固体碱催化剂MgO@SBA-15催化大豆油制备生物柴油的研究

以SBA-15分子筛为载体,采用浸渍法通过负载MgO制备了MgO@SBA-15固体碱催化剂,并对其进行了X射线衍射和N2吸附-脱附等分析表征,考察了焙烧温度、MgO负载量、醇油物质的量比和催化剂用量等因素对催化剂性能的影响。结果表明:MgO负载量为15%(质量分数)的MgO@SBA-15催化剂能够很好地保持SBA-15原有的介孔特征,且MgO在SiO2骨架上高度分散;在焙烧温度500℃、MgO负载量为15%时催化剂活性最佳;在醇油物质的量比为9∶1、催化剂用量为大豆油质量的3%、反应时间为3h的条件下,生物柴油的产率达到91.83%。     

秸秆炭质固体酸催化剂的制备及应用

以秸秆为原料,采用炭化和磺化方法制备炭质磺酸化固体酸催化剂,并通过XRD、SEM和FT-IR对所制备催化剂的结构进行表征。通过催化油酸和甲醇酯化反应制备生物柴油,考察炭化温度、炭化时间、磺化温度和磺化时间对催化剂性能的影响。并研究了不同条件对油酸转化率的影响,优化了制备生物柴油的最佳工艺条件,结果表明:在炭化温度为350℃、炭化时间1h、磺化温度140℃、磺化时间1h的条件下,所制备催化剂具有较高的活性;在反应温度为68℃、反应时间为5h、催化剂质量为油酸质量的7%、甲醇与油酸的物质的量比为12∶1的条件下,生物柴油转化率可达94.83%。     

磷钨杂多酸盐催化制备生物柴油

以离子液体和磷钨酸为原料,制得3种磷钨杂多酸盐杂化材料[BMIM]3PW12O40、[PyPS]3PW12O40和[MIMPS]3PW12O40,对比研究了这3种催化剂在棕榈油和甲醇酯交换催化制备生物柴油中的催化性能,筛选出催化性能最好的[MIMPS]3PW12O40。以[MIMPS]3PW12O40为催化剂,考察了醇油物质的量比、反应时间、反应温度和催化剂用量对生物柴油收率的影响。结果表明:在醇油物质的量比为10、反应时间为6h、反应温度为65℃、催化剂用量为4%条件下,生物柴油收率可达95.2%,[MIMPS]3PW12O40催化剂易于回收,循环使用性能较好。     

Mn-Ce臭氧催化氧化催化剂的制备及其对煤化工废水的处理

以活性氧化铝小球为载体,Mn/Ce双金属为活性组分,通过共沉淀法制备得到活性氧化铝基催化剂,并对催化剂微观形貌进行表征。对比了不同负载量、不同金属配比、不同焙烧温度、不同焙烧时间下催化剂的活性。当催化剂负载为4%(Mn)∶1%(Ce),焙烧温度为400℃,焙烧时间为3h时,催化剂对煤化工废水臭氧催化氧化效果最好。     

碳基固体酸催化大豆油酯交换制备生物柴油

通过一步碳化-磺化法制备了碳基固体酸催化剂,采用IR、XRD以及TG对催化剂进行了表征;并将催化剂用于催化大豆油与甲醇的酯交换反应制备生物柴油中,考察了相关因素对反应的影响,用气相色谱分析生物柴油的产率。实验结果表明,碳基固体酸催化大豆油与甲醇的酯交换反应效果显著,最佳反应条件为:醇油摩尔比36∶1、反应温度130℃、反应时间4h、催化剂用量为大豆油质量的10%时,生物柴油的收率可达95.5%。催化剂重复利用6次,活性下降较小。     

Lewis酸性离子液体催化文冠果种仁油制备生物柴油

以盐酸三乙胺和不同金属氯化物FeCl3,CuCl2,SnCl2,ZnCl2为原料,合成了一系列Lewis酸性离子液体[Et3NH]Cl/MClX,将其用于催化文冠果种仁油和甲醇酯交换制备生物柴油。考察了离子液体的种类,反应温度,醇油摩尔比,催化剂用量和反应时间对生物柴油产率的影响。结果表明:在反应温度为70℃,醇油摩尔比为12,催化剂用量为原料油质量的5%,反应时间7h时,离子液体[Et3NH]Cl-2FeCl3催化酯交换制备生物柴油的产率可达95.4%。[Et3NH]Cl-2FeCl3具有较好的循环使用能力,循环使用6次后,催化性能没有明显降低。制备的生物柴油各项指标符合生物柴油国家标准GB/T20828-2007。     

