Effect of solid residence time on CO<Subscript>2</Subscript> selectivity in a semi-continuous chemical looping combustor

Chemical looping combustion (CLC) is a promising technology for fossil fuel combustion with inherent CO₂ capture and sequestration, which is able to mitigate greenhouse gases (GHGs) emission. In this study, to design a 0.5MW_th pressurized chemical looping combustor for natural gas and syngas the effects of solid residences time on CO₂ selectivity were investigated in a novel semi-continuous CLC reactor using Ni-based oxygen carrier particle. The semi-continuous chemical looping combustor was designed to simulate the fuel reactor of the continuous chemical looping combustor. It consists of an upper hopper, a screw conveyor, a fluidized bed reactor, and a lower hopper. Solid circulation rate (G _s ) was controlled by adjusting the rotational speed of the screw conveyor. The measured solid circulation rate increased linearly as the rotational speed of the screw increased and showed almost the same values regardless of temperature and fluidization velocity up to 800°C and 4 U _mf , respectively. The solid circulation rate required to achieve 100% CH₄ conversion was varied to change G _s -fuel ratio (oxygen carrier feeding rate/fuel feeding rate, kg/Nm³). The measured CO₂ selectivity was greater than 98% when the Gs-fuel ratio was higher than 78 kg/Nm³.     

Characteristic Study of Silicon Nitride Films Deposited by LPCVD and PECVD

This paper analyzes and compares the characteristics of silicon nitride films deposited by low pressure chemical vapor deposition (LPCVD) and plasma enhanced chemical vapor deposition (PECVD), with special attention to the hydrogenation and chemical composition of silicon nitride films. Three different LPCVD processes at various DCS and NH₃ gas flow rates and deposition temperatures, together with PECVD using SiH₄ and NH₃ and ICP CVD using SiH₄ and N₂, were compared. The silicon nitride film deposition rate decreases with an increasing NH₃/DCS ratio in LPCVD, which also leads to an increase in the refractive index and a decrease in the residual stress in the film. There is nearly no hydrogen incorporated in the LPCVD films, which differs from PECVD and ICP CVD that show significant Si-H and N-H bonds. The chemical composition of silicon nitride films is mostly Si-rich, except for the LPCVD process at high NH₃/DCS ratio with near stoichiometric chemistry.     

Carbon-negative syngas production: A comprehensive assessment of biomass pyrolysis coupling chemical looping reforming

This article introduces a pyrolysis chemical looping reforming (PCLR) process that produces carbon-negative syngas in autothermal operation. To enhance the system's carbon negativity, a process configuration with oxygen carrier two-stage regeneration is adopted, enabling internal CO₂ utilization. The PCLR process is systematically evaluated and compared to chemical looping gasification and steam gasification processes in the process performance, energy efficiency, and environmental impact using a process model. Results reveal significant improvements over chemical looping gasification, including 69%, 45%, and 4% improvement in syngas yield, energy efficiency, and environmental benefit. Process analysis demonstrates that decoupling volatile reforming from pyrolysis and combustion enhances syngas quality, energy efficiency, and process flexibility. While the two-stage regeneration sacrifices syngas production, it contributes to a 4% increase in carbon negativity and a 15% reduction in carbon emissions. Thus, the PCLR process effectively overcomes the limitations of chemical looping gasification systems and exhibits excellent process intensification performance.     

Design and operational considerations of catalytic membrane reactors for ammonia synthesis

Production of ammonia using hydrogen derived from renewable electricity instead of hydrocarbon reforming would dramatically reduce the carbon footprint of this commodity chemical. Novel technologies such as catalytic membrane reactors (CMRs) may potentially be more compatible with distributed ammonia production than the conventional Haber–Bosch process. A reactor model is developed based on integrating a standard industrial iron catalyst into a CMR equipped with an inorganic membrane that is selective to NH₃ over N₂/H₂. CMR performance is studied as functions of wide ranges of membrane properties and operating conditions. Conversion and ammonia recovery are dictated principally by the ammonia permeance, and the benefits by using membranes become significant above 100 GPU = 3.4 × 10⁻⁸ mol m⁻² s⁻¹ Pa⁻¹. To be effective, the CMR requires a minimum selectivity for ammonia of 10 over both nitrogen and hydrogen and purity scales with the effective selectivity. Increasing the pressure of operation significantly improves all metrics, and at P = 30 bar with a quality membrane, ammonia is almost completely recovered, enabling direct recycle of unreacted hydrogen and nitrogen without need for recompression. Temperature drives conversion and scales monotonically without thermodynamic limitations in a CMR. Alternatively, the temperature may be reduced as low as 300°C while achieving conversion levels surpassing equilibrium limits at T = 400°C in a conventional reactor.     

