不同形态ZrO2负载Co催化剂上CO+H2吸附与反应行为研究

利用FTIR,TPSR和微量反应技术考察了CO和CO/H2在无定形、四方相和单斜相3种形态氧化锆为载体的钴基催化剂上的吸附和反应行为.结果表明,CO在以不同形态氧化锆为载体的催化剂上的吸附形式和转化行为具有较大差异.在单斜氧化锆为载体的催化剂上生成桥式和多桥式吸附的CO,并容易进一步加氢生成烃类物种,具有较高的反应活性和C5+烃的选择性.而以四方氧化锆为载体的催化剂上桥式吸附的CO较稳定,加氢反应活性较低.     

微乳液法制备Pt-S2O82-/ZrO2-Al2O3型固体超强酸催化剂及其异构化性能

采用微乳液法负载Pt制备了Pt-S2O82-/ZrO2-Al2O3(Pt-SZA-M)固体超强酸催化剂, 以正戊烷异构化反应为探针, 对比了微乳液法和浸渍法负载Pt制备的催化剂(Pt-SZA)的异构化性能, 并采用XRD, FTIR, BET, TG-DTA, TPR和TEM对催化剂进行了表征. 结果表明, 与Pt-SZA催化剂相比, Pt-SZA-M催化剂中Pt粒子的粒径更小(4.5 nm)且尺寸更均一; Pt-SZA-M催化剂的比表面积(109.6 m2/g)比Pt-SZA催化剂(95.0 m2/g)增加了15.4%. Pt-SZA-M催化剂的初始还原温度比Pt-SZA催化剂降低了10~20℃, 表明微乳液法负载Pt可以提高催化剂的氧化活性, 提高氢分子在催化剂上的吸附解离能力. 异构化活性实验结果表明, 与Pt-SZA催化剂相比, Pt-SZA-M催化剂的低温活性得到明显改善, 在反应压力为2.0 MPa、 氢烃摩尔比为4: 1、 质量空速为1.0 h-1的条件下, Pt-SZA-M催化剂在反应温度为230℃时活性达到60.8%, 在100 h内异戊烷的收率可稳定在58.0%左右, 选择性在95.0%以上.     

负载型Sn2(OMe)2Cl2/SiO2催化剂的制备、表征与催化合成碳酸二甲酯

采用表面改性法制备了负载型Sn2(OMe)2Cl2/SiO2双核桥联配合物催化剂,用IR,TPD和微量反应技术研究了催化剂的表面结构、化学吸附性能和反应活性.结果表明,双核桥联配合物Sn2(OMe)2Cl2以O(Me)为桥,Cl为配体,并以Sn-O-Si形式键合到SiO2表面上;CO2与催化剂表面的金属离子Sn4+和桥基配体OMe的O2-形成桥式和甲氧碳酸酯基两种吸附态,CH3OH与催化剂表面的金属离子Sn4+仅形成一种分子吸附态;在413K以下,CO2和CH3OH在Sn2(OMe)2Cl2/SiO2催化剂表面上以近100%的选择性生成碳酸二甲酯;CO2在催化剂表面形成的甲氧碳酸酯基吸附态是生成DMC的关键物种,其与在同一活性中心的分子吸附态甲醇的反应决定了催化剂的活性和产物选择性.     

还原气氛对CoFe/SBA-15催化剂F-T反应性能的影响

考察了不同还原气氛处理CoFe/SBA-15催化剂对F-T反应性能的影响。结果表明,H2气氛下有利于六方钴的生成;催化剂的活性取决于钴含量,随着钴含量的增加,F-T反应中CO转化率增加,C5+选择性增加。随着铁含量的增加,催化剂表现了较高的CO2选择性。CO还原有利于立方钴的生成,导致催化活性相比H2还原的催化剂活性要低。同时CO还原容易产生积炭使催化剂的钴活性位被覆盖,导致甲烷选择性随着钴含量增加而升高。但碳化铁的生成有利于提高20Fe/SBA-15催化剂的活性,有利于低碳烃生成及C2~4烃烯烷比增加。     

中孔分子筛负载的钴基催化剂F-T合成反应研究

以中孔分子筛HMS-2为载体,浸渍法制香钴质量分数为15.00%的钴基催化剂,F-T合成反应研究表明：载体焙烧时间对F-T合成反应性能影响不大;Co/HMS-2催化剂的F-T合成反应在运行141.00h达到483.00K后,在H2/CO摩尔比为2.00,压力2.00MPa,空速500.00h^-1反应条件下,CO转化率达到88.00%,烃选择性保持在98.00%左右,烃分布中C5^+含量可达85.00%左右,进一步运转了384.00h,CO转化率仅下降了9.00%,而烃选择性和烃分布几乎不变,说明Co/HMS-2催化剂F-T合成反应性能和稳定性优异。载体中孔结构在473.00K催化剂开始F-T合成反应24.00h后已经塌陷,随后催化剂结构趋于稳定。     

