超临界汽油中煤焦油加氢裂化催化剂研究

为了提高超临界汽油中煤焦油加氢裂化轻质油的收率,研究了Co-Mo-Pd-Y沸石催化剂制备条件对轻质油收率的影响。分别考察了催化剂负载金属中Co/(Co+Mo)原子比、催化剂焙烧温度、分子筛酸处理浓度、酸处理温度及时间对煤焦油加氢裂化催化反应收率的影响。结果表明:当Co/(Co+Mo)原子比(摩尔比)为0.5,催化剂焙烧温度为550℃,分子筛酸处理浓度为2 mol/L,酸处理温度为70℃及处理时间4 h时,轻质油收率(质量分数)可达81.5%,并且对此条件下制备的催化剂通过N2吸附及XRD进行了表征。制得的催化剂在超临界溶剂中煤焦油加氢裂化反应中表现出较高的活性,煤焦油获得了高的轻质油收率。     

有序介孔CuCoZr催化剂的制备及其催化合成气制乙醇及高级醇性能

改性费托合成催化剂(尤其是CuCo催化剂)在合成气制乙醇及高级醇反应中具有高的催化活性和总醇选择性,被认为是潜在的工业催化剂。采用蒸发诱导自组装(EISA)法和共沉淀(CP)法制备了一系列CuCoZr催化剂,考察了制备方法及EISA法制备的催化剂Cu/Co原子比对合成气制乙醇及高级醇性能的影响。采用N₂物理吸附-脱附、小角X射线衍射(XRD)、原位XRD、透射电镜(TEM)、H₂-程序升温还原(TPR)、CO-程序升温脱附(TPD)和原位红外漫反射光谱(DRIFT)对催化剂进行表征,分析了合成气在Cu/Co原子比为3∶1的Cu₃Co₁Zr催化剂表面的反应路径。结果表明,EISA法制备的Cu Co Zr催化剂为有序介孔结构,比表面积随Cu/Co原子比的增加先增大后减小,其中Cu₃Co₁Zr催化剂比表面积和CO吸附量均为最大,分别为143m²/g和0.33mmol/g,催化剂的Cu晶粒尺寸仅为9.1nm。在催化合成气制醇的反应中CO转化率...     

Fe,Co,Ni改性SAPO-34分子筛上MTO反应的理论研究

为明确分子筛对MTO反应的催化活性和产物选择性的影响,采用色散力矫正的密度泛函理论方法,以SAPO-34分子筛为催化剂,考察了3种不同金属Fe、Co和Ni改性的SAPO-34分子筛布朗斯特(Brnsted,B酸)酸强度的变化,并研究不同酸性的催化剂对甲醇制烯烃(MTO)反应中的低碳烯烃催化活性和选择性的影响及2者间的关联。通过计算去质子化能比较改性前、后SAPO-34分子筛的酸性强度变化,酸性强度顺序为Fe APO-34Co APO-34SAPO-34Ni APO-34。通过计算MTO反应克服的反应能垒,比较低碳烯烃的催化活性和选择性,Fe、Co、Ni金属改性的SAPO-34分子筛对乙烯生成反应的催化活性顺序为Fe APO-34≈Ni APO-34Co APO-34;对丙烯生成反应的催化活性顺序为Fe APO-34≈Co APO-34Ni APO-34;Ni原子的引入比Fe、Co原子的引入提高了乙烯的选择性,而Fe、Co原子的引入比Ni原子的引入提高了丙烯的选择性。     

Mn的添加对Co-Ce-O催化氧化对甲酚性能的影响

应用溶胶-凝胶法制备了Co-Ce-Mn-O催化剂,并应用BET、XRD和微型催化反应装置研究了第三组分Mn的添加量、干燥方法和焙烧温度对Co-Ce-O复合氧化物催化剂结构及其对甲酚(PMP)选择氧化对羟基苯甲醛(PHB)催化性能的影响。结果表明:Mn的添加促进了Co、Ce及Mn组分间的相互分散,从而提高了催化剂的催化性能。经真空干燥、250℃焙烧制得的原子比Mn/Co=1的Co-Ce-Mn-O催化剂的选择氧化催化性能最佳。     

