Oxyfuel Combustion Makes Carbon Capture More Efficient.

Fossil energy carriers cannot be totally replaced, especially if nuclear power stations are stopped and renewable energy is not available. To fulfill emission regulations, however, points such as emission sources should be addressed. Besides desulfurization, carbon capture and utilization have become increasingly important engineering activities. Oxyfuel technologies offer new options to reduce greenhouse gas emissions; however, the use of clean oxygen instead of air can be dangerous in the case of certain existing technologies. To replace the inert effect of nitrogen, carbon dioxide is mixed with oxygen gas in the case of such air combustion processes. In this work, the features of carbon capture in five different flue gases of air combustion and such oxyfuel combustion where additional carbon dioxide is mixed with clean oxygen are studied and compared. The five different flue gases originate from the gas-fired power plant, coal-fired power plant, coal-fired combined heat and power plant, the aluminum production industry, and the cement manufacturing industry. Monoethanolamine, which is an industrially preferred solvent for carbon dioxide capture from gas streams at low pressures, is selected as an absorbent, and the same amount of carbon dioxide is captured; that is, always that amount of carbon dioxide is captured, which is the result of the fossil combustion process. ASPEN Plus is used for mathematical modeling. The results show that the oxyfuel combustion cases need significantly less energy, especially at high carbon dioxide removal rates, e.g., higher than 90%, than that of the air combustion cases. The savings can even be as high as 84%. Moreover, 100% carbon capture was also be completed. This finding can be due to the fact that in the oxyfuel combustion cases, the carbon dioxide concentration is much higher than that of the air combustion cases because of the inert carbon dioxide and that higher carbon dioxide concentration results in a higher driving force for the mass transfer. The oxyfuel combustion processes also show another advantage over the air combustion processes since no nitrogen oxides are produced in the combustion process.

Hybrid Prediction-Driven High-Throughput Sustainability Screening for Advancing Waste-to-Dimethyl Ether Valorization.

Assessing the prospective climate preservation potential of novel, innovative, but immature chemical production techniques is limited by the high number of process synthesis options and the lack of reliable, high-throughput quantitative sustainability pre-screening methods. This study presents the sequential use of data-driven hybrid prediction (ANN-RSM-DOM) to streamline waste-to-dimethyl ether (DME) upcycling using a set of sustainability criteria. Artificial neural networks (ANNs) are developed to generate in silico waste valorization experimental results and ex-ante model the operating space of biorefineries applying the organic fraction of municipal solid waste (OFMSW) and sewage sludge (SS). Aspen Plus process flowsheeting and ANN simulations are postprocessed using the response surface methodology (RSM) and desirability optimization method (DOM) to improve the in-depth mechanistic understanding of environmental systems and identify the most benign configurations. The hybrid prediction highlights the importance of targeted waste selection based on elemental composition and the need to design waste-specific DME synthesis to improve techno-economic and environmental performances. The developed framework reveals plant configurations with concurrent climate benefits (-1.241 and -2.128 kg CO2-eq (kg DME)-1) and low DME production costs (0.382 and 0.492 € (kg DME)-1) using OFMSW and SS feedstocks. Overall, the multi-scale explorative hybrid prediction facilitates early stage process synthesis, assists in the design of block units with nonlinear characteristics, resolves the simultaneous analysis of qualitative and quantitative variables, and enables the high-throughput sustainability screening of low technological readiness level processes.

Extensive comparison of methods for removal of organic halogen compounds from pharmaceutical process wastewaters with life cycle, PESTLE, and multi-criteria decision analyses.

Recycling and disposing wastewater from the pharmaceutical industry are of utmost importance in mitigating chemical waste generation, where unmanaged hazardous waste fluxes could cause massive environmental damage. Air stripping, steam stripping, distillation, and incineration offer significant emission reduction potentials for pharmaceutical applications; however, selecting specific process units is a complicated task due to the high number of influencing screening criteria. The mentioned chemical processes are modelled with the Aspen Plus program. This study examines the environmental impacts of adsorbable organic halogens (AOX) containing pharmaceutical process wastewater disposal by conducting life cycle impact assessments using the Product Environmental Footprint (PEF), IMPACT World + Endpoint V1.01, and Recipe 2016 Endpoint (H) V1.06 methods. The results show that the distillation-based separation of AOX compounds is characterized by the most favourable climate change impact and outranks the PEF single score of air stripping, steam stripping, and incineration by 6.3%, 29.1%, 52.0%, respectively. The energy-intensive distillation technology is further evaluated by considering a wide selection of energy sources (i.e., fossil fuel, nuclear, solar, wind onshore, and wind offshore) using PESTLE (Political, Economic, Social, Technological, Legal, Environmental) analysis combined with multi-criteria decision support to determine the most beneficial AOX disposal scenario. The best overall AOX regeneration performance and lowest climate change impact (7.25 × 10-3 kg CO2-eq (1 kg purified wastewater)-1) are obtained by supplying variable renewable electricity from onshore wind turbines, reaching 64.87% carbon emission reduction compared to the baseline fossil fuel-based process alternative.

