Pd/Na2O/K2O/γ-Al2O3三元催化活性分析与评价

本文以浸渍法制备了活性γ-Al₂O₃涂层及Pd/Na₂O/K₂O/γ-Al₂O₃三元催化剂。考察了γ-Al₂O₃涂层比表面积随高温老化时间变化的规律。在实验室模拟尾气配气系统上，对Pd/Na₂O/K₂O/γ-Al₂O₃三元催化剂的起燃温度、抗高温老化及抗SO₂中毒能力进行了分析与评价。本文的γ-Al2O3涂层能经受1050℃的高温老化。Pd/Na₂O/K₂O/γ-Al₂O₃三元催化剂经900℃高温老化两次共13h后，其最大催化活性几乎不变，其老化样经600℃硫中毒1h后对CO和HC的催化转化率仍在75％以上。Pd/Na₂O/K₂O/γ-Al₂O₃新鲜样的起燃温度为280℃，二次老化样的起燃温度为320～350℃，具有很高三元催化活性。     

K2O/MCM-41在大豆油酯交换反应中的应用

以等体积浸渍法制备了分子筛MCM-41负载碱金属的固体碱催化剂K₂O/MCM-41,利用CO₂程序升温脱附表征技术（CO₂-TPD）对固体催化剂表面性能进行测定,并通过蒸发光散射检测器（HPLC-ELSD）研究了不同碱金属负载量对制备生物柴油效果的影响,确定K₂O的较佳负载质量分数为3.0%。     

钾基CO2吸收剂的碳酸化反应特性

对钾基CO₂吸收剂的碳酸化反应机理进行研究。利用热重分析、XRD、扫描电镜和氮吸附仪进行试验。结果表明：分析纯碳酸钾的组分为K₂CO₃·1.5H₂O,碳酸化反应速率缓慢;先将分析纯碳酸钾样品脱除结晶水后再进行碳酸化反应时,K₂CO₃与气氛中的水蒸气迅速生成K₂CO₃·1.5H₂O,不利于碳酸化反应的进行;由KHCO₃分解产生的K₂CO₃却表现出优越的碳酸化反应性能,20 min内转化率高达85%以上,经过多次循环试验后吸收剂仍保持很高的活性。从微观角度分析了两种改性钾基CO₂吸收剂碳酸化反应机理差异的原因,通过拟合计算得到了这3种钾基吸收剂的碳酸化反应速率常数,为干法K₂CO₃/KHCO₃循环脱除CO₂的研究提供了一定的基础数据。     

Cu1Zr1Ce9Oδ催化剂选择性氧化CO性能的研究

用共沉淀法制备了Cu₁Zr₁Ce₉O_δ催化剂,考察了反应温度和反应气体中各组分对Cu₁Zr₁Ce₉O_δ催化剂上选择性氧化CO反应的影响。结果表明,降温的过程中Cu₁Zr₁Ce₉O_δ催化剂的活性滞后。H₂的存在有利于CO的脱附,促进了低温下选择性氧化CO的反应;而温度较高时,H₂氧化副反应的发生降低了CO的转化率,反应气中H₂O和CO₂降低了催化剂的活性和选择性,最佳反应温度为（160~200） ℃,O₂的进入量取3为宜。     

ＣeＯ２对Cu-ＺnＯ催化剂性质和CO２加氢反应性能的影响

运用活性评价、ＸＲＤ、ＴＰＲ、ＣＯ_２-ＴＰＤ和积炭测定手段,探讨了CeＯ_２对Cu-ＺnＯ催化剂性质和CO_２加氢反应性能的影响。结果表明,催化剂经CeＯ_２改性后,CuＯ晶粒明显长大,致使催化剂还原难度增加;有利于CO歧化反应进行,使催化剂上积炭量增加;CO_２吸附量减少,CO_２加氢生成甲醇的活性增加。     

γ-Al2O3在CeO2-La2O3催化还原SO2中的作用

考察了反应温度对γ-Al₂O₃、CeO₂-La₂O₃和CeO₂-La₂O₃/γ-Al₂O₃催化CO还原SO₂到单质硫活性的影响。采用XRD表征了催化剂反应前后的物相变化。结果表明，温度过低或过高均不利于γ-Al₂O₃催化CO还原SO₂的反应。γ-Al₂O₃的介入提高了CeO₂和La₂O₃的分散性，使Redox 和COS两种反应机理在同一催化剂上的协同作用增强，使CeO₂-La₂O₃/γ-Al₂O₃在催化还原SO₂的反应中具有更低的反应温度和更高的活性。     

