0.25 mm,游离Zn~(2+)向较小粒径富集趋势明显,去除有机质弱化了微团聚体的吸附能力;2)吸附过程为自发吸热反应,热力学Freundlich方程(R2=0.9722~0.9995)整体拟合水平优于Langmiur方程(R2=0.9505~0.9987),土壤吸附能力与有机质、游离氧化铁、CEC呈正相关;3)两种有机酸均以0.1 mmol/L为阈值,随浓度增加均表现为低浓度增强Zn~(2+)积累、高浓度加快迁移,最大吸附量呈"峰形"变化,有机酸浓度"峰值"在去除有机质后增大到1 mmol/L;在未去除有机质土壤及结构单元中,EDTA对Zn~(2+)的释放能力更优,柠檬酸能更好地吸持,大粒径微团聚体0.25~2 mm及原土随有机酸浓度变化吸附量差异明显;去除有机质使两种有机酸促进及抑制功能削弱明显。     

Synthesis of Bio-Diesel and Bio-Lubricant by Transesterification of Vegetable Oil with Lower and Higher Alcohols Over Heteropolyacids Supported by Clay (K-10)

The use of different lower and higher alcohols viz; methanol, ethanol, n-propanol and n-octanol, for the synthesis of methyl, ethyl, propyl and octyl fatty acid esters by transesterification of vegetable oil (triglycerides) with respective alcohols also known as ‘Bio-diesel’ and ‘Bio-lubricants’ was studied in detail. The reactions were carried out in a batch process. The activity with different supports like clay (K-10), activated carbon, ZSM-5, H-beta and TS-1 were compared. The superacids (heteropolyacids, HPA) viz; Dodeca-Tungstophosphoric acid [H₃PO₄·12 WO₃·xH₂O] (TPA) and Dodeca-Molybdo phosphoric acid ammonium salt hydrate [H₁₂Mo₁₂N_3-O₄₀P + aq] (DMAA) was used to increase the acidity and so the activity by loading on the most active support viz; clay (K-10). These HPA loaded on clay as a catalyst was used for the following study: effect of percent HPA loading on clay, effect of different vegetable oils, effect of different alcohols on the triglyceride conversion based on glycerol formation and selectivity based on alkyl esters formation. The data is compared at the best-optimized identical set of operating reaction conditions: 170 °C, 170 rpm, catalyst loading: 5% (w/w of reaction mixture), molar ratio (oil: alcohol): 1:15 and time on stream of 8 h. The generated data is also evaluated based on the reported one.     

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.     

铜铁共掺杂TiO2/膨润土光催化剂的制备及光催化性能

以溶胶-凝胶法、液相沉淀法和机械混合法制备了Cu-Fe双金属掺杂的TiO2/膨润土复合光催化剂,采用XRD、FTIR对其进行了结构表征,以紫外光和可见光催化降解直接天蓝染料废水为模型,考察了制备方法对催化剂光催化性能的影响。结果表明:各催化剂中均有锐钛矿型TiO2生成,且部分TiO2进入了膨润土的蒙脱石层间,改变了其层间的有序性,生成了Ti—O—Si键,实现了TiO2粒子与膨润土的复合。溶胶-凝胶法制备的催化剂中TiO2与膨润土的复合程度最高,Cu2+和Fe3+成功掺入了TiO2晶格,形成了复合半导体,拓宽了TiO2的光谱响应范围,使该催化剂表现出最优的光催化活性,并且该催化剂性能稳定,易于沉降分离,经高温活化再生后仍具有良好的催化活性,可重复多次使用,表现出良好的再生性能。     

Process hazard assessment of energetic ionic liquid with kinetic evaluation and thermal equilibrium

With the continuous development of battery technology, there are new research investments in materials of various parts. In the field of electrolytes, ionic liquids (IL) are considered to be excellent electrolytes and have been widely studied in distinct energy fields. However, it is necessary to pay attention to the safety characteristics of ionic liquids at high temperature due to the application of energy, but there is little research on the reaction and kinetics of ionic liquids. To ensure the safety of ionic liquids, such as high temperature, the common ionic liquid 1-Ethyl-3-methylimidazolium nitrate ([Emim] NO₃) was selected for analysis. The exothermic mode is obtained from the data of differential scanning calorimetry. The basic reaction parameters of [Emim] NO₃ were determined with thermodynamic equation simulation. For ionic liquids in the actual situation, consider adding a heat balance model to estimate its temperature change pattern and find out the hazard temperature and related safety parameters. Temperature changes were estimated by constructing 25.0 g and 50.0 g packages to simulate material reactions and heat transfer in the external environment. The results showed that [Emim] NO₃ had shorter TMR_ad and TCL (<1 day) when the temperature was above 180 °C.     

