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In the second part of this paper (Part II), the potentials and characteristics of an industrial-scale Oxidative Coupling of Methane (OCM) process integrated with CO2-hydrogenation, ethane dehydrogenation, and methane reforming processes are highlighted. This novel process concept comprises a direct conversion of methane to ethane and ethylene and further conversion of the resulted carbon dioxide and remaining unreacted methane, respectively, to methanol and syngas. In this context, the selected experimental results of the catalytic CO2-hydrogenation to methanol reported in the first part of this paper (Part I), were utilized to represent its industrial-scale performance. The experimental results of the mini plant-scale operation of an OCM reactor and CO2 removal units along with the experimental and industrial data available for representing the operation and performance of all process-units in the integrated process structures were utilized to perform a comparative techno-economic environmental analysis using Aspen-Plus simulation and an Aspen Economic Process Analyzer. The experimental procedure and the results of testing the sequence of OCM and CO2-hydrogenation reactors are particularly discussed in this context. It was observed that in the sequential operation of these reactors, ethylene will be also hydrogenated to ethane over the investigated catalysts. Therefore, the parallel-operation of these reactors was found to be a promising alternative in such an integrated process. The main assumptions and the conceptual conclusions made in this analysis are reviewed and discussed in this paper in the light of the practical limitations encountered in the experimentations. In the context of a multi-scale analysis, the contributions of the design and operating parameters in the scale of catalyst and reactor as well as in the process-scale represented by analyzing the type and operating conditions of the downstream-units and the process-flowsheets on the economic and environmental performance of the integrated process structures were studied. Moreover, the economic impacts of extra ethylene and methanol produced respectively via the integrated ethane dehydrogenation and CO2-hydrogenation sections were analyzed in detail. The required capital investment was found to be even smaller than the yearly operating cost of the plant. The environmental impacts and sustainability of the integrated OCM process were found to be enhanced by securing a minimum direct CO2-emission and energy-efficient conversion of CO2 and the unreacted CH4, respectively, to methanol and syngas. Besides producing such value-added by-products, efficient operation of downstream process-units was secured by minimizing the energy usage and ethylene losses. Under the considered conditions in this analysis, the specifications of the finally selected integrated OCM process structure, providing the fastest return of investments (less than 8 years), are highlighted.

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A multi-aspect analysis of low-pressure catalytic hydrogenation of CO2 for methanol production is reported in the first part (part I) of this paper. This includes an extensive review of distinguished low-pressure catalytic CO2-hydrogenation systems. Specifically, the results of the conducted systematic experimental investigation on the impacts of synthesis and micro-scale characteristics of the selected Cu/ZnO/Al2O3 model-catalysts on their activity and stability are discussed. The performance of the investigated Cu/ZnO/Al2O3 catalysts, synthesized via different methods, were tested under a targeted range of operating conditions in this research. Specifically, the performances of these tested Cu/ZnO/Al2O3 catalysts with regard to the impacts of the main operating parameters, namely H2/CO2 ratio (at stoichiometric -3-, average -6- and high -9- ratios), temperature (in the range of 160–260 °C) and the lower and upper values of physically achievable gas hourly space velocity (GHSV) (corresponding to 200 h−1 and 684 h−1, respectively), were analyzed. It was found that the catalyst prepared by the hydrolysis co-precipitation method, with a homogenously distributed copper content over its entire surface, provides a promising methanol yield of 21% at a reaction temperature of 200 °C, lowest tested GHSV, highest tested H2/CO2 ratio (9) and operating pressure (10 bar). This is in line with other promising results so far reported for this catalytic system even in pilot-plant scale, highlighting its potential for large-scale methanol production. To analyze the findings in more details, the thermal-reaction performance of the system, specifically with regard to the impact of GHSV on the CO2-conversion and methanol selectivity, and yield were experimentally investigated. Moreover, the stability of the selected catalysts, as another crucial factor for potential industrial operation of this system, was tested under continual long-term operation for 150 h, the reaction-reductive shifting-atmospheres and also even after introducing oxygen to the catalyst surface followed by hydrogen reduction-reaction tests. Only the latter state was found to affect the stable performance of the screened catalysts in this research. In addition, the reported experimental reactor performances have been analyzed in the light of equilibrium-based calculated achievable performance of this reaction system. In the performed multi-scale analysis in this research, the requirements for establishing a selective-stable catalytic performance based on the catalyst- and reactor-scale analyses have been identified. This will be combined with the techno–economic performance analysis of the industrial-scale novel integrated process, utilizing the selected catalyst in this research, in the form of an add-on catalytic system under 10 bar pressure and H2/CO2 ratio (3), for efficiently reducing the overall CO2-emission from oxidative coupling of methane reactors, as reported in the second part (part II) of this paper.