Methanol production in an optimized dual-membrane fixed-bed reactor

Coupling reaction and separation in a membrane reactor improves the reactor efficiency and reduces purification cost in the following stages. This paper focuses on modeling and optimization of methanol production in a dual-membrane reactor. In this configuration, conventional methanol reactor is supported by Pd/Ag membrane tubes for hydrogen permeation and alumina–silica composite membrane tubes for water vapor removal from the reaction zone. A steady state heterogeneous one-dimensional mathematical model is developed to predict the performance of this novel configuration. In order to verify the accuracy of the model, simulation results of the conventional reactor is compared with available industrial plant data. The main advantages of the optimized dual-membrane reactor are: higher CO₂ conversion, the possibility of overcoming the limitation imposed by thermodynamic equilibrium, improvement of the methanol production rate and its purity. Genetic algorithm as an exceptionally simple evolution strategy is employed to maximize the methanol production as the objective function. This configuration has enhanced methanol production rate by 13.2% compared to industrial methanol synthesis reactor.     

Improved Design of the Lurgi Reactor for Methanol Synthesis Industry

Current studies are devoted to promote the production yield of the methanol synthesis process for treating large feed capacities in Algerian methanol manufacture industry by designing new reactor technologies. In order to achieve a high yield of methanol, the performance of methanol synthesis is improved by substituting the quench reactor by a new Lurgi reactor. The design of operating parameters of the Lurgi reactor involves the effect of CO₂ injection on methanol production yield and the catalyst deactivation. The simulation results demonstrate that under the same industrial operating conditions the conversion rate of reactants increases from 23 % in the quench reactor to 37 % in the Lurgi reactor and the methanol yield can be increased by 33 % when substituting the quench reactor by the Lurgi reactor     

The process design and simulation for the methanol production on the FPSO (floating production,storage and off-loading) system

A process for methanol production from 100 MM scfd of stranded gas and CO₂ is proposed and simulated using a commercial process simulator, PRO/II v.9.1, for a FPSO (floating production, storage, off-loading) system. The process consists of Steam-CO₂ Reforming (SCR), methanol synthesis, a Reverse Water-Gas Shift (RWGS) reaction and ancillaries with recycle streams to SCR and RWGS. All reactors were simulated using the Gibbs reactor model. Also, the Plug Flow Reactor (PFR) model with reaction rate equations was used for the methanol reactor and the result was compared to the Gibbs reactor model. To maximize the use of the carbon source in stranded gas and CO₂ while avoiding an undesirable increase in process size, the optimum recycle ratios were calculated with a satisfying constraint, a steam-to-carbon ratio ≥ 1 in the SCR. In the proposed Methanol-FPSO process the RWGS reactor can maximize CO₂ utilization and case studies were performed to analyze the influence of RWGS.     

Thermodynamic Analysis for Quantifying Fuel Cell Grade H2 Production by Methanol Steam Reforming

Steam reforming of methanol in fixed‐bed and hybrid reactors, namely, traditional fixed‐bed reactor (FBR1), fixed‐bed reactor with H₂‐selective membrane (FBR2), and fixed‐bed reactor with CO₂ adsorption (FBR3) is thermodynamically analyzed. The performance of these reactors is compared in terms of quality and quantity of H₂ production for fuel cell application. In FBR2 and FBR3, the contents of undesired products CO, CH₄, and carbon are highly reduced.     

Optimization-based identification of CO2 capture and utilization processing paths for life cycle greenhouse gas reduction and economic benefits

This paper introduces a mathematical formulation to identify promising CO₂ capture and utilization (CCU) processing paths and assess their production rates by solving an optimization problem. The problem is cast as a multi-objective one by simultaneously maximizing a net profit and life cycle greenhouse gas (GHG) reduction. Three case studies are illustrated using an exemplary CCU processing network. The results indicate the optimal solution is greatly influenced by the scale of CO₂ emission source, market demand, and hydrogen availability. Moreover, with the current system of measuring the GHG reduction regarding a business-as-usual level, if the aim is to achieve a GHG reduction within a national boundary, the question of whether CCU plants producing a product of same functionality through conventional means, which the CO₂-based product can replace, exists in the country can come into consideration. This systematic identification will assist decision-making regarding future R&D investment and construction of large-scale CCU plants.     

Sustainable Dimethyl Carbonate Production from Ethylene Oxide and Methanol

A large-scale dimethyl carbonate (DMC) production process from ethylene oxide (EO), CO₂, and methanol was simulated and optimized. Unlike most industrial processes of DMC production, the direct conversion of EO and CO₂ to ethylene carbonate (EC) and EC transesterification to DMC were performed in a single reactor. The reaction volume and the reactor operating pressure were selected as decision variables and evaluated. The key performance parameters, e.g., conversion per pass and CO₂ intensity, were compared with conventional commercialized routes or novel promising processes in the literature.     