用原位红外技术研究Ag-MoO3/ZrO2催化丙烯气相环氧化反应

制备了对丙烯直接气相环氧化具有优良催化性能的Ag-MoO₃/ZrO₂催化剂, 采用原位FT-IR技术研究了丙烯、环氧丙烷及丙烯和氧气混合气在载体和催化剂上的吸附及反应行为. 研究表明, 丙烯在ZrO₂载体和20%Ag-4%MoO₃/ZrO₂催化剂上吸附后, 均不发生化学反应, 而环氧丙烷在ZrO₂载体上吸附后于400 ℃发生开环反应, 在20%Ag-4%MoO₃/ZrO₂催化剂上吸附后于300 ℃发生开环反应. 当丙烯和氧气混合气在ZrO₂载体上共吸附后, 随着反应温度从室温升高至400 ℃, 二者开始反应生成CO₂和H₂O; 混合气在20%Ag-4%MoO₃/ZrO₂催化剂上共吸附后于350 ℃开始反应. 对比非负载型Ag-MoO₃催化剂的研究结果可见, ZrO₂载体的存在使催化剂的活性下降的同时, 提高了对产物环氧丙烷的选择性.     

用原位红外技术研究Ag-MoO3/ZrO2催化丙烯气相环氧化反应

制备了对丙烯直接气相环氧化具有优良催化性能的Ag-MoO₃/ZrO₂催化剂, 采用原位FT-IR技术研究了丙烯、环氧丙烷及丙烯和氧气混合气在载体和催化剂上的吸附及反应行为. 研究表明, 丙烯在ZrO₂载体和20%Ag-4%MoO₃/ZrO₂催化剂上吸附后, 均不发生化学反应, 而环氧丙烷在ZrO₂载体上吸附后于400 ℃发生开环反应, 在20%Ag-4%MoO₃/ZrO₂催化剂上吸附后于300 ℃发生开环反应. 当丙烯和氧气混合气在ZrO₂载体上共吸附后, 随着反应温度从室温升高至400 ℃, 二者开始反应生成CO₂和H₂O; 混合气在20%Ag-4%MoO₃/ZrO₂催化剂上共吸附后于350 ℃开始反应. 对比非负载型Ag-MoO₃催化剂的研究结果可见, ZrO₂载体的存在使催化剂的活性下降的同时, 提高了对产物环氧丙烷的选择性.     

Li助剂对Co/AC催化剂上CO加氢制直链混合伯醇反应性能的影响

采用CO加氢反应、X射线衍射、程序升温还原和CO程序升温脱附等技术研究了Li助剂对活性炭负载的Co催化剂(Co/AC)上CO加氢反应性能的影响.结果表明,Li的添加抑制了气态烃的生成,提高了C5+和直链混合伯醇的选择性,但催化剂活性下降.这可能源于Li的加入抑制了Co2+物种的还原,降低了反应速控步骤—强吸附CO的解离...     

Effects of Li Promoter on the Performance of Co/AC Catalysts for CO Hydrogenation to Mixed Linear a-Alcohols

采用CO加氢反应、X射线衍射、程序升温还原和CO程序升温脱附等技术研究了Li助剂对活性炭负载的Co催化剂(Co/AC)上CO加氢反应性能的影响.结果表明,Li的添加抑制了气态烃的生成,提高了C5+和直链混合伯醇的选择性,但催化剂活性下降.这可能源于Li的加入抑制了Co2+物种的还原,降低了反应速控步骤—强吸附CO的解离能力.另外,Li也促进了Co2C物种的生成,使得产物中混合醇的比例增加.     

锆改性钴基费-托合成催化剂催化性能的研究

 考察了助剂锆和金属钴负载量对锆改性Co／Al2O3催化剂催化性能的影响．结果表明，锆助剂能够高度分散在氧化铝载体上，而活性组分钴以一定尺寸存在；锆的添加能够明显地提高Co／Al2O3催化剂的催化活性和C5＋烃选择性，但助剂锆含量对催化剂催化性能的影响不大；在锆存在下，催化剂的催化活性随金属钴含量先升高后降低．进一步的研究表明，催化剂上烃形成速率的提高可能是由于锆助剂能够增加催化剂的活性位数目，增强桥式CO吸附的强度，在Co－ZrO2间形成界面．     

Platinum carbonyl derived catalysts on inorganic and organic supports: a comparative study

