Suppressing the excessive hydrogenation capacity of palladium has great significance for selective hydrogenation of acetylene. Herein, an amino acid (histidine or His in abbreviation) modified Pd/SiO 2 catalyst (Pd-His/SiO 2 ) for selective hydrogenation of acetylene was prepared by incipient wetness impregnation, followed by hydrogen reduction at 240 °C. The intense interaction between Pd and histidine greatly affects the structure and properties of Pd-His/SiO 2 . The Pd nanoparticles are highly dispersed on the support with an average diameter of 1.0 nm and positively charged. The use of histidine weakens the adsorption of acetylene and ethylene on the metal. Especially, the adsorption of di-σ-bonded ethylene is significantly impaired on the catalyst, which is beneficial to improve the ethylene selectivity. The conversion of acetylene is up to 100.0 % at 160 °C on Pd-His/SiO 2 while the ethylene selectivity reaches 81.5 %. A 50-hour test at 160 °C confirms the good stability of Pd-His/SiO 2 .
A series of silica supported Pd (Pd/SiO2) catalysts were prepared in various HCl concentrations (CHCl) of the impregnation solution with different electrostatic interactions between Pd precursor and support, and their catalytic properties were evaluated by the selective hydrogenation of nitrile butadiene rubber (NBR). The results show that with the CHCl increasing from 0.1 to 5 M, the particle size of Pd nanoparticles dramatically decreases from 24.2 to 5.1 nm and stabilizes at ∼5 nm when CHCl is higher than 2 M. Using the catalysts prepared with a high CHCl (>2 M), an excellent hydrogenation degree (HD) of ∼94% with 100% selectivity to C═C can be acquired under mild conditions. Interestingly, the HD could be remarkably increased from 65 to 92% by increasing only CCl– from 0.1 to 2 M with the addition of NaCl while keeping CH+ at 0.1 M. This is because PdCl42– is the predominant existing form of precursor at high CCl–, which has a strong electrostatic attraction with the positively charged support favorable for the formation of small-sized Pd nanoparticles over silica. Notably, Pd leaching behavior during the hydrogenation reaction is closely related to CH+, and the higher the CH+, the less Pd residues are detected in the hydrogenated NBR. Our contribution is to provide a facile strategy to synthesize effective and stable Pd/SiO2 catalysts via adjusting the electrostatic interaction, which exhibits a high activity and selectivity for NBR hydrogenation.
In this paper, the deactivation causes of the Pd/SiO 2 catalyst for continuous liquid-phase selective hydrogenation of 6,10,14-trimethylpentadeca-13-en-2-one in 2000 h of pilot plant test were systematically investigated by N 2 adsorption–desorption, thermogravimetric and differential thermal analyses, scanning electron microscope, transmission electron microscope, X-ray diffraction, X-ray fluorescence, experiments of CO poisoning and regeneration, and laboratory retests of the deactivated catalyst samples. The pore textures of Pd/SiO 2 catalysts were not destructed during the pilot test, while there were no obvious carbonaceous deposits appearing on the deactivated catalyst samples. The sintering and crystallization of Pd metal nanoparticles were found, which could be partially accountable for the deactivation of Pd/SiO 2 catalysts. Though Pd leaching did not take place in the pilot test, the Pd active phase could be slightly poisoned by sulfur impurities from feedstock hydrogen. Combining the results of CO poisoning and regeneration experiments with those of compositional analyses of fresh and circulating hydrogen in the pilot test, it could be concluded that CO poisoning should be another important reason for the deactivation of the Pd/SiO 2 catalyst due to high concentration of CO in the reaction system of pilot test and relatively low reaction temperature in the middle and at the bottom of the catalyst bed. Fortunately, the CO poisoned Pd/SiO 2 catalyst in the pilot test could be in situ regenerated by installing a purifier for CO elimination from the circulating hydrogen and increasing the temperature of the whole catalyst bed to slightly higher than 383 K.
Pore diffusion effect plays a crucial role in heterogeneous hydrogenation of unsaturated polymers. However, how large pore size can eliminate the pore diffusion limitation remains a controversial issue. Herein, we prepared a series of Pd/SiO 2 catalysts with graded pore sizes and investigated the effect of pore size on hydrogenation activity of nitrile butadiene rubber (NBR). It is found that when the catalyst pore size (D cat ) is 7 times of the diameter of NBR chains (D NBR ), the Weisz modulus Φ can be reduced to < 0.3 thus the internal mass transfer limitation can be eliminated, making NBR easier to approach the active sites. Consequently, the catalysts with the D cat /D NBR > 7 exhibit excellent catalytic activity (96.7%) and selectivity (100%) to C = C. This work emphasizes that the pore size of catalysts can regulate the pore transfer limitation and the accessibility of internal active sites, providing useful guidance for the design of efficient macromolecular hydrogenation catalysts.
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