CO2 utilization for methanol production; Optimal pathways with minimum GHG reduction cost

Mitigating CO₂ emissions from industries and other sectors of our economy is a critical component of building a sustainable economy. This paper investigates two different methanol synthesis routes based on CO₂ utilization (CO₂ capture and utilization [CCU], and tri-reforming of methane [TRM]), and compares the results with the conventional methanol production using natural gas as the feedstock (NG-MeOH). A comprehensive techno-economic analysis (TEA) model that includes the findings of the life cycle assessment (LCA) models of methanol production using various CO₂ utilization pathways is conducted. Economic analysis is conducted by developing a cost model that is connected to the simulation models for each production route. Compared to the conventional process (with a GHG emission of 0.6 kg CO₂/kg MeOH), the lifecycle GHG reduction of 1.75 and 0.41 kg CO₂/kg MeOH are achievable in the CCU and TRM pathways, respectively. Furthermore, the results indicate that, under current market conditions and hydrogen production costs, methanol production via CO₂ hydrogenation will result in a cost approximately three times higher than that of the conventional process. The integrated TEA–LCA model shows that this increased cost of production equates to a required life cycle GHG reduction credit of $279 to $422 per tonne of CO₂ utilized, depending on construction material and selected pathway. Additionally, when compared to the CO₂ hydrogenation route, the tri-reforming process (TRM-MeOH) can result in a 42% cost savings. Furthermore, a minimum financial support of $56 per tonne utilized CO₂ will be required to make the TRM-MeOH process economically viable.     

Wind und Kohle: Die technische Photosynthese

The increasing energy demand, the associated CO₂ emissions, and the concurrently decreasing reserves of fossil fuels require new concepts for sustainable energy production. The so‐called Adam‐and‐Eve principle for CO₂‐free production of methanol from coal and nuclear energy is revisited and adapted to today's circumstances. Electrolysis of water using renewable electricity is applied for H₂ production. Simultaneously, coal and the oxygen formed during electrolysis are burned in an oxyfuel process, generating electricity and relatively pure CO₂. Hydrogen from electrolysis and CO₂ are converted to methanol, which can then be used as chemical‐ and energy feedstock.     

Tailoring the Reactor Properties in the Small-Scale Sorption-Enhanced Methanol Synthesis

The performance of a fixed-bed and entrained flow reactor for the sorption-enhanced methanol synthesis from CO₂ is assessed by modelling. Both reactors achieve good performance but show possible drawbacks. The fixed bed reactor requires several units working in parallel, while the entrained flow reactor needs a large volume due to the high superficial particle velocity. We propose a new reactor type, which combines a circulating sorbent with a fluidized bed methanol catalyst in bubbling regime. This solution achieves high CO₂ conversion with high space velocity in a continuous manner.     

Increasing ethylene production as a high value hydrocarbon in Fischer-Tropsch (FT) reactor: A concept reactor for combining FT with oxidative coupling of methane

The paper proposes a concept configuration of reactors for coupling OCM and FTS, and presents systematic simulation results. FTS section is a combination of fixed bed and membrane fluidized bed reactor, and feed of the FT reactor is supplied by OCM. The reactor configuration is compared with the consecutive reactors of OCM and one fixed bed FT reactor. Effects of CH₄/O₂ ratio, percent of N₂ in the feed, contact time, and input temperature on the yield of ethylene and valuable hydrocarbons are studied. The results show that compared with one FTS reactor configuration, the dual FTS reactor configuration is more effective and thus gives much higher product yields. Furthermore, a main decrease is observed in the formation of CO₂ and CH₄.     

Sulfation Rates of Particles in Calcium Looping Reactors

The sulfation reaction rate of CaO particles in three reactors comprising a post‐combustion calcium looping system is discussed: a combustion chamber generating flue gases, a carbonator reactor to capture CO₂ and SO₂, and an oxy‐fired calciner to regenerate the CO₂ sorbent. Due to its strong impact on the pore size distribution of CaO particles, the number of carbonation/calcination cycles arises as a new important variable to understand sulfation phenomena. Sulfation patterns change as a result of particle cycling, becoming more homogeneous with higher number of cycles. Experimental results from thermogravimetric tests demonstrate that high sulfation rates can be measured under all conditions tested, indicating that the calcium looping systems will be extremely efficient in SO₂ capture.     