γ-Al2O3负载铜锌氧化物催化剂的N2O催化分解性能

以γ-Al₂O₃为载体,采用共浸渍法合成了负载量为35%（以CuO与ZnO总质量计）的CuZn金属氧化物催化剂,分别考察了金属助剂（Co、Ni,、Mg、Fe、Mn、Ba和Ce）对催化剂的影响。采用XRD、BET和H₂-TPR等方法对制备的催化剂进行表征,在微反装置上对催化剂的N₂O催化分解活性进行评价。结果表明,合成的CuZn氧化物催化剂均具有CuxZn_1-xAl₂O₄的类Co₃O₄尖晶石结构;加入金属助剂使催化剂的比表面积不同程度得到提高,催化剂的N₂O催化分解反应活性不仅与Cu³⁺还原为Cu²⁺的温度有关,还与晶粒尺度大小和催化剂比表面积等有关;其中,含金属助剂Ni的催化剂具有相对较高的N2O催化分解反应活性,其N₂O完全转化温度为567 ℃。除含金属助剂Ba催化剂以外,加入其他金属助剂有利于N₂O催化分解反应进行。     

二氧化碳加氢合成二甲醚CuO-ZnO-Al2O3/HZSM-5型催化剂的研究

以乙醇为溶剂，草酸作沉淀剂，采用共沉淀浸渍法制备了性能优良的二氧化碳加氢合成二甲醚催化剂(CuO-ZnO-Al₂O₃/HZSM-5)，在245℃、2.0MPa、2400h-1、H₂/CO₂=2.79的条件下，CO2转化率达22.61%，二甲醚选择性为45.90%，甲醇选择性为14.81%，含氧化合物收率为13.73%。对CuO-ZnO-Al₂O₃/HZSM-5催化剂进行了反应条件及活性稳定性的初步考察。     

工艺条件对Ni/Al2O3和Ni/CeO2-Al2O3催化剂在甲烷自热重整制氢反应中催化性能的影响

采用共沉淀法制备γ-Al₂O₃载体和不同Ce添加量的CeO₂-Al₂O₃载体,然后用浸渍法制备Ni负载质量分数10%的Ni/γ-Al₂O₃和Ni/CeO₂-Al₂O₃催化剂。在固定床微反装置中考察了反应温度、原料气配比和CH₄空速等工艺条件对Ni/γ-Al₂O₃和Ni/Ce₃₀Al₇₀O_δ催化剂在甲烷自热重整制氢反应中催化性能的影响。结果表明,添加Ce的催化剂催化性能有较大提高,在Ni/Ce₃₀Al₇₀O_δ催化剂上,反应温度750 ℃时, CH₄转化率94.3％,与Ni/Al₂O₃催化剂相比,提高20％。Ni/γ-Al₂O₃和Ni/CeO₂-Al₂O₃催化剂的CH₄转化率均随反应温度的升高而增大。原料气中n(O₂)∶n(CH₄)和n(H₂O)∶n(CH₄)的增加均能提高各催化剂的CH₄转化率。但n(O₂)∶n(CH₄)和n(H₂O)∶n(CH₄)的变化对各催化剂的催化性能的影响不同。随着n(O₂)∶n(CH₄)的增大,产物中n（H₂）∶n（CO）降低,n（CO₂）∶n(CO＋CO₂)升高;而n(H₂O)∶n(CH₄)增大时,产物中n（H₂）∶n（CO）和n（CO₂）∶n(CO＋CO₂)均升高。随着CH₄空速的增加,Ni/Al₂O₃催化剂上CH₄转化率、n（H₂）∶n（CO）和n（CO₂）∶n(CO＋CO₂)均较大程度下降;而在Ni/Ce₃₀Al₇₀O_δ催化剂上,随着CH₄空速的增加,CH₄转化率、n（H₂）∶n（CO）和n(CO₂）∶n(CO＋CO₂)变化不大。     

工业化甲醇催化剂在CO2加氢制备甲醇过程中的应用研究

系统地将工业化甲醇催化剂应用于CO₂加氢制备甲醇反应中,考察5种工业化甲醇催化剂在CO₂加氢反应中的反应活性,运用ICP、N₂-物理吸附、XRD和H₂-TPR等手段对催化剂进行表征。结果表明,Cu/Zn/Al催化剂具有较高的CO₂加氢反应活性,在温度220 ℃和压力3 MPa条件下,CO₂转化率为22.9%,甲醇选择性为64.8%。催化剂活性与组分含量、晶粒大小、比表面积和孔结构等因素有关,CuO和ZnO组分含量越高,催化活性越好,适度晶粒大小的CuO物种可能是该反应中有效催化活性位前驱体,反应规律与甲酸铜中间体理论基本吻合;高比表面积和规整孔结构均有助于提高催化活性。     

