Methanol Production Process Research Articles

Multi-objective optimization of ammonia and methanol production processes considering uncertain feedstock compositions of shale/natural gas

This paper presents a multi-objective optimization strategy for monetizing shale/natural gas to two important products: ammonia and methanol. This study considers the uncertainty associated with the composition of the feed shale/natural gas stream. The decision variables are the feed flow and the relative allocation of the feedstock to each process. Economic and environmental objectives are used in optimization. The economic objective is to maximize the net profit while considering revenue and production costs. The environmental objective is to minimize total annual CO2 emissions associated with providing the process with the required heat and power for the reformer and the compressors, respectively. Process simulation is carried out using Aspen HYSYS. The improved multi-objective differential evolution algorithm (I-MODE) is used for the optimization strategy. A random generator routine is developed for the creation of uncertain parameter values. The programs are linked through Visual Basic for Applications as a medium to exchange data. After applying the optimization strategy, the results showed an improvement in the objective functions, where the decision-maker can choose the point in a Pareto front according to the specific tradeoff of the targeted objectives. The results offer alternatives with an increase in the net benefit of up to 26.8% with only an increase in emissions of 4.5%.

FIEMA, a system of fuzzy inference and emission analytics for sustainability-oriented chemical process design

In the quest to achieve sustainable development goals, developments in sustainability-oriented chemical process design are key to innovation in the chemical industry, especially important for processes aiming for sustainable fuels. One of the greatest challenges is the difficulty of modeling the highly complex interactions among the design variables, such as catalyst technology attributes, and greenhouse gas emissions. Most of the computational aids crucial to deal with the complexity of chemical processes require data that is either unavailable or uncertain at an early stage of design. The multistage integrated system for sustainable design proposed in this paper boosts these computational aids by applying data science techniques to allow uncertainty to be handled more efficiently, thereby facilitating the modeling of the interactions between the properties of new materials or processes and sustainability indicators. In this system, current data connectivity methods are used to find paths of correlation among catalysts properties and greenhouse gas emissions. The key feature of the proposed system relies on the integration through multiple stages of Fuzzy Inference systems and a data-driven technique for Emissions Analytics, FIEMA.11FIEMA: Fuzzy Inference and Emission Analytics. The algorithm in FIEMA provides a semi-supervised learning approach to emission analytics: it determines data clusters by a C-means algorithm and subsequently builds fuzzy sets for multiple stages of input–output inference. The proposed FIEMA system was demonstrated in an effort to determine the optimal configurations of the properties of catalysts to minimize the probability of associated greenhouse gas emissions for a methanol production process. The results showed the potential of this approach to reduce the search space of catalyst material designs by suggesting promising configurations for oxygen storage capacity, mechanical strength, lifetime, size, and poisoning level. The research impacts of this study contribute to the development of clean fuels by a computationally-efficient system for early design, and by the determination of catalysts development paths that assure an actual reduction of the life-cycle emissions.

System-level analysis for continuous BTX production from shale gas over Mo/HZSM-5 catalyst: Promotion effects of CO2 co-feeding on process economics and environment

Benzene, toluene, and xylene (BTX) production from shale-derived CH4, C2H6, and C3H8 is considered an energy-efficient technology substituting their naphtha-cracking counterparts. However, the economics of BTX production from shale gas remains questionable because of the rapid deactivation of the catalyst, originating from the coke generation. Herein, we present a BTX production strategy with CO2 co-feeding for catalyst stability enhancement and additional H2 production. Our process prevents coke deposition on the active sites of Mo and zeolite, and improves the operation time of reactors compared to that of shale gas without CO2 co-feeding. Concurrently, H2 and CO are produced with BTX owing to the dry reforming reaction of hydrocarbons over the Mo/HZSM-5 catalyst. Most importantly, the economics of BTX production with CO2 co-feeding is evaluated using individual system components integrated with two different CH4 conversion processes (steam-reforming-based H2 and methanol production). The BTX production with CO2 co-feeding lowers the methanol production cost by additionally producing methanol generated by CO from the BTX reactor, while the H2 production cost increases. Moreover, the life cycle assessment proves that the CO2 emission during the methanol production process is significantly reduced by recycling the CO2 produced in the subsequent process.

