Cover illustration
(Timothy G. Walmsley, Nathan S. Lal, Petar S. Varbanov, Jiří J. Klemeš, pp. 630-642)
Ever increasing energy costs and environmental concern drives a cycle of continuous process energy improvement in the chemical and process industries. To remain competitive in the short-term and sustainable in the long-term, industrial companies and sites need to identify projects to retrofit and revamp their technology to keep pace with more energy-efficient new plants. Such options in
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This contribution is a preliminary techno-economic assessment of a biogas-based oxidative coupling of methane (OCM) process. Biogas is frequently utilized as a renewable energy source within small scale combined heat and power plants or as a natural gas substitute. The activation of methane also enables its utilization as a feedstock to produce chemicals. In this sense, the OCM process allows for the direct conversion of methane into ethylene, which is a major building block for the chemical and polymer industries. Biogas resulting from the anaerobic digestion of vinasse, a liquid effluent from bioethanol industry, is treated for contaminant removal and its methane content is converted into ethylene, which is then purified as the main product. The biogas cleaning process is assessed based on literature data, while an experimentally validated simulation model is used to assess the OCM process. A techno-economic evaluation is then performed through a Monte Carlo simulation, wherein uncertain parameters take random values between reasonable bounds. The net present value results positive in 74% of the cases, indicating that the project is profitable under a wide range of scenarios. Some performance improvement opportunities have been identified and highlighted to guide future studies in the topic.
The fouling phenomena can create significant operational problems in the industry by deteriorating heat recuperation, especially in heat exchangers with enhanced heat transfer. For a correct prediction of fouling development, the reliable fouling models must be used. The analysis of existing fouling models is presented. The chemical reaction and transport model developed earlier for a description of fouling on intensified heat transfer surfaces is used for modeling of plate heat exchanger (PHE) subjected to fouling. The mathematical model consists of a system of differential and algebraic equations. The integration of it is performed by finite difference method with developed software for personal computer. For countercurrent streams arrangement in PHE the solution of two-point boundary problem is realized on every time step. It enables to estimate local parameters of heat transfer process with fouling formation and its development in time with the growth of deposited fouling layer. Two examples of model application in cases of PHEs working at sugar factory and in district heating network are presented. The comparison with experimental data confirmed the model validity and the possibility of its application to determine the performance of PHE subjected to fouling.
The aim of this paper is to develop a novel heat exchanger network (HEN) retrofit method based on a new automated retrofit targeting (ART) algorithm. ART uses the heat surplus-deficit table (HSDT) in combination with the Bridge Retrofit concepts to generate retrofit bridges option, from which a retrofit design may be formulated. The HSDT is a tabular tool that shows potential for improved re-integration of heat source and sink streams within a HEN. Using the HSDT, retrofit bridges—a set of modifications that links a cooler to a heater to save energy—may be identified, quantified, and compared. The novel retrofit method including the ART algorithm has been successfully implemented in Microsoft ExcelTM to enable analysis of large-scale HENs. A refinery case study with 27 streams and 46 existing heat exchangers demonstrated the retrofit method’s potential. For the case study, the ART algorithm found 68903 feasible unique retrofit opportunities with a minimum 400 kW·unit−1 threshold for heat recovery divided by the number of new units. The most promising retrofit project required 3 new heat exchanger units to achieve a heat savings of 4.24 MW with a favorable annualised profit and a reasonable payback period.
Dehydration of isopropanol applying batch heteroazeotropic distillation with toluene as entrainer (E) is investigated. The composition of the feed is near to that of the isopropanol (A)-water (B) azeotrope. The effects of recycling the entrainer and the off-cut are studied by dynamic simulation with a professional flow-sheet simulator. Three consecutive batches (one production cycle) is studied. Both operational modes (Mode I: decantation after distillation and Mode II: decantation during distillation) are simulated. For Mode II, calculations are performed both for Strategy A (distillate from the aqueous (E-lean) phase only) and Strategy B (partial withdrawal of the organic (E-rich phase), as well). The E-rich phase, the final column hold-up and the off-cut (Mode II only) are recycled to the next batch. The influence of the following parameters are determined: quantity of entrainer, reflux ratios of the steps. The variations caused by the recycling in the 2nd and 3rd batches are also shown. The best results (lowest specific energy demand and highest recovery of A) are obtained by Mode II, Strategy A. Recycling increases the recovery, and drastically diminishes the entrainer consumption. However, it makes the production slower and decreases the quantity of fresh feed that can be processed.
