Publishing type：Research paper (scientific journal)   Publisher：Elsevier BV  

DOI： 10.1016/j.csite.2021.101363

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Authorship：Corresponding author   Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：Kagaku Kogaku Ronbunshu  

A model-based approach was employed to examine the applicability of a micro-Kalina cycle of up to 20 kW (about 373 K) with a working fluid of ammonia/water for low-grade geothermal heat energy. It was found possible to generate 15‒24 kW using hot springs (353‒393 K, 10,000 kg/h). It was also found that the micro-Kalina cycle shows a temperature glide like a Lorenz cycle under the simulation conditions, and that it had higher power generation performance than the organic Rankin cycle.

DOI： 10.1252/kakoronbunshu.47.143

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Publisher：Molecules  

The microwave-assisted heating reaction of N-acetyl glucosamine (GlcNAc) in sulfolane is described. The reaction produces two major products that are assignable to 1,6-anhydro-2-acetamido-2-deoxy-β-d-glucopyranose (AGPNAc) and 1,6-anhydro-2-acetamido-2-deoxy-β-d-glucofuranose (AGFNAc). In order to reveal a general feature of the system, the 3, 5, and 10 min reactions were performed at 140, 160, 180, 200, and 220 ◦C to clarify the time course changes in the conversion of GlcNAc and the yields of the two produced 1,6-anhydrosugars. Temperature is a crucial factor that significantly affects the conversion of GlcNAc. The yields of AGPNAc and AGFNAc are also drastically changed depending on the reaction conditions. The 5-min reaction at 200 ◦C is shown to be the optimal condition to generate the 1,6-anhydrosugars with a high efficiency in which AGPNAc and AGFNAc are produced in the yields of 21% and 44%, respectively. Consequently, the microwave-assisted heating reaction of GlcNAc in sulfolane is shown to be a simple and promising pathway to generate 1,6-anhydrosugars consisting of amino monosaccharide backbones, which have high potentials as raw materials leading to biological oligosaccharides and biomimetic polysaccharides.

DOI： 10.3390/molecules25081944

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Publisher：Applied Catalysis A: General  

The catalytic toluene hydrogenation over Ni/SiO2 was carried out using H2 or a H2/H2O mixture. The toluene conversion and MCH selectivity were evaluated under partial steam pressures 0−10 kPa, at H2/toluene molar ratios 1–5, and at temperatures 393−453 K. In the absence of steam, toluene conversion increased with increasing H2 partial pressure, and the MCH selectivity decreased with increasing temperature. In the presence of steam, the toluene conversion showed near-constant activities over the entire range of steam partial pressures, and the MCH selectivity increased with increasing steam partial pressure. This result indicated that the addition of steam inhibited byproduct formation. To clarify the effects of steam on the side-reaction, the byproducts composition was analyzed using a gas chromatograph. The results showed that the addition of steam inhibited demethylation, the ring-opening reaction of MCH, the disproportionation of toluene, and isomerization to convert six-membered ring compounds into five-membered ring compounds.

DOI： 10.1016/j.apcata.2019.117374

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Language：English   Publishing type：Research paper (scientific journal)  

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Language：Japanese   Publishing type：Research paper (scientific journal)  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：The Society of Chemical Engineers, Japan  

Batch distillation is a useful separation technique for obtaining a pure product from a multi-component mixture. However, it is less energy-efficient than continuous distillation. This paper describes the system we developed for an internally heat-integrated batch distillation column (Batch or Semi-batch HIDiC) to minimize the energy consumption of the batch distillation process. We simulated the isopropyl alcohol dehydration process as a non-ideal system. The applicability of the system was examined using a commercial process simulator, Aspen Plus Dynamics (R) to evaluate energy-saving performance. The energy evaluations of the Batch and the Semi-batch HIDiC model were compared against the conventional batch distillation model. It was found that with the Semi-batch HIDiC, this system has the potential to reduce process time and energy consumption more effectively than with conventional batch distillation.

