A Review of Techniques for the Process Intensification of Fluidized Bed Reactors

Fluidized beds enable good solids mixing,high rates of heat and mass transfer,and large throughputs,but there remain issues related to fluidization quality and scale-up.In this work I review modification techniques for fluidized beds from the perspective of the principles of process intensification(PI),that is,effective bubbling suppression and elutriation control.These techniques are further refined into(1)design factors,e.g.modifying the bed configuration,or the application of internal and external forces,and(2)operational factors,including altering the particle properties(e.g.size,density,surface area)and fluidizing gas properties(e.g.density,viscosity,or velocity).As far as two proposed PI principles are concerned,our review suggests that it ought to be possible to gain improvements of between 2 and 4 times over conventional fluidized bed designs by the application of these techniques.

Process Intensification in Pneumatically Agitated Slurry Reactors

Pneumatically agitated slurry reactors,including bubble column reactors and airlift loop reactors(ALRs),are important gas-liquid-solid multiphase reactors.These reactors have been widely applied in many processes,especially in the biological fermentation and energy chemical industry,due to their low shear stress,good mixing,perfect mass-/heat-transfer properties,and relatively low costs.To further improve the performance of slurry reactors(i.e.,mixing and mass/heat transfer)and to satisfy industrial require-ments(e.g.,temperature control,reduction of back-mixing,and product separation),the process intensi-fication of slurry reactors is essential.This article starts by reviewing the latest advancements in the intensification of mixing and mass/heat transfer in these two types of reactors.It then summarizes process-intensification methods for mixing and separation that allow continuous production in these slurry reactors.Process-intensification technology that integrates directional flow in an ALR with simple solid-liquid separation in a hydrocyclone is recommended for its high efficiency and low costs.This arti-cle also systematically addresses vital considerations and challenges,including flow regime discrimina-tion,gas spargers,solid particle effects,and other concerns in slurry reactors.It introduces the progress of numerical simulation using computational fluid dynamics(CFD)for the rational design of slurry reactors and discusses difficulties in modeling.Finally,it presents conclusions and perspectives on the design of industrial slurry reactors.

Membrane Crystallization for Process Intensification and Control:A Review

Crystallization is a fundamental separation technology used for the production of particulate solids.Accurate nucleation and growth process control are vitally important but difficult.A novel controlling technology that can simultaneously intensify the overall crystallization process remains a significant challenge.Membrane crystallization(MCr),which has progressed significantly in recent years,is a hybrid technology platform with great potential to address this goal.This review illustrates the basic concepts of MCr and its promising applications for crystallization control and process intensification,including a state-of-the-art review of key MCr-utilized membrane materials,process control mechanisms,and optimization strategies based on diverse hybrid membranes and crystallization processes.Finally,efforts to promote MCr technology to industrial use,unexplored issues,and open questions to be addressed are outlined.

Integrated UV-based photo microreactor-distillation technology toward process intensification of continuous ultra-high-purity electronic-grade silicon tetrachloride manufacture

Ultra-high-purity silicon tetrachloride(SiCl4)is demanded as an electronic-grade chemical to meet the stringent requirements of the rapidly developing semiconductor industry.The high requirement for ultra-high-purity SiCl4 has created the need for a high-efficient process for reducing energy consumption as well as satisfying product quality.In this paper,a mass of production technology of ultra-high-purity SiCl4 was successfully developed through chlorination reaction in the ultraviolet(UV)-based photo microreactor coupled with the distillation process.The influences of key operational parameters,including temperature,pressure,UV wavelength and light intensity on the product quality,especially for hydrogen-containing impurities,were quantified by the infrared transmittance of Fourier transform infrared spectroscopy(FT-IR)at 2185 cm^-1and 2160 cm^-1indicating that chara cteristic vib rational modes of Si-H bonds,as well as the operating conditions of distillation were also investigated as key factors for metal impurities removing.The advanced intensification of SiCl4 manufactured by the integration of photo microreactor and distillation achieves the products with superior specifications higher than the standard commercial products.