中国科大钴基催化剂在二氧化碳加氢反应中的活性物相研究获进展

<正>近日,中国科学技术大学研究钴(Co)基催化剂在CO_2加氢反应中的活性物相。研究人员将N原子引入到Co催化剂中构筑出Co_4N催化剂,并通过原位机理研究发现,Co_4NH_x是该催化过程中真正的活性物相。CO_2加氢反应一方面可以利用CO_2合成化工原料,缓解CO_2的排放压力,实现碳能源的循     

扬子石化公司PTA装置TA单元氧化反应操作条件的优化

介绍了本厂PTA装置TA单元的氧化反应操作条件的优化情况。优化工作是在研究了影响氧化反应的各因素基础上进行的,认为影响氧化反应因素主要为:①Co、Mn催化剂的浓度;②Br浓度及Br与Co、Mn的原子比;③溶剂比;④含水量;⑤温度、压力;⑥尾氧量的控制。针对上述情况,制定了高、低负荷运行及开车引发期的优化工艺条件。     

溶胶-凝胶燃烧法制备La_(0.6)Sr_(0.4)Co_(1-x)Mn_xO_3催化剂及其应用于苯的催化氧化

以丙烯酰胺辅助柠檬酸为络合试剂,采用溶胶-凝胶燃烧法制备La0.6Sr0.4Co1-xMnxO3催化剂(x=0.3、0.5、0.7)并与La Co O3进行比较,进行XRD、BET、SEM、XPS和苯的催化氧化性能和稳定性表征。结果表明,催化活性顺序为:La0.6Sr0.4Co0.7Mn0.3O3La0.6Sr0.4Co0.5Mn0.5O3La0.6Sr0.4Co0.3Mn0.7O3La Co O3。La0.6Sr0.4Co1-xMnxO3催化剂生成钙钛矿相的同时还伴生少量Sr CO3杂相。与La Co O3对比,La0.6Sr0.4Co1-xMnxO3催化剂拥有更大的比表面积、孔容和抗团聚性,具有更好的催化氧化活性。在La0.6Sr0.4Co1-xMnxO3(x=0.3、0.5、0.7)催化剂中,La0.6Sr0.4Co0.7Mn0.3O3催化剂比其他两种催化剂具有更高的钙钛矿相结晶度和更多的表面吸附氧与晶格氧,活性最高。78 h稳定性测试结果表明,La0.6Sr0.4Co0.7Mn0.3O3催化剂表现出良好的稳定性。     

Co负载量对Co/TiO2催化CO2甲烷化性能影响

采用沉淀-沉积法制备出w(Co)=10%、15%、20%和25%的Co/TiO_2催化剂,并用于催化CO_2甲烷化反应。通过XRD、TEM、N_2吸附-脱附、H_2程序升温还原(H_2-TPR)和CO_2程序升温脱附(CO_2-TPD)对催化剂进行了表征与测试。结果表明,Co的负载影响了催化剂中Co3O4晶粒尺寸、比表面积、孔径以及催化剂的还原性能,且Co物种与TiO_2载体发生了强相互作用。其中,w(Co)=20%的Co/TiO_2催化剂中Co颗粒平均尺寸约为8nm,比表面积及孔径分别为40.9 m2/g和6.96 nm,且Co分散度达10.1%,从而更有利于CO_2甲烷化反应。此外,w(Co)=20%的Co/TiO_2催化剂表面具有最大的中强碱位量(28μmol/g),从而可活化更多的CO_2。活性测试结果表明,当反应温度为400℃、压力0.5 MPa、原料气空速3 600 m L/(g·h)、V(H_2)/V(CO_2)=4时,w(Co)=20%的Co/TiO_2催化剂的活性最好,其CO_2转化率和CH_4选择性可分别达到69.9%和98.3%,且在20 h内保持稳定。     