Thermodynamics of Hydrogen Production Based on Coal Gasification Integrated with a Dual Chemical Looping Process

The performance of an innovative hydrogen production technology, which is based on a coal gasification system integrated with a dual chemical looping process, namely, chemical looping air separation (CLAS) and calcium looping CO₂ absorption (CaL), is evaluated. CLAS offers an advantage over other mature technologies in that it can reduce capital costs considerably. CaL is an efficient method for hydrogen production and CO₂ capturing. The proposed technologies are studied by Aspen Plus based on the Gibbs free energy minimization principle. The key factors in terms of reduction temperature, gasification pressure, temperature of water‐gas shift reaction, and water consumption, which proved to have a significant impact on the performance of the whole hydrogen generation process, are discussed.     

Oxygen uncoupling behaviour for ilmenite ore oxygen carrier generated from a calcination treatment mixed with natural manganese ore

Chemical looping with O₂ uncoupling aims at using an oxygen carrier (OC) with O₂ uncoupling behaviour to promote fuel conversion. Natural ilmenite ores have been considered highly promising OCs for chemical looping technology; however, they do not possess any O₂ uncoupling behaviour. Mn-modified ilmenite ores as OCs are capable of O₂ uncoupling, while most of them are synthesized via complicated procedures by using costly chemicals. In this study, a strategy of calcination treatment on ilmenite ores mixed with manganese ores has been established to introduce Mn into the ilmenite OCs, endowing them with O₂ uncoupling behaviour in a simple and low-cost manner. The O₂ uncoupling behaviour from Mn-modified ilmenite ores is mainly due to the newly formed (Fe_1−xMn_x)₂O₃/(Fe_1−xMn_x)₃O₄ crystal phases generated during the calcination treatment, which also alleviate the thermodynamic limit of the Mn₂O₃-Mn₃O₄ redox pair. As a result, the Mn-modified ilmenite ore OCs can release O₂ at high temperatures when decreasing the oxygen partial pressure. But more importantly, the reduced OCs can be restored in the air isothermally. This established simple calcination treatment method can be used as a low-cost strategy for producing ilmenite-based OCs with O₂ uncoupling behaviour. The O₂ uncoupling behaviour is expected to be beneficial to chemical looping combustion of fuels, promote fuel conversion, minimize OC loading, and reduce energy consumption.     

Modularization strategy for syngas generation in chemical looping methane reforming systems with CO2 as feedstock

This study considers a CO₂ feedstock in conventional methane reforming processes and metal oxide lattice oxygen based chemical looping reforming. Lattice oxygen from iron‐titanium composite metal oxide provides the most efficient co‐utilization of CO₂ with CH₄. A modularization chemical looping strategy is developed to further improve process efficiencies using a thermodynamic rationale. Modularization leverages the ability of two or more reactors operating in parallel to produce a higher quality syngas than a single reactor operating alone while offering a direct solution to scale up of multiple parallel reactor processes. Experiments conducted validate the thermodynamic simulation results. Simulation and experimental results ascertain that a cocurrent moving bed in a modularization system can operate under CO₂ neutral or negative conditions. The results for a modularization process system for 7950 m³ per day (50,000 barrels per day) of liquid fuel indicate a ～23% reduction of natural gas usage over baseline‐case. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3343–3360, 2017     

Aligned carbon nanotubes fabricated by thermal CVD at atmospheric pressure using Co as catalyst with NH3 as reactive gas

Co is used as a catalyst for chemical vapor deposition (CVD) of vertically aligned multi-walled carbon nanotubes (CNTs) in a tube furnace at atmospheric pressure. C₂H₂ and NH₃ were used for the carbon feedstock and reaction control, respectively. The CVD process parameters determine the chemical properties of the Co particles and subsequently the morphologies and field emission behavior of CNTs as they strongly depend upon the catalyst condition. The flow rate ratio of NH₃ to C₂H₂ is shown to be central to the synthesis of vertically aligned CNTs. Repeatable synthesis of vertically aligned CNTs at atmospheric pressure in a tube furnace is cost effective for large area deposition of such structures which may be used, for example, in vacuum field emission devices.     

