Catalytic hydrogenation of CO2 from 600 MW supercritical coal power plant to produce methanol: A techno-economic analysis

Electricity and water from renewable hydropower plant are used as input for electrolysis unit to generate hydrogen, while CO₂ is captured from 600 MW supercritical coal power plant using post-combustion chemical solvent based technology. The captured CO₂ and H₂ generated through electrolysis are used to synthesize methanol through catalytic thermo-chemical reaction. The methanol synthesis plant is designed, modeled and simulated using commercial software Aspen Plus^®. The reactor is analyzed for two widely adopted kinetic models known as Graaf model and Vanden-Bossche (VB) model to predict the methanol yield and CO₂ conversion. The results show that the methanol reactor based on Graaf kinetic model produced 0.66 tonne of methanol per tonne of CO₂ utilized which is higher than that of the VB kinetic model where 0.6 tonne of methanol is produced per tonne of CO₂ utilized. The economic analysis reveals that 1.2 billion USD annually is required at the present cost of both H₂ production and CO₂ abatement to utilize continuous emission of 3.2 million tonne of CO₂ annually from 600 MW supercritical coal power unit to synthesize methanol. However, sensitivity analysis indicates that methanol production becomes feasible by adopting anyone of the route such as by increasing methanol production rate, by reducing levelised cost of hydrogen production, by reducing CO₂ mitigation cost or by increasing the current market selling price of methanol and oxygen.     

Application of the pack cementation process on SiC/SiC ceramic matrix composites

The potentials and limitations of a halide-activated pack cementation process on SiC/SiC Ceramic Matrix Composites for the development of bond coats as part of environmental barrier coating (EBCs) systems were investigated. Different pack compositions using chromium, aluminum and alloys of these elements were tested and the kinetics of coating formation were examined in addition to their microstructure. The results and their analogy to diffusion couples were discussed and it was shown that coating elements which form silicides and carbides are promising candidates for coatings deposited on SiC/SiC via pack cementation. Based on such considerations a two-step pack cementation was proposed, which used chromium, one of the suitable elements, in a first step, to finally achieve an alumina-forming coating. The oxidation resistance of the developed coating was tested via thermogravimetric analysis and compared to the uncoated material. The coating protected the fiber-matrix interface of the SiC/SiC Ceramic Matrix Composites from oxidation.     

Oxidation and ablation behaviour of multiphase ultra-high-temperature ceramic Ta0·5Zr0·5B2–Si–SiC protective coating for graphite

To provide reliable oxidation protection for carbon materials under harsh high-temperature aerobic environments, a dense monolayer-multiphase ultra-high-temperature ceramic Ta_0·5Zr_0·5B₂–Si–SiC (TZSS) coating was fabricated by a combination of dipping and in-situ reaction. The oxidation resistance of the TZSS coating was investigated at 1923 K in air. The results indicated that the TZSS coating could offer at least 70 h of oxidation protection for the matrix material. The synergistic oxygen-blocking effect of the thick oxide layer formed during the oxidation test and the inner coating, played a key role in the oxidation protection process. These were responsible for the excellent oxidation resistance ability of the TZSS coating. Additionally, the ablation performance of the TZSS coating was also investigated under increased heat flux from 2.4 MW/m² to 4.2 MW/m². The ablation behaviours changed from the oxidation and evaporation of coating materials to mechanical scouring, corresponding to increased mass and linear ablation rates. Interestingly, after ablation for 40 s under a heat flux of 4.2 MW/m², a new microstructure composed of “lath-like” Ta₄Zr₁₁O₃₂ solid solution grains was found in the ablation center. This oxide layer possessed few micropores, which could provide reliable protection for the matrix material under ultra-high-temperature oxygen-containing airflow erosion, thus preventing further damage to the composite.     

