MeOH Production Research Articles

Lifecycle assessment of methanol production from blast furnace gas.

A technological scenario configuration for producing methanol (MeOH) from blast furnace gas (BFG) with natural gas (NG)-based energy generation was evaluated by a rigorous life cycle assessment. The new BFG scenario was compared to a conventional BFG scenario-BFG energy generation with NG-based MeOH production. In all, 18 environmental impact categories were estimated for both technological BFG scenario configurations on a conceptual plant level. The results of a case study in South Korea indicated that the new BFG scenario performs better for 12 environmental impacts (20-97% lower), but fossil resource depletion is worse because NG is used for the displacement of energy generation. The robustness of the environmental impact results for the new BFG scenario was supported by a case study, which highlighted that the primary source for the displacement of energy generation is crucial.

Neighboring Zn-Zr Sites in a Metal-Organic Framework for CO2 Hydrogenation.

ZrZnOx is active in catalyzing carbon dioxide (CO2) hydrogenation to methanol (MeOH) via a synergy between ZnOx and ZrOx. Here we report the construction of Zn2+-O-Zr4+ sites in a metal-organic framework (MOF) to reveal insights into the structural requirement for MeOH production. The Zn2+-O-Zr4+ sites are obtained by postsynthetic treatment of Zr6(μ3-O)4(μ3-OH)4 nodes of MOF-808 by ZnEt2 and a mild thermal treatment to remove capping ligands and afford exposed metal sites for catalysis. The resultant MOF-808-Zn catalyst exhibits >99% MeOH selectivity in CO2 hydrogenation at 250 °C and a high space-time yield of up to 190.7 mgMeOH gZn-1 h-1. The catalytic activity is stable for at least 100 h. X-ray absorption spectroscopy (XAS) analyses indicate the presence of Zn2+-O-Zr4+ centers instead of ZnmOn clusters. Temperature-programmed desorption (TPD) of hydrogen and H/D exchange tests show the activation of H2 by Zn2+ centers. Open Zr4+ sites are also critical, as Zn2+ centers supported on Zr-based nodes of other MOFs without open Zr4+ sites fail to produce MeOH. TPD of CO2 reveals the importance of bicarbonate decomposition under reaction conditions in generating open Zr4+ sites for CO2 activation. The well-defined local structures of metal-oxo nodes in MOFs provide a unique opportunity to elucidate structural details of bifunctional catalytic centers.

CO2 Hydrogenation to Methanol over Ce and Zr Containing UiO-66 and Cu/UiO-66

Direct hydrogenation of CO2 to methanol is an interesting method to recycle CO2 emitted e.g., during combustion of fossil fuels. However, it is a challenging process because both the selectivity to methanol and its production are low. The metal-organic frameworks are relatively new class of materials with a potential to be used as catalysts or catalysts supports, also in the reaction of MeOH production. Among many interesting structures, the UiO-66 draws significant attention owing to its chemical and thermal stability, developed surface area, and the possibility of tuning its properties e.g., by exchanging the zirconium in the nodes to other metal cations. In this work we discuss—for the first time—the performance of Cu supported on UiO-66(Ce/Zr) in CO2 hydrogenation to MeOH. We show the impact of the composition of UiO-66-based catalysts, and the character of Cu-Zr and Cu-Ce interactions on MeOH production and MeOH selectivity during test carried out for 25 h at T = 200 °C and p = 1.8 MPa. Significant increase of selectivity to MeOH was noticed after exchanging half of Zr4+ cations with Ce4+; however, no change in MeOH production occurred. It was found that the Cu-Ce coexistence in the UiO-66-based catalytic system reduced the selectivity to MeOH when compared to Cu/UiO-66(Zr), which was ascribed to lower concentration of Cu0 active sites in Cu/UiO-66(Ce/Zr), and this was caused by oxygen spill-over between Cu0 and Ce4+, and thus, the oxidation of the former. The impact of reaction conditions on the structure stability of tested catalyst was also determined.