The consequences of changes planned in the European Union legislation relevant to the disposal of sewage sludges are discussed. A specific municipal waste water treatment plant is analyzed in terms of drying and subsequent combustion or pyrolysis of the produced stabilized sludge, and the respective net energy balances are carried out. A simplified economic analysis of the two disposal options is presented, which suggest that combustion of the sludge would be economically infeasible while pyrolysis of the sludge in a modular, self-sufficient container unit can bring a small financial benefit due to the selling of the produced phosphorus-rich biochar.
Methyl acetate is considered low toxicity volatile solvent produced either as a by-product during methanol carbonylation or via acetic acid esterification with methanol. In both cases, pure methyl acetate has to be isolated from the reaction mixture. Simulation of methyl acetate separation from its mixture with methanol by extraction distillation was carried out in ASPEN+ software. In total three case studies were assumed using two different extraction solvents and two solvent regeneration strategies. In case A, novel extraction solvent 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid, was considered. Raw material separation was achieved in an extraction distillation column while the solvent regeneration was accomplished in a second distillation column in this case. In case study B, the same extraction solvent was used; however, its regeneration was carried out in a single-effect evaporator. Dimethyl sulfoxide was the second extraction solvent selected. Its use in methyl acetate-methanol separation is presented in case study C. As high purity of dimethyl sulfoxide was required for the methyl acetate-methanol azeotrope breaking, its regeneration was carried out in the second distillation column only. To simulate the ternary methyl acetate–methanol–extraction solvent mixtures separation, vapor–liquid equilibrium was predicted based on the NRTL equation. Further, unknown properties of the considered ionic liquid and variation of these properties with temperature were predicted and introduced into the ASPEN+ components properties database. Based on these data, optimum operation parameters of the respective separation equipment were established. In all case studies, the same condition had to be fulfilled, namely minimum methyl acetate content in the distillate from the extraction distillation column of 99.5mol-%. Results of simulations using the respective optimum operation parameters were employed in the economic evaluation of the three separation unit designs studied. It was found that the least energy-demanding design corresponds to the case study B in terms of both capital as well as operation expenses.
An innovative and efficient design of solar receivers/reactors can enhance the production of clean fuels via concentrated solar energy. This study presents a new jet-type burner nozzle for gaseous feedstock injection into a cavity solar receiver inspired from the combustion technology. The nozzle design was adapted from a combustion burner and successfully implemented into a solar receiver and studied the influence of the nozzle design on the fluid mixing and temperature distribution inside the solar receiver using a 7 kW solar simulator and nitrogen as working fluid. Finally, a thorough computational fluid dynamics (CFD) analysis was performed and validated against the experimental results. The CFD results showed a variation of the gas flow pattern and gas mixing after the burner nozzle adaptation, which resulted an intense effect on the heat transfer inside the solar receiver.
Due to the foreseen growth of sustainable energy utilization in the upcoming years, storage of the excess production is becoming a rather serious matter. In this work, a promising solution to this issue is investigated using one of the most emerging technologies of electricity conversion: reversible solid oxide cells (RSOC). A detailed model was created so as to study the RSOC performance before implementing it in the global co-electrolysis Aspen PlusTM model. The model was compared to experimental results and showed good agreement with the available data under steady state conditions. The system was then scaled up to a 10 MW co-electrolysis unit operating at 1073 K and 3 bar. The produced syngas is subsequently directed to a methanation unit to produce a synthetic natural gas (SNG) with an equivalent chemical power of 8.3 MWth. Additionally, as a result of a heat integration analysis, the methanation process provides steam and electricity to operate the rest of the units in the process. A final CO2 capture step is added to ensure the required specifications of the produced SNG for gas network injection. Lastly, the overall performance of the power-to-gas process was evaluated taking into account the energy consumption of each unit.
Biomass is of growing interest as a secondary energy source and can be converted to fuels with higher energy density especially by pyrolysis or gasification. Understanding the mechanism and the kinetics of biomass pyrolysis (thermal decomposition) and gasification (conversion of organic material to gases) could be the key to the design of industrial devices capable of processing vast amounts of biomass feedstock. In our work real product components obtained in pyrolysis were took into consideration as well as char and oil as lumped components, and the kinetic constants for a biomass model compound (cellulose) pyrolysis and gasification were identified based on a proposed simplified reaction mechanism within a compartment model structure. A laboratory scale reactor was used for the physical experiments containing consecutive fast pyrolysis and gasification stages using alkali metal (K) containing feedstock, which has a significant effect on the cellulose pyrolysis and gasification. The detailed model was implemented in MATLAB/Simulink environment, and the unknown kinetic parameters were identified based on experimental data. The model was validated based on measurement data, and a good agreement was found. Based on the validated first principle model the optimal parameters were determined as 0.15 mL/min steam flow rate, and 4% K content.
