Ca/SBA-15固体碱催化剂的合成、表征及其催化餐饮废油制备生物柴油的研究

采用溶胶凝胶法,以正硅酸四乙酯为硅源、乙酸钙为钙源、P123为模板剂,经一步焙烧制备了Ca/SBA-15固体碱催化剂,通过XRD、FTIR、TEM以及N2吸附-脱附等方法对催化剂的相关理化性质进行了表征,并用于催化纯化后的餐饮废油与甲醇的酯交换反应制备生物柴油。结果表明:在钙硅物质的量比为0.2、焙烧温度为700℃的条件下制备的0.2Ca/SBA-15-700固体碱催化剂具有最佳的催化效果;0.2Ca/SBA-15-700固体碱催化剂能够很好保持SBA-15原有的二维六方相有序介孔结构,BET比表面积为406.7m2·g-1;在醇油物质的量比为12、催化剂用量为5%、氮气气氛中65℃反应7h制得的生物柴油产率达到94.7%;催化剂经洗涤和干燥,无需活化可继续使用,连续使用5次后,催化活性有所下降,但生物柴油产率仍保持在86%以上。     

国产镍基催化剂加氢性能研究

国产镍基催化剂用于棕榈油加氢制硬化油的实验结果与进口催化剂进行比较表明,其催化性能基本达到替代进口催化剂的水平;在此基础上,通过正交试验得出国产催化剂YM9002用于棕榈油加氢过程中的最佳工艺操作条件为反应压力2.5 MPa,反应时间60 min,催化剂用量为0.3%。     

Hydrocracking of Waste Cooking Oil into Biofuel Using Mesoporous Silica from Parangtritis Beach Sand Synthesized with Sonochemistry

Silicon - The high content of silica is present in beach sand and this silica can be synthesized into mesoporous silica (MS) using the sonochemistry assisted with dodecyl-amine (DDA) as a...     

P/SBA-15催化合成十六烷基苯

采用负载磷酸的SBA-15分子筛作为催化剂,以苯和十六碳烯为原料,经烷基化反应合成十六烷基苯。在微型液相固定床反应器上考察了反应温度、空速、体系压力、磷酸负载量以及苯烯摩尔比等反应条件对催化剂性能的影响。研究结果表明,磷酸的适宜负载量约为7%(质量分数),适宜反应条件为反应温度180℃、空速为2.0 h-1、体系压力为2.0 MPa和苯、烯摩尔比为10。在此条件下,十六碳烯的转化率可达到94.5%,十六烷基苯选择性可达93%。催化剂单程寿命达到120 h以上。负载磷酸的SBA-15催化剂呈现较好的催化活性和稳定性。     

Influence of the Procedure to Immobilize Lipase on SBA-15 for Biodiesel Production from Palm Kernel Oil

Catalysis Letters - Microbial lipase from Burkholderia cepacia was immobilized by covalent bond and physical adsorption on SBA-15 mesoporous support and its catalytic efficiency was measured in the...     

Co‐processing of Waste Cooking Oil and Light Cycle Oil with NiW/(Pseudoboehmite + SBA‐15) Catalyst

Light cycle oil (LCO) and waste sunflower cooking oil (WSO) were co‐processed with the aim of obtaining more environmentally friendly fuels. Partial hydrogenation of naphthalene was also investigated as a model reaction. Commercial NiW/SiO₂‐Al₂O₃, as a reference catalyst, and NiW/(pseudoboehmite + SBA‐15), as a new research catalyst, were tested. Liquid products were analyzed by simulated distillation, elemental analysis, and FTIR spectroscopy. Elemental analysis indicated higher efficiency of the research catalyst in hydrodesulfurization, hydrodenitrogenation, and hydrodeoxygenation of pure LCO and mixed feedstock containing WSO. Reactions with pure WSO resulted in less sulfur leaching into the product and a lower degree of deoxygenation compared with the commercial catalyst.     

Glycerol Esters from Real Waste Cooking Oil Using a Robust Solid Acid Catalyst

Notwithstanding the food-for-fuel debate, turning waste cooking oil and fat (WCO) into a valuable product is a classic example of green chemistry. We demonstrate that sulfated zirconia and lanthanum-supported sulfated zirconia are good catalysts for the esterification of WCO free fatty acids (FFAs) with glycerol, giving high-value monoglycerides. Various catalysts were first screened using palmitic acid as a model FFA. Subsequently, six 10-kg batches of actual WCO were collected from commercial cookeries over a period of 28 weeks, pre-treated in a purpose-built decanter and esterified with industrial grade glycerol using heterogeneous catalysis. Good yield and turnovers were obtained. The pre-treatment stage and the catalytic esterification experiments are described and discussed.     