Preparation of PEDOT-modified double-layered hollow carbon spheres as Pt catalyst support for methanol oxidation

In this paper, Pt nanoparticles (Pt NPs) deposited hybrid carbon support is prepared by modifying double-layered hollow carbon spheres（DLHCs）with poly(3,4-ethylenedioxythiophene) (PEDOT) and used as anode catalyst of methanol oxidation. The structure of nanocomposites is characterized by SEM, TEM, FT-IR, XRD and XPS, confirming the greatly enhanced synergistic effect between the PEDOT and DLHCs, and illustrating the uniform distribution of Pt NPs on the PEDOT/DLHCs composite surface with a small particle size (~2.63 nm). Cyclic voltammetry, chronoamperometry and impedance spectroscopy applied to determine the electrocatalytic activity of catalysts, it is found that the synthesized PEDOT/DLHCs/Pt possesses excellent characteristics such as large electrochemically active surface area and high mass activity of 59.45 m² g⁻¹ and 807 mA mg⁻¹ in 0.5 M H₂SO₄ containing 1 M methanol solution, which is almost 1.24 and 2.8 times greater than those of commercial Pt/C, and the catalyst exhibits superior stability after 500 durability cycles. The enhanced electrocatalytic behavior can be ascribed to the excellent electronic conductivity of PEDOT-modified DLHCs and the strong binding of PEDOT/DLHCs to Pt NPs, suggesting that the PEDOT/DLHCs/Pt is a promising electrocatalyst for direct methanol fuel cell.     

Hydrogen production employing Cu(BDC) metal–organic framework support in methanol steam reforming process within monolithic micro-reactors

Cu(BDC) metal–organic framework (MOF) was used as a support for the copper (Cu) catalyst applied in the methanol steam reforming (MSR) process at low temperatures (130–250 °C) with a feed WHSV = 9.2 h^?1 within the monolithic reactor. Also, the effects of diverse promoters were examined on the catalytic activities of the Cu/X–Cu(BDC) (X = Ce, Zn, Gd, Sm, La, Y, Pr) catalysts. Results showed that the Ce/Sm–Cu(BDC) supports exhibited highest activities, lowest reduction temperatures and largest specific surface areas, which caused highest distributions of the active copper metal nanoparticles on the supports. The reactor tests displayed that the activities of Cu/X–Cu(BDC) (X = Ce, Zn, Gd, Sm, La, Y, Pr) catalysts followed the order X = Ce > Sm > Y > La > Pr > Cu(BDC) > Zn > Gd. The highest activities of Ce and Sm containing catalysts were attributed to the presence of CeO₂ and Sm₂O₃ caused the oxygen vacancies on the catalyst surface which had positive effects on the methanol reforming process. The time-on-stream stability tests showed the highest resistance of the Cu/Ce–Cu(BDC) catalyst to the carbon formation during 32 h. Consequently, the Cu/Ce–Cu(BDC) with the highest stability, methanol conversion and carbon monoxide selectivity could be used in practical industrial applications.     

Intensification of hydrogen production from methanol steam reforming by catalyst segmentation and metallic foam insert

This paper is a numerical study about the catalyst morphology CuO/ZnO/Al₂O₃ effects on the hydrogen production from methanol steam reforming, for proton exchange membrane fuel cells (PMEFC). The study is focused on the influences of the metal foam insert, catalyst layer segmentation, and metal foam as catalyst support on the reactor performance: hydrogen yield and methanol conversion. According to the carried simulations, it is found that these configurations improve the reformer performances compared to the continuous catalyst layer configuration. The insertion of metal foam increases the efficiency of up to 75.41% at 525 K. Also, at this reaction temperature, the segmentation of the catalyst layer in similar parts increases the reformer efficiency by 2.11%, 4.23%, 6.77%, and 8.6% for 2, 4, 8, and 16 identical parts, respectively. As well as, the metal foam as catalyst support is more efficient compared to the other configurations, the efficiency is equal to 64% at T = 495 k.     

