Ni catalyst promotion of a Cis-selective Pd catalyst for canola oil hydrogenation

A Ni catalyst was added to a cis-selective Pd catalyst in an attempt to further improve the Pd catalyst's cis-selectivity and activity for canola oil hydrogenation. The system was tested under reaction conditions known to be suitable for cis-selective hydrogenation with the Pd catalyst (50 ppm Pd, 70 °C, and 5.2 MPa). Although inactive on its own under these conditions, the addition of 100 ppm Ni increased the hydrogenation activity (from 2.12 to 2.49 10⁻² min⁻¹). Further addition of Ni up to 1000 ppm resulted in no further improvements in activity. The trans isomer contents of the oils hydrogenated with Pd and the Pd/Ni systems were similar. The level of conjugated dienes decreased rapidly during hydrogenation with both Pd alone and with the Pd/Ni combination and no changes in conjugation were detected in the presence of the Ni catalyst alone. The increased activity of the Pd/Ni system over Pd alone was attributed to adsorption of catalyst poisons from the oil by Ni.     

无机膜的应用与展望

本文综述了无机膜的发展、制备方法和应用。     

助剂对Pd/树脂醚化催化剂催化性能的影响 Ⅰ.铝助剂的影响

研究了不同助剂对Ｐｄ／树脂醚化催化剂在临氢条件下对催化裂化汽油Ｃ５馏份与甲醇和Ｈ２反应的催化性能的影响。结果表明，在Ｐｄ／树脂醚化催化剂中引入Ｚｒ、Ｔｉ、Ｂ、Ｓｎ和Ａｌ等助剂后，都能改善催化剂的醚化、双键异构和二烯烃选择性加氢活性，其中以Ａｌ、Ｓｎ为最好。Ａｌ助剂的体积质量和负载方式对Ｐｄ－Ａｌ／树脂醚化催化剂的活性有影响。ＢＥＴ方法和Ｘ－射线荧光光谱分析（ＸＦＳＡ）表明，Ａｌ助剂对Ｐｄ－Ａｌ／树脂醚化催化剂的表面积、孔结构和Ｐｄ离子交换量影响较小。     

Formation of C4 species in the deactivation of a Pd/SiO2 catalyst during the selective hydrogenation of acetylene

The deactivation characteristics of Pd/SiO₂ in the selective hydrogenation of acetylene were correlated with changes in the amount of the C4 species produced. The amounts of butenes produced changed in parallel with the catalyst activity, indicating that the rate limiting step for butene production was the same as that for acetylene hydrogenation. On the other hand, the amount of 1,3-butadiene produced changed, showing a maximum with catalyst deactivation because 1,3-butadiene is an intermediate in the sequential reaction process which involves both the production and consumption of 1,3-butadiene. This was verified by a simultaneous TG/reaction experiment showing that 1,3-butadiene was a precursor of green oil. The catalyst showed a self-regenerative behavior in its activity and the amounts of C4 species produced during the early stage of deactivation because two opposite factors, which contributed to either the lowering or the promotion of activity, were involved in the process. A specific type of polymer species, produced during the initial period of deactivation, is proposed to be responsible for the promotion of catalyst activity.     

乙炔在磁稳定床中的选择性加氢研究

 制备了一种磁性Pd/Al₂O₃催化剂，采用磁稳定床考察了活性组分负载量、反应条件及CO浓度对乙炔加氢反应性能的影响。结果表明，当反应温度80℃、反应压力1.5MPa、空速9000h－1、磁场强度（H）25kA/m时，乙炔转化率为100％，乙烯选择性可达81％，具有优良的乙炔加氢活性和乙烯选择性，优于相同反应条件下的进口催化剂；250h稳定性实验结果表明，磁性Pd/Al2O3催化剂具有良好的初活性和乙烯选择性，催化剂性能稳定。     