Effects of Energy Intensification of Pressure-Swing Distillation on Energy Consumption and Controllability.

The aim of process integration is the efficient use of energy and natural resources. However, process integration can result in a more precise process operation, that is, it influences controllability. Pressure-swing distillation processes are designed for the separation of azeotropic mixtures, but their inherent heat integration option can be utilized to significantly reduce their energy consumption. One maximum-boiling and three minimum-boiling azeotropes are considered to study and compare the nonintegrated and integrated alternatives with the tool of mathematical modeling where ASPEN Plus and MATLAB software are used. The results show that the heat-integrated alternatives result in 32-45% energy savings that are proportional to the emission reduction and the consumption of natural resources. As far as the operability is concerned, the heat-integrated alternatives show worse controllability features than the nonintegrated base case. This can be due to the loss of one controllability degree of freedom. This recommends using more sophisticated control structures for the sake of safe operation if process integration is applied.

Improving green hydrogen production from Chlorella vulgaris via formic acid-mediated hydrothermal carbonisation and neural network modelling.

This study investigates the formic acid-mediated hydrothermal carbonisation (HTC) of microalgae biomass to enhance green hydrogen production. The effects of combined severity factor (CSF) and feedstock-to-suspension ratio (FSR) are examined on HTC gas formation, hydrochar yield and quality, and composition of the liquid phase. The hydrothermal conversion of Chlorella vulgaris was investigated in a CSF and FSR range of -2.529 and 2.943; and 5.0 wt.% - 25.0 wt.%. Artificial neural networks (ANNs) were developed based on experimental data to model and analyse the HTC process. The results show that green hydrogen formation can be increased up to 3.04 mol kg-1 by applying CSF 2.433 and 12.5 wt.% FSR reaction conditions. The developed ANN model (BR-2-11-9-11) describes the hydrothermal process with high testing and training performance (MSEz = 1.71E-06 & 1.40E-06) and accuracy (R2 = 0.9974 & R2 = 0.9781). The enhanced H2 yield indicates an effective alternative green hydrogen production scenario at low temperatures using high-moisture-containing biomass feedstocks.

Vapor-Liquid Equilibrium Study of the Monochlorobenzene-4,6-Dichloropyrimidine Binary System.

The number of newly synthesized and produced organic chemicals has increased extremely quickly. However, the measurements of their physical properties, including their vapor-liquid equilibrium (VLE) data, are time-consuming. It so happens that there is no physical property data about a brand-new chemical. Therefore, the importance of calculating their physicochemical properties has been playing a more and more important role. 4,6-Dichloropyrimidine (DCP) is also a relatively new molecule of high industrial importance with little existing data. Therefore, their measurements and the comparison with the calculated data are of paramount concern. DCP is a widespread heterocyclic moiety that is present in synthetic pharmacophores with biological activities as well as in numerous natural products. Isobaric VLE for the binary system of 4,6-dichloropyrimidine and its main solvent monochlorobenzene (MCB) was measured using a vapor condensate and liquid circulation VLE apparatus for the first time in the literature. Density functional-based VLE was calculated using the COSMO-SAC protocol to verify the laboratory results. The COSMO-SAC calculation was found to be capable of representing the VLE data with high accuracy. Adequate agreement between the experimental and calculated VLE data was acquired with a minimal deviation of 3.0 × 10-3, which allows for broader use of the results.

Development of Anhydrous Ethanol Purification: Reduction of Acetal Content and Vapor-Liquid Equilibrium Study of the Ethanol-Acetal Binary System.

Acetaldehyde diethyl acetal (herein called acetal) is an important pollutant of anhydrous ethanol. Isobaric vapor-liquid equilibrium (VLE) of an ethanol-acetal binary system was measured using a vapor condensate and liquid circulation VLE still. The experimental data were correlated with Wilson, nonrandom two-liquid (NRTL), and universal quasichemical (UNIQUAC) activity coefficient models, which were found suitable for representing the VLE data. Proper agreements between experimental and calculated VLE data were obtained, which were then confirmed with consistency tests. The applicability of the novel VLE data was demonstrated during an investigation of an anhydrous ethanol purification column. Reduction of the concentration of acetal and other pollutants was examined and optimized in a flowsheet environment. The modeling results were verified in a laboratory with an experimental distillation column, confirming a correct agreement between the results. It must be highlighted that the developed method is suitable for the production of pharmacopeial quality anhydrous alcohol, based on reliable, verified VLE data. The results show the importance of accurate VLE data in critical compositions (low pollutant content); moreover, aiming at high product purity, experimental validation has paramount importance. The consistency between the three platforms (VLE and distillation experiments and flowsheet simulation) confirms the accuracy of the developed method.

Pervaporative Dehydration of Methanol Using PVA/Nanoclay Mixed Matrix Membranes: Experiments and Modeling.

