甲烷催化燃烧用介孔ZrO2担载CuO催化剂

以介孔ZrO2为载体,采用湿式浸渍法制备了担载型铜基催化剂,以甲烷催化燃烧为模型反应考察了不同铜含量对催化剂结构和性能的影响,并采用N2吸附-脱附、程序升温还原 (TPR) 和X射线衍射 (XRD)等技术对催化剂进行了表征.结果显示CuO/ZrO2催化剂具有优良的甲烷催化燃烧性能;铜含量为5%质量分率的催化剂表现出最好的低温催化活性和优良的稳定性,甲烷转化率达到90 %时对应的反应温度 (T90) 低至358 ℃;若铜含量继续增加,活性组分CuO会发生聚集,导致催化剂的低温活性降低.     

MgO/La2O2CO3催化剂上的低温甲烷氧化偶联

共沉淀法制备的MgO/La2O2CO3催化剂使甲烷氧化偶联(OCM)在炉温460℃时开始反应,且使反应在50℃炉温下至少24 h。助剂Ni的加入降低了起始和最低反应温度,使催化剂在380℃的炉温下开始反应,之后在无热源的情况下可使反应至少24 h。助剂Zn的加入提高了反应活性,使C2的选择性提高了6%,但同时对低温反应不利,反应在炉温100℃下6 h后自动停止。OCM体系中的强放热反应为OCM温和反应提供了热源。催化剂中的La2O2CO3是维持低温甲烷氧化偶联反应的关键H活性组分。     

载体及活性组分对甲烷低温燃烧催化性能的影响

以一定浓度的Pd为活性组分,-γA l2O3为载体,用浸渍法制备了甲烷低温燃烧催化剂,运用固定床反应装置着重研究载体对甲烷低温燃烧反应的催化性能的影响。同时采用同一种载体条件下,重点考察不同浓度的单一活性组分Pd或Pt和(Pt-Pd)双活性组分催化剂对甲烷低温燃烧反应的催化性能的影响。结果表明,由不同载体,负载同一浓度活性组份制备出的催化剂活性有较大差异。(Pt-Pd)/A l2O3双组分燃烧催化剂,性能优于单一组分的Pd/A l2O3或Pt/A l2O3催化剂,(Pd-Pt)/A l2O3体系具有较高的甲烷催化燃烧活性,催化燃烧的起燃温度最低。相比当(Pd 0.2%-Pt 0.1%)/A l2O3时催化剂活性最高,CH4转化率50%的温度为345℃,完全转化温度为405℃。通过1 000 h稳定性试验,显示出甲烷完全氧化温度为405℃左右,具有较好的低温活性及热稳定性。     

M(0.1)Mn(15)/Hβ催化剂的低温NH3选择还原NO性能

NH₃选择性催化还原（NH₃-SCR）氮氧化物可有效减少固定源NOx的排放,目前,工业上应用的钒钛体系催化剂活性窗口温度为(300~400) ℃,不能用于低温脱硝,开发低温NH₃-SCR烟气脱硝催化剂成为研究热点之一。采用浸渍法制备M(0.1)Mn(15)/Hβ（M=Ni、Fe、Mg、Ca、Sr,0.1为M与Mn物质的量比）系列催化剂。通过X射线衍射、扫描电子显微镜和H2-程序升温还原反应等方法对催化剂进行表征,在固定床微型反应器上考察催化剂NH3选择还原NO的催化性能。结果表明,加入金属助剂Ni,催化剂活性得到改善,反应温度降低,T85和T95分别为157 ℃和 171 ℃。     

助剂MgO对甲烷二氧化碳重整Co/BaTiO3催化剂催化性能的影响

采用溶胶-凝胶法在Co/BaTiO3催化剂中引入助剂MgO,考察了其对甲烷二氧化碳重整Co/BaTiO3催化剂的催化反应性能的影响,利用X射线衍射仪(XRD)、H2程序升温还原(H2-TPR)对催化剂进行了表征,结果表明,助剂MgO使钴催化剂中的活性Co2O3组分增多,还原性和分散性能较好;在n(CO2)∶n(CH4)为1∶1、气相空速(GHSV)为12 000 h-1、反应温度为700℃的条件下,催化剂Co-MgO/BaTiO3表现出良好的催化性能,且反应初期甲烷转化率可达到94.87%,CO选择性可达85.21%,H2收率可达74.08%。     