For improving wastewater quality, one of the dare of steelworks is reducing cyanide in wastewater of gas washing treatment of blast furnaces. Costs of existing treatments, stringent environmental regulations and changeable composition of water from gas treatment, have led to study how available treatments can be modified and to examine new ones. Ozonation is one of cyanide treatments, tested within a European project. A process model was set up with Aspen Plus®, to assess operating conditions and wastewater distinctive characteristics and to demonstrate treatment robustness. Process was modeled by theoretical reactors, taking into account all more affecting reactions. A genetic algorithm was exploited to find kinetic parameters of these reactions. After validation, the model was used to analyse scenarios, by considering also real contexts. Pilot tests were extended, process knowledge was enhanced and suggestions were obtained. To promote cyanide removal with ozone, temperature and pH values were 30°C and 10, respectively. With an ozone (mg/h)/water (L/h) ratio of 100 mg/L, batch mode ensure reaching cyanide regulation limit (0.2 mg/L) after maximum 4.5 h, if initial amount was less than 20 mg/L. Higher removal was obtained than in continuous mode due to constraints related to this last run. Higher wastewater contamination needed further time and more ozone.
Waste-to-energy supply chains are important potential contributors to minimising the environmental impacts of municipal solid waste by reducing the amounts of waste sent to landfill, as well as the fossil fuel consumption and environmental footprints. Accounting for the spatial and transport properties of the waste-to-energy supply chains is crucial for understanding the problem and improving the supply chain designs. The most significant challenge is the distributed nature of the waste generation and the household energy demands. The current work proposes concepts and a procedure for targeting the size of the municipal solid waste collection zone as the first step in the waste-to-energy supply chains synthesis. The formulated concepts and the provided case study reveal trends of reducing the net greenhouse gas savings and energy recovery by increasing the collection zone size. Population density has a positive correlation with the greenhouse gas saving and energy recovery performance. For smaller zone size the energy recovery from waste approaches and in some cases may surpass the energy spent on waste transportation. The energy recovery and greenhouse gas savings remain significant even for collection zones as large as 200 km2. The obtained trends are discussed and key directions for future work are proposed.
Process plants should be designed to be economically viable and environmentally friendly, while also being operable and maintainable during process implementation. The safety of processes is among the most important considerations in obtaining results that are more acceptably realistic, as it is linked to the availability and reliability of the process. Inherent safety can effectively be enhanced in the early stages of the design, when the main decisions on process design are made. The aim of this study is to enhance and select the appropriate risk assessment method and to incorporate it into process synthesis, using a mathematical programming approach. A mixed-integer, nonlinear programming (MINLP) model was used for the synthesis of a methanol production process, considering risk assessment during the synthesis. Risk assessment is performed simultaneously with the MINLP process synthesis, where the risk is determined either for the whole process as overall risk, or on a per unit-of-a-product basis. For the latter, a new measurement is proposed: the inherent risk footprint. The results of a case study led to two main conclusions: (i) Significantly safer designs can be obtained at negligible economic expense, and (ii) at higher production capacities, a lower inherent risk footprint can be achieved. The results also indicate that designs obtained using this method can have significantly increased inherent safety, while remaining economically viable.
Grid stability is being challenged by the increasing integration of power plants with volatile power generation into the energy system. Power supply fluctuations must be compensated by energy system flexibility. The storability of the energy carrier enables biogas plants to generate power flexibly. In this study, the technical and economic effects of providing positive secondary control energy reserves with an Austrian biogas plant were assessed. The plant’s main focus lies in biomethane production with the option of heat and power generation through combined heat and power (CHP) units. A detailed simulation model of the investigated biogas plant was developed, which is presented in this work. Ex-post simulations of one year of flexible plant operation were conducted with this model. The findings show that the installed biogas storage capacity is sufficient to provide control energy reserves while simultaneously producing biomethane. Profitability of providing control energy reserves largely depends on the prices at the control energy market and on CHP unit start-up costs. A cost efficiency analysis demonstrated that investing in a hot water tank with a volume of 5 m3 for short-term heat storage turned out to be economically viable.