Effect of dielectric packing materials on the decomposition of carbon dioxide using DBD microplasma reactor

Carbon dioxide (CO₂) decomposition was performed at a normal atmosphere and room temperature in dielectric barrier discharge microplasma reactors to reduce CO₂ emissions and convert CO₂ into valuable chemical materials. The outlet gases, including CO₂, CO, and O₂, were analyzed with gas chromatography. The results indicated that the conversions of CO₂ in dielectric material‐packed reactors were all higher than that in nonpacked reactors. Particle size, dielectric constant, particle morphology, and acid‐base properties of the dielectric materials (including quartz wool, quartz sand, γ‐Al₂O₃, MgO, and CaO) all affected the CO₂ decomposition process. The conversion of CO₂ and energy efficiency achieved the highest values of 41.9 and 7.1% in a CaO‐packed reactor for the higher dielectric constant and basicity of CaO. Quartz wool was also an excellent dielectric packing material because its fiber structure provided rigid sharp edges. © 2014 American Institute of Chemical Engineers AIChE J, 61: 898–903, 2015     

Optimal design of combined cycle power plants with fixed-bed chemical-looping combustion reactors

Process intensification options are explored for near-carbon-neutral, natural-gas-fueled combined cycle (CC) power plants, wherein the conventional combustor is replaced by a series of chemical-looping combustion (CLC) reactors. Dynamic modeling and optimization are deployed to design CLC-CC power plants with optimal configuration and performance. The overall plant efficiency is improved by optimizing the CLC reactor design and operation, and modifying the CC plant configuration and design. The optimal CLC-CC power plant has a time-averaged efficiency of 52.52% and CO₂ capture efficiency of 96%. The main factor that limits CLC-CC power plant efficiency is the reactor temperature, which is constrained by the oxygen carrier material. CLC exhaust gas temperature during heat removal and gas compressor to gas turbine pressure ratio are the most important operating variables and if properly tuned, CLC-CC power plants can reach high thermodynamic efficiencies. © 2018 American Institute of Chemical Engineers AIChE J, 65: e16516 2019     

Mixed oxygen ionic-carbonate ionic conductor membrane reactor for coupling CO2 capture with in situ methanation

CO₂ methanation is one of the vital reactions to utilize CO₂ and realize power to gas process. To decrease the CO₂ capture cost and alleviate the hot spots during the strong exothermic methanation reaction, here, we report a coupling of CO₂ capture process with in situ CO₂ methanation process through a ceramic-molten carbonate (MC) dual phase membrane reactor over the Ni-based catalyst. The performance of the membrane reactor was systematically investigated and compared with the traditional fixed-bed reactor. The results show that the performance of the membrane reactor is higher than that of the fixed-bed reactor, since the produced steam through the methanation process can be partially removed through the dual-phase membrane, which promotes the reaction shift to right side. A stability test shows no obvious degradation within 32 h. These results indicate that the membrane reactor is promising for coupling CO₂ capture with in situ methanation process.     

Methanol synthesis from CO2 and H2 in multi-tubular fixed-bed reactor and multi-tubular reactor filled with monoliths

This work investigates the impact of catalyst structuring into particles or monoliths on methanol production from only CO₂ and H₂ at a large scale. Methanol synthesis in multi-tubular reactors is evaluated using packed-bed and monolithic reactors by modeling heat and mass transfer in each reactor. The obtained simulation results show that, at low gas hourly space velocity (GHSV = 10,000 h⁻¹), the performances of both reactor technologies are similar. In this case, the packed-bed reactor technology is the most appropriate technology due to its simplicity of installation and operation. At high GHSV (25,000 h⁻¹), the packed-bed reactor technology is limited by a considerable pressure drop that causes an important loss in productivity due to thermodynamic equilibrium, whereas the monolithic reactors exhibit negligible pressure drop and achieve far better performances.     

Dynamic modeling and operability analysis of a dual-membrane fixed bed reactor to produce methanol considering catalyst deactivation

The goal of this research is dynamic operability analysis of dual-membrane reactor considering catalyst deactivation to produce methanol. A dynamic heterogeneous one-dimensional model is developed to predict the performance of this configuration. In this configuration, a conventional reactor has been supported by a Pd/Ag membrane tube for hydrogen permeation and alumina–silica composite membrane tube to remove water vapor from the reaction zone. To verify the accuracy of the considered model, the results of conventional reactor are compared with the plant data. The main advantages of the dual-membrane reactor are: higher catalyst activity and lifetime, higher CO₂ conversion and methanol production.     