La改性固体超强酸S_2O_8~(2-)/ZrO_2-Al_2O_3的制备及催化性能研究

采用共沉淀-浸渍法制备了固体超强酸S2O82-/ZrO2-Al2O3催化剂,并加入La对催化剂进行改性。以柠檬酸三丁酯的合成为探针反应评价催化剂的活性,并通过红外光谱、X射线衍射、NH3程序升温脱附等方法对催化剂进行表征,考察制备条件及La的引入对催化剂结构和性能的影响。结果表明:(NH4)2S2O8溶液浸渍浓度为0.5mol/L,锆铝氧化物物质的量比为1∶1,600℃焙烧4h后于1%(质量分数)的La(NO3)3溶液浸渍所得的催化剂活性较好,柠檬酸的转化率可达93.69%。La的引入可以提高催化剂对S2O82-的结合能力,抑制活性组分的分解,增加催化剂的酸强度和酸总量,提高催化剂的活性。     

活性炭负载酸性离子液体催化制备生物柴油

以活性炭(AC)负载酸性离子液体[Hmim-BS][HSO4]制备的[Hmim-BS][HSO4]/AC为催化剂,以大豆油和甲醇为原料,通过酯交换反应生成生物柴油。考察了离子液体负载量、催化剂用量、反应时间、反应温度以及醇油摩尔比等因素对生物柴油收率的影响。研究结果表明:在催化剂负载量为30%,催化剂用量为大豆油质量的7.5%,140℃下反应5h,生物柴油收率超过92%。重复使用4次后,生物柴油收率仍可达到83%左右,表现出良好的催化性能。     

镧系六铝酸盐催化剂的制备及其催化甲烷燃烧活性研究

用共沉淀法制备了镧系六铝酸盐LaMnxAl12-xO19(x=0、1、2、3、4、5、6)催化剂,通过X射线衍射、差热分析、扫描电镜和比表面积分析等实验技术及甲烷催化燃烧,对催化剂的结构和性质进行了考察。研究了锰离子掺杂对催化剂结构以及甲烷催化燃烧活性的影响。结果表明,催化剂在1200℃焙烧后可以形成完整的六铝酸盐晶型,且具有较高的催化性能和高温稳定性,不同含量的Mn离子掺杂对催化剂的比表面积和活性有较大的影响。LaMn2Al10O19催化剂具有较好的活性,其起燃温度(T10%/℃)为506℃,完全转化温度(T90%/℃)为696℃。     

SO_4~(2-)/炼锌水淬渣固体酸的制备及催化性能研究

用炼锌水淬渣废物为原料,采用半湿法浸渍和干法老化结合的方法制备了SO2-4/水淬渣固体酸催化剂,考察了浸渍浓度、焙烧温度、老化温度等制备条件对其催化油酸和甲醇酯化制备生物柴油催化性能的影响,并对SO2-4/水淬渣和硫酸处理水淬渣絮凝体烘干物进行NH3-TPD酸性测试和比表面积分析。实验结果表明,制备条件对SO2-4/水淬渣固体酸的催化性能有很大的影响,将最佳制备条件下得到的催化剂用于油酸和甲醇的酯化反应,在催化剂用量18%,醇油比15∶1,温度120℃,反应时间8h的反应条件下,酯化率可达90%以上,且该催化剂重复使用4次后,酯化率仍在50%以上,经H2SO4活化后其催化活性又可恢复。     

La1-xSrxMnAl11O19-δ催化剂的甲烷燃烧性能研究

采用反相微乳液-共沉淀法制备了一系列以La、Sr作为镜面阳离子、锰离子作为活性组分的六铝酸盐催化剂La1-xSrxMnAl11O19-δ(x=0.2、0.4、0.5、0.6、0.8)。利用X射线衍射、比表面积分析等分析方法及甲烷燃烧对催化剂的结构和性质进行了考察,主要考察了不同含量的La和Sr离子的掺杂量对催化剂结构及对甲烷催化燃烧活性的影响。结果表明,La和Sr同时作为镜面阳离子,不但可以形成完整的六铝酸盐,而且所制备的催化剂具有较高的催化活性。不同含量的La和Sr离子掺杂对于催化剂的特性有较大影响。当x=0.5时,所制备的催化剂La0.5-Sr0.5MnAl11O19-δ具有较高的催化活性,起燃温度T10%=502℃,至683℃甲烷完全转化。催化剂在低转化率下的宏观动力学实验结果表明,甲烷催化燃烧在La1-xSrxMnAl11O19-δ催化剂上为一级动力学反应,反应速率受催化剂固有性质控制。     