蜂窝状改性菱铁矿SCR脱硝催化剂的研究

为了开发低温选择性催化还原(SCR)脱硝催化剂,采用混合法制备蜂窝状改性菱铁矿SCR脱硝催化剂,研究掺杂Mn改性对菱铁矿催化剂SCR脱硝活性的影响,并借助比表面积测试(BET)、X射线衍射分析(XRD)等手段对催化剂进行表征。结果表明,菱铁矿粉末与偏钛酸以7:3比例混合,添加硝酸锰和其他黏合剂,经搅拌混合、挤出成型、高温煅烧等工序,可制备出成型好、强度高、催化脱硝活性强的蜂窝状改性菱铁矿SCR脱硝催化剂。掺杂Mn改性后增大了催化剂的比表面积和表面酸性,降低了结晶度,使催化剂的中低温催化脱硝效率有较大提高,在180～270℃反应温度区间高于90%。能应用于燃煤锅炉尾部低温低尘烟气的SCR脱硝。     

La掺杂对SrMnO3催化剂结构和催化性能的影响

采用溶胶-凝胶法制备了钛矿型氧化物Sr1-xLaxMnO3(x=0.02,0.04,0.06,0.08)催化剂。并用并采用X射线衍射(XRD)等手段对催化剂的结构进行了分析研究。揭示了La掺杂对催化剂的钙钛矿结构,甲烷催化燃烧性能的影响规律。结果表明,在La3+掺杂部分取代Sr2+后,(x=0-0.08)时催化剂形成了单一相钙钛矿结构。与SrMnO3催化剂相比,X=0.08催化剂的甲烷燃烧催化活性最好(T10=395.8℃,T90=610.0℃)     

稀土Cu/HZSM-5催化剂NH_3选择性催化还原法低温脱硝性能

采用浸渍法制备Re(x)Cu/HZSM-5(Re=La,Ce,Pr,Nd;x=0.5,1,2)系列催化剂。采用XRD和H_2-TPR等对催化剂进行表征,在微型固定床反应器中评价催化剂低温NH_3选择还原NO的催化活性。结果表明,Re(x)Cu/HZSM-5(Re=La,Ce,Pr,Nd;x=0.5,1,2)催化剂具有较好的低温NH_3选择还原NO催化活性,以La为助剂和添加质量分数1%的La(1)Cu/HZSM-5催化剂低温脱硝活性较好,T85和T95分别为153℃和164℃,活性温度窗口宽,(153~362)℃时,NO转化率超过95%。     

SrxCa1-xNiAl11O19催化剂的制备及其催化甲烷燃烧活性研究

用异丙醇盐水解法制备SrxCa1-xNiAl11O19(x=1.0,0.75,0.5,0.25,0)催化剂,通过X射线衍射、比表面积分析等实验技术及甲烷燃烧,对催化剂的结构和性质进行了考察。研究了掺杂不同量的钙离子对催化剂的结构以及对甲烷催化燃烧活性的影响。结果表明,催化剂在1 200℃焙烧后可以形成完整的六铝酸盐晶型,同时具有较高的催化性能和高温稳定性,不同量的Ca离子掺杂对于催化剂的比表面积有较大的影响。Sr0.25Ca0.75NiAl11O19催化剂具有较好活性,其起燃温度(T10%/℃)为590℃,完全转化温度(T90%/℃)为730℃。     

Ni-Mn/Al_2O_3催化剂在浆态床中CO甲烷化催化性能

采用共浸渍法制备了Ni-Mn/Al2O3催化剂,考察了助剂Mn的含量对催化剂结构及浆态床CO甲烷化性能的影响。采用XRD、H2-TPR、BET、TEM、H2-化学吸附等表征对催化剂进行了测试分析,结果表明,Mn助剂的引入能够促进Ni物种在载体表面的分散,减弱Ni物种与载体的相互作用,降低催化剂的还原温度,提高催化剂的比表面积,减小活性金属Ni的晶粒尺寸。随着Mn含量的增加,Ni-Mn/Al2O3催化剂的甲烷化性能先升后降,其中以Mn含量为4%(质量分数)时的催化甲烷化性能最佳,添加过量的Mn导致活性组分Ni被部分覆盖,催化甲烷化性能下降。通过对16Ni4Mn/Al2O3催化剂样品的浆态床反应温度及反应压力的研究发现,当反应温度为280℃、反应压力为1.5 MPa时,催化剂样品16Ni4Mn/Al2O3的CO转化率及CH4选择性分别达到96.2%和88.8%。     

