Techno-economic feasibility assessment of sorption enhanced gasification of municipal solid waste for hydrogen production

Waste-to-fuel coupled with carbon capture and storage is forecasted to be an effective way to mitigate the greenhouse gas emissions, reduce the waste sent to landfill and, simultaneously, reduce the dependence of fossil fuels. This study evaluated the techno-economic feasibility of sorption enhanced gasification, which involves in-situ CO₂ capture, and benchmarked it with the conventional steam gasification of municipal solid waste for H₂ production. The impact of a gate fee and tax levied on the fossil CO₂ emissions in economic feasibility was assessed. The results showed that the hydrogen production was enhanced in sorption enhanced gasification, that achieved an optimum H₂ production efficiency of 48.7% (T = 650 °C and SBR = 1.8). This was 1.0% points higher than that of the conventional steam gasification (T = 900 °C and SBR = 1.2). However, the total efficiency, which accounts for H₂ production and net power output, for sorption enhanced gasification was estimated to be 49.3% (T = 650 °C and SBR = 1.8). This was 4.4% points lower than the figure estimated for the conventional gasification (T = 900 °C and SBR = 1.2). The economic performance assessment showed that the sorption enhanced gasification will result in a significantly higher levelised cost of hydrogen (5.0 €/kg) compared to that estimated for conventional steam gasification (2.7 €/kg). The levelised cost of hydrogen can be reduced to 4.5 €/kg on an introduction of the gate fee of 40.0 €/t_MSW. The cost of CO₂ avoided was estimated to be 114.9 €/tCO₂ (no gate fee and tax levied). However, this value can be reduced to 90.1 €/tCO₂ with the introduction of an emission allowance price of 39.6 €/tCO₂. Despite better environmental performance, the capital cost of sorption enhanced gasification needs to be reduced for this technology to become competitive with mature gasification technologies.     

Economic competitiveness of compact steam methane reforming technology for on-site hydrogen supply: A Foshan case study

On-site hydrogen production through steam-methane reforming (SMR) from city gas or natural gas is believed to be a cost-effective way for hydrogen-based infrastructure due to high cost of hydrogen transportation. In recent years, there have been a lot of on-site hydrogen fueling stations under design or construction in China. This study introduces current developments and technology prospects of skid-mounted SMR hydrogen generator. Also, technical solutions and economic analysis are discussed based on China's first on-site hydrogen fueling station project in Foshan. The cost of hydrogen product from skid-mounted SMR hydrogen generator is about 23 CNY/kg with 3.24 CNY/Nm³ natural gas. If hydrogen price is 60 CNY/kg, IRR of on-site hydrogen fueling station project reaches to 10.8%. While natural gas price fall to 2.3 CNY/Nm³, the hydrogen cost can be reduced to 18 CNY/kg, and IRR can be raised to 13.1%. The conclusion is that skid-mounted SMR technology has matured and is developing towards more compact and intelligent design, and will be a promising way for hydrogen fueling infrastructures in near future.     

Robust optimal operation of continuous catalytic reforming process under feedstock uncertainty

The continuous catalytic regenerative (CCR) reforming process is one of the most significant sources of hydrogen production in the petroleum refining process. However, the fluctuations in feedstock composition and flow rate could significantly affect both product distribution and energy consumption. In this study, a robust deviation criterion based multi-objective optimization approach is proposed to perform the optimal operation of CCR reformer under feedstock uncertainty, with simultaneous maximization of product yields and minimization of energy consumption. Minimax approach is adopted to handle these uncertain objectives, and the Latin hypercube sampling method is then used to calculate these robust deviation criteria. Multi-objective surrogate-based optimization methods are next introduced to effectively solve the robust operational problem with high computational cost. The level diagram method is finally utilized to assist in multi-criteria decision-making. Two robust operational optimization problems with different objectives are solved to demonstrate the effectiveness of the proposed method for robust optimal operation of the CCR reforming process under feedstock uncertainty.     

Ammonia production using iron nitride and water as hydrogen source under mild temperature and pressure

Ammonia generation was studied in the reaction between water and nitrogen-containing iron at 323 K and atmospheric pressure. Similar to metallic Fe, the interstitial compound Fe₃N reduced water through Fe oxidation to produce hydrogen gas, while the N combined with atomic hydrogen to produce ammonia as a byproduct. The addition of carbon dioxide to this system accelerated the reaction with concomitant consumption of carbon dioxide. The promoted ammonia production upon addition of carbon dioxide can be attributed to the generation of atomic hydrogen from the redox reaction of carbonic acid and Fe, as well as removal of used Fe from the reaction system through the formation of a soluble carbonato complex. When carbonate was added to the reaction system, the production rates of ammonia and hydrogen increased further. The results here confirmed that ammonia can be synthesized from iron nitride under mild conditions by utilizing carbon dioxide.     

