用于生物柴油清洁生产的磁性固体催化剂CaO/MgO/Fe_3O_4

制备了具有磁性和催化活性的双功能催化剂CaO/MgO/Fe3O4,用于催化花生油酯交换制备生物柴油的清洁生产过程。对CaO/MgO/Fe3O4进行了XRD、TEM、FT-IR和磁性等表征分析,探讨了CaO/MgO/Fe3O4催化剂的重复利用性能。结果表明,用Mg(Ac)2溶液等体积浸渍磁性基质Fe3O4,在N2气氛中600℃焙烧2 h,可得到具有磁性的载体5%MgO/Fe3O4;再用Ca(Ac)2溶液等体积浸渍MgO/Fe3O4,并在N2气氛中700℃煅烧,得到具有磁性且催化活性较高的催化剂10%CaO/MgO/Fe3O4。该催化剂具有核壳结构,磁核平均直径约为35 nm。在催化剂用量10%,醇油摩尔比12∶1,反应温度65℃,反应2 h的条件下酯交换转化率可达90%以上。在磁场的吸引下该催化剂能快速与反应体系分离,催化剂回收率达90%。但CaO/MgO/Fe3O4重复利用性能较差,其原因是在搅拌反应过程中催化活性组分逐渐从催化剂上脱落所致。     

Influence of alkali metal doping on surface properties and catalytic activity/selectivity of CaO catalysts in oxidative coupling of methane

Surface properties （viz. surface area, basicity/base strength distribution, and crystal phases） of alkali metal doped CaO （alkali metal/Ca= 0.1 and 0.4） catalysts and their catalytic activity/selectivity in oxidative coupling of methane （OCM） to higher hydrocarbons at different reaction conditions （viz. temperature, 700 and 750 ℃; CH4/O2 ratio, 4.0 and 8.0 and space velocity, 5140-20550 cm^3 ·g^-1·h^-1） have been investigated. The influence of catalyst calcination temperature on the activity/selectivity has also been investigated. The surface properties （viz. surface area, basicity/base strength distribution） and catalytic activity/selectivity of the alkali metal doped CaO catalysts are strongly influenced by the alkali metal promoter and its concentration in the alkali metal doped CaO catalysts. An addition of alkali metal promoter to CaO results in a large decrease in the surface area but a large increase in the surface basicity （strong basic sites） and the C2＋ selectivity and yield of the catalysts in the OCM process. The activity and selectivity are strongly influenced by the catalyst calcination temperature. No direct relationship between surface basicity and catalytic activity/selectivity has been observed. Among the alkali metal doped CaO catalysts, Na-CaO （Na/Ca = 0.1, before calcination） catalyst （calcined at 750 ℃）, showed best performance （C2＋ selectivity of 68.8% with 24.7% methane conversion）, whereas the poorest performance was shown by the Rb-CaO catalyst in the OCM process.     

Transesterification of ethyl butyrate with methanol using MgO/CaO catalysts

A series of mixtures of MgO/CaO with different Mg/Ca molar ratios (between 3 and 15), as well as the corresponding pure oxides, was prepared by the coprecipitation method in a basic medium and subsequent calcination. Their textural and structural characterization was carried out by using XRD, FT-IR, SEM and N₂ sorption at 77 K. The alkalinity was studied by CO₂-TPD and catalytic decomposition of 2-propanol. The MgCa oxides obtained after calcination at 1073 K exhibit X-ray diffraction patterns with clearly visible signals corresponding to crystalline CaO and MgO. Textural properties are improved by the presence of Mg, with the porosity increased and the particle sizes decreased with respect to pure CaO. FT-IR spectroscopy reveals the presence of surface carbonate. These catalysts are active in the transesterification of ethyl butyrate with methanol at 333 K and atmospheric pressure, a model reaction to evaluate the potential of these basic catalysts in triglycerides transesterification for biodiesel production. The highest activity was found for a Mg:Ca molar ratio of 3, with conversion close to 60%, whereas MgO was inactive. Moreover, lixiviation of the active phase was not observed thus excluding the contribution of the homogeneous catalysis to the studied transesterification process.     