Techno-economic analysis of coke oven gas and blast furnace gas to methanol process with carbon dioxide capture and utilization

This paper documents a process for converting coke oven gas (COG) and blast furnace gas (BFG) from steel refineries into methanol. Specifically, we propose the use of blast furnace gas (BFG) as an additional carbon source. The high CO2 and CO content of BFG make it a good carbon resource. In the proposed process, CO2 is recovered from the BFG and blended with H2O, H2, and CH4-rich COG to reform methane. Optimized amounts of H2O and CO2 are used to adjust the (H2 – CO2)/(CO + CO2) molar ratio in order to maximize the amount of methanol that is produced. In addition, the desulphurization process was modified to enable the removal of sulfur compounds, especially thiophene, from the COG. The process design and simulation results reported herein were then used to determine any potential environmental and economic benefits. This research is based on off-gas conditions provided by ArcelorMittal Dofasco (AMD), Hamilton, Ontario. In order to determine which conditions are most desirable for this retrofit strategy, potential greenhouse gas reduction and economic benefits were analyzed. In particular, this analysis focused on the heating utility chosen for methane reformation prior to methanol synthesis. To this end, COG, BFG, and natural gas (NG) were compared. The results showed that using BFG/NG as a heating utility can produce greater economic gains, and that synthesizing COG + BFG to methanol results in greater economic and environmental gains than solely producing electricity (the status quo). Compared to current operating procedures, the proposed process could potentially increase net present values by up to $54 million. The carbon efficiency achieved was up to 72%. An additional 0.73 kg of CO2 from BFG is needed for every 1 kg of MeOH produced. About 52% of feedstock energy is converted to MeOH, with another 33% recovered in the form of utilities. The exergy efficiency of the recommended version of the system is about 61%. The business case for converting CO2 into methanol highly depends on the local electricity grid carbon intensity. For Ontario, it can reduce direct CO2 emissions by 228 ktonne per year, and fix up to 246 ktonne CO2 into methanol per year. In addition, analyses of location effects, CO2 taxes, electricity prices, electricity carbon intensity, methanol prices, and income taxes indicated that MeOH production is highly recommended for Ontario, Mexico, the USA, and China applications. For USA, build MeOH plant is recommended for Finland, whether to do this retrofit or not is inconclusive. For Finland, the results are inconclusive, other strategies may be equally suitable. Aspen Plus Simulation files and other source code have been open-sourced and are available to the reader.

Quant itative Risk Assessment for Two Step Process Route of MeOH Production Plant Using Recycled CO 2 with HYSYS

A new technology of methanol (MeOH) production by using carbon dioxide CO2 has changed world prospective regarding methanol production. These will contribute to the mitigation of CO2 which become the major gas in greenhouse gas. The study of this paper is to use quantitative risk assessment (QRA) for this process route to determine the risk tolerance levels, it acceptability in methanol production region and comparing to the old process route which used synthesis of natural gases. With the help of process simulators HYSYS, it can provide precise information regarding the process route at any given time. ALOHA software is implanted in this case study to help in identify the safe zone and vulnerability mapping of each of the process route. Lastly, by comparing the tolerance levels between new and old process route, it can determine which is more preferable to implemented in industrial production.

CO2 reduction by C3N4-TiO2 Nafion photocatalytic membrane reactor as a promising environmental pathway to solar fuels

We investigated CO2 photocatalytic reduction coupling, for the first time in literature, the assets offered by the continuous operating mode using C3N4-TiO2 photo-catalyst embedded in a dense Nafion matrix. The reactor performance was analyzed under UV–vis light in terms of productivity, selectivity and converted carbon. Reaction pressure was specifically investigated for its effect as a “driver” in determining reactor performance, modulating products removal from the reaction volume. In addition, the membrane reactor performance was explored as a function of H2O/CO2 feed molar ratio and contact time. The higher feed pressure (5 bar) led to a lesser MeOH production and a greater amount of HCHO, owing to a hindered desorption, which promoted partial oxidation reactions. Total converted carbon instead did not vary significantly with reaction pressure. Membrane reactor with C3N4-TiO2 photocatalyst resulted more performant than other photocatalytic membrane reactors in terms of carbon converted (61 μmol gcatalyst−1 h−1).