Influence of Rare-earth Elements on Mechanical Properties of Palladium

The influence of 0.1-0.6 at.-%RE additions (RE= La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb) on themechanical properties of Pd was studied. All above RE additions increased not only the strengthproperties at ambient temperature but also the tensile strength, creep rupture time and activation en-ergy at high temperatures, simultaneously increased the elongation of Pd. In the range of dilute con-centration, the strength properties of Pd-RE alloy enhanced linearly with RE concentration. Whenthe strength properties of Pd-RE alloys were normalized at 0.1 at.-%RE, it was found that light REelements had stronger effect on the properties of Pd than heavy RE, whereas Eu, Yb, Ce had anoma-lous effect. In all Pd-RF alloys, Pd-Eu alloy had the highest strength properties, successively Pd-Yband Pd-Ce alloy. The effect mechanisms of RE in alloy, such as purifying impurities, increasingrecrystallization temperature, refining grain size. expanding crystal lattice, increasing dislocation den-sity and decreasing stacking fault energy, forming stable RE oxidation by internal oxidation, and soon, were observed. They were strengthening sensitive factors. The influence of the factors onstrength properties and elongation of Pd was discussed.     

乙烯直接氧化合成乙酸

用常规固定床反应器考察了Pd-SiW12/SiO2催化剂还原条件对乙烯直接氧化合成乙酸催化性能的影响。催化剂用H2在200－300℃还原后Pd 的分散度较高，其催化活性远高于肼在液相中还原的催化剂，在乙烯气相氧化合成乙酸反应的原料气中，适量1，2－二氯乙烷的存在有助于提高乙酸的选择性和时空产率，初步考察了Pd-Se-SiW12/SiO2催化剂连续206h运转的稳定性，结果表明，催化剂中Pd晶粒的长大和硅钨酸的流失是造成催化剂失活的主要原因。     

多孔钯的制备及其结构与性能

研究了以钯粉和碳酸钠为原料制备多孔钯的烧结-溶解新工艺，用FESEM分析了多孔钯的微观结构形貌，并进一步研究了制备的多孔钯的力学性能和氢同位素的交排换代性能。结果表明，烧结-溶解工艺能稳定地制备出孔隙率为85．29％-87．82％的多孔钯，其压缩强度大于2MPa。室温下孔隙率为87.30％的多孔钯对氘的单位质量吸收量为0．0767L／g，氢同位素排代交换率为86．2％。     

Application of an analytical phase transformation model

Employing isothermal and isochronal differential scanning calorimetry, an analytical phase transformation model was used to study the kinetics of crystallization of amorphous Mg82.3Cu17.7 and Pd40Cu30P20Ni10 alloys. The analytical model comprised different combinations of various nucleation and growth mechanisms for a single transformation. Applying different combinations of nucleation and growth mechanisms, the nucleation and growth modes and the corresponding kinetic and thermodynamic parameters, have been determined. The influence of isothermal pre-annealing on subsequent isochronal crystallization kinetics with the increase of pre-annealing can be analyzed. The results show that the changes of the growth exponent, n, and the effective overall activation energy Q, occurring as function of the degree of transformation, do not necessarily imply a change of nucleation and growth mechanisms, i.e. such changes can occur while the transformation is isokinetic.     

NO reduction by CH4 over Pd/Co-sulfated zirconia catalysts

A series of sulfated zirconia supported Pd/Co catalysts was synthesized by the sol–gel method and examined for NO_x reduction by methane. The NO conversion increased up to a Co/S ratio of 0.43, and then decreased at a higher Co loading (Co/S = 0.95). Sulfate content was also essential for obtaining high selectivity to molecular nitrogen. A catalyst loaded with 0.06 wt.% Pd, 2.1 wt.% Co and 2.1 wt.% S (Pd/Co-SZ-2) exhibited remarkable performance under lean conditions and displayed stability in a long-term durability test using a synthetic reaction mixture containing 10% water vapor. This catalyst exhibited the highest sulfur retention most probably as cobalt sulfide. Besides, the catalytic oxidation of NO to NO_y groups was confirmed by FT-IR, in agreement with the general mechanism for the SCR of NO by hydrocarbons. In the absence of oxygen in the feed stream, the catalyst was highly active for NO reduction with methane. IR stretching bands assigned to N₂O and adsorbed nitro groups were identified upon adsorbing NO on Pd/Co-SZ-2. This indicates that under rich conditions disproportionation of NO to N₂O and NO₂ occurs and confirms that the formation of NO₂ species is an essential step for NO reduction by CH₄.