Synthesis of micronized CaO assisted by NH4HCO3 with Ca(OH)2 and its application in heterogeneously catalyzing transesterification reaction for producing biodiesel

Micronized CaO with pores was synthesized by calcining the reaction product CaCO₃ from NH₄HCO₃ and Ca(OH)₂. Scanning electron microscopy, X‐ray diffraction, energy dispersive X‐ray spectroscopy, X‐ray fluorescence, Fourier transform infrared spectroscopy, and Brunauer–Emmett–Teller analysis were used to characterize CaO, which confirmed that after calcining at 800°C for 2 hr, CaCO₃ was completely converted into porous micronized CaO with a surface area of about 7.295 m²/g and a particle size of 0.5–1.5 μm. The porous CaO microparticles were used as heterogeneous catalysts for producing biodiesel from transesterification of soybean oil and methanol. The influences of reaction time, calcined temperature, and reusability of CaO were explored. The experiments showed that CaO has high catalytic activity for transesterification reaction, and the yield of biodiesel reaches more than 98% under the conditions of methanol/oil mole ratio of 9, and the catalyst amount (catalyst/oil) of 3% after reaction for 2.5 hr. The CaO catalyst can be recycled easily and it also has the advantage of low pollution. Simple synthetic route, low cost, high catalytic activity, good reusability, and great potential for industrialization are the advantages of the porous micronized CaO catalyst that was proposed in this work.     

KF/MgO 催化碳酸二甲酯与月桂醇酯交换合成碳酸二月桂酯

 研究了 KF/MgO 催化剂对碳酸二甲酯 (DMC) 与月桂醇酯交换反应制备碳酸二月桂酯 (DDC) 的催化性能. 考察了催化剂 KF 负载量及焙烧温度对反应的影响, 并采用 X 射线衍射、傅里叶变换红外光谱、扫描电镜和 N2 吸附-脱附等对催化剂进行了表征. 结果表明, 催化剂 KF/MgO 在空气中较高温度焙烧后生成新相 K2MgF4 和 K2CO3, 它们为催化剂的主要活性组分. 催化性能测试结果表明, 该催化剂具有良好的催化活性, KF 的最佳负载量为 30%, 催化剂的最佳焙烧温度为 873 K. 还考察了反应条件对 KF/MgO 催化剂性能的影响. 当在反应物月桂醇:DMC 摩尔比 = 4, 催化剂用量为反应物总质量的 0.75%, 反应时间为 4 h 的条件下, 反应性能最佳, DMC 转化率和 DDC 收率分别为 86.7% 和 86.2%.     

CaO-MgO@CoFe_2O_4磁性固体碱的制备及其大豆油酯交换反应催化性能

以草酸盐为前驱体采用两步法制备了一种以CaO-MgO作为活性组分,以CoFe_2O_4作为磁核的磁性固体碱催化剂,并用于大豆油与甲醇的酯交换反应合成生物柴油。对制备的磁性固体碱催化剂进行了磁滞回线、X-射线衍射(XRD)、CO_2-TPD及透射电镜(TEM)表征。考察了不同核壳物质的量比、焙烧温度、反应温度、反应时间、醇油物质的量比以及催化剂用量等因素对大豆油转化为生物柴油产率的影响。结果表明,采用核壳物质的量比为1∶6、焙烧温度为700℃所制备的CaO-MgO@CoFe_2O_4催化剂,当醇油物质的量比为12、催化剂用量为大豆油质量的1.0%时,在65℃下反应时间3 h,生物柴油收率高达97.1%。该催化剂具有较好的重复利用性能,重复利用四次后生物柴油的收率仍可达90%。     

Utilisation of Non-Edible Source (Pongamia pinnata Seeds Shells) for Producing Methyl Esters as Cleaner Fuel in the Presence of a Novel Heterogeneous Catalyst Synthesized from Waste Eggshells

Waste eggshells were considered for synthesising a precursor (CaO) for a heterogeneous catalyst, further impregnated by alkali caesium oxide (Cs₂O). The following techniques were used to characterise the synthesised catalysts: X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and Temperature Programmed Desorption (CO₂-TPD). The synthesised catalyst revealed its suitability for transesterification to produce biodiesel. The biodiesel production process was optimised, and it showed that the optimal biodiesel yield is 93.59%. The optimal set of process parameters is process temperature 80 °C, process time 90 min, methanol-to-oil molar ratio 8 and catalyst loading 3 wt.%. It has been found that the high basicity of the catalyst tends to give a high biodiesel yield at low methanol-to-oil ratio 8 when the reaction time is also less (90 min). The fuel properties of biodiesel also satisfied the standard limits defined by ASTM and the EN standards. Thus, the synthesised catalyst from waste eggshells is highly active, improved the biodiesel production conditions and PPSS oil is a potential nonedible source.     