Detoxification of hexavalent chromium in wastewater containing organic substances using simonkolleite-TiO2 photocatalyst

Innovative simple method for the preparation of simonkolleite-TiO₂ photocatalyst with different Zn contents was achieved. The prepared photocatalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), FT-IR, Raman and diffuse reflectance spectroscopy techniques. The photocatalytic activities of the materials were evaluated for the simultaneous detoxification of hexavalent chromium (Cr(VI)) and oxidation of organic compounds commonly present in wastewater under simulated solar light. The best photoreduction efficiency of Cr(VI) has been achieved at 1000 ppm simonkolleite-TiO₂ photocatalyst of 5% Zn/TiO₂ weight ratio, and pH value of 2.5 to enhance the adsorption onto catalyst surface. Photoreduction was significantly improved by using formic acid as holes scavenger owing to its chemical adsorption on the catalyst surface. Finally, 100% photoreduction of Cr(VI) could be achieved using formic/simonkolleite-TiO₂ systems under sunlight.     

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.     

New method for acrylic acid recovery from industrial waste water via esterification with 2-ethyl hexanol

Acrylic acid (AA) is an important component for the production of acrylate polymer. In a typical acrylic manufacturing unit, waste water contains AA in a range of 4–15 wt.% contributes to the high values of chemical oxygen demand. Due to the toxicity of AA to the aquatic organism, this wastewater should be treated before it is discharged to the environment. The waste water could be evaporated before sending to the incineration which was neither economic feasible nor environmental friendly. Esterification of wastewater containing carboxylic acid with alcohol could be a promising method to recover the acid by converting it to ester while purifying the wastewater. In the present study, recovery of AA via esterification with 2-ethyl hexanol (2EH) was investigated. The model industrial wastewater with various concentration of AA (10–100% w/w) was reacted with 2EH to produce 2-ethyl hexyl acrylate (2EHA) in the setups with total reflux and continuously water removal. These Amberlyst-15 (ion exchange resin) catalyzed reactions were carried out under the mass transfer resistance free region. The performance of both systems was compared. The yield for the reactions of the AA solutions with the AA concentrations of 30–80% was enhanced significantly when the reactions were carried out using the second setup. The kinetic data of the esterification of dilute AA was well described by the Eley–Rideal (ER) kinetic model incorporated with a correction factor to consider the catalyst fouling effect and pseudo-homogeneous (PH) kinetic model for the AA polymerization. The findings have shown the potential of recovering AA from the waste water stream via esterification. The concentrated AA solutions or larger amount of inhibitor should be adopted to prevent the catalyst fouling by the deposition of poly-acrylic acid on the catalyst surface.     

Theoretical and experimental studies on the thermal decomposition of 1-butyl-3-methylimidazolium dibutyl phosphate

Ionic liquid, an organic molten salt, has efficient flame-retardant performance. Few researchers have attempted to study its flame-retardant mechanism. Moreover, thermal stability and pyrolysis products have a great impact on the flame retardancy. Therefore, this paper focused on the phosphate ionic liquid of 1-butyl-3-methylimidazolium dibutyl phosphate ([Bmim][DBP]) and analyzed its thermal decomposition products and characteristics. The major bond energies of [Bmim][DBP] were calculated using B3LYP/6–311++G(d,p)//M06–2X/6–311++G(d,p) level. The experimental results show that the pyrolysis products were as followed: alkane or alkene with a carbon chain length of 1–4; imidazole and its derivatives; esters. Furthermore, Gas chromatography-mass spectrometer and Fourier transform infrared spectrometer were utilized to measure the gaseous products and solid phase products of [Bmim][DBP], which were obtained during thermogravimetric analysis. The results of theoretical and experimental analysis were highly consistent. Finally, the possible flame-retardant mechanism of [Bmim][DBP] was proposed.     

柠檬酸对膨润土吸附镍离子的影响研究

采用平衡吸附法,研究了柠檬酸对膨润土吸附镍离子的影响.吸附结果表明,当Ni2 初始质量浓度为30 mg/L时,振荡反应90 min,介质pH为5,投加量为5 g/L时,膨润土对Ni2 显示了较好的吸附性能.动力学研究表明该吸附过程符合Lagergren二级动力学模型,等温吸附实验表明其吸附行为符合Freundlich模型.离子强度增大及柠檬酸存在时,会降低其吸附能力.解吸实验发现,通过柠檬酸间接与膨润土结合的Ni2 结合牢固程度较差,更易解吸出来.表明柠檬酸的存在对镍离子的吸附有抑制作用.     

Optimization of Biodiesel Production from Jojoba Oil

The use of fatty acid methyl ester (FAME), produced from agricultural oils as a fuel in diesel engines has been proposed as an alternative to diesel from fossil resources. Vegetable oils are produced from numerous oil seed crops. Of the several renewable sources and yet not widely known, jojoba oil appears to be promising scope for cultivation in arid and semi arid areas. The chemical structure of jojoba oil allows its use as a constituent in many lubricating oil formulation. In the present work, the process of synthesis of methyl esters from jojoba oil as alternative vegetable oil, using a basic catalyst, has been developed and optimized by application of the Factorial Design and Response Surface Methodology. According to this study, the maximum yield of esters (83.5%) can be obtained, working at the maximum level of initial concentration of catalyst (1.35%) and a medium level for the operation temperature (25°C). The model has been proven to adequately describe the experimental range studied and allows to scale-up the process.