We have developed a whole-cell bioconversion system for the production of D-1,2,4-butanetriol (BT) from renewable biomass. A plasmid pETduet-xylB-yjhG-T7-adhP-T7-mdlC was constructed and transformed to Escherichia coli BL21(DE3) to obtain the whole cells of E. coli BL21-XYMA capable of bioconversion D-xylose to BT. Then, the factors including carbon sources, nitrogen sources, metal ions, and culture conditions (pH, temperature, IPTG) were identified, and their effects on the whole-cell activity for BT production were investigated. To obtain the highest whole-cell activity, the optimal cultivation parameters are: 15 g·L−1 yeast extract, 5 g·L−1 sucrose, 3 g·L−1 KH2PO4, 5 g·L−1 NaCl, 3 g·L−1 NH4Cl, 0.25 g·L−1 MgSO4∙7H2O and 1 mL·L−1 the mixture of trace elements. With the optimized whole cells of E. coli BL21-XYMA, 60 g·L−1 of xylose was converted to 28 g·L−1 BT with a molar yield of 66.0%, which is higher than those reported in the biotechnological system.
Hierarchical ZSM-5 zeolite aggregates with different sizes of nanocrystals were synthesized using different amounts of the mesoporogen 3-aminopropyltriethoxysilane. The effect of the crystal size on the catalytic cracking of n-heptane was investigated and the Thiele modulus and effectiveness factor were used to determine the reaction rate-limiting step. The crystal size affected the textual properties of the catalysts but not the acidic properties of the catalysts. The reaction rate was first order with respect to the n-heptane concentration. Cracking over hierarchical zeolites with nanocrystal sizes larger than about 50 nm took place under transition-limiting conditions, whereas the reaction over hierarchical zeolites with nanocrystal sizes of 15 or 30 nm proceeded under reaction control conditions. Hierarchical ZSM-5 zeolite aggregates with smaller nanocrystals had better selectivity for light olefins which can be ascribed to the shorter diffusion path lengths and lower diffusion resistance in these catalysts. Furthermore, these catalysts had lower coking levels which can be attributed to the substantial number of mesopores which prevent the formation of coke precursors.
A noble-metal-free catalyst based on both Mn3O4 and MnO was prepared by using the dielectric barrier discharge technique at moderate temperature. The prepared catalyst shows a higher electrocatalytic activity towards the oxygen reduction reaction than the catalyst prepared by using the traditional calcination process. The enhanced activity could be due to the coexistence of manganese ions with different valences, the higher oxygen adsorption capacity, and the suppressed aggregation of the catalyst nanoparticles at moderate temperature. The present work would open a new way to prepare low-cost and noble-metal-free catalysts at moderate temperature for more efficient electrocatalysis.
Nanorod hydroxyapatite (NRHA)/graphene oxide (GO) composites with weight ratios of 0.4, 1.5, and 5 have been fabricated by a facile ultrasonic-assisted method at room temperature and atmospheric pressure. The chemical structure properties and morphology of the composites were characterized by field emission source scanning electron microscope, X-ray diffraction, transmission electron microscopy, and high-resolution transmission electron microscopy. The results indicate that the NRHA/GO composites have an irregular surface with different degree wrinkles and are stable, and NRHA are well combined with GO. In addition, the biomimetic mineralization mechanism of hydroxyapatite on the NRHA/GO composites in simulated body fluid (SBF) is presented. The presence of a bone-like apatite layer on the composite surface indicate that the NRHA/GO composites facilitate the nucleation and growth of hydroxyapatite crystals in SBF for biomimetic mineralization. Moreover, the NRHA-1.5/GO composite and pure GO were cultured with MC3T3-E1 cells to investigate the proliferation and adhesion of cells. In vitro cytocompatibility evaluation demonstrated that the NRHA/GO composite can act as a good template for the growth and adhesion of cells. Therefore, the NRHA/GO composite could be applied as a GO-based, free-template, non-toxic, and bioactive composite to substitute for a damaged or defect bone.