纯四方相硫化氧化锆催化剂的制备及其生物柴油合成应用研究

将过硫酸铵浸渍于直接合成的纳米氧化锆晶体表面,经300-500℃高温焙烧处理获得硫化氧化锆催化剂。采用X射线衍射（XRD）、氮气吸附-脱附、氨气程序升温脱附（NH₃-TPD）、傅里叶红外光谱（FT-IR）、扫描电镜（SEM）和能谱仪（EDS）等分析手段对催化剂的结构性能进行了表征。结果表明,所有的催化剂均展现出纯四方相结构和高的结晶度。其中,经500℃热处理获得的催化剂拥有最高的硫含量和酸性位,将其应用于大豆油与甲醇酯交换反应合成生物柴油,获得了脂肪酸甲酯收率高达84.6%的催化效果,进一步表明该催化剂表面存在优越的超强酸位。     

Biodiesel Production via the Transesterification of Soybean Oil Using Waste Starfish (Asterina pectinifera)

Calcined waste starfish was used as a base catalyst for the production of biodiesel from soybean oil for the first time. A batch reactor was used for the transesterification reaction. The thermal characteristics and crystal structures of the waste starfish were investigated by thermo-gravimetric analysis and X-ray diffraction. The biodiesel yield was determined by measuring the content of fatty acid methyl esters (FAME). The calcination temperature appeared to be a very important parameter affecting the catalytic activity. The starfish-derived catalyst calcined at 750 °C or higher exhibited high activity for the transesterification reaction. The FAME content increased with increasing catalyst dose and methanol-over-oil ratio.     

CaO/MgO和CaO/Ca9Al6O18同时捕集CO2/SO2的循环吸收特性

以葡萄糖酸钙与葡萄糖酸镁及L-乳酸铝为前驱物,湿法制得了四种CaO/MgO和CaO/Ca₉Al₆O₁₈吸收剂,并进行了同时捕集CO₂/SO₂的实验。考察了吸收剂种类、质量配比、SO₂浓度及煅烧温度等对吸收剂吸收性能的影响。结果表明,CaO/MgO(质量比为75%/25%)吸收剂和CaO/Ca₉Al₆O₁₈(质量比为75%/25%)吸收剂分别保持了最好的吸收CO₂能力和最好的循环稳定性。SO₂严重阻碍了吸收剂对CO₂的捕集。SO₂浓度越高,吸收剂吸收CO₂能力下降的越快,但同时吸收SO₂的转化率也越高。数次循环后,总的Ca利用率开始上升,且SO₂浓度越高,上升趋势越明显。煅烧温度对CaO/MgO吸收剂和CaO/Ca₉Al₆O₁₈吸收剂循环吸收特性的影响略有不同。     

氧化钙和氟化钾负载高岭土固体碱催化制备新型生物柴油

以高岭土为载体,利用浸渍法制备了氧化钙和氟化钾负载高岭土固体碱(GCK);利用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、红外光谱(FT-IR)和哈密特指示剂法等技术手段对催化剂进行表征;考察了KF负载量和反应条件对月桂酸甲酯(ML)与乙二醇单甲醚(EGME)酯交换反应制备新型生物柴油产率的影响。 结果表明,GCK碱强度(H_)在7.2~18.4之间,KCaF₃为主要活性组分,当氟化钾负载量为25%、EGME与ML摩尔比3.0、催化剂用量相对于ML的质量分数为4.5 %、120 ℃下反应2 h,新型生物柴油的收率高达97.1%。 最后对催化剂的重复利用性能进行了考察。     