炭载Pt-Co-La催化甲基环己烷脱氢的研究

采用浸渍法制备了负载在废轮胎热解炭（PTC）上的三金属体系催化剂(1Pt-1Co)-xLa,其中,Pt的负载量为0.2%,Pt-Co原子比为1∶1,La以不同原子比加入。N₂吸脱附、H₂-TPR、CO脉冲吸附对催化剂表征的结果表明,适量La的加入有利于提高活性组分的分散度,促进活性组分的还原,尤其是对Pt-Co的共还原作用具有一定的促进作用。催化甲基环己烷（MCH）脱氢反应的结果表明,La的加入显著提高了单、双金属催化剂的活性。     

铜钴复合氧化物催化剂溶胶——凝胶法合成及二甲苯燃烧催化性能研究

溶胶——凝胶法合成了系列铜钴复合氧化物催化剂 ,用 XRD和 TPR谱对其所制样品进行了表征 ,着重研究了铜钴原子比对样品的晶体结构还原性能以及二甲苯燃烧催化活性的影响。结果表明 ,二甲苯燃烧催化活性与样品的还原温度 ,铜钴原子比密切相关 ,当 Cu/Co=2∶ 1时 ,其样品的还原温度最低 ,二甲苯的燃烧催化活性最高     

Enhanced activity of carbon-supported PdCo electrocatalysts toward electrooxidation of ethanol in alkaline electrolytes

Carbon-supported Pd and PdCo (1: 2, 1: 1, 2: 1 and 3: 1) catalysts were synthesized by chemical reduction with NaBH₄. Their electrochemical properties were investigated by cyclic voltammetry, chronoamperometry and CO stripping voltammetry in alkaline electrolytes, and compared with commercial Pt/C and PtRu(1: 1)/C catalysts. In electrochemical oxidation of ethanol in an alkaline electrolyte, marked improvements in the current density and onset potential were observed by incorporating Co into Pd/C to form PdCo/C alloy electrocatalysts. The best catalyst PdCo (1: 1)/C showed performance superior to the commercial Pt/C or PtRu/C catalysts. It is shown that the incorporated Co facilitates the oxidation of strongly-adsorbed carbonaceous intermediate species on the surface of Pd by forming OH^? group and reacts away the intermediates from Pd surface. Thus, PdCo(1: 1)/C catalyst is a promising anode catalyst for direct ethanol fuel cells with alkaline electrolytes.     

Probing palladium-cobalt/NaY catalysts by neopentane conversion

Neopentane conversion in hydrogen was used as a catalytic probe for zeolite encaged PdCo particles. Activity and selectivity strongly depend on the pretreatment conditions. PdCo/NaY catalysts exhibit higher isomerization selectivity than Pd/NaY in conformity with previous results on SiO₂ supported Pd and PdCo. This is remarkable, because reduced Co/SiO₂ displays 100% selectivity for hydrogenolysis. The isomerization selectivity thus appears to be a useful measure for the extent of alloying between Pd and Co.On leave from Institute of Physical Chemistry, Polish Academy of Sciences, Warsaw, Poland.     

PdCo/SiO2双金属催化剂用于杂环储氢载体的高效脱氢

乙基咔唑/十二氢乙基咔唑（N-ethylcarbazole/dodecahydro-N-ethylcarbazole,NECZ/12H-NECZ）体系被认为在有机液体储氢领域具有较大的开发应用前景,但高活性、选择性的脱氢催化剂的设计开发制约着其工业应用。基于此,设计开发出一种具有高脱氢活性和高选择性的双金属催化剂Pd₁Co₃/ SiO₂（Pd质量分数为1.25%）,对其结构进行了XPS、XRD、HRTEM等表征分析,并评价了其催化十二氢乙基咔唑的脱氢性能。与5.0%（质量分数）Pd/SiO₂相比,表明引入一定量的Co金属形成的PdCo合金可提高12H-NECZ脱氢反应效率和NECZ选择性,动力学与DFT计算发现双金属催化剂可以有效降低三步基元反应的能垒,大幅提升第二步基元反应（8H-NECZ到4H-NECZ）的脱氢反应速率。研究结果为揭示12H-NECZ脱氢反应机理和高效脱氢反应催化剂的设计与开发提供了新的思路。     