The synthetic chromosome rearrangement and modification by loxP-mediated evolution (SCRaMbLE) system has been used to improve prodeoxyviolacein (PDV) production in haploid yeast containing chromosome synV. To rapidly and continuously generate genome diversification with the desired phenotype, the multiplex SCRaMbLE iterative cycle strategy has been developed for the screening of high PDV production strains. Whole-genome sequencing analysis reveals large duplications, deletions, and even the whole genome duplications. The deletion of YER151C is proved to be responsible for the increase. This study demonstrates that artificial DNA rearrangement can be used to accelerate microbial evolution and the production of biobased chemicals.
This paper analyses factors affecting the production of greenhouse gases from the treatment of residual municipal waste. The analysis is conducted so that the environmentally-friendly decision-making criteria may be later implemented into an optimisation task, which allocates waste treatment capacities. A simplified method of life cycle assessment is applied to describe environmental impact of the allocation. Global warming potential (GWP) is employed as a unit to quantify greenhouse gases (GHG) emissions. The objective is to identify the environmental burdens and credits measured by GWP for the three fundamental methods for treatment of residual waste unsuitable for material recovery. The three methods are waste-to-energy (WTE), landfilling and mechanical-biological treatment (MBT) with subsequent utilization of refuse-derived fuel. The composition of the waste itself and content of fossil-derived carbon and biogenic carbon are important parameters to identify amounts of GHG. In case of WTE, subsequent use of the energy, e.g., in district heating systems in case of heat, is another important parameter to be considered. GWP function dependant on WTE capacity is introduced. The conclusion of this paper provides an assessment of the potential benefits of the results in optimisation tasks for the planning of overall strategy in waste management.
Water splitting is a highly promising approach for the generation of sustainable, clean hydrogen energy. Tremendous efforts have been devoted to exploring highly efficient and abundant metal oxide electrocatalysts for oxygen evolution and hydrogen evolution reactions to lower the energy consumption in water splitting. In this review, we summarize the recent advances on the development of metal oxide electrocatalysts with special emphasis on the structural engineering of nanostructures from particle size, composition, crystalline facet, hybrid structure as well as the conductive supports. The special strategies relay on the transformation from the metal organic framework and ion exchange reactions for the preparation of novel metal oxide nanostructures with boosting the catalytic activities are also discussed. The fascinating methods would pave the way for rational design of advanced electrocatalysts for efficient water splitting.
With the development of carbon catalysts, graphene-based metal-free catalysts have drawn increasing attention in both scientific research and in industrial chemical production processes. In recent years, the catalytic activities of metal-free catalysts have significantly improved and they have become promising alternatives to traditional metal-based catalysts. The use of metal-free catalysts greatly improves the sustainability of chemical processes. In view of this, the recent progress in the preparation of graphene-based metal-free catalysts along with their applications in catalytic oxidation, reduction and coupling reactions are summarized in this review. The future trends and challenges for the design of graphene-based materials for industrial organic catalytic reactions with good stabilities and high catalytic performance are also discussed.
Hydrocracking of petroleum feedstock represents a compelling route for the production of industrial clean fuels, which has triggered the continuous research and development of core technology related areas such as catalysts, reaction engineering and engineering design. This review particularly focuses on the research and development of catalysts and catalytic processes for hydrocracking of petroleum feedstock in China. Hydroprocessing technologies of China keep pace with the up-to-date progress of the world, and some of the technologies have achieved leading role in the world. It is noted that China Petroleum and Chemical Corporation has a full range of hydroprocessing technologies and provides corresponding “tailor-made” catalysts. Through the efforts of several generations, 20 categories of the catalysts including more than 60 brands have been developed, among which more than 40 brands have been successfully applied for more than 130 times. Importantly, the pivotal technical improvements including the deep drawing vacuum gas-oil (VGO) and de-asphalting oil hydrocracking technology to improve material adaptability, the high value-added hydrogenation technology to convert high aromatic diesel conversion to naphtha, the hydrocracking technology using VGO-catalytic diesel blends, the Fushun Research Institute of Petroleum and Petrochemicals’ diesel to gasoline and diesel hydrocracking technologies, and the Sheer hydrocracking technology to reduce energy are reviewed.
A survey addressing the uses of bismuth oxide in photocatalysis is presented. The richness of literature on such a specific topic proves the growing importance of this compound as a valid tool in pollution abatement and environmental decontamination. Many research groups have focused their activity on how to improve the photocatalytic properties of this semiconductor and several solutions have been adopted in the synthesis method, often based on wet-chemical processes. The impressive development of nanoscience helped in understanding and identifying process variables and operative conditions aiming at optimizing the yield of this promising photocatalytic material in the utilization of solar energy.