Process intensification in gas/liquid/solid reaction in trickle bed reactors: A review

As an important form of reactors for gas/liquid/solid catalytic reaction,trickle bed reactors (TBRs) are widely applied in petroleum industry,biochemical,fine chemical and pharmaceutical industries because of their flexibility,simplicity of operation and high throughput.However,TBRs also show inefficient production and hot pots caused by non-uniform fluid distribution and incomplete wetting of the catalyst,which limit their further application in chemical industry.Also,process intensification in TBRs is necessary as the decrease in quality of processed crude oil,caused by increased exploitation depths,and more restrictive environmental regulations and emission standards for industry,caused by increased environment protection consciousness.In recent years,lots of strategies for process intensification in TBRs have been proposed to improve reaction performance to meet the current and future demands of chemical industry from the environmental and economic perspective.This article summarizes the recent progress in techniques for intensifying gas/liquid/solid reaction in TBRs and application of intensified TBRs in petroleum industry.

Process intensification for the synthesis and purification of battery-grade Li_(2)CO_(3)with microfluidics

Battery-grade lithium carbonate(Li_(2)CO_(3))with a purity of higher than 99.5 wt%is of great importance as a high value-added lithium salt.However,influences of different reaction systems and process control on product purity remain unclear.Herein,a membrane dispersion microreactor was used to enhance the mass transfer of preparation and purification processes in homogeneous and heterogeneous system.Synthetic systems of Na_(2)CO_(3)–LiCl,NH_(4)HCO_(3)–LiCl,and NH_(3)·H_(2)O−CO_(2)−LiCl,CO_(2)purification based on carbonation and decomposition were adopted.The Li_(2)CO_(3)purity was increased by the improvement of mixing performance.The carbonation time was reduced by 62.5%and 58.3%for the NH_(3)·H_(2)O−CO_(2)and CO_(2)purification systems,respectively.In the two ammonia-based systems,Li_(2)CO_(3)particles with a purity of 99.7–99.8 wt%were one-step prepared with a size of 3–5μm,which also met the requirement of the battery-grade standard.The purity was further increased to 99.9 wt%by CO_(2)purification and LiHCO_(3)decomposition.The investigation could provide a feasible alternative for the controllable preparation of battery-grade Li_(2)CO_(3)in one or multiple steps.

A review on plasma-based CO_(2) utilization:process considerations in the development of sustainable chemical production

Plasma-based processes,particularly in carbon capture and utilization,hold great potential for addressing environmental challenges and advancing a circular carbon economy.While significant progress has been made in understanding plasma-induced reactions,plasma-catalyst interactions,and reactor development to enhance energy efficiency and conversion,there remains a notable gap in research concerning overall process development.This review emphasizes the critical need for considerations at the process level,including integration and intensification,to facilitate the industrialization of plasma technology for chemical production.Discussions centered on the development of plasma-based processes are made with a primary focus on CO_(2) conversion,offering insights to guide future work for the transition of the technology from laboratory scale to industrial applications.Identification of current research gaps,especially in upscaling and integrating plasma reactors with other process units,is the key to addressing critical issues.The review further delves into relevant research in process evaluation and assessment,providing methodological insights and highlighting key factors for comprehensive economic and sustainability analyses.Additionally,recent advancements in novel plasma systems are reviewed,presenting unique advantages and innovative concepts that could reshape the future of process development.This review provides essential information for navigating the path forward,ensuring a comprehensive understanding of challenges and opportunities in the development of plasma-based CCU process.