湿法炼锌赤铁矿法沉铁行为

湿法炼锌工艺过程中赤铁矿法沉铁技术是一种沉淀渣量小、分离效率高的锌、铁分离方法。针对湿法炼锌工艺过程中赤铁矿法沉铁技术开展了硫酸亚铁的氧化水解沉淀行为的研究，考察了时间、酸度、温度、硫酸盐浓度、晶种返回量等主要因素对赤铁矿法沉铁效果的影响、沉淀产物的析出特性和物相表征。     

Highly selective CuO/γ–Al2O3 catalyst promoted with hematite for efficient methanol dehydration to dimethyl ether

A recent alternative for replacing traditional hydrocarbons like gasoline, diesel, and natural gas, is the use of dimethyl ether (DME), which is more environmentally friendly. One of the ongoing challenges is to catalyze methanol dehydration for selectively producing the DME (2CH₃OH → CH₃OCH₃ + H₂O). It is established that the CuO catalyst over alumina performs the methanol dehydration, but the formation of by-products is the main drawback. For these reasons, we synthesized a CuO/γ–Al₂O₃ catalyst promoted with hematite aiming to enhance the activity toward DME at atmospheric conditions. The resulting bimetallic catalyst (CuO-Fe₂O₃/Al₂O₃) performed a 70% conversion at 290 °C, which is similar to other catalysts recently reported in the literature but done in harsh conditions. In addition, this bimetallic catalyst exhibited a 100% in selectivity toward the DME production. XPS spectra of the fresh and used catalyst suggested that the chemical oxidation states of Cu and Fe remain without change. After regenerating the catalyst at 600 °C for 2 h in air, it performed at a similar catalytic conversion, confirming the reusability of the as-synthesized material and reducing the environmental impact.     

Oxidation behavior and high-temperature flexural property of CVD-SiC-coated PIP-C/SiC composites

Polymer infiltration pyrolysis (PIP) was used to prepare carbon fiber-reinforced silicon carbide (C/SiC) composites, and chemical vapor deposition (CVD) was employed to fabricate SiC coating. The oxidation behavior at 1700?°C and the flexural property at 1200?°C were tested. SiC coating exerted remarkable oxidation effects on PIP-C/SiC composites. In the absence of coating, PIP-C/SiC composites lost 29.2% of its mass, with merely 6.74% of the original flexural strength retained. In contrast, CVD-SiC coated PIP-C/SiC composites had the mass loss of 10.2% and the flexural strength retention ratio of 23.4%. In high-temperature tests, SiC coating played an important role in the flexural strength of PIP-C/SiC composites. The flexural strength of uncoated composites became 330.7?MPa, and that of coated ones reduced from 655.3 to 531.2?MPa.     

Techno-economic feasibility of methanol synthesis using dual fuel system in a parallel process design configuration with control on green house gas emissions

Recently, the methanol production has received a lot of attraction in the process industries due to its wide applications in the synthesis of many commercial chemicals and fuels. Most of the coal to methanol processes suffers from higher water consumption, greenhouse gas (GHG) emissions and lower yields. The aim of this study is to develop a novel energy efficient and economic viable process that may not only increase the methanol production capacity but also offers the less energy requirements with improved process economics. In this study, coal gasification process is sequentially integrated in the parallel design configuration with the natural gas reforming technology to enhance the heating value of the resulting syngas for methanol production. To achieve this aim, two case studies have been developed and compared in terms of overall process performance and economics. Case 1 represents the conventional coal to methanol process, whereas, case 2 represents the conceptual design of integrating the gasification and reforming technologies for enhanced methanol production. The process efficiencies calculated for case 1 and case 2 is 63.2% and 70.0%, respectively. It has been seen from results that the methanol production energy for case 1 and case 2 is 0.69 kg/W and 0.76 kg/W, respectively. In terms of process economics, the methanol production cost for case 1 and case 2 has been estimated as 250 €/tonne and 234 €/tonne, respectively. The comparative analysis showed that the case 2 design not only offers higher process performance but also enhances the process feasibility compared to the conventional coal based processes.