Business Model Development for a High-Temperature (Co-)Electrolyser System

There are increasing international efforts to tackle climate change by reducing the emission of greenhouse gases. As such, the use of electrolytic hydrogen as an energy carrier in decentralised and centralised energy systems, and as a secondary energy carrier for a variety of applications, is projected to grow. Required green hydrogen can be obtained via water electrolysis using the surplus of renewable energy during low electricity demand periods. Electrolysis systems with alkaline and polymer electrolyte membrane (PEM) technology are commercially available in different performance classes. The less mature solid oxide electrolysis cell (SOEC) promises higher efficiencies, as well as co-electrolysis and reversibility functions. This work uses a bottom-up approach to develop a viable business model for a SOEC-based venture. The broader electrolysis market is analysed first, including conventional and emerging market segments. A further opportunity analysis ranks these segments in terms of business attractiveness. Subsequently, the current state and structure of the global electrolyser industry are reviewed, and a ten-year outlook is provided. Key industry players are identified and profiled, after which the major industry and competitor trends are summarised. Based on the outcomes of the previous assessments, a favourable business case is generated and used to develop the business model proposal. The main findings suggest that grid services are the most attractive business sector, followed by refineries and power-to-liquid processes. SOEC technology is particularly promising due to its co-electrolysis capabilities within the methanol production process. Consequently, an “engineering firm and operator” business model for a power-to-methanol plant is considered the most viable option.

Concept design, technical performance, and GHG emissions analysis of petroleum coke direct chemical looping hydrogen highly integrated with gasification for methanol production process

Petroleum coke gasification for methanol production process has excellent application prospects for the clean utilization of high‑sulfur coke while limiting pollutant emissions from coke combustion. However, the process still suffers from high-energy use and a large CO2 generation caused by composition adjustment. This study proposes a novel petroleum coke chemical looping hydrogen-assisted gasification process for methanol production. Mass-energy coupling is realized by replacing the water gas shift unit with the chemical looping hydrogen unit, and the high temperature gasified gas heats the fuel reactor and in turn the feedstock. Two chemical looping hydrogen scenarios with an operating pressure of 3.0 and 0.1 MPa are considered. The methanol exergy can be increased from 484 to 1030 and 1028 MW by doubling the petroleum coke consumption through the chemical looping integration. The exergy efficiency of the new process is correspondingly increased from 51.6 to 57.1 and 55.2 % with 63.02 and 63.71 % reductions in direct CO2 emissions, as compared to the only gasification route. The calculated life cycle energy consumption and greenhouse gases emissions of the new processes are 40.02/43.84 GJ/t and 693/1055 kg CO2 eq/t, 15.14/7.05 % and 49.09/22.45 % lower than that of the benchmark process. The integration of high-pressure chemical looping technology can introduce significant technical and environmental benefits for methanol production from the petroleum coke.

Solar energy exploitation and storage in a novel hybrid thermo-electrochemical process with net-zero carbon emissions

The remarkable growth in global energy demand and greenhouse gas emissions necessitates the development of methods for efficient and reliable exploitation of sustainable and carbon-neutral energy sources. Chemical hydrogen storage is one of the efficient methods for converting renewable energy into valuable fuels for energy storage and transportation. This paper designs a novel hybrid process for simultaneous production of liquid methanol, ammonia, and heavy hydrocarbons using the combustion products of hydrocarbons emitted from industrial plants and methane. It mainly consists of several subprocesses including thermo-electrochemical cycle, CO2 capture, ammonia and liquid methanol production, and gas to liquid (GTL). CO2 is captured and utilized for the production of liquid methanol. Photovoltaic panels and parabolic trough collectors provide electrical and part of the thermal required in the process. The structure produces 17.95 kg h−1 methanol, 45.54 kg h−1 heavy hydrocarbons, and 20.44 kg h−1 ammonia. The thermal efficiencies of the methanol production cycle, GTL cycle, and the hybrid structure are 86.64%, 51.06%, and 15.00%, respectively. Exergy analysis indicates that photovoltaic panels have the maximum exergy destruction share (71.09%) followed by reactors (18.72%). Sensitivity analysis results show that the decline in the mass flow rate of methane from 9 to 5 kg h−1 leads to an increase in the integrated structure's total thermal and exergy efficiencies to 18.28% and 28.54%, respectively. Besides, a decrease in the mass flow rate of CO2 from 30 to 10 kg h−1 raises the exergy efficiency of the integrated structure to 21.99%. The methanol production rate and exergy efficiency of the methanol production cycle are reduced to 6.932 kg h−1 and 34.62%.