MgO/NaY催化糠醛和丙酮合成航空燃料中间体的性能研究

采用"机械混合-焙烧"方法制备了负载型固体碱催化剂MgO/NaY,研究了糠醛与丙酮在水-乙醇体系中的羟醛缩合反应,考察了催化剂负载量、原料配比、反应温度、反应时间等因素对催化剂性能的影响。结果表明,20%MgO/NaY催化剂表现出最佳的催化性能,在85℃条件下反应8 h后,糠醛转化率达到99.6%,亚糠基丙酮(FA)和二亚糠基丙酮(F₂A)选择性分别达到42.2%和57.1%,缩合产物的总收率为98.6%。高温促进反应中间体向产物的转化,有利于提高产物的总选择性。改变糠醛/丙酮的摩尔比可调控两种缩合产物的选择性,较高的糠醛/丙酮摩尔比有利于提高F₂A的选择性,但会降低整体反应速率。重复性评价表明,催化剂具有较好的再生性能。     

焙烧温度对CuMgAl催化剂催化糠醛气相加氢制糠醇性能的影响

采用分步沉淀过程制得质量比m(CuO)∶m(MgO)∶m(Al_2O_3)为25∶26∶49的CuMgAl类水滑石前驱体,经过不同温度焙烧制得CuMgAl-t催化剂。通过BET、热重、XRD、H_2-TPR和CO_2-TPD对催化剂进行表征,在固定床中考察CuMgAl-t催化剂催化糠醛气相加氢制糠醇的性能。结果表明,焙烧温度影响催化剂活性、稳定性及对产物的选择性,低温焙烧的催化剂经还原后可获得较多活性中心,高温焙烧的催化剂表面具有更多的碱性位,CuMgAl催化剂经450℃焙烧表面存在适宜的活性中心和碱性位。在常压、反应温度180℃、氢醛物质的量比5∶1、糠醛体积空速0.3h~(-1)的条件下,CuMgAl-450催化剂上糠醛的转化率和糠醇的选择性分别达到98.64%和97.66%。     

Effect of Calcination Temperature on La-Modified Al2O3 Catalysts for Vapor Phase Hydrofluorination of Acetylene to Vinyl Fluoride

A La-modified Al₂O₃ catalyst was prepared with deposition-precipitation method. The effect of calcination temperature on the reactivity for vapor phase hydrofluorination of acetylene to vinyl fluoride. The catalysts calcined at different temperatures were characterized using NH₃-TPD, pyridine-FTIR, X-ray diffraction, and Raman techniques. It was found that the calcination process could not only change the structure of these catalysts but also modify the amount of surface acidity on the catalysts. The catalyst calcined at 400 oC exhibited the highest conversion of acetylene (94.6%) and highest selectivity to vinyl fluoride (83.4%) and lower coke deposition selectivity (0.72%). The highest activity was related to the largest amount of surface acidity on the catalyst, and the coke deposition was also related to the total amount of surface acidic sites.     

Aldol condensation of furfural and acetone on layered double hydroxides

The Aldol condensation of furfural (Fur) with acetone (Ac) to 4-(2-Furyl)-3-buten-2-one (FAc) is one of the most important processes in the aqueous-reforming of oxygen-containing biomass derivatives and has been carried out in the presence of solid-base catalysts, calcined-rehydrated Layered Double Hydroxides (LDH). The Mg-Al Layered Double Hydroxides has been prepared by the coprecipitation, calcination and regeneration from mixed oxides by rehydration. The catalyst prepared with different Mg/Al molar ratios showed different catalytic performance and the best catalyst was with the Mg/Al molar ratio of 2.5. Phenol adsorption showed that the best catalyst had the largest numbers of accessible basic sites. The appropriate rehydration temperature and time for mixed oxides obtained by calcination were also investigated. The Mg-Al LDH catalysts can be regenerated by calcination at 773 K and rehydration in decarbonate water, but the regeneration is complex and incomplete. In addition, the catalyst calcined at high temperature also had activity, which was attributed to the formation of the Mg-Al spinels.     

锂-铝类水滑石催化大豆油酯交换制备生物柴油

采用共沉淀法制备了不同锂-铝比[n(Li)/n(Al)]的Li-Al类水滑石,经不同温度下焙烧得到复合氧化物;将复合氧化物作为大豆油与甲醇反应制备生物柴油的催化剂,考察了其对大豆油酯交换反应的催化性能.结果表明,n(Li)/n(Al)=13的类水滑石在400℃下焙烧得到的复合氧化物对大豆油酯交换反应具有极高的催化活性....     

