Desulfurization of Petroleum Components with Hydrogen Permeated through Metal

在这项研究中，我们建造了一个钯膜反应器，并研究了氢透过膜的反应，作为一种独特的试剂，用于脱除石油馏分中的杂原子。(1)膜反应器：该反应器由两个刀口法兰组成，在两个刀口法兰之间放置一层厚度为0.05 mm的薄钯膜，并在其间放置一个铜垫片。该膜将反应器分成两部分。通过在一段中引入氢，在另一段中引入反应物，使氢原子透过钯膜而发生反应(渗透氢)。(2)渗透氢的反应性：比较了渗透氢与反应物混合提供的反应性(吸附氢)的反应性。结果表明，渗透氢对吡啶加氢和噻吩加氢脱硫的催化活性高于吸附氢。氢气压力越高，这种差异就越明显。在573~673K温度范围内，噻吩氢的渗透和吸附活化能分别为32kcal/mol和42kcal/mol。这些结果表明，通过膜提供的氢原子处于不同于正常吸附方式的状态。

In this study, we constructed a palladium membrane reactor and investigate the reaction of hydrogen permeated through membrane, which is expected to have a unique feature as a reagent, for the elimination of hetero-atoms from petroleum fractions.(1) The membrane reactor : The reactor consisted of two knife-edge flanges between which a thin palladium membrane, 0.05 mm thick, was put with a copper gasket. The membrane divided the reactor into two parts. By introducing hydrogen in one part and the reactant in other part, the reaction of hydrogen atoms supplied by permeating through the palladium membrane (permeated hydrogen) was followed.(2) The reactivity of permeated hydrogen : The reactivity of permeated hydrogen was compared with those supplied by mixing with the reactants (adsorbed hydrogen). The permeated hydrogen showed an activity higher than that of the adsorbed hydrogen for hydrogenation of pyridine and hydrodesulfurization of thiophene. The difference was more marked at higher pressures of hydrogen. The activation energies of hydrodesulfurization of thiophene in a temperature range of 573-673 K were 32 and 42 kcal/mol for permeated and adsorbed hydrogen, respectively. These results suggest that the hydrogen atoms supplied through the membrane are in a state different from those adsorbed by normal manner.