La改性Cu/Zn/Al催化剂的制备及其催化纤维素液化性能

采用共沉淀法制备了不同La含量改性Cu/Zn/Al的催化剂,通过热重分析(TG/DTG)、X射线衍射(XRD)、比表面积测定(BET)、H₂程序升温还原(H₂-TPR)等表征手段对改性催化剂进行评价,分析结果表明,La助剂能够促进活性组分在载体表面的分散,很好地维持了催化剂的孔结构,适量助剂La的添加可促进CuO、ZnO两相间相互融合,增加活性中心的分散度,使CuO更加易于还原,但过多的La含量会使催化剂的性能发生改变,导致催化剂的活性降低。在超临界甲醇中使用La改性Cu/Zn/Al催化剂催化液化微晶纤维素,发现添加少量的La可有效地提高催化液化效果,相较于为添加助剂的Cu/Zn/Al催化剂,MCC转化率与醇类收率都得到了明显的提高。通过GC-MS分析,可以得到液化产物主要有醇类、酯类、酮类、醛类、烷烃等物质,添加助剂后提高了醇类产物的选择性。设置单因素实验,可知改性后Cu_1.2Zn_4.8Al_1.9La_0.1催化剂的最佳反应条件为:反应温度320℃,反应时间75min,催化剂用量75%。     

La_(1-x)Cu_x MnO_3/HZSM-5催化乙醇制正丁醛

采用改进的柠檬酸络合法制备La_(1-x)Cu_xMnO_3系列复合氧化物,研磨法制备La_(0.8)Cu_(0.2)MnO_3/HZSM-5催化剂,用X射线粉末衍射进行物相分析,考察无氧条件下对乙醇制正丁醛的催化活性。结果表明,在反应温度500℃和空速3 184 h~(-1)的条件下,La_(1-x)Cu_xMnO_3系列复合氧化物中La_(0.8)Cu_(0.2)MnO_3催化活性较高,乙醇转化率为47.53%,正丁醛选择性为37.72%;对于La_(0.8)Cu_(0.2)MnO_3/HZSM-5催化剂,当HZSM-5的质量分数为14%时,催化效果最好,乙醇转化率为60.42%,正丁醛选择性为46.81%。     

Pt的加入提高了PdO/Al2O3催化剂反应活性

采用共沉淀法同时制备了PdO/M-Al2O3(M=Ce、Zr、Ce-Zr)和PtO-PdO/M-AlO3催化剂.考察了Pt的加入对PdO/M-Al2O3催化剂的影响,助剂Ce、Zr改性的PtO-PdO/Al2O3催化剂的甲烷催化燃烧反应性能以及催化剂预处理对催化反应性能的影响.结果表明,PtO-PdO/Ce-Al2O3...     

Pt的加入提高了PdO/Al2O3催化剂反应活性

采用共沉淀法同时制备了PdO/M-Al2O3（M=Ce、Zr、Ce-Zr）和PtO-PdO/M-Al2O3催化剂。考察了Pt的加入对PdO/M-Al2O3催化剂的影响,助剂Ce、Zr改性的PtO-PdO/Al2O3催化剂的甲烷催化燃烧反应性能以及催化剂预处理对催化反应性能的影响。结果表明,PtO-PdO/Ce-Al2O3催化剂的活性最好,其甲烷完全转化温度为475℃,比PdO/Ce-Al2O3催化剂低90℃。另外,用蒸馏水反复洗涤的催化剂相比于未经蒸馏水洗涤的催化剂具有较低的甲烷起燃温度和完全转化温度。     

La1-xAgxCoO3钙钛矿催化剂的制备及烟碳颗粒催化燃烧性能

采用柠檬酸溶胶-凝胶法制备La_1-xAg_xCoO₃系列钙钛矿催化剂,并对催化剂进行XRD和H₂-TPR表征。XRD结果表明,LaCoO₃钙钛矿中掺杂Ag,部分Ag进入晶格,同时部分Ag以单质形式存在于钙钛矿表面。H₂-TPR结果表明,Ag的掺杂有利于提高LaCoO₃催化剂的低温还原性能。在此基础上,考察催化剂在紧密接触条件下对标准碳和烟碳的催化燃烧性能,发现LaCoO₃钙钛矿可降低标准碳的起燃温度,在LaCoO₃催化剂中掺入Ag,标准碳的燃烧温度进一步降低。催化剂对标准碳的催化燃烧活性随着Ag添加量的增加而逐渐增加。La_1-xAg_xCoO₃催化剂对烟碳的催化燃烧具有较好活性,但Ag含量对催化剂在烟碳催化燃烧中的活性影响较小。为了在烟碳催化燃烧性能和降低卷烟燃烧温度之间建立关联,将催化剂添加到烟丝表面,考察催化剂的添加对卷烟最高燃烧温度的影响,结果表明,当催化剂添加量为烟丝质量的5%时,卷烟的最高燃烧温度可降低28 ℃。     