Co改性的Pd/C催化剂在转移加氢中的应用研究

通过调整Co和Pd的浸渍顺序制备了不同的钴改性的Pd/C催化剂,考察了催化剂在3,5-二羟基苯甲酸转移加氢制备3,5-二氧代环己烷羧酸反应中的活性。确认先浸渍钴后浸渍钯、并在300℃以氢气还原得到的Co-Pd/C催化剂具有最佳活性,反应转化率和选择性分别达到94.6%和99.5%。对该催化剂以BET、TPR、XRD、SEM、TEM、XPS等手段进行了表征。结果表明,先浸渍的钴占据了活性炭的微孔使最可几孔径由2.72nm增大为3.32nm,并且与一些对反应不利的官能团作用,使后浸渍的钯主要分布在催化剂的大孔中,避免了过多深度加氢副产物的生成。催化剂活性组分为零价的钯,其平均粒径约10nm,以有利于转移加氢的聚集态存在,使催化剂获得了较高的活性和选择性。     

Trial for diameter-selective synthesis of single-walled carbon nanotubes

The diameter-controlled synthesis of single-walled carbon nanotubes (SWNTs) has been examined experimentally. The catalysis of the Rh and Pd atoms has been confirmed by blending with Co atoms at 950 °C in a furnace, although the Rh/Pd catalyst has not been recorded to act efficiently at this temperature before. Raman spectra indicate that the Rh/Co and Pd/Co catalysts can synthesize narrow-diameter SWNTs more selectively than the Fe/Co and Ni/Co catalysts, which can only synthesize SWNTs with slightly larger diameters. These results suggest that by changing the combination of catalysts, the persistent problem of controlling the diameter of SWNTs can be solved without any expensive setup or complicated techniques.     

Kinetics and mechanism of oxygen reduction reaction at CoPd system synthesized on XC72

Studies are presented of the kinetics and mechanism of oxygen electroreduction reaction on CoPd catalysts synthesized on carbon black XC72. As shown both in model conditions and in the tests within the cathodes of hydrogen-oxygen fuel cells with proton conducting electrolyte, CoPd/C system features a higher activity, as compared to Co/C. The highest activity in the oxygen reduction reaction is demonstrated by the catalysts with the Pd:Co atomic ratio being 7:3 and 4:1. The structural studies (XPS and XRD, and also the data of CO desorption measurements) evidence the CoPd alloy formation, which is reflected in the negative shift of the bonding energy maximum as compared to Pd/C and in the appearance of the additional CO desorption maximums on the voltammograms. It is found by means of structural research that CoPd alloy is formed in the course of the catalyst synthesis which features a higher catalytic activity of the binary systems. Besides, CoPd/C catalyst is more stable in respect to corrosion than Pd supported on carbon black. The measurements on the rotating disc electrode and rotating ring-disc electrode evidence that CoPd/C system provides the predominant oxygen reduction to water in the practically important range of potentials (E > 0.7 V). The proximity of kinetic parameters of the oxygen reduction reaction on CoPd/C and Pt/C catalysts points to the similar reaction mechanism. The slow step of the reaction is the addition of the first electron to the adsorbed and previously protonated O₂ molecule. The assumptions are offered about the reasons causing the higher activity and selectivity of the binary catalyst towards oxygen reduction to water, as compared to Co/C. The studies of the most active catalysts within the fuel cell cathodes are performed.     

Effect of Palladium on Iron Fischer–Tropsch Synthesis Catalysts

Studies were conducted to investigate the effect of Pd on the Fischer–Tropsch Synthesis (FTS) selectivity, activity and kinetics as well as on the water–gas shift activity of an iron catalyst. Two palladium promoted catalysts (Pd0.002/Fe100 and Pd0.005/Fe100) were prepared from a base Fe100/Si5.1 (atomic ratio) catalyst. Results of FTS over the two palladium promoted catalysts were compared to those obtained from the K/Fe/Si base catalyst and a Cu/K/Fe/Si catalyst. The results indicate that Pd enhanced the FT activity while the selectivity for CO₂ and CH₄ changed little compared to the results for the base catalyst and the Cu promoted catalyst. Palladium promotion had a negative effect on the C₂—C₄ olefin to paraffin ratio. Pd promotion led to a higher WGS rate than the other two catalysts at high syngas conversions. A higher WGS rate compared to the FTS rate was obtained only for the Pd promoted catalysts. The FTS rate constant for the Pd promoted catalyst is higher than the base catalyst but lower than for the Cu promoted catalyst.     