Reaction mechanisms and catalysis in the one-step synthesis of methylal via methanol oxidation

This paper reports on the scaling-up of a one-step methanol production process from the laboratory scale to the pilot scale. This lays the foundation for the industrialization of a one-step process for preparing dimethoxymethane (DMM) from methanol. The results of the stability tests indicate that the Fe–Mo/HZSM-5(80) catalyst has high stability and resistance to carbon build-up, and that the circulating fluidized bed has a good regeneration effect. In addition, in-situ DRIFTS was used to investigate the effects of the reaction time, Mo–Fe ratio, and carrier Si–Al ratio on the reaction and product distribution. It was found that the synergistic effect of oxidation centres and acid centres was the fundamental basis for the excellent catalytic performance of the Fe–Mo/HZSM-5 (80) catalyst. Further, the reaction mechanisms underlying the one-step synthesis of methylal via methanol oxidation were proposed.

Comparative Techno-economic analysis of methanol production via carbon dioxide reforming of landfill gas using a highly active and stable Nickel-based catalyst

The economic viability of a methanol production process through carbon dioxide reforming of landfill gas using a newly developed nickel-based catalyst was assessed. The development of the catalyst and techno-economic analysis of the designed process were targeted. The nickel-based catalyst showed a highly active and stable performance even at an extremely high gas hourly space velocity of 1,620,000 mL g−1h−1. The high activity of the catalyst was due to the abundant nickel active sites (metallic nickel particles) on its surface. Coke formation was suppressed by the small particle size of nickel and relatively high oxygen storage capacity, resulting in a stable catalytic performance. In the process simulation, the methanol production system based on the nickel-based catalyst (new process) leveraged its smaller reformer size and more efficient heat utilization compared to those of a previously reported system based on a rhodium-based catalyst (base process) because of its higher gas hourly space velocity. The process simulation was conducted based on the gas hourly space velocity of 312,346 mL g−1h−1. The unit production costs of methanol were reduced from 184.0 $ ton−1 in the base process to 117.5 $ ton−1 in the new process. In addition, profitability analysis based on the global market price of methanol demonstrated that the new process exhibited a positive net present value, indicating economic feasibility, whereas the base process was not viable in the worst-case scenario (lowest market price of methanol).

Techno-economic analysis of integrated hydrogen and methanol production process by CO2 hydrogenation

Global climate change is one of the major concerns of today's world. Indeed, the carbon capture and sequestration (CCS) has a great potential to abate global climate changes but the economic infeasibility of this process has motivated the researchers to develop methods for direct utilization of captured carbon dioxide (CO2) to value-added end products. For instance, the methanol production by hydrogenation of CO2 is extensively investigated for over two decades but the high operating cost of this process, especially for hydrogen production, has discouraged its commercial implementation. In this work, a high temperature solid oxide electrolyzer (SOE) as a source of hydrogen production (12.16 ton/hr) from steam is integrated with the CO2 hydrogenation process to reduce the cost of methanol production. Integration of SOE with methanol production process resulted into 22.3% reduction in the cost of hydrogen as compared to the alkaline water electrolyzer. Consequently, the cost of 63.5 ton/hr methanol production was reduced, from 1063 $/ton to 701.5 $/ton, by employing SOE and optimizing the process flowsheet (by considering seven different configurations of the flowsheet, along with heat and process integrations). It is anticipated that a further reduction in the cost of methanol production by aforementioned process is possible by the advancement of hydrogen production technology, especially the high performance materials development and commercialization of electrolyzers.

