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Kinetic Investigation on Selective CO2 Hydrogenation to Formic Acid over Rhodium Hydrotalcite (Rh-HT) Catalyst

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Abstract

A heterogeneous catalyst, rhodium hydrotalcite (Rh-HT), was synthesized, characterized, and explored for kinetic studies for the hydrogenation of CO2 to formic acid using molecular hydrogen in an autoclave. The catalyst was efficient for the selective formation of formic acid at a moderate temperature with up to 5 catalytic cycles without any significant loss in catalytic activity. The detailed kinetic investigations were performed by determining the rate of formic acid formation as a function of time, catalyst amount, total pressure, partial pressure of CO2, partial pressure of H2, reaction volume, v/v ratio of the mixed solvent of methanol and water, agitation speed, and temperature in a wide range of variation. The rates were found to be dependent on all these parameters. The formic acid formation rate followed the first-order kinetics with respect to the partial pressures of CO2 and H2, and catalyst amount. The best reaction conditions obtained from the kinetic parametric optimisation were, 50 bar total pressure (1/1 p/p, CO2 and H2); 60°C temperature; a mixture of methanol:water solvent (5/1 v/v, 60 mL); 24 h time; and 500 rpm agitation speed to get a TON of 15840 for formic acid with no additional base. The thermodynamic performance of the heterogeneous catalyst Rh-HT was appreciably associated with highly negative entropy. The performance of the catalyst was effectively enhanced by the mixture of water and methanol as a solvent. The mechanistic routes for CO2 hydrogenation to formic acid are proposed and discussed based on the kinetic and experimental observations involving the role of the molecular effect of water used in the solvent.

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Funding

CSMCRI communication no. IMC 03, CSIR-CSMCRI–56/2022. The authors thank the Council of Scientific and Industrial Research (CSIR), New Delhi, India for the financial support through the Network Project on Clean Coal Technology (Tap Coal, CSC 0102) and the Analytical Division and Central Instrumentation Facility of CSIR Central Salt and Marine Chemicals Research Institute, Bhavnagar, for providing instrumental analysis.

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Authors and Affiliations

  1. Inorganic Materials and Catalysis Division, Council of Scientific and Industrial Research (CSIR), Central Salt and Marine Chemicals Research Institute, G.B. Marg, 364002, Bhavnagar, Gujarat, India

    Minaxi S. Maru, Sanwala Ram & Ram S. Shukla

  2. Academy of Scientific and Innovative Research (AcSIR), Council of Scientific and Industrial Research (CSIR), Central Salt and Marine Chemicals Research Institute, G.B. Marg, 364002, Bhavnagar, Gujarat, India

    Sanwala Ram & Ram S. Shukla

  3. Department of Chemical Sciences, P.D. Patel Institute of Applied Sciences – PDPIAS, Charotar University of Science and Technology, 388421, Changa, Anand, Gujarat, India

    Minaxi S. Maru

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Abbreviations and notation: HT, hydrotalcite; Rh-HT, rhodium hydrotalcite; RRh-HT, recycled rhodium hydrotalcite catalyst; RWGS, reverse water gas shift; PXRD, powder X-ray diffraction; FT-IR, Fourier-transform infrared spectroscopy; BET, Brunauer–Emmett–Teller method; XPS, X-ray photoelectron spectroscopy; ICP, inductive coupled plasma; HPLC, high-performance liquid chromatography; FE-SEM/EDX, field emission scanning electron microscopy with energy-dispersive X-ray spectroscopy; TON, number of moles of product formed per mole of rhodium in catalyst.

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Fig. A-1.
figure 12

HPLC diagrams of formic acid formed by the hydrogenation of CO2 (a) and standard formic acid solution (b).

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Fig. A-2.
figure 13

SEM-EDX graph of Rh-HT catalyst.

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Maru, M., Ram, S. & Shukla, R.S. Kinetic Investigation on Selective CO2 Hydrogenation to Formic Acid over Rhodium Hydrotalcite (Rh-HT) Catalyst. Kinet Catal 64, 276–293 (2023). https://doi.org/10.1134/S0023158423030060

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