High-efficiency utilization of CO2 in the methanol production by a novel parallel-series system combining steam and dry methane reforming

Global warming caused by the accumulation of atmospheric CO2 has received widespread attention in recent years. The direct CO2 integration process in NG-based methanol (MeOH) synthesis plant is one of the predominant CO2 utilization technologies. However, a large amount of water produced in the MeOH reactor increasing the difficulty in the subsequent purification system and the high direct CO2 emissions are caused by the low CO2 conversion rate. In view of such issues, we propose an innovative MeOH production approach based on a parallel-series system combining steam methane reforming (SMR) and dry methane reforming (DMR) to achieve a high-efficiency utilization of CO2. In this approach, the CO2 from SMR and that from additional feeding are converted into CO with a proper amount in the DMR reformer, and thus the content of CO2 in the make-up gas becomes more appropriate than that of existing processes, and the conversion rate of CO2 to MeOH could be obviously increased, what is more, the corresponding direct emissions of CO2 could be significantly reduced. On the other hand, the carbon efficiency is introduced to evaluate the conversion efficiency of all raw material (i.e., CH4 and CO2) containing the carbon atoms. The comparative evaluations are carried out using Aspen Plus V8.4® and the proposed improved process is demonstrated to be more efficient than existing ones from views of technological, economic, and environmental metrics.

Improving methanol synthesis from carbon-free H2 and captured CO2: A techno-economic and environmental evaluation

Carbon Capture, Utilization and Storage (CCUS) is a widely discussed method that can help reduce carbon emissions of energy intensive plants. The goal of this work is to evaluate from a techno-economic point of view such a plant that uses captured CO2 and renewable H2 obtained in a carbon-free way and produces methanol (MeOH). The paper presents (i) the impact of using a higher conversion rate (30%) than in previously reported works, (ii) the use of a gas turbine and (iii) the addition of organic Rankine cycles (ORC) for reducing the energy consumption. The CCUS plant uses 142.6*106 kg of CO2 annually, reduces the amount of CO2 emitted by 140*106 kg/year and produces 100*106 kg/year of MeOH. H2 is obtained on site, using a water-electrolyzing unit; this consumes 130 MWe and generates the necessary H2 for the process. The proposed MeOH production plant is designed and simulated in ChemCAD. Total purchased equipment cost and operational costs are estimated using the process flow modeling. Key performance indicators (KPI) are calculated using the mass and energy balances obtained. The calculated capital costs are similar to previously reported results in the literature. A rigorous mass and energy integration of the plant resulted in an energetically fully self-sufficient MeOH plant, not taking into account the water-hydrolyzing unit. Electricity price is the main contributor for operational costs, either this should be halved, MeOH prices should increase two times or CO2 prices should increase to 0.255 €/kg to make the process economically viable.

Eliminating reverse water gas shift reaction in CO2 hydrogenation to primary oxygenates over MFI-type zeolite supported Cu/ZnO nanocatalysts

This study reports the synthesis of Cu/ZnO supported on Al2O3, SiO2, ZrO2 and solid acid catalyst ZSM-5 for the hydrogenation of CO2 to methanol (MeOH). The activity of all the supported catalysts except Cu/ZnO supported on ZSM-5 (CZZSM) tested at 250°C and 2.25MPa for 13h time-on-stream (TOS) showed carbon monoxide as byproduct due to the nefarious reverse water gas shift reaction (RWGS) that typically compete with MeOH production during CO2 hydrogenation. Methyl formate and dimethyl ether which are value added specialty chemicals were the byproducts when CZZSM was tested and their production mechanism was ascribed to the acidity of the ZSM-5 support. According to the NH3-TPD and CO2-TPD studies, CZZSM has considerable acidity of 15.02μmol/m2 which is about 20 folds higher than the 0.74μmol/m2 measured for the basic sites. Furthermore, the extreme high resolution scanning electron microscopy (XHR-SEM) and BET results showed that the ZSM-5 framework, structural and textural properties were retained after the synthesis of CZZSM which showed that the synthesis protocol was expedient. Thus, the effect of the solid acid catalyst was easily evaluated. In addition, the XHR-SEM, TEM and XRD results showed that the Co-oxide particles were highly dispersed nano-particle with average size of 2.4nm. The CZZSM achieved and impressive CO2 conversion of 20.25% with average space-time yield of 60 and 16gproductgcat−1min−1, and selectivity of 77.70% and 10.0% for MeOH and MeF, respectively which are promising for industrial application.