抽放煤层气（CH4-CO2-Air）制合成气的研究——固溶体的形成对NiO/MgO催化剂性能的影响

采用浸渍法制备了NiO/MgO催化剂，用TPR、XRD、BET、H2(O2)化学吸附等技术对催化剂进行了表征，对催化剂在甲烷空气部分氧化与CO2重整耦合制合成气反应中的催化性能进行了评价。结果表明，在800 ℃焙烧的催化剂中，NiO完全与MgO形成NixMg1－xO固溶体。与低温焙烧的NiO/MgO催化剂相比，虽然NixMg1－xO固溶体催化剂的还原度较低，但可以获得较高的金属分散度和较小的金属粒径，能有效抑制积炭的生成，在反应过程中显示出良好的活性稳定性。对于900 ℃焙烧的催化剂，由于形成了更多难还原的体相固溶体，催化剂的初活性较低。     

焙烧温度对酯加氢制醇Cu-Al-Ba催化剂性能的影响(英文)

通过共沉淀法在不同焙烧温度下制备了新型无铬Cu-Al-Ba催化剂.测试了其在高压釜中将棕榈油甲酯加氢制备高碳醇的反应性能.结果表明催化剂的焙烧温度对催化性能有较大影响.在从150℃升至750℃的过程中,高碳醇的收率显示了三个阶段的变化,相应地,催化剂前驱体的热重(TG-DTG)曲线也显示了三个阶段的失重.X射线衍射(XRD)、X射线荧光(XRF),透射电镜-能谱分析-选区电子衍射(TEM-EDS-SAED)、N2物理吸附和程序升温还原(TPR)表征表明,催化剂是由一种孔雀石-勃石-碳酸钡前驱体制得的.在300或550℃焙烧后,催化剂组成为晶态的CuO、BaCO3和非晶态的Al2O3.其中,非晶态的Al2O3为CuO的高分散提供了大的比表面,杆状的BaCO3组分有利于提供微孔结构.在更高的焙烧温度750℃,新物相BaAl2O4的形成破坏了催化剂中的非晶态结构,导致其比表面积和孔容的急剧下降,并引起CuO物种的聚结.550℃焙烧的催化剂显示了最高的高碳醇收率,达到92.3%,这归因于其大的比表面积、大孔容和较高的CuO分散性.     

The role of MgO in the thermal behavior of MgO–silica fume pastes

The compounds of MgO–silica fume (SF) pastes constitute magnesium silicate hydrate (M–S–H) in a new generation of basic castables. However, Mg(OH)₂ is a common reaction product with the formation of M–S–H. This study aims to reduce the formation of Mg(OH)₂ in MgO–SF pastes. In this study, MgO powders were prepared by calcining magnesite at different temperatures and then mixed with SF and water to prepare MgO–SF pastes. The properties of MgO powders were characterized, and the pH values in the pore solutions of MgO–SF pastes were measured. The MgO–SF pastes cured for 90 days were calcined at 500, 700, 900 and 1200 °C, and the microstructure was characterized afterward. The results showed that both the reactivity of MgO powders and the pH value of the pore solution of MgO–SF pastes were diverse, which essentially depended on the grain sizes and the crystalline degree of MgO. Increasing the calcination temperature of MgO was beneficial to reduce the formation of Mg(OH)₂ or even stop it when using MgO calcined at 1450 °C. Enstatite and forsterite formed for all MgO–SF pastes after calcination. However, the microstructure of MgO–SF paste with MgO calcined at 1450 °C was denser than others. MgO–SF pastes were suitable for the new-generation refractory castables. Notably, using MgO calcined at 1450 °C is more appropriate.     

Catalytic Oxidation of Dimethyl Ether to Hydrocarbons over SnO2/MgO and SnO2/CaO Catalysts

A novel reverse microemulsion method was used to prepare SnO2/MgO and SnO2/CaO catalysts. It was found that both the catalysts were active for the reaction of catalytic oxidation of dimethyl ether (DME) in the temperature range of 275 to 300℃. SnO2/CaO catalyst exhibits much higher activity than SnO2/MgO. On SnO2/CaO catalyst, DME conversion of 21.8% was obtained at 300℃, while selectivities to methyl formate (MF) and dimethoxyethane (DMET) of 19.1% and 59.0% respectively were obtained at 275℃.