Fumed silica, silica gel, silica-alumina and cross-linked (5.5%) polystyrene have been functionalized with quaternary ammonium groups and the Chini cluster [Pt₁₂(CO)₂₄]²⁻ has been anchored onto these functionalized materials by ion pairing. A catalyst has also been prepared by the adsorption of Na₂[Pt₁₂(CO)₂₄] on unfunctionalized fumed silica. The catalytic activities of the resultant materials, and that of commercially purchased 5% platinum on alumina have been studied for the hydrogenation of a variety of unsaturated compounds. The substrates studied are: α-acetamidocinnamic acid, cyclohexanone, acetophenone, methyl pyruvate, ethyl acetoacetate, nitrobenzene and benzonitrile. Compared to the polystyrene supported catalyst, the inorganic oxide supported catalysts have higher surface areas and for most of the substrates have notably higher activities. The functionalized fumed silica-based catalyst gives higher conversions than functionalized silica gel and silica-alumina-based catalysts. In the hydrogenation of acetophenone and ethyl acetoacetate, the functionalized fumed silica-based catalyst show superior activity compared to the commercial platinum catalyst, and the catalyst made by conventional adsorption method. In benzonitrile hydrogenation with all the cluster-derived catalysts a hydrazine derivative is selectively formed, but when the commercial platinum catalyst is used benzyl amine is the main product.     

负载型Fe－Co双金属催化剂的CO加氢反应性能研究及其原位FT－IR表征

负载于γ－Ａｌ_２Ｏ_３上的ＰＰＮ［ＦｅＣｏ_３（ＣＯ）_（１２）］簇合物作为催化剂前体，在ＣＯ加氢反应中显示出了较好的催化活性和对低碳烃的选择性。本文系统地考察了反应温度、反应时间、合成气比和气体空速对ＣＯ加氢反应，ＣＯ转化率和产物分布的影响。借助于ＩＣＰ分析、电镜和原位ＦＴ－ＩＲ跟踪技术，对负载型双金属簇催化剂的金属负载量、催化剂表面状态和脱羰过程中催化剂表面结构的变化进行了分析和表征，获得了一些有意义的结果。     

Rh基催化剂上CO加氢制C2含氧化合物的红外光谱研究

 用红外光谱法考察了Rh-Mn-Li-Ti/SiO2催化剂在CO加氢反应过程中表面吸附物种随压力、温度和H2/CO比的改变而变化的规律. 结果表明,高压有利于提高催化剂表面吸附的CO浓度和活性,高温有利于CO解离; 而高温、高压条件不但促进了CO吸附,而且提高并平衡了CO的解离和插入之间的相对活性,促进了C2含氧化合物的生成. H2/CO比的增大有利于CO在催化剂表面的吸附,从而促进了CO插入,尤其是CO的解离和加氢活性,但是过高的H2/CO比将导致过高的CO解离和加氢活性,引起CO插入活性的削弱而最终导致C2含氧化合物生成活性的下降. 同时,考察了助剂(Mn, Li和Ti)对Rh基催化剂表面吸附物种的影响. 结果表明,助剂的加入可提高C2含氧化合物的生成活性.     

Low-temperature hydrogenation of maleic anhydride to succinic anhydride and γ-butyrolactone over pseudo-boehmite derived alumina supported metal(metal = Cu,Co and Ni) catalysts

The pseudo-boehmite derived alumina supported metal(Cu,Co and Ni) catalysts prepared by the impregnation method were investigated in hydrogenation of maleic anhydride(MA) to succinic anhydride(SA) and γ-butyrolactone.The catalysts were characterized by ICP-AES,N_2 adsorptiondesorption,XRD,H_2-TPR,CO-TPD,dissociative N_2O adsorption and TEM and the results showed that the alumina possessed mesoporous feature and the metal species were well dispersed on the support.Compared to Cu/Al_2O_3 and Co/Al_2O_3,Ni/Al_2O_3 exhibited higher catalytic activity in the MA hydrogenation with 92%selectivity to SA and nearly 100%conversion of MA at 140 °C under 0.5 MPa of H_2 with a weighted hourly space velocity of 2 h ~1(MA).The stability of Ni/Al_2O_3 catalyst was also investigated.     