Metallic monolith supported LaMnO3 perovskite-based catalysts in methane combustion

Metallic monolith supported LaMnO₃ perovskite-based catalysts are characterized by a high activity in methane combustion (95.5% conversion at 745 °C) and by a high thermal resistance. The activity of the catalysts depends on the duration and temperature of LaMnO₃ calcination. The same relation holds for the chemical composition of the catalyst surfaces when they are determined by the XPS method. The shortening of the time of LaMnO₃ perovskite calcination from 12.5 h to 8 h (700 °C) reduces the conversion of methane over a fresh catalyst. This is attributable to the lower amount of manganese (Mn:La = 0.48) on the surface of this catalyst compared to the catalyst whose perovskite was calcined for 12.5 h (Mn:La = 1.8). The extension of calcination time from 8 h to 12.5 h (at 700 °C) brings about a decrease in the specific surface area (SSA) from about 13.7 m²/g to 9.4 m²/g. After approximately 6 h on stream, the activities of the two catalysts become comparable. Aging of the catalyst with an LaMnO₃ active layer at 920 °C for 24 h reduces methane combustion to 82.5% (at 745 °C). The aging process changes the catalyst surface, where Al and C content increases and the Mn:La ratio decreases. The activity of the monolithic LaMnO₃ catalyst rises with the increase in the amount of the active layer from 11.5% to 17.8%. Methane conversion is greater over catalysts with an LaMnO₃ than with an LaCoO₃ active layer, but the LaMnO₃ catalysts show a lower resistance to thermal shocks.     

The oxidative dehydrogenation of ethane over alkali-doped lanthanum-calcium oxide catalysts

The oxidative dehydrogenation of ethane has been investigated over Li-, Na- and K-doped La/CaO catalysts at temperatures of 550–650°C. The addition of alkali metals to La/CaO increases the ethylene selectivity. For Li- and Na-doped La/CaO catalysts, the ethane conversion remains almost unaltered. The increase of ethylene selectivity over the two catalysts is believed to be mainly caused by coordinative action of lithium and lanthanum or sodium and lanthanum. However, the Li-doped La/CaO catalyst exhibits stronger coordinative action than the Na-doped La/CaO catalyst. Catalyst characterization reveals that the strong coordinative action of components in Li/La/CaO is probably related to the chemical and crystal structure of the catalyst which is favorable for oxidative dehydrogenation of ethane. The results also show that addition of potassium, being a poor dopant, to La/CaO results in a sharp decrease in catalytic activity.     

K-, CeO2-, and Mn-promoted Ni/Al2O3 catalysts for stable CO2 reforming of methane

Reforming of methane with carbon dioxide into syngas over Ni/γ-Al₂O₃ catalysts modified by potassium, MnO and CeO₂ was studied. The catalysts were prepared by impregnation technique and were characterized by N₂ adsorption/desorption isotherm, BET surface area, pore volume, and BJH pore size distribution measurements, and by X-ray diffraction and scanning electron microscopy. The performance of these catalysts was evaluated by conducting the reforming reaction in a fixed bed reactor. The coke content of the catalysts was determined by oxidation conducted in a thermo-gravimetric analyzer. Incorporation of potassium and CeO₂ (or MnO) onto the catalyst significantly reduced the coke formation without significantly affecting the methane conversion and hydrogen yield. The stability and the lower amount of coking on promoted catalysts were attributed to partial coverage of the surface of nickel by patches of promoters and to their increased CO₂ adsorption, forming a surface reactive carbonate species. Addition of CeO₂ or MnO reduced the particle size of nickel, thus increasing Ni dispersion. For Ni–K/CeO₂–Al₂O₃ catalysts, the improved stability was further attributed to the oxidative properties of CeO₂. Results of the investigation suggest that stable Ni/Al₂O₃ catalysts for the carbon dioxide reforming of methane can be prepared by addition of both potassium and CeO₂ (or MnO) as promoters.