Intensification of Ethylene Production from Naphtha via a Redox Oxy-Cracking Scheme： Process Simulations and Analysis

Ethylene production by the thermal cracking of naphtha is an energy-intensive process （up to 40 GJ heat per tonne ethylene）, leading to significant formation of coke and nitrogen oxide （NOx）, along with 1,8- 2 kg of carbon dioxide （CO2） emission per kilogram of ethylene produced, We propose an alternative pro- cess for the redox oxy-cracking （ROC） of naphtha, In this two-step process, hydrogen （H2） from naphtha cracking is selectively comhusted by a redox catalyst with its lattice oxygen first, The redox catalyst is subsequently re-oxidized by air and releases heat, which is used to satisfy the heat requirement for the cracking reactions, This intensified process reduces parasitic energy consumption and CO2 and NOx emissions, Moreover, the formation of ethylene and propylene can he enhanced due to the selective com-bustion of H2, In this study, the ROC process is simulated with ASPEN Plus^R based on experimental data from recently developed redox catalysts, Compared with traditional naphtha cracking, the ROC process can provide up to 52% reduction in energy consumption and CO2 emissions, The upstream section of the process consumes approximately 67% less energy while producing 28% more ethylene and propylene for every kilogram of naphtha feedstock,

Microfluidic field strategy for enhancement and scale up of liquid-liquid homogeneous chemical processes by optimization of 3D spiral baffle structure

Due to the scale effect, the uniform distribution of reagents in continuous flow reactor becomes bad when the channel is enlarged to tens of millimeters. Microfluidic field strategy was proposed to produce high mixing efficiency in large-scale channel. A 3D spiral baffle structure(3SBS) was designed and optimized to form microfluidic field disturbed by continuous secondary flow in millimeter scale Y-shaped tube mixer(YSTM). Enhancement effect of the 3SBS in liquid-liquid homogeneous chemical processes was verified and evaluated through the combination of simulation and experiment. Compared with 1 mm YSTM, 10 mm YSTM with 3SBS increased the treatment capacity by 100 times, shortened the basic complete mixing time by 0.85 times, which proves the potential of microfluidic field strategy in enhancement and scale-up of liquid-liquid homogeneous chemical process.

Microchannel reactive distillation for the conversion of aqueous ethanol to ethylene

Here we demonstrate the proof-of-concept for microchannel reactive distillation for alcohol-to-jet application:combining ethanol/water separation and ethanol dehydration in one unit operation.Ethanol is first distilled into the vapor phase,converted to ethylene and water,and then the water co-product is condensed to shift the reaction equilibrium.Process intensification is achieved through rapid mass transfer-ethanol stripping from thin wicks using novel microchannel architectures-leading to lower residence time and improved separation efficiency.Energy savings are realized with integration of unit operations.For example,heat of condensing water can offset vaporizing ethanol.Furthermore,the dehydration reaction equilibrium shifts towards completion by immediate removal of the water byproduct upon formation while maintaining aqueous feedstock in the condensed phase.For aqueous ethanol feedstock(40%_w),71% ethanol conversion with 91% selectivity to ethylene was demonstrated at 220℃,600psig,and 0.28 h^(-1) wt hour space velocity.2.7 stages of separation were also demonstrated,under these conditions,using a device length of 8.3 cm.This provides a height equivalent of a theoretical plate(HETP),a measure of separation efficiency,of ^(3).3 cm.By comparison,conventional distillation packing provides an HETP of ^(3)0 cm.Thus,9,1 × reduction in HETP was demonstrated over conventional technology,providing a means for significant energy savings and an example of process intensification.Finally,preliminary process economic analysis indicates that by using microchannel reactive distillation technology,the operating and capital costs for the ethanol separation and dehydration portion of an envisioned alcoholto-jet process could be reduced by at least 35% and 55%,respectively,relative to the incumbent technology,provided future improvements to microchannel reactive distillation design and operability are made.