Current trends in structural development and modification strategies for metal-organic frameworks (MOFs) towards photocatalytic H2 production: A review

Photocatalytic H₂ generation using semiconductor photocatalysts is considered as a cost-effective and eco-friendly technology for solar to energy conversion; however, the present photocatalysts have been recognized to depict low efficiency. Currently, porous coordination polymers known as metal-organic frameworks (MOFs) constituting flexible and modifiable porous structure and having excess active sites are considered to be appropriate for photocatalytic H₂ production. This review highlights current progress in structural development of MOF materials along with modification strategies for enhanced photoactivity. Initially, the review discusses the photocatalytic H₂ production mechanism with the concepts of thermodynamics and mass transfer with particular focus on MOFs. Elaboration of the structural categories of MOFs into Type I, Type II, Type III and classification of MOFs for H₂ generation into transition metal based, post-transition metal based, noble-metal based and hetero-metal based has been systematically discussed. The review also critically deliberate various modification approaches of band engineering, improvement of charge separation, efficient irradiation utilization and overall efficiency of MOFs including metal modification, heterojunction formation, Z-scheme formation, by introducing electron mediator, and dye based composites. Also, the MOF synthesized derivatives for photocatalytic H₂ generation are elaborated. Finally, future perspectives of MOFs for H₂ generation and approaches for efficiency improvement have been suggested.     

Techno-economical evaluations of decarbonized hydrogen production based on direct biogas conversion using thermo-chemical looping cycles

Hydrogen production by biogas conversion represent a promising solution for reduction of fossil CO₂ emissions. In this work, a detailed techno-economic analysis was performed for decarbonized hydrogen production based on biogas conversion using calcium and chemical looping cycles. All evaluated concepts generate 100,000 Nm³/h high purity hydrogen. As reference cases, the biogas steam reforming design without decarbonization and with CO₂ capture by gas-liquid chemical absorption were also considered. The results show that iron-based chemical looping design has higher energy efficiency compared with the gas-liquid absorption case by 2.3 net percentage points as well as a superior carbon capture rate (99% vs. 65%). The calcium looping case shows a lower efficiency than chemical scrubbing, with about 2.5 net percentage points, but the carbon capture rate is higher (95% vs. 65%). The hydrogen production cost increases with decarbonization, the calcium looping shows the most favourable situation (37.14 €/MWh) compared to the non-capture steam reforming case (33 €/MWh) and MDEA and iron looping cases (about 42 €/MWh). The calcium looping case has the lowest CO₂ avoidance cost (10 €/t) followed by iron looping (20 €/t) and MDEA (31 €/t) cases.     

Estimates of daily oxygen consumption,carbon dioxide and methane emissions,and heat production for beef and dairy cattle using spot gas sampling

A simulation study was conducted to examine accuracy of estimating daily O₂ consumption, CO₂ and CH₄ emissions, and heat production (HP) using a spot sampling technique and to determine optimal spot sampling frequency (FQ). Data were obtained from 3 experiments where daily O₂ consumption, emissions of CO₂ and CH₄, and HP were measured using indirect calorimetry (respiration chamber or headbox system). Experiment 1 used 8 beef heifers (ad libitum feeding; gaseous exchanges measured every 30 min over 3 d in respiration chambers); Experiment 2 used 56 lactating Holstein-Friesian cows (restricted feeding; gaseous exchanges measured every 12 min over 3 d in respiration chambers); Experiment 3 used 12 lactating Jersey cows (ad libitum feeding; gaseous exchanges measured every hour for 1 d using headbox style chambers). Within experiment, averages of all measurements (FQALL) and averages of measurements selected at time points with 12, 8, 6, or 4 spot sampling FQ (i.e., sampling every 2, 3, 4, and 6 h in a 24-h cycle, respectively; FQ12, FQ8, FQ6, and FQ4, respectively) were compared. Within study a mixed model was used to compare gaseous exchanges and HP among FQALL, FQ12, FQ8, FQ6, and FQ4, and an interaction of dietary treatment by FQ was examined. A regression model was used to evaluate accuracy of spot sampling within study [i.e., FQALL (observed) vs. FQ12, FQ8, FQ6, or FQ4 (estimated)]. No interaction of diet by FQ was observed for any variables except for CH₄ production in experiment 1. No FQ effect was observed for gaseous exchanges and HP except in experiment 2 where CO₂ production was less (5,411 vs. 5,563 L/d) for FQ4 compared with FQALL, FQ12, and FQ8. A regression analysis between FQALL and each FQ within study showed that slopes and intercepts became farther from 1 and 0, respectively, for almost all variables as FQ decreased. Most variables for FQ12 and FQ8 had root mean square prediction error (RMSPE) less than 10% of the mean and concordance correlation coefficient (CCC) greater than 0.80, and RMSPE increased and CCC decreased as FQ decreased. When a regression analysis was conducted with combined data from the 3 experiments (mixed model with study as a random effect), results agreed with those from the analysis for the individual studies. Prediction errors increased and CCC decreased as FQ decreased. Generally, all the estimates from FQ12, FQ8, FQ6, and FQ4 had RMSPE less than 10% of the means and CCC greater than 0.90 except for FQ6 and FQ4 for O₂ consumption and CH₄ production. In conclusion, the spot sampling simulation with 3 indirect calorimetry experiments indicated that FQ of at least 8 samples (every 3 h in a 24-h cycle) was required to estimate daily O₂ consumption, CO₂ and CH₄ production, and HP and to detect changes in those in response to dietary treatments. This sampling FQ may be considered when using techniques that measure spot gas exchanges such as the GreenFeed and face mask systems.     