Electrochemical activity towards ORR of mechanically alloyed PdCo supported on Vulcan carbon and carbon nanospheres

A PdCo catalyst with an atomic ratio of 2:1 was synthesized from elemental powders by mechanical alloying. The structural characterization and composition of the catalyst were determined by X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. Both the electrocatalytic activity of the catalyst for oxygen reduction in acidic media, as well as attempts to support it on Vulcan XC-72 carbon powder and carbon nanospheres were evaluated by cyclic voltammetry, rotating disc electrode and rotating ring-disk electrode techniques. The X-ray diffraction studies indicated that an intermetallic PdCo compound with an average crystallite size of 25 nm was obtained. According to kinetic and thermodynamic parameters, the electrocatalytic activity of the catalyst toward oxygen reduction was determined as PdCo/CNS > PdCo/C with first-order kinetics, a four-electron multielectronic transference pathway, and a negligible amount of hydrogen peroxide produced. Activation energy values of 40 ± 1 kJ mol^?1 and 68 ± 1 kJ mol^?1 were determined for reactions with PdCo/CNS and PdCo/C, respectively.     

Comparative Study on CO2 Hydrogenation to Higher Hydrocarbons over Fe-Based Bimetallic Catalysts

This paper reports on notable promotion of C₂ ⁺ hydrocarbons formation from CO₂ hydrogenation induced by combining Fe and a small amount of selected transition metals. Al₂O₃-supported bimetallic Fe–M (M = Co, Ni, Cu, Pd) catalysts as well as the corresponding monometallic catalysts were prepared, and examined for CO₂ hydrogenation at 573 K and 1.1 MPa. Among the monometallic catalysts, C₂ ⁺ hydrocarbons were obtained only with Fe catalyst, while Co and Ni catalysts yielded higher CH₄ selectively than other catalysts. The combination of Fe and Cu or Pd led to significant bimetallic promotion of C₂ ⁺ hydrocarbons formation from CO₂ hydrogenation, in addition to Fe–Co formulation discovered in our previous work. CO₂ conversion on Ni catalyst nearly reached equilibrium for CO₂ methanation which makes this catalyst suitable for making synthetic natural gas. Fe–Ni bimetallic catalyst was also capable of catalyzing CO₂ hydrogenation to C₂ ⁺ hydrocarbons, but with much lower Ni/(Ni+Fe) atomic ratio compared to other bimetallic catalysts. The addition of a small amount of K to these bimetallic catalysts further enhanced CO₂ hydrogenation activity to C₂ ⁺ hydrocarbons. K-promoted Fe–Co and Fe–Cu catalysts showed better performance for synthesizing C₂ ⁺ hydrocarbons than Fe/K/Al₂O₃ catalyst which has been known as a promising catalyst so far.     

Selective hydrogenation of cyclopentadiene over supported metal catalysts

The selective hydrogenation of cyclopentadiene to cyclopentene has been studied in the liquid phase using Pd and Pd Me/Al₂O₃ bimetallic catalysts (Me = Mn, Ni, Co, W). The highest activity was obtained with Pd Co and Pd W/Al₂O₃. For these catalysts, no hydrogen or CO chemisorption was detected although Pd could be seen by XPS at 335·8 eV; it is considered that new species, more active for the selective hydrogenation of cyclopentadiene, appeared at the catalyst surface. The sulfur resistance towards thiophene has also been studied. It was observed that the highest sulfur resistance is coincident with the highest activity. XPS analysis shows that the poisoning species is thiophene adsorbed on the catalyst surface.