Effect of Gasifying Medium on the Coal Chemical Looping Gasification with CaSO4 as Oxygen Carrier

The chemical looping gasification uses an oxygen carrier for solid fuel gasification by supplying insufficient lattice oxygen. The effect of gasifying medium on the coal chemical looping gasification with CaSO₄ as oxygen carrier is investigated in this paper. The thermodynamical analysis indicates that the addition of steam and CO₂ into the system can reduce the reaction temperature, at which the concentration of syngas reaches its maximum value. Experimental result in thermogravimetric analyzer and a fixed-bed reactor shows that the mixture sample goes through three stages, drying stage, pyrolysis stage and chemical looping gasification stage, with the temperature for three different gaseous media. The peak fitting and isoconversional methods are used to determine the reaction mechanism of the complex reactions in the chemical looping gasification process. It demonstrates that the gasifying medium (steam or CO₂) boosts the chemical looping process by reducing the activation energy in the overall reaction and gasification reactions of coal char. However, the mechanism using steam as the gasifying medium differs from that using CO₂. With steam as the gasifying medium, parallel reactions occur in the beginning stage, followed by a limiting stage shifting from a kinetic to a diffusion regime. It is opposite to the reaction mechanism with CO₂ as the gasifying medium.     

A target‐oriented solid‐gas thermochemical sorption heat transformer for integrated energy storage and energy upgrade

An innovative target‐oriented solid‐gas thermochemical sorption heat transformer is developed for the integrated energy storage and energy upgrade of low‐grade thermal energy. The operating principle of the proposed energy storage system is based on the reversible solid‐gas chemical reaction whereby thermal energy is stored in form of chemical bonds with thermochemical sorption process. A novel thermochemical sorption cycle is proposed to upgrade the stored thermal energy by using a pressure‐reducing desorption method during energy storage process and a temperature‐lift adsorption technique during energy release process. Theoretical analysis showed that the proposed target‐oriented thermochemical sorption heat transformer is effective for the integrated energy storage and energy upgrade, and the low‐grade thermal energy can be upgraded from 87 to 171^°C using a group of sorption working pair MnCl₂‐CaCl₂‐NH₃. Moreover, it can give the flexibility of deciding the temperature magnitude of energy upgrade by choosing appropriate sorption working pairs. © 2012 American Institute of Chemical Engineers AIChE J, 59: 1334–1347, 2013     

Gas-phase elemental mercury removal by novel carbon-based sorbents

To develop cost-effective carbon-based sorbents used in gas-phase elemental mercury removal, the performance of commercial bamboo charcoal (BC) produced from renewable bioresource of bamboo and modified BC was investigated with a bench-scale fixed-bed reactor. The simple impregnation method was used to modify the BC using ZnCl₂, NH₃·H₂O and HNO₃ separately. BET, XPS, elemental analysis and FT-IR were used to determine the pore structure and surface chemistry of the sorbents. The characterization of the physical and chemical properties of sorbents in relation to Hg⁰ adsorption capacity provided important information on the Hg⁰ adsorption mechanism. This suggested that the modified BCs have excellent adsorption potential for elemental mercury at a relatively higher temperature of 140 °C except for the NH₃·H₂O impregnated BC. The amount of Hg⁰ absorbed depends on the concentration of impregnant used. The impregnation has increased the sorbents’ active sites for mercury adsorption and the specific reaction mechanism has been further analyzed.     

Physical mixtures as simple and efficient alternative to alloy carriers in chemical looping processes

Chemical looping combustion is a clean combustion technology for fossil or renewable fuels. In a previous demonstration, chemical looping was applied to CO₂ activation via reduction to CO with concurrent production of synthesis gas (CO + H₂) from CH₄ via rationally designed Fe‐Ni alloys. Here, it is demonstrated that that a simple physical mixture can even outperform the equivalent alloy based on an intricate gas phase mediated coupling between the two metals: Ni cracks methane to carbon and H₂. The latter then reduces iron oxide carrier, forming steam, which gasifies the carbon deposits on Ni to produce a mixture of CO + H₂, thus regenerating the active Ni surface. It was suggested that the principle demonstrated here—the gas phase‐mediated coupling of two solid reactants with distinct functionalities—should be applicable broadly toward oxidation reactions and hence opens a new avenue for rational design of chemical looping processes. © 2016 American Institute of Chemical Engineers AIChE J, 63: 51–59, 2017     