CexZr1-xO2/Co/C-N催化CO2加氢性能研究

将不同比例的铈锆前驱体负载到ZIF-67,氮气气氛焙烧制备CexZr1-xO2/Co/C-N催化剂,对催化剂进行了XRD,H2-TPR、XPS表征,并在固定床反应器评价其CO2加氢制甲醇性能。XRD结果表明,在铈中加入适量锆形成铈锆固溶体,铈锆固溶体与钴物种较强的相互作用力可以阻止表明金属Co的氧化。但过量加入的锆又会削弱这一作用力,部分金属Co被氧化为Co3O4。H2-TPR结果表明适量的锆的加入改善催化剂的还原性能,催化剂还原温度降低。XPS证实了25%Ce0.67Zr0.33O2/Co/C-N催化剂中含有更多的氧空穴及氮含量,氧空穴和碱性氮都有利于CO2的解离吸附。优化后的25%Ce0.67Zr0.33O2/Co/C-N 催化剂在225 oC,2 MPa,GHSV = 6 L/gcat/h反应条件下取得最高甲醇时空收率,为3.0 mmol/gcat/h。     

An operando DRIFTS investigation into the resistance against CO2 poisoning of a Rh/alumina catalyst during toluene hydrogenation

CO(2) is a major contaminant of renewable H(2) derived from biomass fermentation. The effect of the presence of CO(2) on the activity of alumina-supported Pt and Rh catalysts used for the hydrogenation of toluene at 348 K was investigated. The use of operando diffuse reflectance spectroscopy (DRIFTS) was crucial in unravelling the changes in the nature and abundance of species adsorbed at the sample surface and relating those to the changes of catalytic activity. Rhodium supported on alumina was only partly deactivated by the introduction of CO(2) during the hydrogenation of toluene, contrary to the case of Pt/alumina. Rh was only partially covered by carbonyl species derived from CO(2) and it was shown that toluene could successfully compete with some of the linearly adsorbed carbonyls for adsorption. The alumina support stored many CO(2)-derived adsorbates (carbonates, hydrogenocarbonates, carboxylates) that could spill over to the metal and form carbonyl species even after the removal of CO(2) from the feed.     

Modification of the surface adsorption properties of alumina-supported Pd catalysts for the electrocatalytic hydrogenation of phenol

The electrocatalytic hydrogenation (ECH) of phenol has been studied using palladium supported on gamma-alumina (10% Pd-Al2O3) catalysts. The catalyst powders were suspended in aqueous supporting electrolyte solutions containing methanol and short-chain aliphatic acids (acetic acid, propionic acid, or butyric acid) and were dynamically circulated through a reticulated vitreous carbon cathode. The efficiency of the hydrogenation process was measured as a function of the total electrolytic charge and was compared for different types of supporting electrolyte and for various solvent compositions. Our results show that these experimental parameters strongly affect the overall ECH efficiency of phenol. The ECH efficiency and yields vary inversely with the quantity of methanol present in the electrolytic solutions, whereas the presence of aliphatic carboxylic acids increased the ECH efficiency in proportion to the chain length of the specific acids employed. In all cases, ECH efficiency was directly correlated with the adsorption properties of phenol onto the Pd-alumina catalyst in the studied electrolyte solution, as measured independently using dynamic adsorption isotherms. It is shown that the alumina surface binds the aliphatic acids via the carboxylate terminations and transforms the catalyst into an organically functionalized material. Temperature-programmed mass spectrometry analysis and diffuse-reflectance infrared spectroscopy measurements confirm that the organic acids are stably bound to the alumina surface below 200 degrees C, with coverages that are independent of the acid chain length. These reproducibly functionalized alumina surfaces control the adsorption/desorption equilibrium of the target phenol molecules and allow us to prepare new electrocatalytic materials to enhance the efficiency of the ECH process. The in situ grafting of specific aliphatic acids on general purpose Pd-alumina catalysts offers a new and flexible mechanism to control the ECH process to enhance the selectivity, efficiency, and yields according to the properties of the specific target molecule.     

EFFECTS OF BINDERS ON THE PRODUCTION OF LIGHT ALKENES FROM SYNGAS OVER K-Fe-MnO/SILICALITE-2 CATALYST I. EFFECT OF VARIOUS BINDERS ON CO HYDROGENATION

The performance of the K-Fe-MnO/Si-2 catalyst for the production of light olefins via Co hydrogenation changes obviously with the addition of binders. The results of CO hydrogenation. TPR, Mossbauer spectra CI0TPF, CO/H2-TPSR and C2H4/H2-TPSR are employed to investigate the effects of various binders on the physical-chemical states and catalytic behaviors of K-Fe-MnO/Si-2 catalyst to produce light olefins via syngas, TiO2 can promote the reduction of Fe and strengthen the adsorption of CO resulting in raising olefin selectivity. Other binders such as Al2O3, SiO2, MgO, once added into the catalyst, may cause formation of inorganic salts between FeO and Binders leading to a decrease of Fe reduction and a loss of olefin selectivity for CO hydrogenation. Especially, For K-Fe-MnO/Si-2 catalyst with Al2O3 binder directly, the strong secondary reactions of ethylene during CO hydrogenation cause a very poor light olefin selectivity, which will be improved greatly by modifying Al2O3.