DOI： 10.1252/jcej.18we159

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Language：English   Publishing type：Research paper (scientific journal)  

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Language：English   Publishing type：Research paper (scientific journal)  

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Language：English   Publishing type：Research paper (scientific journal)  

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Publisher：Journal of the Japan Petroleum Institute  

A modified Petlyuk process with a reboiler at the bottom of the prefractionator eliminates the need for a vapor interconnection between the main column and the prefractionator and thus improves operability. However, the effect of this configuration on the operability has not been clarified. To elucidate this, the operability of a modified Petlyuk process with a reboiler at the bottom of the prefractionator for the separation of benzene, toluene, and p-xylene ternary mixture. The effect of the bottom-out to feed ratio of the prefractionator on the separation characteristics of the modified Petlyuk process was investigated for different feed flow rates. The operation range of the modified Petlyuk process was clarified by presenting the conditions satisfying the product specifications as a contour plot for the feed flow rate and the bottom-out to feed ratio of the prefractionator. The operability of the modified Petlyuk process was compared with that of the original Petlyuk process. A dynamic simulation verified that the product specifications can be satisfied simply by adjusting the bottom-out to feed ratio of the prefractionator for a disturbance of the feed flow rate.

DOI： 10.1627/jpi.62.45

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：公益社団法人 石油学会  

<p>固定層反応器内に充填したPt担持Al₂O₃またはTiO₂触媒を用い，トルエン水素化反応試験を常圧 · 398〜473 Kの条件で実施した。トルエン，水素，MCH分圧はそれぞれ60～91，9～23，9～17 kPaで変化させた。反応温度423 K上において，Pt担持触媒はPt/Al₂O₃，Pt/TiO₂（アナターゼ，A），Pt/TiO₂（アナターゼ／ルチル混合物，AR），Pt/TiO₂（ルチル，R）の順で高い活性を示したが，398 KではPt/TiO₂(A)が特筆して高い活性を示した。担体化学種がPt触媒活性に及ぼす影響を評価するために，速度論解析を行った。吸着挙動が触媒活性に及ぼす影響を議論するために，Langmuir-Hinshelwood型の反応速度式を適用した。速度論解析から，反応速度定数の大きさだけでは，観測した触媒活性の序列を説明できないことが分かった。このことから，速度定数だけでは反応速度の大きさを説明できないと考えた。また，吸着平衡定数から算出した被覆率と反応速度の相関から，トルエン · MCH被覆率が反応速度とほとんど相関がないのに対し，水素被覆率と反応速度には比較的強い相関があることが分かった。</p>

DOI： 10.1627/jpi.62.28

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CiNii Books

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Publisher：Processes  

Our previous study reported that operation in multiple steady states contributes to an improvement in reaction conversion, making it possible to reduce the energy consumption of the reactive distillation process for tert-amyl methyl ether (TAME) synthesis. This study clarified the factors responsible for an improvement in the reaction conversion for operation in the multiple steady states of the reactive distillation column used in TAME synthesis. The column profiles for those conditions, in which multiple steady states existed and those in which they did not exist, were compared. The vapor and liquid flow rates with the multiple steady states were larger than those when the multiple steady states did not exist. The effect of the duty of the intermediate condenser, which was introduced at the top of the reactive section, on the liquid flow rate for a reflux ratio of 1 was examined. The amount of TAME production increased from 55.2 to 72.1 kmol/h when the intermediate condenser was operated at 0 to -5 MW. Furthermore, the effect of the intermediate reboiler duty on the reaction performance was evaluated. The results revealed that the liquid and vapor flow rates influenced the reaction and separation performances, respectively.

DOI： 10.3390/pr6120241

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Publishing type：Research paper (scientific journal)  

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Publishing type：Research paper (scientific journal)  

© 2018 The Society of Chemical Engineers, Japan. Heat-pump-assisted distillation columns such as the vapor recompression column (VRC), self-heat recuperation column (SHRC), and heat integration column (HIDiC) have attracted attention in industry because of their strong impact on energy savings in chemical processes. Compared to conventional distillation columns, these systems have the advantage of reducing operation and construction costs, but little work has been done to evaluate the cost of these systems. This study employed the commercial process simulator Aspen Plus® to evaluate energy saving and economic performances. The heat-pump-assisted distillation distillation systems were economically superior to the conventional process for separation of a propylene-propane mixture. In particular, a thermally optimized HIDiC reduced energy consumption and total annual cost by 64 and 56% respectively in comparison with the conventional distillation process.