Sol–gel Synthesis of LaBO<Subscript>3</Subscript>/Attapulgite (B=Mn,Fe, Co,Ni) Nanocomposite for NH<Subscript>3</Subscript>-SCR of NO at Low Temperature

LaBO₃/attapulgite (ATP) (B=Mn, Fe, Co, Ni) composites were prepared by sol–gel method using citric acid as complex agent. The products were characterized by X-ray diffraction transmission electron microscopy, energy-dispersive spectroscopy, Battett–Emmett–Teller, fourier-transform infrared, H₂ temperature-programmed reduction and temperature-programmed desorption of NH₃ measurements. The catalytic activity of LaBO₃/ATP nanocomposites was evaluated via selective catalytic reduction of NO with NH₃ by fixed bed denitration equipment at low-temperature. The impact of the various B-site elements on the NO conversion was investigated. Results showed that the adsorption capacity of NH₃ played significant role in the low temperature denitrification process, and Mn was the best B-site element where LaMnO₃/ATP achieves 81% conversion of NO at 250 °C.     

Chelation-activated multiple-site reversible chemical absorption of ammonia in ionic liquids

Developing new and facile strategies for multiple-site reversible chemical absorption of pollutant gases is of wide interests in chemical engineering research. Herein, a series of lithium (Li)-triethylene glycol (TEG)–chelated ionic liquids (ILs) with crown-ether-like cation and different anions were designed. The Li-TEG–chelated ILs were prepared in quantitative yields by simply mixing equimolar TEG and Li salts. It is found that the chelation of TEG with Li⁺ activates the hydroxyl sites in TEG for strong interaction with ammonia (NH₃). Thus, the hydroxyl sites chelated with Li⁺, as well as the chelation-unsaturated Li⁺, provide the multiple sites for chemical absorption of NH₃ in Li-TEG–chelated ILs. Moreover, the absorption of NH₃ in Li-TEG–chelated ILs is totally reversible, with the NH₃ solubilities remaining unchanged after eight times of recycling. The results obtained herein can provide useful guidance for the construction of gas absorbents with high capacity and excellent reversibility.     

Promotion effect and mechanism of MnOx doped CeO2 nano-catalyst for NH3-SCR

MnO_x-CeO₂ (denoted as Mn–Ce) nanorod and MnO_x-CeO₂ nanooctahedra catalysts were synthesized by the hydrothermal method and were used for selective catalytic reduction of NO with NH₃. The catalytic performance tests showed that the NO removal efficiency of CeO₂ catalysts was obviously improved after loading MnO_x. The structure and properties of catalysts had been characterized by SEM、TEM、XRD、BET、XPS、H₂-TPR、NH₃-TPD and in situ DRIFTS. It was found that Mn–Ce catalyst were of uniform core-shell structure, higher concentrations of Mn⁴⁺ and Ce³⁺, better reducibility, the increase of weak acid sites. The results of in situ DRIFTS indicated that the NH₃-SCR reaction should obey the E–R mechanism. Moreover, the promotion effect and mechanism of MnO_x doped CeO₂ was demonstrated, which improved the catalytic activity of Mn–Ce catalysts.     

Insights into the intrinsic interaction between series of C1 molecules and surface of NiO oxygen carriers involved in chemical looping processes

Understanding and modulating the interaction between various reactive molecules and oxygen carriers are the key issue to achieve process intensification of chemical looping technology. C1 chemical molecules play an important role in many reactions involved with chemical looping processes. However, up to now, there is still a lack of systematic and in-depth understanding of the adsorption mechanism of C1 molecules on the surface of oxygen carriers (OCs). In this work, the intrinsic interaction between a series of C1 molecules composed of CH₄, CO, CO₂, CH₃OH, HCHO and HCOOH and surface of NiO OCs in the chemical looping process have been studied using density functional theory calculations. Various adsorption configurations of C1 molecules and also different adsorption sites of NiO have been considered. The structural features of stable configuration of C1 molecules on the surface of NiO OCs have been obtained. Further, the interacted sites, types and strengths of C1 molecules on the surface of NiO have been directly pictured by the independent gradient model methods. Also, the nature of the interaction between C1 molecule and NiO surface has been investigated with the aid of energy decomposition analysis from a quantitative view.     