New Integrated Process for the Efficient Production of Methanol, Electrical Power, and Heating

In this paper, a novel process is developed to cogenerate 4741 kg/h of methanol, 297.7 kW of electricity, and 35.73 ton/h of hot water, including a hydrogen purification system, an absorption–compression refrigeration cycle (ACRC), a regenerative Organic Rankine Cycle (ORC), and parabolic solar troughs. The heat produced in the methanol reactor is recovered in the ORC and ACRC. Parabolic solar troughs provide thermal power to the methanol distillation tower. Thermal efficiencies of the integrated structure and the liquid methanol production cycle are 78.14% and 60.91%, respectively. The process’s total exergy efficiency and irreversibility are 89.45% and 16.89 MW. The solar thermal collectors take the largest share of exergy destruction (34%), followed by heat exchangers (30%) and mixers (19%). Based on the sensitivity analysis, D17 (mixture of H2 and low-pressure fuel gas before separation) was the most influential stream affecting the performance of the process. With the temperature decline of stream D17 from −139 to −149 °C, the methanol production rate and the total thermal efficiency rose to 4741.2 kg/h and 61.02%, respectively. Moreover, the growth in the hydrogen content from 55% to 80% molar of the feed gas, the flow rate of liquid methanol, and the total exergy efficiency declined to 4487 kg/h and 86.05%.

Flexible Methanol Production Process Using Biomass/ Municipal Solid Waste and Hydrogen Produced by Electrolysis and Natural Gas Pyrolysis

Flexible Methanol Production Process Using Biomass/ Municipal Solid Waste and Hydrogen Produced by Electrolysis and Natural Gas Pyrolysis

Life cycle assessment of methanol production by natural gas route

Climate change is becoming a major concern worldwide, and sustainable development of the processes is becoming ever so important. Being one of the largest chemical commodities produced and consumed worldwide, the sustainability study of the methanol production process was conducted using a life cycle assessment approach. The natural gas route was selected for this study. The ‘Cradle to Gate’ approach was used to calculate the impact associated with the methanol produce from raw material extraction to the final product. To assess hotspots, the process was divided into 5 sub-sections. The reforming process resulted in a higher carbon footprint. The distillation and synthesis sections were the major contributor to ecological as well as human toxicity. Coal-based electricity production created a higher impact compared to other conventional and non-conventional energy sources. Based on our analysis, the recommendations are given based on several materials and impact categories such as electricity consumption, catalyst regeneration, metal extraction, and processing to make methanol production more environmentally sustainable.

Pressurized chemical looping methane reforming to syngas for efficient methanol production: Experimental and process simulation study

This study investigates the potential of applying pressurized chemical looping reforming (CLR) mechanism for syngas to methanol production process combining of experimental demonstration of methane reforming to syngas and simulation for integration in methanol production. The experimental study was conducted using the internally circulating reactor (ICR) that was specially designed to enable pressurized CLR operation where several experimental cases were completed using a NiO-based oxygen carrier. Up to 4 kW of methane feed was reformed to syngas, achieving high conversion efficiencies and high syngas recovery and purity at pressurized conditions up to 4 bar. Co-feeding H2O or CO2 was found to affect mainly the H2/CO ratio. The simulation study evaluated the potential of integrating the CLR process for large scale methanol production through comprehensive thermodynamic analysis using Aspen plus. The results revealed that CLR-based methanol plant is a highly attractive pathway achieving higher methanol production efficiency outperforming the conventional autothermal reforming (ATR) -based plant by ∼5% efficiency. The main benefits of the CLR-based system is the avoidance of the air separation unit required for ATR plants, and the extra power generation through the gas turbine utilizing the hot exhaust gas of the air reactor. A detailed sensitivity study was also conducted to study the effects of the CLR operating pressure, and the reduced syngas purity caused by possible gas leakage in the ICR, on the overall methanol plant performance.