Photocatalytic Reduction of CO2 with Water into Methanol and Ethanol Using Graphene Derivative–TiO2 Composites: Effect of pH and Copper(I) Oxide

Fuels derived from CO2 can contribute to neutralize the carbon balance in the atmosphere and can be converted into easily transportable liquid chemicals, such as methanol (MeOH) or ethanol (EtOH). In this work, a composite prepared from graphene oxide (GO) and titanium dioxide (TiO2) is applied to the photocatalytic water reduction of CO2 into renewable fuels under UV/vis light irradiation. The pH was identified as a key variable towards selective MeOH formation. The prepared GO–TiO2 composite exhibited superior photocatalytic activity for EtOH production (144.7 μmol g−1 h−1) at pH 11.0 and for MeOH production (47.0 μmol g−1 h−1) at pH 4.0. The effect of copper species in the GO–TiO2 composite is also assessed and its influence on the photocatalytic reaction inferred. The photocatalysts prepared with copper nitrate as copper precursor exhibited the highest rate of MeOH production at pH 11.0. Accordingly, a conceptual scheme in which the photogenerated electrons are used to reduce CO2 is proposed.

Investigation of power-to-methanol processes coupling electrolytic hydrogen production and catalytic CO2 reduction

The purpose of this research work is to perform the techno-economic assessment of a Power-to-MeOH technology that couples a model water eletrolyzer (either a polymer electrolyte or a solid oxide technology) with a model catalytic CO2 reactor. Simulations were made using ASPEN Plus V8.0. Regarding the SOEC/Methanol process, results of the simulation confirm the predominance of CAPEX on MeOH production cost. Cost reductions and lifespan improvement of SOEC technologies are found to be the major cost reduction drivers. Also, the speed at which the SOEC/Methanol facility is constructed is found to affect significantly the competitiveness of this process. Regarding the PEM/Methanol process, the cost breakdown analysis confirms the predominance of OPEX on the methanol cost, a value that is moderately impacted when the lifespan of the electrolyser is doubled. The energy efficiency of the electrolyser is therefore a key driver for a reduction of methanol production costs. Using state-of-the-art technologies, a methanol cost of 891 €/tonne was determined for the PEM/Methanol process and a methanol cost of 5459 €/tonne was determined for the SOEC/Methanol process. These costs represent respectively 2.5 and 15 times the current market price for methanol. However, promising methanol cost reductions are foreseeable by improving the water electrolysis technologies.

CO2 conversion in a photocatalytic continuous membrane reactor

CO2 was photocatalytically reduced over TiO2–Nafion membranes in a continuous flow membrane reactor. MeOH production is considered as a relevant advance over the existing literature results which mostly propose CH4 as the reaction product.

By-product co-feeding reveals insights into the role of zinc on methanol synthesis catalysts

abstract Article history:Received 17 October 2011Received in revised form 20 January 2012Accepted 31 January 2012Available online 9 February 2012Keywords:Methanol synthesisBy-product co-feedingMethyl formateDimethyl etherZinc oxide Co-feedingoftworelevant by-products ofmethanol synthesis, viz.dimethyl ether and methylformate,inCO+H 2 andCO+CO 2 +H 2 streamswasusedasastrategytogainunderstandingofthereactionoverternaryCu/ZnO/Al 2 O 3 and binary Cu/ZnO, Cu/Al 2 O 3 , and ZnO/Al 2 O 3 catalysts. While dimethyl ether does not participate in theprocess, the addition of methyl formate remarkably increases the MeOH production by its oxygen-assistedsplit into active intermediate species (CH 3 O⁎ and HCOO⁎). Specifically, a breakthrough role was assigned toZnO as catalytic partner for methyl formate conversion to methanol, since even the Cu-free ZnO/Al 2 O 3 sampleshowsaconsiderableMeOHyieldonMeFco-feeding.Alternatively,intheZn-freeCu/Al 2 O 3 sample,thepresenceofcarbon dioxideintheinlet mixturewas crucialtoactivatethe methylformate conversion path,likelybecauseCO