Glycerol Esters from Real Waste Cooking Oil Using a Robust Solid Acid Catalyst

Notwithstanding the food-for-fuel debate, turning waste cooking oil and fat (WCO) into a valuable product is a classic example of green chemistry. We demonstrate that sulfated zirconia and lanthanum-supported sulfated zirconia are good catalysts for the esterification of WCO free fatty acids (FFAs) with glycerol, giving high-value monoglycerides. Various catalysts were first screened using palmitic acid as a model FFA. Subsequently, six 10-kg batches of actual WCO were collected from commercial cookeries over a period of 28 weeks, pre-treated in a purpose-built decanter and esterified with industrial grade glycerol using heterogeneous catalysis. Good yield and turnovers were obtained. The pre-treatment stage and the catalytic esterification experiments are described and discussed.

     

Hydroconversion of Waste Cooking Oil into Bio‐Jet Fuel over a Hierarchical NiMo/USY@Al‐SBA‐15 Zeolite

The direct conversion of waste cooking oil (WCO) into bio‐jet fuel was investigated over a core‐shell hierarchical USY@Al‐SBA‐15 zeolite‐supported NiMo catalyst. The core‐shell structure showed better acid and pore size distributions. The synergetic effect of the core‐shell micropore and mesopore structure significantly contributed to enhancing the selectivity for the jet fuel (C_9–15 hydrocarbons) from 9.3 % over NiMo/USY up to 35.7 % over NiMo/USY@Al‐SBA‐15, with high isomerization (iso‐/n‐paraffins ratio = 2.7) and moderate aromatic fraction (18.7 %). The decarboxylation reaction was selectively enhanced. Optimal selectivity for jet fuel (39.7 %) was obtained at 380 °C and a high H₂/oil ratio would decrease the yield of jet fuel. This catalyst showed excellent stability for the hydroconversion of WCO to hydrocarbons.     

Influence of Impurities and Oxidation on Hydroconversion of Waste Cooking Oil into Bio-jet Fuel

The influences of impurities and oxidation evolution of waste cooking oil on the preparation of bio-jet fuel via hydroconversion were studied. The hydrogenation active sites and acid sites were covered by heavy metals, sulfides, and basic nitrogen compounds, resulting in the increase of selectivity for bio-jet fuel by decreasing the selectivity of diesel, aromatics, and iso-alkanes. The effects of impurities, oxidation on the reaction pathway, and product distribution became more distinct with higher catalyst acidity. The evolution and variation of naphthalene, indan, and phenanthrene obtained from cyclic fatty acids influenced the properties of fuel or evoked the catalyst deactivation. This work will help to design new catalysts for selective conversion of waste cooking oil into bio-jet fuel.     

炼油加氢裂化催化剂技术进展

概述了炼油加工业中加氢裂化催化剂的优点，介绍了其技术研究进展状况，并从炼油工艺，环境保护等方面分析了炼油用加氢裂化催化剂的现状及发展趋势。     

以废食用油为原料的生物柴油研制

介绍了废食用油脂在KF/CaO催化剂作用下,与乙醇通过酯交换反应,生产生物柴油的研究。通过研究废食用油的预处理,反应时间,反应温度,原料与催化剂配比及催化剂用量等操作条件对反应的影响,摸索反应的最佳操作条件。实验结果表明,KF/CaO催化剂,在活性白土为载体,在KF与CaO质量比为1/3时,温度为800℃,烧制4 h时得到的催化剂活性最好。该反应得最适宜的操作条件是：醇油体积比为6∶1,催化剂量KF/CaO为原料油质量的2%,反应温度为70℃,反应时间为60min。     

K_2O/CaO-SBA-15催化大豆油制备生物柴油研究

通过浸渍法制备固体碱催化剂:K2O-SBA-15、CaO-SBA-15和K2O/CaO-SBA-15,用于催化大豆油和无水甲醇发生酯交换反应制备生物柴油,并进行X射线衍射(XRD),氮气吸附脱附表征。结果表明,负载固体碱后,没有改变介孔分子筛SBA-15的规则孔道结构,并且碱金属氧化物均匀负载在SBA-15的孔壁上。按三组分四因素的正交试验设计方案进行实验,表明各因素影响制备生物柴油的程度依次为:反应时间反应温度醇油摩尔比催化剂用量。反应的最佳条件为:以3%K2O/3%CaO-SBA-15为催化剂,反应温度60℃,反应时间3h,醇油摩尔比为16:1,催化剂用量为油重的3%,可得生物柴油产率为87.12%。     