Enhancement of liquid-liquid micromixing performance in curved capillary microreactor by generation of Dean vortices

Micromixing efficiency is an important parameter for evaluating the multiphase mass transfer performance and reaction efficiency of microreactors.In this work,the novel curved capillary reactor with different shapes was designed to generate Dean flow,which was used to enhance the liquid-liquid micromixing performance.The Villermaux-Dushman probe reaction was employed to characterize the micromixing performance in different curved capillary microreactors.The effects of experiment parameters such as liquid flow rate,inner diameter,tube length,and curve diameter on micromixing performance were systematically investigated.Under the optimal conditions,the minimum value of the segmentation factor XS was 0.008.It was worth noting that at the low Reynolds number(Re<30),the change of curved shape on the capillary microreactor can significantly improve the micromixing performance with XS reduced by 37.5%.Further,the correlations of segment index XS with dimensionless factor such as Reynolds number or Dean number were developed,which can be used to predict the liquid-liquid micromixing performance in capillary microreactors.

A new green process for biodiesel production from waste oils via catalytic distillation using a solid acid catalyst-Modeling, economic and environmental analysis

The challenges in the chemical processing industry today are environmental concerns, energy and capital costs. Catalytic distillation(CD) is a green reactor technology which combines a catalytic reaction and separation via distillation in the same distillation column. Utilization of CD in chemical process development could result in capital and energy savings, and the reduction of greenhouse gases. The efficacy of CD and the economic merits, in terms of energy and equipment savings, brought by CD for the production of biodiesel from waste oil such as yellow grease is quantified. Process flow sheets for industrial routes for an annual production of 10 million gallon ASTM purity biodiesel in a conventional process(reactor followed by distillation) and CD configurations are modeled in Aspen Plus. Material and energy flows, as well as sized unit operation blocks, are used to conduct an economic assessment of each process. Total capital investment, total operating and utility costs are calculated for each process. The waste oil feedstock is yellow grease containing both triglyceride and free fatty acid. Both transesterification and esterification reactions are considered in the process simulations. Results show a significant advantage of CD compared to a conventional biodiesel processes due to the reduction of distillation columns, waste streams and greenhouse gas emissions. The significant savings in capital and energy costs together with the reduction of greenhouse gases demonstrate that process intensification via CD is a feasible and new green process for the biodiesel production from waste oils.

Conceptual Design of a Butyl-levulinate Reactive Distillation Process by Incremental Refinement

Butyl-levulinate has been identified as a promising fuel candidate with high oxygen content. Its com- bustion in diesel engines yields very low soot and NOx emissions. It can be produced by the esterification of butanol and levulinic acid, which themselves are platform chemicals in a biorenewables-based chemical supply chain. Since the equilibrium of esterification limits the conversion in a conventional reactor, reactive distillation can be applied to overcome this limitation. The presence of the high-boiling catalyst sulfuric acid requires a further separation step downstream of the reactive distillation column to recover the catalyst for recycle. Optimal design specifications and an optimal operating point are determined using rigorous flowsheet optimization. The challenging optimization problem is solved by a favorable initialization strategy and continuous reformulation. The design identified has the potential to produce a renewable transportation fuel at reasonable cost.

Carbon monoxide production using a steel mill gas in a combined chemical looping process

Up to 9% of the global CO_(2) emissions come from the iron and steel industry. Here, a combined chemical looping process to produce CO, a building block for the chemical industry, from the CO_(2) -rich blast furnace gas of a steel mill is proposed. This cyclic process can make use of abundant Fe_(3)O_(4) and CaO as solid oxygen and CO_(2) carriers at atmospheric pressure. A proof of concept was obtained in a laboratory-scale fixed bed reactor with synthetic blast furnace gas and Fe_(3)O_(4) /CaO = 0.6 kg/kg. CO production from the proposed process was investigated at both isothermal conditions(1023 K) and upon imposing a temperature program from 1023 to 1148 K. The experimental results were compared using performance indicators such as CO yield, CO space time yield, carbon recovery of the process, fuel utilisation, and solids’ utilisation.The temperature-programmed CO production resulted in a CO yield of 0.056 ± 0.002 mol per mol of synthetic blast furnace gas at an average CO space time yield of 7.6 mmol kgFe^(-1) s^(-1) over 10 cycles, carbon recovery of 48% ± 1%, fuel utilisation of 23% ± 2%, and an average calcium oxide and iron oxide utilisation of 22% ± 1% and 11% ± 1%. These experimental performance indicators for the temperature-programmed CO production were consistently better than those of the isothermal implementation mode by 20% to 35%. Over 10 consecutive process cycles, no significant losses in CO yield were observed in either implementation mode. Process simulation was carried out for 1 million metric tonnes per year of equivalent CO_(2) emissions from the blast furnace gas of a steel mill to analyse the exergy losses in both modes of operation. Comparison of the exergy efficiency of the temperature-programmed process to the isothermal process showed that the former is more efficient because of the higher CO concentration achievable,despite 20% higher exergy losses caused by heat transfer required to change temperature.