Incorporating the occupational health in the optimization for the methanol process

The analysis of social aspects, such as occupational health, is as important as economic and environmental criteria in the design of sustainable chemical processes. Occupational health analyzes the relationship between work and health while enabling the identification of hazards that can cause injuries due to chronic exposure of the workers. This paper presents a multi-objective optimization approach for the methanol production process from natural/shale gas, different alternatives are proposed for the process configurations based on different equipment and technologies. The objective functions consist of maximizing the net profit, minimizing the total annual CO2 emissions, and minimizing the occupational health hazard. The Process Route Healthiness Index is used to evaluate occupational health. The process model is developed using the Aspen HYSYS® process simulator. To carry out the optimization, a metaheuristic algorithm is used; the improved multi-objective differential evolution (I-MODE) algorithm was used with programming in Microsoft Excel visual basic for applications. Linking routines are established to enable the transfer of values of the process variables. A set of decision variables are established in a search interval whose manipulation has a considerable impact on the performance of the objective functions. The results offer feasible alternatives for the values of the search variables and show a considerable improvement in the specified objective functions. Different scenarios are proposed to prioritize each of the objectives for which the decision-maker can make a selection of the best values and the configuration that best suits specific interests.

The Economic Evaluation of Methanol and Propylene Production from Natural Gas at Petrochemical Industries in Iran

This investigation scrutinizes the economic features and potential of propylene and methanol production from natural gas in Iran because greenhouse gas emissions released by natural gas-based production processes are lower than coal-based ones. Considering the advantage of Iran’s access to natural gas, this study evaluates and compares the economic value of different plans to complete the value chain of propylene production from natural gas and methanol in the form of four units based on three price scenarios, namely, optimistic, realistic, and pessimistic, using the COMFAR III software. Iran has been ranked as the second most prosperous country globally based on its natural gas reserves. Methanol and propylene production processes via natural gas will lower the release of greenhouse gas. This, increasing the investment and accelerating the development of methanol and propylene production units driven by natural gas will lead the world to a low emission future compared to coal-based plants. The economic evaluation and sensitivity analysis results revealed that the conversion of methanol to propylene is more attractive for investment than the sale of crude methanol. The development of methanol to propylene units is more economical than constructing a new gas to propylene unit because of the lower investment costs.

Techno-economic assessment and early-stage screening of CO2 direct hydrogenation catalysts for methanol production using knowledge-based surrogate modeling

We herein report the development of a new knowledge-based assessment platform for the early-stage screening of carbon dioxide (CO2) direct hydrogenation catalysts. To accomplish this goal, a new methanol production process was simulated via CO2 direct hydrogenation by employing knowledge-based surrogate models. In the proposed platform, the sizing and costing information, as well as the mass and energy balances, were determined based on selected key variables, including the CO2 feed amount, the conversion and selectivity of the catalyst, the temperature and pressure of the reaction, and the vent-out fraction. Four evaluation criteria, including the unit production cost, the carbon and energy efficiencies, and the reduction of CO2, were applied to assess the technical, economic, and environmental capabilities of the methanol production process. As a motivating example, we analyzed the energy efficiency and economics of the methanol production process using a Cu/Zn/Al/Zr catalyst at different operating temperatures and pressures. We then applied the assessment platform to 38 CO2 hydrogenation catalysts reported in the literature to analyze the technical and economic merits and barriers that are required to establish R&D goals and directions in the early R&D stages of catalyst discovery.