DOI： 10.1252/kakoronbunshu.44.303

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Publisher：ScienceAsia  

Phytosterols can be recovered from natural resources using molecular distillation, cold crystallization, which require large energy consumption. Adsorption was considered as a feasible alternative method. In this study, kinetics, isotherm and thermodynamics of stigmasterol adsorption on styrene-divinylbenzene with two different functional groups, strong base (SB-R) and weak base (WB-R), were investigated using a model solution of stigmasterol in n-heptane. Isothermal adsorption experiments were performed in temperature range of 298-313 K and concentration range of 0.3-6.0 mg/gsol. For both SB-R and WB-R cases, kinetics of adsorption was analysed based on pseudofirst- order and pseudo-second-order models and the results revealed that pseudo-second-order model agreed with the experimental data much better than pseudo-first-order model. Analysis of isotherm data based on Langmuir, Freundlich and linear models showed that Freundlich was the best model that could predict behaviour of sterol adsorption for both SB-R and WB-R cases. In addition, thermodynamics parameters (δG, δH andδS) indicated that the sterol adsorptions on these adsorbents were spontaneous, exothermic and favourable at low temperature.

DOI： 10.2306/scienceasia1513-1874.2018.44.346

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Language：English   Publishing type：Research paper (scientific journal)  

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Publisher：Chemical Engineering and Processing - Process Intensification  

We have previously reported the existence of steady-state solutions where reaction conversion is improved within multiple steady states, which appear in the reactive distillation column for tert-amyl methyl ether (TAME) synthesis. In the present study, we examined the energy-saving performance of a reactive distillation process that comprises a reactive distillation column and two recovery distillation columns for multiple steady state conditions using steady-state process simulation. Bifurcation analysis revealed that the multiple steady state did not exist under a reflux ratio of 1, but existed under reflux ratios of 2, 3, and 4. The reboiler duty required to obtain high-purity TAME increased with increase in reflux ratio. The evaluation of energy consumption revealed that the reboiler duties of the second recovery column at the steady-state solutions in the multiple steady state were lower than that at the steady-state solution of reflux ratio 1. Due to the high reaction conversion and reduction of the reboiler duty in the second recovery column, the energy inputs per mole of TAME product at steady-state solutions of the multiple steady state with reflux ratios of 2, 3, and 4 reduced by 17, 12, and 6%, respectively, compared to that for reflux ratio 1.

DOI： 10.1016/j.cep.2018.05.020

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

Pressure-driven membrane filtration processes such as microfiltration and ultrafiltration are still hindered by concentration polarization and membrane fouling. Generally in these filtration processes, concentration polarization causes decline of permeate flux and rejection, and fouling leads to permeate flux decline with the increase of rejection. The use of high shear stress for cross flow filtrations has long been considered one of the most efficient methods for overcoming these problems. However, circumferential fluid motion of the hollow fiber membrane surface is also important to avoid formation of a high concentration layer on the surface. In this study, ultrafiltration of humic acid aqueous solution using a polyethersulfone hollow fiber membrane was selected as a model case, and a membrane module with a helical baffle installed around the membrane was used. With the insertion of the baffle, normalized permeate flux and rejection became higher than those without the baffle at the wide range of the feed flow rate. In order to identify the cause of the improvement, CFD simulation was conducted for different baffle geometries. Swirling flow motion generated by the helical baffle around the membrane became more dominant with the lower aperture ratio of the cross sectional area, and there existed the optimum value for the swirling flow generation in terms of the variation of the helical baffle pitch length. The intensity of this fluid motion was characterized by Swirl number and it was found out that high separation performance was obtained at the high Swirl number. (C) 2017 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.seppur.2017.07.012

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Publishing type：Research paper (scientific journal)   Publisher：MDPI AG  

DOI： 10.3390/polym10060638

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Ceramic Society of Japan  

Herein, we report that -MnO2 thin films wet-chemically deposited on electro-conductive substrates exhibited good sensing abilities toward hydrogen peroxide and glucose without the assistance of immobilized enzymes, as well as the excellent supercapacitic performance described in our previous paper. High-sensitivity values of 380mA/(M·cm2) (H2O2) and 300mA/(M·cm2) (glucose) were attained with low detection limits of 0.7-mol/dm3 (H2O2) and 0.6-mol/dm3 (glucose). The good sensitivities and low detection limits were attributed to the large surface area of accumulated MnO2 nanosheets and their firm adhesion to the substrates. The method presented herein can be used for facile film deposition with good controllability and reproducibility.

DOI： 10.2109/jcersj2.17268

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Language：English   Publishing type：Research paper (scientific journal)  

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Language：English   Publishing type：Research paper (scientific journal)  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Chemical Society of Japan  

Hybridized microparticles composed of mesoporous manganese dioxide (MPMO) core and fullerene C60 nanocrystal (NCs) shell were fabricated by co-reprecipitation method. Double layer capacitance as well as fast surface redox reaction of MPMO contributes to increase the energy density, whereas C60 NCs contributes to the reduction of IR loss to enhance the power density. The coating of MPMO with C60 NCs resulted in a greatly improved pseudocapacitor performance, owing to the improved conductivity to allow fast charging/ discharging.