基于化学链燃烧的吸收剂引导的焦炉煤气水蒸气重整制氢过程模拟

建立了基于化学链燃烧供能的吸收剂引导的焦炉煤气水蒸气重整制氢系统,该系统包含吸收剂引导的焦炉煤气重整反应器（SECOGSR）、燃料反应器和空气反应器。该系统能产生高纯H₂［93.23%（mol）］,仅通过冷凝即可实现CO₂的捕获,分离能耗低。采用Aspen Plus软件对吸收剂引导的焦炉煤气重整制氢过程进行了模拟,得到优化的反应条件为：温度650℃,压力1.5 MPa,Ca/C=1,H₂O/C=4。并对系统进行了模拟,以NiO/Y₂O₃/ZrO₂(0.73/0.022/0.248,摩尔比）为化学链燃烧的载氧体和载能体,在满足反应器自热平衡和系统吸放热平衡的基础上,重整1mol焦炉煤气,燃料反应器和空气反应器所需的焦炉煤气、空气及载氧体NiO/Y₂O₃/ZrO₂的量分别为0.139、0.648、3.11 mol。该系统消耗1 mol焦炉煤气的产H₂量为1.30 mol,捕获的CO₂的量为0.355 mol。     

Design framework for dimethyl ether (DME) production from coal and biomass-derived syngas via simulation approach

A comprehensive thermodynamic study was conducted to evaluate the comparative efficacy of methanol and dimethyl ether (DME) synthesis using CO₂ rich syngas feed. The first part of our study included assessing the relative performances of the methanol synthesis system, two step DME synthesis system, and one step DME synthesis system in terms of the CO_x conversion and product yield (methanol/DME) based on the Gibbs free energy minimization approach. The wide range of composition of CO₂-enriched syngas feed produced by the coal and biomass gasification was simulated using Aspen Plus and the following evaluation parameters were analyzed for a broad parameter range: reaction temperature (180–280°C), reaction pressure (10–80 bar), stoichiometry number (SN) (0–11), and CO₂/(CO₂ + CO) molar feed ratio (0–1) for isothermal as well as adiabatic conditions. Based on the equilibrium yield, one-step DME synthesis was discovered as the most viable process to utilize the co-gasification derived syngas effectively. In the second part of our study, the overall process efficiency was inspected through the process design of 1 tonnes per day (TPD) DME plant inclusive of heat integration, resulting in significant CO₂ abatement and DME production with high product purity and minimum energy consumption. Consequently, one-step DME production via CO₂-enriched syngas obtained through the coal or biomass gasification process is identified as the leading technology based on energy utilization and CO₂ abatement.     

An optimization‐oriented green design for methanol plants

BACKGROUND: A new design for a methanol plant is proposed in which CO₂ addition, as one of the important parameters, is used to optimize the synthesis gas composition. An attempt has been made to assess the environmental features as well as the process operability of the proposed plant, in which the required CO₂ is provided from reformer flue gas. As a starting point, simulation of a conventional reference methanol case (RMC) and also the proposed green integrated methanol case (GIMC) are performed to obtain operational and kinetic parameters. In order to compare properly GIMC and RMC, the objective function is defined so that SynGas production, and thereby methanol production, in the GIMC is equal to that of the RMC. RESULTS: In the optimization the optimum values of decision variables are calculated using a genetic algorithm. In the best case, the eco‐efficiency indicators of GIMC would decrease to 330.3 kg CO₂ tonne^?1 MeOH, which is 15% lower than that of RMC. The environmental damage cost of 2.9 million dollars could also be prevented in GIMC when compared with RMC. CONCLUSION: It was found that the CO₂ needed in GIMC could be provided by an environmentally friendly process and that the GIMC is a cleaner process compared with RMC. Furthermore, the proposed GIMC would be capable of reducing CO₂ emission while its mitigation potential depends significantly on the type of solvent employed in the GIMC. The results obtained show that environmental damage cost would be important and should be considered in the process design. Copyright © 2012 Society of Chemical Industry     

Methanol synthesis in a novel axial-flow, spherical packed bed reactor in the presence of catalyst deactivation

Since in the foreseeable future liquid hydrocarbon fuels will play a significant role in the transportation sector, methanol might be used potentially as a cleaner and more reliable fuel than the petrochemical-based fuels in the future. Consequently, enhancement of methanol production technology attracts increasing attention and, therefore, several studies for developing new methanol synthesis reactors have been conducted worldwide. The purpose of this research is to reduce the pressure drop and recompression costs through the conventional single-stage methanol reactor. To reach this goal, a novel axial-flow spherical packed bed reactor (AF-SPBR) for methanol synthesis in the presence of catalyst deactivation is developed. In this configuration, the reactor is loaded with the same amount of catalyst in the conventional single-stage methanol reactor. The reactants are flowing axially through the reactor. The dynamic simulation of the spherical reactors has been studied in the presence of long-term catalyst deactivation for four reactor configurations and the results are compared with the achieved results of the conventional tubular packed bed reactor (CR). The results show that the three and four stages reactor setups can improve the methanol production rate by 4.4% and 7.7% for steady state condition. By utilizing the spherical reactors, some drawbacks of the conventional methanol synthesis reactors such as high pressure drop, would be solved. This research shows how this new configuration can be useful and beneficial in the methanol synthesis process.