Continuous,efficient and safe synthesis of 1-oxa-2-azaspiro[2.5]octane in a microreaction system

1-Oxa-2-azaspiro[2.5]octane,as one of N-H oxaziridines,is a selective electrophilic aminating agent for N-,S-,C-,and O-nucleophiles.It has the features of stereoselectivity and the absence of formation of strongly acidic or basic byproducts,leading to considerable interest in the development of organic synthetic methods.Currently,the economically feasible route of production of 1-oxa-2-azaspiro[2.5]octane is the reaction of cyclohexanone with ammonia and sodium hypochlorite.However,due to strong exothermic reactions,massive gas release and heterogeneous reaction,the controllability,efficiency and safety of the reaction are in great difficulty using batch technology.In this paper,a microreaction system containing predispersion,reaction and phase separation was introduced into the preparation of 1-oxa-2-azaspiro[2.5]octane.The research results showed that precise control of the process including droplet dispersion,temperature control,reaction time control and fast continuous phase separation,was the key to process intensification.Under optimal conditions,the concentration of 1-oxa-2-azaspiro[2.5]octane in product obtained by microreaciton system(~2.0 mol·L^(-1))was much higher than that obtained by batch technology(0.2-0.4 mol·L^(-1)),which demonstrated that the continuous-flow synthesis would be a more efficient substitute for batch synthesis.Meanwhile,the results of the derivation experiments also showed that the aminating agent solution with higher concentration was more advantageous in the applications.

Numerical study on the hydrodynamics behavior of a central insert microchannel

In this work, the computational fluid dynamics method is used to study the liquid hydrodynamics behavior in the microchannel without central insert(MC1) and the central insert microchannel(MC2), respectively. The maximum deviation between simulation and experiment is 24%. The formations of flow patterns are explained based on contours and force analysis where the flow pattern maps are established by two-phase flow rate. The effects of aqueous phase viscosity and two-phase flow rate on the characteristic sizes of each flow pattern are also explored. Specifically, four unconventional flow patterns are found in MC2, namely the unique droplet flow, the unique slug flow, the unique coarse annular flow and the unique film annular flow. Though the insert occupies part of the channel, the pressure difference in the channel is significantly reduced compared with MC1. Moreover, the insert significantly changes the formation velocity range of each flow pattern, greatly broadens the formation range of annular flow and also has an important influence on the characteristic size of the flow pattern. The organic-phase dimensionless axial size(Lo/W) and the dimensionless radial size(Do/W) of the droplet(slug) are negatively related to the aqueous-phase viscosity(μa) and flow rate(ua). The Do/W of the annular is negatively correlated with μaand positively correlated with organic-phase flow rate(uo). This study provides direct numerical evidence that the insert is key to the formation of bicontinuous phase flow pattern, as well as further strengthens our understanding of the flow characteristics and optimization design of insert microchannels.