均匀凝胶法制备CuO-ZnO-Al2O3-Cr2O3/HZSM-5催化二氧化碳加氢合成二甲醚

采用均匀凝胶法制备了CuO-ZnO-Al2O3-Cr2O3/HzSM-5催化剂,采用X射线衍射(XRD)、傅立叶红外光谱(FT-IR)和热重-差热分析(TG-DTA)进行了表征,并在固定床微型反应器中考察了反应温度、反应压力,CuO与ZnO质量比、Al2O3和Cr2O3的质量分数对CuO-ZnO-Al23-Cr2O3/HzSM-5催化剂在CO2加氢制备二甲醚反应中催化性能的影响.结果表明,在533 K,3MPa,H2与CO2体积比为3和反应混合气体积空速为1600 h-1的条件下,在CuO与ZnO质量比2,Al2O3和Cr2O3分别占催化剂质量的10.0%和1.5%的CuO-ZnO-Al2O3-Cr2 O3/HZSM-5催化剂作用下,CO2的单程转化率达到28.94%,二甲醚的选择性和收率分别为31.76%和8.76%,甲醇和二甲醚的总收率达到13.98%.     

沉淀温度对CO2加氢合成二甲醚催化剂的影响

考察了沉淀温度对二氧化碳加氢合成二甲醚催化剂CuO-ZnO-Al2O3/HZSM-5的影响,研究结果表明,沉淀温度为343 K时,所制备的催化剂前驱体的晶形完整且晶相组成均一,焙烧后的催化剂中CuO和ZnO的相互分散程度较好,催化剂中氧化铜物种比较容易还原,复合催化剂表面具有较强的酸性中心,对于二氧化碳加氢直接合成二甲醚的催化活性最为理想.     

Activity and Selectivity of a Nanostructured CuO/ZrO2 Catalyst in the Steam Reforming of Methanol

Steam reforming of methanol for production of hydrogen can be carried out over copper based catalyst. In the work presented here, the catalytic properties of a CuO/ZrO₂ catalyst (8.5wt%) synthesised by a templating technique were investigated with respect to activity, long term stability, CO formation, and response to oxygen addition to the feed. The results were obtained using a fixed bed reactor and compared to a commercial methanol synthesis catalyst CuO/ZnO/Al₂O₃. It is shown that, depending on the time on stream, the temporary addition of oxygen to the feed has a beneficial effect on the activity of the CuO/ZrO₂ catalyst. After activation, the CuO/ZrO₂ catalyst is found to be more active (per copper mass) than the CuO/ZnO/Al₂O₃ system, more stable during time on stream (measured up to 250h), and to produce less CO. Structural characterisation by means of X-ray powder diffraction (XRD) and X-ray absorption spectroscopy (XAS) reveals that the catalyst (as prepared) consists of crystalline, tetragonal zirconia with small domain sizes (about 60Å) and small/disordered crystallites of CuO.     

CO<Subscript>2</Subscript> hydrogenation to methanol over Cu/ZnO catalysts synthesized via a facile solid-phase grinding process using oxalic acid

Reduced Cu/ZnO catalyst was synthesized through solid phase grinding of the mixture of oxalic acid, copper nitrate and zinc nitrate, followed by subsequent calcination in N₂ atmosphere without further H₂ reduction. The catalysts were characterized by various techniques, such as XRD, TG-DTA, TPR and N₂O chemisorption. Characterization results suggested that during the calcination in N₂, as-ground precursor (oxalate complexes) decomposed to CuO and ZnO, releasing considerable amount of CO, which could be used for in situ reduction of CuO to Cu^o. The in situ reduced O/I-Cu/ZnO catalyst was evaluated in CO₂ hydrogenation to methanol, which exhibited superior catalytic performance to its counterpart O/H-Cu/ZnO catalyst obtained through conventional H₂ reduction. The decomposition of precursor and reduction of CuO happened simultaneously during the calcination in N₂, preventing the growth of active Cu⁰ species and aggregation of catalyst particles, which was inevitable during conventional H₂ reduction process. This method is simple and solvent-free, opening a new route to prepare metallic catalysts without further reduction.     