Encouraged by the industrial problem of removing water from methanol solutions, a simple exfoliation method is applied to prepare polyvinyl alcohol (PVA)/laponite nanoclay mixed matrix membranes (MMMs). The membranes are used for the pervaporative dehydration of the methanol-water solution. The influence of the nanoclay content on the pervaporation performance is investigated. The results show that the PVA10 membrane containing 10 wt% Laponite loading exhibits excellent separation efficiency; therefore, all the experimental work is continued using the same membrane. Additionally, the effects of feed concentration and temperature on methanol dehydration performance are thoroughly investigated. The temperatures are ranging from 40-70 °C and the water feed concentrations from 1-15 wt% water. A maximum separation factor of 1120 can be observed at 40 °C and the feed water concentration of 1 wt%. Remarkably, two solution-diffusion models, the Rautenbach (Model I) and modified method by Valentínyi et al. (Model II), are used and compared to evaluate and describe the pervaporation performance of the mixed matrix membrane. Model II proves to be more appropriate for the modeling of pervaporative dehydration of methanol than Model I. This work demonstrates that PVA/nanoclay mixed matrix membranes prepared can efficiently remove water from methanol aqueous solution with pervaporation and the whole process can be accurately modeled with Model II.

Facile Preparation of a Laponite/PVA Mixed Matrix Membrane for Efficient and Sustainable Pervaporative Dehydration of C1-C3 Alcohols.

The exfoliation method was applied for the preparation of high-water selective mixed matrix membranes (MMMs), especially for the dehydration of C1-C3 alcohol-water solutions. Herein, a facile and easy method was employed to fabricate physically cross-linked Laponite nanosilicate clay-PVA MMMs without additional cross-linking by a one-step synthesis route for water dehydration from methanol, ethanol, and isopropanol aqueous solutions. The morphologies, chemical structures, thermal stabilities, and surface hydrophilicity of Laponite-PVA MMMs were investigated properly by different characterization techniques. The Laponite concentration has affected the fractional free volume of the membranes, as proven by positron annihilation lifetime spectroscopy analysis. The MMMs displayed both a significant improvement in the separation factor and remarkable enhancement in the permeation fluxes for the three alcohol systems. The influence of the operating temperature on the MMM performance was investigated for the methanol/water solution. The methanol permeability was 100-fold lower than that of the water, indicating that the membranes are more water selective. Particularly, the Laponite-PVA membrane with 5 mg/mL Laponite loading exhibits excellent separation efficiency for C1-C3 dehydration having water permeabilities higher than most other polymeric membranes from the other literature studies of 2.82, 2.08, and 1.56 mg m-1 h-1 kPa-1 for methanol, ethanol, and isopropanol/water systems, respectively. This membrane development allows a more efficient and sustainable separation of aqueous alcoholic mixtures.

Membrane Flash Index: Powerful and Perspicuous Help for Efficient Separation System Design.

There are different factors and indices to characterize the performance of a pervaporation membrane, but none of them gives information about their capabilities in the area of liquid separation compared to the most convenient alternative, which is distillation. Membrane flash index (MFLI) can be considered the first and only one that shows if the membrane is more efficient or not than distillation and quantifies this feature too. Therefore, the MFLI helps select the best separation alternative in the case of process design. In this study, the evaluation and capabilities of membrane flash index are comprehensively investigated in the cases of six aqueous mixtures: methyl alcohol-water, ethyl alcohol-water, isobutyl alcohol-water, tetrahydrofuran-water, N-butyl alcohol-water, and isopropanol-water. It must be concluded that the separation capacity of organophilic type membranes is remarkably lower than hydrophilic membranes in all cases of separation. The study of the MFLI is extended with the consideration of other binary interaction parameters like separation factor, permeation flux, selectivity, and pervaporation separation index (PSI) in order to find a descriptive relationship between them. For the same membrane material type, descriptive function can be determined between feed concentration and MFLI and PSI and separation factor, which can be used to calculate each other's value. On the basis of the indices and especially the MFLI, a significant help can be given to the process design engineer to select the right liquid separation alternative and, in the case of pervaporation, find the most appropriate membrane.

Co-Hydrothermal gasification of Chlorella vulgaris and hydrochar: The effects of waste-to-solid biofuel production and blending concentration on biogas generation.

This study investigates enhanced biogas production via co-Hydrothermal gasification (co-HTG) of wet Chlorella vulgaris biomass and hydrochar (HC). Hydrothermal carbonization was applied to valorize struvite containing waste microalgae stream into solid bio-fuel with improved combustion properties. The effects of HC quality and mixing ratio are investigated on biogas yield, composition and carbon conversion ratio. The results show that the application of blending components promotes H2, CH4 formation and selectivity in hydrothermal gasification. The total co-HTG gas yield is increased from 19.13 to 46.95 mol kg-1 at 650 °C and 300 bar by applying 5 wt% HC blending concentration and reduced level of volatile matter content (24.61 wt%). The obtained high hydrogen, methane yields and carbon conversion ratio (19.49, 2.98 mol kg-1, 82.31%, respectively) indicate effective hydrothermal upgrading potentials in case of wet and waste biomass feedstocks.