Methanolysis of amides under high-temperature and high-pressure conditions with a continuous tubular reactor

The methanolysis of amides,which is widely employed in the synthetic organic chemistry,hardly occurs under mild conditions.To safely and controllably intensify the methanolysis reaction with hightemperature and high-pressure environment,a continuous tubular reaction technology is developed,whose space-time yield is over twice of that of the conventional batch reaction.The methanolysis of acetanilide is selected as the representative reaction,and the influences of temperature,pressure,reactant and catalyst concentration,and residence time on the reaction performances are systematically investigated.Taking the advantages of precise temperature and reaction time control by the tubular reactor,the kinetics of acetanilide methanolysis are determined and compared to the kinetics of acetanilide hydrolysis reaction.The tubular reaction method is also employed to test a variety of other amides to show the effects of substituents,steric hindrance,and alkalinity on the reaction rate of methanolysis.

A novel method for extracting vanadium by low temperature sodium roasting from converter vanadium slag

Long-term high temperature in conventional vanadium extraction process would cause particles to be sintered and wrapped, thus reducing extraction efficiency of vanadium. Based on the purpose of directional conversion and process intensification, this work proposed a combination of low temperature sodium roasting and high efficiency selective oxidation leaching in vanadium extraction. The investigation of the reaction mechanism suggested that the structure of vanadium slag was changed by roasting, which also caused the fracture of spinel.The addition of MnO2 promoted the directional oxidation of low-valent vanadium into high valence. It also found that Na2S2O8 could oxidize low-valent vanadium effectively in leaching. The leaching efficiency of vanadium reached 87.74% under the optimum conditions, including a roasting temperature of 650 ℃, a roasting time of 2.0 h, a molar ratio of sodium-to-vanadium of 0.6, a MnO2(roasting additive) dosage of 5 wt% and a Na2S2O8(leaching oxidant) dosage of 5 wt%. This percentage is 7.18% higher than that of direct roasting-andleaching under the same conditions.

Current status and future development of solvent-based carbon capture

Solvent-based carbon capture is the most commercially-ready technology for economically and sustainably reaching carbon emission reduction targets in the power sector. Globally, the technology has been deployed to deal with flue gases from large scale power plants and different carbon-intensive industries. The success of the technology is due to significant R＆D activities on the process development and decades of industrial experience on acid gas removal processes from gaseous mixtures. In this paper, current status of PCC based on chemical absorption--commercial deployment and demonstration projects, analysis of different solvents and process configurations--is reviewed. Although some successes have been recorded in developing this technology, its commercialization has been generally slow as evidenced in the cancellation of high profile projects across the world. This is partly due to the huge cost burden of the technology and unpredictable government policies. Different research directions, namely new process development involving process intensification, new solvent development and a combination of both, are discussed in this paper as possible pathways for reducing the huge cost of the technology.

Promoting Xylene Production in Benzene Methylation using Hierarchically Porous ZSM-5 Derived from a Modified Dry-gel Route

Methylation of benzene is an alternative low-cost route to produce xylenes, but selectivity to xylene remains low over conventional zeolitic catalysts. In this work, a combined dry-gel-conversion and steam-assisted- crystallization method is used to synthesize hierarchically porous zeolite ZSM-5 with varied Si/AI malar ratios. X-ray diffraction （XRD）, N2 physisorption, NH3-temperature programmed desorption （TPD）, scanning electronic microscopic （SEM） measurement and Fourier transform infrared （FT-IR） are employed to characterize the struc- ture and acidity of both hierarchically porous zeolites and their conventional counterparts. The method is found to be applicable to ZSM-5 with molar ratios of Si/A1 from 20 to 180. The ZSM-5 zeolites are used as catalysts for benzene methylation at 460 ℃ to investigate the effect of additional porosity and Si/A1 ratios. At low Si/AI ratios, the benzene conversions over conventional and hierarchical ZSM-5 are close, and selectivity to toluene is high over hierarchical ZSM-5. It is found that hierarchical porosity markedly enhances the utility of zeolite and the se- lectivity towards xylenes via improved mass transport at higher Si/Al ratios. Under an optimized hierarchical ZSM-5 catalvst, xvlene selectivity reaches 34.9% at a Si/AI ratio of 180.