Hydrogen production from steam reforming of methanol over CuO/ZnO/Al2O3 catalysts: Catalytic performance and kinetic modeling

A series of CuO/ZnO/Al_2O_3, CuO/ZnO/ZrO_2/Al_2O_3 and CuO/ZnO/CeO_2/Al_2O_3 catalysts were prepared by coprecipitation and characterized by N_2 adsorption, XRD, TPR, N_2O titration and HRTEM. The catalytic performances of these catalysts for the steam reforming of methanol were evaluated in a laboratory-scale fixed-bed reactor at 0.1 MPa and temperatures between 473 and 543 K. The results showed that the catalytic activity depended greatly on the catalyst reducibility and the specific surface area of Cu. An approximate linear correlation between the catalytic activity and the Cu surface area was found for all catalysts investigated in this study.Compared to CuO/ZnO/Al_2O_3, the ZrO_2-doped CuO/ZnO/Al_2O_3 exhibited higher activity and selectivity to CO,while the CeO_2-doped catalyst displayed lower activity and selectivity. Finally, an intrinsic kinetic study was carried out over a screened CuO/ZnO/CeO_2/Al_2O_3 catalyst in the absence of internal and external mass transfer effects. A good agreement was observed between the model-derived effluent concentrations of CO(CO_2) and the experimental data. The activation energies for the reactions of methanol-steam reforming, water-gas shift and methanol decomposition over CuO/ZnO/CeO_2/Al_2O_3 were 93.1, 85.1 and 116.5 k J·mol~(-1), respectively.     

CO2对CuO/ZnO/Al2O3催化剂前体老化及催化性能的影响

采用并流共沉淀法制备CuO/ZnO/Al2O3甲醇合成催化剂前体,在通入CO2条件下老化,采用XRD、FT-IR、DTG、H2-TPR、XPS等表征手段对制备的前体及焙烧后的催化剂进行表征,研究不同CO2通入量对前体晶相转变、微观结构及其焙烧后催化性能的影响。研究结果表明,老化阶段通入CO2后,沉淀母液的pH值趋于7,产生CO32?离子,进而影响Zn2+的沉淀,促进Cu2+进入Zn5(CO3)2(OH)6晶格中取代Zn2+形成绿铜锌矿(Zn,Cu)5(CO3)2(OH)6物相,有助于增强焙烧后催化剂的Cu-Zn之间协同作用,增加活性组分Cu分散度。CO2通入量为40 mL/min时,制备的催化剂在浆态床合成甲醇过程中表现出良好的催化活性和稳定性,甲醇时空收率（STY）达到301.78 g/(kg?h),失活率仅为0.15%/d,与未通入CO2辅助老化制备的催化剂相比,时空收率提高了9.72%,平均失活率降低了33.33%。     

助剂对微波辐射制备浆态床合成甲醇铜基催化剂性能影响

采用并流共沉淀法,在微波辐射老化的条件下,制备了CuO/ZnO/Al2O3/X（X=ZrO2,Fe2O3,MnO2）四元铜基合成甲醇催化剂,考察了第四组分元素对催化剂前驱体物相组成及浆态床合成甲醇性能的影响。通过XRD,TG,EDS等对催化剂及其前驱体的微观结构进行了表征。结果发现,助剂Zr、Fe、Mn的加入均不同程度的促进了Cu,Zn组分间的相互作用,有利于活性物相绿铜锌矿及锌孔雀石的生成。与CuO/ZnO/Al2O3三元催化剂相比,助剂ZrO2、Fe2O3、MnO2的加入均提高了催化剂合成甲醇的活性。其中ZrO2对铜基催化剂活性影响较大,CO转化率从43.51%提高到了59.18%,提高了36%;甲醇时空收率从256.9 mg/（gcat·h）提高到了372.8 mg/（gcat·h）,提高了45%。     

ZnO对CuO-ZnO/Al2O3催化剂催化甘油氢解性能的影响

以氧化铝为载体,采用浸渍法制备了负载型CuO-ZnO/Al2O3催化剂,通过XRD、XPS、TPR手段表征催化剂上CuO和ZnO的分布和化学形态。结果表明,CuO-ZnO/Al2O3催化剂催化甘油氢解反应中,CuO是活性组分,ZnO的引入可以降低CuO与载体氧化铝的相互作用强度,有利于CuO的还原,提高催化剂甘油氢解活性;催化剂表面呈缺电子状态的Cu物种是甘油氢解的活性中心。当活性组分CuO质量分数为12%,n(Cu)∶n(Zn)=1∶1.5时,CuO-ZnO/Al2O3催化剂催化甘油氢解活性最高,甘油转化率可达97.82%,对1,2-丙二醇选择性达94%。     

In-situ study of reduction of copper catalysts

Isothermal hydrogen interaction with unsupported CuO and 15%CuO/ZnO at about 419–427 K has been followed by in-situ X-ray diffraction as monoclinic CuO is replaced by zero-valent Cu° without direct evidence of formation of intermediate Cu₂O. Surprisingly, less than half of the copper phases within such samples is X-ray detectable. X-ray analysis indicates that reduction of crystalline CuO in CuO/ZnO catalysts may not be retarded by ZnO, but TPR-TGA suggests that reduction of more amorphous CuO may be so retarded.