Recent advances of ammonia synthesis under ambient conditions over metal-organic framework based electrocatalysts

Ammonia (NH₃) is an essential chemical and a promising fuel, but its industrially produced process is carbon-intensive and highly energy-consuming. Developing a green and sustainable NH₃ synthesis route is extremely urgent. Electrochemical ammonia synthesis (EAS) powered by renewable electricity energy under ambient conditions is fascinating, while exploring the efficient electrocatalysts and suitable nitrogen source is critical. Due to the unique characteristics of adjustable porosity and component, large specific surface area and diverse structure, metal-organic frameworks (MOFs) and their various derivatives have captured immense interest in EAS. Herein, the advance in EAS via electrocatalytic reduction reactions (ERRs) from various nitrogen source under ambient conditions over MOF-based electrocatalysts is timely summarized, aiming to offer a deep insight to the structure-activity relationship of MOF-based electrocatalysts for EAS. Current challenges and future prospects for EAS are proposed at the end of this review as well.     

Catalytic activity of chromium spinels in SCR of NO with NH3

Series of chromium spinels MCr₂O₄ (M = Mg, Zn, Fe, Co, Ni, Cu, Mn) were tested in the selective catalytic reduction (SCR) of NO with NH₃. Catalytic activity and selectivity to N₂O depend on the nature of the divalent metal M. The studies by TPR, XPS and chemical analysis lead to the conclusion that the surface layer of all chromium spinels decomposes to simple oxide species containing M²⁺/M³⁺ and Cr³⁺/Cr⁶⁺ redox systems. An increase in the oxidation potential of the redox system is accompanied by a decrease in the selectivity to N₂O in agreement with the mechanism of the reaction proposed by the Niiyma group.     

Studies in mineralization of aqueous aniline using Fenton and wet oxidation (FENTWO) as a hybrid process

A hybrid process for mineralization of aqueous aniline using Fenton and wet oxidation (FENTWO) is studied. It is important to have maximum conversion of ‘N’ atoms from the waste to N₂. The conversion of input ‘N’ atoms in aniline to N₂ was 15% during wet oxidation without the Fenton process and was improved to 50% with the Fenton process. Therefore, a hybrid process of Fenton followed by wet oxidation was studied for mineralization of the aqueous aniline stream. The parameters for the Fenton process were optimized (pH, catalyst, H₂O₂ to catalyst (FeSO₄) ratio, quantity of H₂O₂). The waste obtained after the Fenton process was then treated by wet oxidation for mineralization by having homogeneous CuSO₄ as the catalyst by keeping FeSO₄ therein. This combined catalyst was found to be more effective for the degradation of the intermediates formed in the Fenton process. Wet oxidation (WO) was studied in the temperature range 473–513 K and the oxygen partial pressure range 0.345–1.38 MPa at pH 6.5. The kinetic data was modeled using a power law rate expression in terms of chemical oxygen demand (COD). The optimum temperature for formation of more N₂ gas was found to be 493 K. The treated waste stream was found to contain oxalic acid using HPLC, and NH₄⁺, NO₃^? and NO₂^? ions using ion chromatography analysis. Copyright © 2007 Society of Chemical Industry     

Plasma enhanced chemical deposition of nanocrystalline silicon carbonitride films from trimethyl(phenylamino)silane

Synthetic process for nanocrystalline silicon carbonitride films was developed using plasma-chemical decomposition of a new organosilicon reagent, namely, trimethyl(phenylamino)silane Me₃SiNHPh. Synthesis was carried out from the gaseous mixtures, such as Me₃SiNHPh + He, Me₃SiNHPh + N₂, and Me₃SiNHPh + NH₃, in a reactor in the wide temperature range (473–973 K) under the low pressure (4–5 × 10⁻² Torr). Polished wafers of Si(100), Ge(111), and silica glass were used as substrates. Dependences of the chemical and phase compositions, the surface morphology, and the silicon carbonitride optical properties on the process temperature were studied using FTIR and Raman spectroscopy, energy dispersive spectroscopy (EDS), atomic force microscopy (AFM), scanning electron microscopy (SEM), ellipsometry, and spectrophotometry.