The traditional industrial process for hydrogenation of benzoic acid to cyclohexanecarboxylic acid (CCA) has drawbacks of low-activity and fast deactivation of the Pd/C catalyst due to the poisoning of CO arising from the decarboxylation of CCA. A novel rapidly quenched skeletal NiCrFe promoter (RQ NiCrFe) is developed for the methanation of CO to harmless CH4. Evaluations in bench-scale autoclave and in traditional industrial equipment verified that RQ NiCrFe was very effective in promoting the activity of the Pd/C catalyst in the hydrogenation of benzoic acid. In order to solve the catalyst recycle and separation problem introduced by RQ NiCrFe, the industrial process was modified by incorporating a hydraulic cyclone and a magnetic separator to the separation unit. The modified process showed merits of lower costs of catalyst and operation, higher productivity, and better product purity than the traditional process.