Techno-Economic and Carbon Footprint Analyses of a Coke Oven Gas Reuse Process for Methanol Production

This paper focuses on the best way to produce methanol by Coke Oven Gas (COG) conversion and by carbon dioxide capture. The COG, produced in steelworks and coking plants, is an interesting source of hydrogen that can be used to hydrogenate carbon dioxide, recovered from flue gases, into methanol. The architecture of the reuse process is developed and the different process units are compared by considering a hierarchical decomposition. Two case studies are selected, process units are modelled, and flowsheets are simulated using computer-aided design software. A factorial techno-economic analysis is performed together with a preliminary carbon balance to evaluate the economic reliability and the environmental sustainability of the proposed solutions. The production costs of methanol are equal to 228 and 268 €/ton for process configurations involving, respectively, a combined methane reforming of COG and a direct COG separation to recover hydrogen. This cost is slightly higher than the current price of methanol on the market (about 204 €/ton for a process located in the USA in 2013). Besides, the second case study shows an interesting reduction of the carbon footprint with respect to reference scenarios. The carbon dioxide capture from flue gases together with COG utilization can lead to a competitive and sustainable methanol production process depending partly on a carbon tax.

CO2 utilization for methanol production; Part I: Process design and life cycle GHG assessment of different pathways

The process design and life cycle assessment (LCA) of various methanol production processes, including the conventional natural gas reforming process and alternative CO2 utilization-based pathways, are performed in this work. Three main technologies are considered for the CO2 conversion to methanol: direct CO2 hydrogenation, dry reforming and tri-reforming of methane. For each pathway, a process simulation that includes the CO2 capture from typical flue gas of a cement kiln, the methanol synthesis and purification steps, is performed using the Aspen engineering suite. In addition, for each process, several heat integration measures are considered to maximize thermal efficiency. According to the simulation results, the thermal efficiency of the direct CO2 hydrogenation process (47.8 % LHV) is higher than the dry reforming (40.6 % LHV) while it is lower than the conventional (68.4 % LHV) and tri-reforming (57.9 % LHV) processes. The LCA results showed that the direct CO2 hydrogenation pathway is an environmentally friendly option, only when the electricity GHG intensity is lower than 0.17 kg CO2 equivalent per kWh of electricity. As a result, in the context of Canada, the CO2 hydrogenation options can be recommended only for the provinces where low-carbon electricity is available, such as Quebec, British Columbia, Manitoba and Ontario.

Techno-Economic and Environmental Analysis for Direct Catalytic Conversion of CO2 to Methanol and Liquid/High-Calorie-SNG Fuels

Catalytic hydrogenation of CO2 has great potential to significantly reduce CO2 and contribute to green economy by converting CO2 into a variety of useful products. The goal of this study is to assess and compare the techno-economic and environmental measures of CO2 catalytic conversion to methanol and Fischer–Tropsch-based fuels. More specifically, two separate process models were developed using a process modeler: direct catalytic conversion of CO2 to Fischer–Tropsch-based liquid fuel/high-calorie SNG and direct catalytic conversion of CO2 to methanol. The unit production cost for each process was analyzed and compared to conventional liquid fuel and methanol production processes. CO2 emissions for each process were assessed in terms of global warming potential. The cost and environmental analyses results of each process were used to compare and contrast both routes in terms of economic feasibility and environmental friendliness. The results of both the processes indicated that the total CO2 emissions were significantly reduced compared with their respective conventional processes.

Economically feasible thermochemical process for methanol production from kenaf

This paper presents a thermochemical process design and techno-economic analysis for the production of methanol (MeOH) from Kenaf cultivated in Korea. The proposed process combines three main subsystems to allow for the processing of 2000 tons of kenaf a day: kenaf-to-syngas, syngas-to-MeOH, and a combined heat and power cycle. In the first subsystem, clean syngas is produced from kenaf via a two-step carbonization and steam gasification process. The clean syngas is then catalytically upgraded to MeOH using a commercial Cu/ZnO/Al2O3 catalyst. The third subsystem allows for the generation of heat and electricity to close the energy balance by combusting the biomass residues. Energy analysis and optimization of the heat exchanger network allowed for all energy requirements to be satisfied internally, high overall energy efficiency (60.6%), and the selling of 3.3 MW of excess electricity. Furthermore, an economic feasibility analysis of the process showed that the minimum selling price of MeOH (99.9 wt%) was 0.413 US$/kgMeOH. Importantly, the process economics could be in the range of the market price with respect to incorporating different types of H2 production technology into the process.