Effect of nickel concentration on biohydrogen production: Organic solid waste vs. glucose

In recent years, alternative renewable energy generation sources have been investigated, highlighting the dark fermentation process due to it’s potential to obtain hydrogen-rich gas, which can be used as an energy source. Different trace metals intervene in this biological process. Nickel is one of the most important because it is a component of the [Ni–Fe] hydrogenase enzyme that catalyzes the oxidation of H₂ in numerous bacteria. The aim of this study was to evaluate the effect of nickel on biohydrogen production from organic solid waste (OSW). The experimental setup was carried out in batch tests using OSW as the substrate, glucose as a reference compound and the valuation of Ni²⁺ doses on the operation in a Sequencing Batch Reactor. The results of the batch tests showed that when using glucose as a substrate, 2 mg Ni²⁺/g VS_inoculum generated the highest hydrogen production (774 ± 7.3 mL H₂/L/d) and highest yield (55.8 ± 3.4 mL H₂/g of glucose), which was 34.4% higher than the control. Testing of different concentrations of nickel using OSW as a carbon source showed that the highest production was obtained without Ni²⁺ addition since the nickel concentration in the residue was 0.17 ± 0.06 mgNi/gVS; consequently, hydrogen production was not affected by the lack of Ni. The addition of 0.5 mg Ni²⁺/g VS_inoculum decreased acetate and butyrate production and increased caproate production.     

An integrated dimensionality reduction and surrogate optimization approach for plant-wide chemical process operation

With liquefied natural gas becoming increasingly prevalent as a flexible source of energy, the design and optimization of industrial refrigeration cycles becomes even more important. In this article, we propose an integrated surrogate modeling and optimization framework to model and optimize the complex CryoMan Cascade refrigeration cycle. Dimensionality reduction techniques are used to reduce the large number of process decision variables which are subsequently supplied to an array of Gaussian processes, modeling both the process objective as well as feasibility constraints. Through iterative resampling of the rigorous model, this data-driven surrogate is continually refined and subsequently optimized. This approach was not only able to improve on the results of directly optimizing the process flow sheet but also located the set of optimal operating conditions in only 2 h as opposed to the original 3 weeks, facilitating its use in the operational optimization and enhanced process design of large-scale industrial chemical systems.     

Hydrogen production by supercritical water gasification of lignin over CuO–ZnO catalyst synthesized with different methods

In this study, lignin was gasified in supercritical water with catalysis of CuO–ZnO synthesized by deposition precipitation, co-precipitation and sol-gel methods. Sol-gel synthesized CuO–ZnO showed the highest catalytic performance, and the gasification efficiency was increased by 37.92% with it. The XRD, SEM-EDS and N₂ adsorption/desorption analysis showed that the priority of the sol-gel catalyst was the smallest crystallite size, largest specific surface area and high dispersion. For sol-gel synthesized CuO–ZnO, the increase of CuO/ZnO ratio improved the gasification efficiency but reduced H₂ selectivity. And the catalytic activity was reduced with the calcination temperature above 600 °C due to enlarged crystallites and reduced pores. During sol-gel preparation, both the addition of ethanol and PEG in the solvent reduced the agglomeration and improved the catalytic activity. With CuO–ZnO prepared with 1 g PEG + water as the solvent, the highest H₂ yield of 6.86 mol/kg was obtained, which was over 1.5 times of that without catalyst.