固体超强酸SO42-/TiO2-Al2O3的制备及其催化合成冰片

采用溶胶-凝胶法和浸渍法制备了系列SO_4~(2-)/TiO_2-Al_2O_3固体超强酸催化剂,运用XRD、NH_3-TPD、FT-IR、PyFTIR、XPS、SEM等技术手段,研究了复合催化剂材料的结构与性质,初步探讨了固体超强酸SO_4~(2-)/TiO_2-Al_2O_3催化剂的构效关系,得到适宜的催化剂制备条件为:n(TiO_2)/n(Al_2O_3)=1∶2、硫酸浸渍浓度1mol/L、催化剂焙烧温度500℃。考察了物料物质的量比、催化剂用量、反应时间等对催化合成冰片的影响。结果表明,在物料物质的量比为1∶0.4,催化剂用量为α-蒎烯质量的7%,采用程序升温方式(65℃-1h,75℃-4h,90℃-1h)加热的条件下,固体超强酸SO_4~(2-)/TiO_2-Al_2O_3催化剂的催化活性最高,α-蒎烯的转化率高达100%,龙脑的收率高达59.74%,SO_4~(2-)/TiO_2-Al_2O_3固体超强酸催化剂在重复使用6次的条件下,α-蒎烯的转化率均不变,龙脑的收率下降2.99%,催化剂的重复使用性良好。     

Studies on nanosized iron based modified catalyst for Fischer-Tropsch synthesis application

To improve catalytic performance iron based catalyst, the effects of some metal promoters, especially potassium, copper and other transition metal oxides as well as different supports have been reported. A series of Fe/K/Cu catalysts promoted with magnesium and ceria by precipitation method, followed by impregnation method; keeping Cu and K content same. The catalysts were characterized by XRD, N2 physisorption, TPR and TEM techniques. From XRD, the presence of hematite (Fe2O3) phase was detected in all precipitated iron catalysts and CFe2.5 phase in all used catalysts. TPR results showed that addition of Mg facilitated the reduction of Fe2O3 and decrease in reduction temperature. The catalytic performance was investigated in a fixed-bed reactor at 250 degrees C, 2 MPa pressure and H2/CO molar ratio of 2. Concentration of Mg was found to affect the CO conversion and product distribution. It was found that precipitated iron catalyst Fe/Mg/Cu/K with Mg/Fe ratio of 0.1 showed highest conversion (60.6%) and C5(+) selectivity (92.4%) among all catalysts tested.     

钙钛矿型La0.9Sr0.1NiO3催化剂的合成条件及其可见光催化活性的研究

采用溶胶-凝胶法制备了钙钛矿型La0.9Sr0.1NiO3复合氧化物光催化剂,通过TG-DTA、XRD、可见光催化性能等对合成产物的热分解过程、物相结构和可见光催化活性进行了研究;采用单因素实验探究了合成工艺条件(柠檬酸用量、pH值、煅烧温度、煅烧时间)对合成产物的物相结构和可见光催化性能的影响。结果表明,在柠檬酸用量与金属离子的总量比为1∶1,pH=1.5,400℃预处理4h,700℃煅烧4h时可制备出单一相的六方晶系的La0.9-Sr0.1NiO3晶体;在500 W氙灯的照射下,当La0.9Sr0.1NiO3催化剂用量为1.20g/500mL时,在180min内对13.2mg/L的甲基橙溶液的脱色率达到62.1%。     

Preparation and characterization of hydrotalcite-like materials from flyash for transesterification

In the present study, attempts were made to synthesize Mg–Al hydrotalcite-like materials with bifunctional properties from flyash and flyash-based zeolite by coprecipitation method. The synthesized hydrotalcite and their corresponding Mg–Al mixed oxides obtained after calcination were characterized for their structural, compositional, thermal, and morphological properties. The synthesized hydrotalcite had Mg/Al ranging from 1.3 to 2.3. The activity of the synthesized catalyst was estimated in transesterification of mustard oil, and the effects of reaction time, catalyst concentration, and methanol-to-oil molar ratio on biodiesel production were also investigated. A maximum yield of 93.4 % was obtained with methanol-to-oil molar ratio of 12:1, 7 wt% catalyst concentration for 6 h of reaction at 65 °C. The average value of activation energy of biodiesel in the conversion range of 0.2 < X < 0.9 was 130.5 kJ mol^?1. This study showed the potential application of flyash and its use in modified Mg–Al hydrotalcite materials as heterogeneous catalysts in biodiesel production.     