Leaf and root pectin methylesterase activity and 13C/12C stable isotopic ratio measurements of methanol emissions give insight into methanol production in Lycopersicon esculentum

Plant production of methanol (MeOH) is a poorly understood aspect of metabolism, and understanding MeOH production in plants is crucial for modeling MeOH emissions. Here, we have examined the source of MeOH emissions from mature and immature leaves and whether pectin methylesterase (PME) activity is a good predictor of MeOH emission. We also investigated the significance of below-ground MeOH production for mature leaf emissions. We present measurements of MeOH emission, PME activity, and MeOH concentration in mature and immature tissues of tomato (Lycopersicon esculentum). We also present stable carbon isotopic signatures of MeOH emission and the pectin methoxyl pool. Our results suggest that below-ground MeOH production was not the dominant contributor to daytime MeOH emissions from mature and immature leaves. Stable carbon isotopic signatures of mature and immature leaf MeOH were similar, suggesting that they were derived from the same pathway. Foliar PME activity was related to MeOH flux, but unexplained variance suggested PME activity could not predict emissions. The data show that MeOH production and emission are complex and cannot be predicted using PME activity alone. We hypothesize that substrate limitation of MeOH synthesis and MeOH catabolism may be important regulators of MeOH emission.

Short term changes in methanol emission and pectin methylesterase activity are not directly affected by light in <i>Lycopersicon esculentum</i>

Abstract. Plants are an important source of atmospheric methanol (MeOH), the second most abundant organic gas after methane. Factors regulating phytogenic MeOH production are not well constrained in current MeOH emission models. Previous studies have indicated that light may have a direct influence on MeOH production. As light is known to regulate cell wall expansion, it was predicted that light would stimulate MeOH production through the pectin methylesterase (PME) pathway. MeOH emissions normalized for stomatal conductance (gs) did not, however, increase with light over short time scales (20–30 min). After experimentally controlling for gs and temperature, no light activation of PME activity or MeOH emission was observed. The results clearly demonstrate that light does not directly influence short-term changes in MeOH production and emission. Our data suggest that substrate limitation may be important in regulating MeOH production over short time scales. Future investigation of the long-term impacts of light on MeOH production may increase understanding of MeOH emission dynamics at the seasonal time scale.

Effect of Dimethyl Ether Synthesis on Methanol- and Iron-making Integrated System.

In a previous study the catalysts for synthesizing dimethyl ether ((CH 3 ) 2 O, DME) from blast furnace gas were successfully developed for increasing methanol (CH 3 OH, MeOH) yield. The objective of this study is to design a new MeOH-Iron production system through DME synthesis based on the results, to evaluate a system from exergy concept and to compare with a previously proposed MeOH-Iron production system. Then, effect of the systematic combination and auxiliary fuel injections to a blast furnace on exergy consumption in the system was mainly assessed. As a result, the exergy consumption of the new system for hot-metal production became 10% lower than the previous one. At the same time, its exergy consumption for MeOH production decreased as much as 36% of the previous one, showing thermodynamic advantage of DME synthesis. The amount of MeOH production had great dependence on a kind of auxiliary fuels through top gas composition of a blast furnace (BF). It was concluded that MeOH production with DME synthesis and the injection of COM or PC to BF was best systematic combination for maximizing MeOH production from BF offgas.

Promoting role of Fe in enhancing activity and selectivity of MeOH production from CO and H2 catalysed by SiO2-supported Ir

Addition of Fe to Ir/SiO2 catalysts used in CO hydrogenation improves the yield of and selectivity towards MeOH (90% carbon efficiency), owing to suppression of methanation.

Net energy analysis of methanol and ethanol production

Methanol (MeOH) and ethanol (EtOH) are industrial alcohols that can be used as liquid fuels. They may be obtained from renewable or non-renewable feedstocks. The production processes and end uses are analyzed in order to assess the potential energy savings introduced by alcohol production from renewable instead of nonrenewable feedstock. Whereas MeOH production from wood brings about energy savings, EtOH production from corn may or may not save energy depending on the end use of the alcohol. If the alcohol is used as a motor fuel, no overall energy savings are found. The economics and total labor requirements of each process are also considered.