利用废食用油制备生物柴油的研究

对利用废食用油制备生物柴油的预酯化-酯交换工艺进行了研究。结果表明,预酯化的最佳工艺条件为：乙醇用量为80 mL、催化剂浓硫酸用量为1 g、反应时间为3 h、反应温度为70℃;酯交换的最佳工艺条件为：乙醇用量为60 mL、催化剂氢氧化钾用量1 g、反应时间为40 min、反应温度为70℃。在此条件下可使50 mL废食用油的酸值由40.27 mg KOH/g降到1.52 mg KOH/g,粗生物柴油的产率可达93.71%。     

加氢裂化尾油异构脱蜡催化剂及工艺研究

本文介绍了一种含有中孔硅铝磷分子筛 (SA PO -11) 和贵金属组分的双功能异构脱蜡催化剂,该催化剂可以由含蜡的加氢裂化尾油生产粘度指数120 以上的VHV I润滑油基础油馏分, 而且不需要溶剂脱蜡。还研究了工艺条件对催化剂反应性能的影响。     

Effect of Water on the Ethanolysis of Waste Cooking Soybean Oil Using a Tin(II) Chloride Catalyst

Biodiesel production from cheap lipid raw materials is economically welcome, but a high free fatty acids (FFA) content makes it incompatible with traditional alkaline catalysts. Although liquid mineral acids are alternatively used, serious drawbacks such as high corrosiveness and large effluent generation, as well as the impossibility of catalyst reuse compromises its application. Contrarily, solid acid catalysts appear to be an attractive option; however, the water present or generated during FFA esterification provokes the leaching and deactivation of these catalysts. Thus, in this work we have evaluated the use of tin chloride SnCl₂, which is less corrosive, water tolerant, and a recyclable Lewis acid catalyst, on FFA ethanolysis using waste cooking oil samples (WCO). Additionally, the main kinetic parameters of the reactions were assessed. Compared to pTSA (p-toluenesulfonic-acid), a catalyst also evaluated, SnCl₂ efficiently promoted FFA ethanolysis even in the presence of high amounts of water (ca. 0.1–5.0% w/w). Moreover, the homogeneous SnCl₂ catalyst was easily recovered and reused successively, without loss of activity.     

HPWA/SBA-15催化合成2-叔丁基对甲酚

以SBA-15负栽磷钨酸(HPWA)为催化剂,甲基叔丁基醚(MTBE)和对甲酚为原料,在小型固定床反应器上进行了合成2-叔丁基对甲酚的试验研究,试验考察了HPWA负载量、反应温度、反应空速及原料配比对反应转化率、选择性的影响.试验结果表明,经HPWA改性后SBA-15的酸性增强,对甲酚转化率增大.适宜的反应条件为,反应温度160 ℃,HPWA负载量40%,空速3.0 h-1,原料MTBE和甲酚摩尔比为1.5.在适宜的条件下,对甲酚的转化率65.87%,2-叔丁基对甲酚的选择性97.81%.     

Direct Synthesis of Hydrogen Peroxide from Hydrogen and Oxygen over Palladium Catalyst Supported on SO3H-Functionalized SBA-15

Palladium catalyst supported on SO₃H-functionalized SBA-15 (denoted as Pd/SO₃H-SBA-15) was applied to the direct synthesis of hydrogen peroxide from hydrogen and oxygen. For comparison, palladium catalyst supported on SBA-15 (denoted as Pd/SBA-15) was also employed for the direct synthesis of hydrogen peroxide. Selectivity for hydrogen peroxide, yield for hydrogen peroxide, and final concentration of hydrogen peroxide over Pd/SO₃H-SBA-15 catalyst were much higher than those over Pd/SBA-15 catalyst. The high catalytic performance of Pd/SO₃H-SBA-15 catalyst was attributed to the enhanced acid amount of SO₃H-SBA-15 support, which served as an alternate acid source in the direct synthesis of hydrogen peroxide from hydrogen and oxygen.     

乙醇与餐饮废油制备生物柴油的工艺研究

以餐饮废油和乙醇为原料,以氢氧化钾为催化剂,采用酯交换法制备生物柴油。考查了醇油摩尔比、催化剂用量、反应时间和温度对原料转化率的影响。正交试验结果表明,餐饮废油与乙醇酯交换反应的最佳反应条件为：醇油摩尔比12∶1,催化剂用量1.25%,反应温度78℃,反应时间1.5h。在此反应条件下,餐饮废油转化率达65.12%;在此基础上引入四氢呋喃作助溶剂,转化率可提高至86%~90%。     

地沟油酶法制生物柴油的GC-MS测定

地沟油制的生物柴油成分复杂,通过气相色谱-质谱法测定脂肪酸甲酯、游离脂肪酸的峰形和相对位置,由此可确定各成分的含量,并准确计算出生物柴油的转化率和产率.