Facile synthesis of layered sodium disilicates as efficient and recoverable nanocatalysts for biodiesel production from rapeseed oil

In this study, α, β and δ phases of layered sodium disilicates were synthesized and used as heterogeneous catalysts for transesterification of rapeseed oil with methanol to methyl esters (biodiesel). The catalysts were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) technique, Fourier transform infrared spectroscopy (FT-IR), N₂ adsorption-desorption, and thermogravimetric analysis (TGA-DTA). δ-Na₂Si₂O₅ showed better catalytic efficiency than the other two phases of sodium disilicate, and showed excellent activity at the optimized conditions. The transesterification conditions, such as the catalyst dosage, molar ratio of methanol to oil, reaction temperature and reaction time were investigated. The results revealed that with a catalyst loading of 4?wt%, methanol to oil ratio of 30:1, reaction temperature of 65?°C and reaction time of 3?h, conversion of biodiesel reached 97.8%.     

纳米晶镁铝水滑石制备机理及抗毒性研究

以尿素为沉淀剂制备纳米晶镁铝水滑石,考察不同镁铝比制备的纳米晶镁铝水滑石催化剂对大豆油酯交换的影响以及催化剂的抗水抗酸性和使用寿命,并探讨纳米晶镁铝水滑石的合成机理.随镁铝摩尔比增加,酯交换反应所需时间减少,当m(Mg2 ):m(Al3 )=3:1时,转化率高达94.2%;当m(Mg2 ):m(Al3 )=4:1时,使用寿命最长,可重复使用5次.纳米晶镁铝水滑石具有较强抗水抗酸性,故在进行酯交换反应中无须脱水脱酸.     

焙烧温度对CO2-CH4重整制合成气NiO/γ-Al2O3催化剂性能的影响

采用水解-沉积法, 在不同焙烧温度下制备了cat-500、cat-600、cat-700和cat-800系列NiO/γ-Al₂O₃催化剂。XRD和H₂-TPR分析表明, 焙烧温度高于700 ℃, 活性组分与载体具有强烈的金属-载体相互作用(SMSI), 具体表现为活性组分前驱体以尖晶石NiAl₂O₄的形式存在。反应后催化剂的XRD、TG-DTG、TPH等表征结果表明, cat-700和cat-800试样的Ni晶粒尺寸分别为9.8和8.7 nm, 小于cat-500和cat-600试样(分别为15.7和13.6 nm), 分散性更好; 且催化剂表面积炭为丝状碳, 其不会导致催化剂失活, 但大量积累会引起床层压降升高, 影响催化剂的反应性能。cat-800试样110 h寿命试验表明, 高温焙烧制备的Ni基催化剂活性和稳定性均较高, CO₂转化率达95%左右, 失活速率仅为0.0536%/h。     

TiO_2/AC复合光催化剂制备及性能研究

以TiCl4乙醇溶液为前驱物、煤质活性炭为载体,通过溶胶-凝胶法制备活性炭(AC)/TiO2复合光催化剂。利用扫描电子显微镜(SEM)、X-射线衍射仪(XRD)和BET比表面积孔径测定仪等对制备的样品进行表征。以光催化降解甲基橙溶液为模型反应,表征其光催化活性,考察了TiCl4/乙醇体积比、煅烧温度和煅烧时间等制备条件对光催化活性的影响。结果表明:在TiCl4/乙醇体积比为1∶20,500℃煅烧2h时,光催化降解甲基橙的活性最高,降解率达到95%;TiCl4/乙醇体积比和煅烧温度对光催化活性影响较大,煅烧时间对光催化活性影响甚小。含少量金红石相的TiO2有利于光催化降解甲基橙。     

Parameters affecting oleochemical production from waste bleaching earth via alcoholysis

The edible oil industry is one of the largest industries in the world. In the edible oil refining process, large amounts of waste are discarded every day. Evaluation of these wastes is vital for environmental issues. Most of this waste is due to the bleaching process in which bleaching earths are largely used. Due to its high adsorption capacity, bleaching earth adsorbs oil nearly 40% of its weight. In order to evaluate this waste for oleochemical production, alcoholysis reactions were investigated. Parameters affecting the reaction, such as catalyst type and amount, alcohol type, alcohol:oil molar ratio and temperature, were investigated. The reactions were conducted in the presence of different catalysts such as NaOH, NaOCH₃ and homogeneous alkali polymeric gel catalyst (HAPJEK) and performed at a temperature range of 60–78°C and in the presence of a catalyst (1–2% based on oil weight) at alcohol:oil molar ratios of 5:1–7:1. Based on optimisation by response surface methodology (RSM), the critical synthesis conditions for 210 min reaction time with a maximum of 85.8% methyl ester content were determined as temperature: 68.4°C, catalyst amount 1.5% based on oil weight and methanol/oil molar ratio: 6.4.