DOI： 10.1246/cl.171138

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Publisher：Kagaku Kogaku Ronbunshu  

Process data of a commercial-scale batch distillation column for separation of a ternary mixture of 2-propanol/ water/n-hexane was analyzed, and a simulation model capable of predicting dynamic conditions was developed. The developed model was applied to batch distillation in a commercial plant, and the operation performances were studied. By adjusting the conventional operating conditions, it was found possible to improve the function and performance of the process and achieve energy-saving.

DOI： 10.1252/kakoronbunshu.44.350

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SOC CHEMICAL ENG JAPAN  

In order to intensify a phase transfer catalytic reactor with the third liquid phase, it is necessary to optimize multiple operation variables that are concerned with the mass transfer rate. In the present paper, we propose a systems approach by application of a rate based model for mass transfer between two phases. Application of the developed rate based model performs simulation with higher accuracy than the conventional partition equilibrium model, for numerical analysis of behavior of a batch process for the synthesis of 4-benzyloxy-vanillin by using tetrabutylammonium bromide as the phase transfer catalyst. Moreover, influences of the rotational speed of the impeller on changes in the overall mass transfer coefficients are analyzed by using estimation equations for the Sauter diameter and the specific interfacial area of the dispersed phase. Consequently, it is found that the assumption of spherical droplets for the dispersed phase is not applicable in the application of the estimation equations. Then, the sensitivity analysis based on the rate based model demonstrates that characteristics of liquid-liquid dispersion in the agitated triphase reactor is complex due to the role of the third phase as a surfactant.

DOI： 10.1252/jcej.16we376

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SOC CHEMICAL ENG JAPAN  

Porous titania (TiO2) particles were prepared using a sol-gel technique employing Alkylketene Dimers (AKD) as a template. The effects of incremental additions of AKD as a template material on crystal structure, surface and internal morphology, and pore properties were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and nitrogen adsorption/desorption. The prepared titania had more than one pore size on its surface and internally. Incremental addition of AKD caused an increase in specific surface area. The prepared porous titania with the addition of AKD at 5 wt% exhibited a high specific surface area of 124 m(2)/g, which is markedly higher than in titania without AKD (53.5 m(2)/g). To quantitatively evaluate the porous structure, we performed fractal analysis over a wide scale using box-counting, small X-ray scattering (SAXS) and the FHH (Frenkel-Halsey-Hill) method. Porous titania showed fractal properties, both on its surface and internally.

DOI： 10.1252/jcej.16we366

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SPRINGER  

In this study, gamma- and delta-MnO2 thin films were deposited onto F-doped tin oxide glass substrates via a chemical bath deposition technique in which manganese (II) ions were oxidized by bromate ion in a homogeneous solution. The addition of cetyltrimethylammonium chlorate to the starting solutions resulted in the deposition of the delta-phase. The thin films showed rectangular cyclic voltammograms even at higher scan rates. The delta-phase films showed better specific capacitance than the gamma-phase films. A 200-nm-thick delta-MnO2 film showed an excellent specific capacitance of 750 F/g at a scan rate of 10 mV/s.

DOI： 10.1007/s10854-016-4795-8

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：SOC CHEMICAL ENG JAPAN  

A model for an internally heat integrated reactive distillation process without a compressor was developed, and the synthesis of methyl acetate from methanol and acetic acid was simulated. The applicability was evaluated by using the process simulator Aspen Plus. The steady state simulation showed that the energy consumption of the heat integrated reactive distillation process was lower than that of conventional reactive distillation.

DOI： 10.1252/kakoronbunshu.42.56

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Language：English  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Springer Science and Business Media Deutschland GmbH  

A purpose of this chapter is to investigate application methods for a niche GA to design of Reactive Distillation (RD) process involving the production and separation of ethyl acetate. First, optimization system based on the Multi- Niche Crowding – Genetic Algorithm (MNC-GA) is demonstrated to be effective in searching preferable designs of RD process using multiple feeds from each reactant. It is seen that the MNC-GA allows the search to yield various design solutions without causing remarkable performance degradation for searching the best design. Thus, authors investigate application methods for utilizing the various design solutions from the viewpoint of analysis of operability of searched process. It is shown that the multiple preferable designs obtained using the MNC-GA are useful for searching more preferable designs by steady-state process simulation and for sensitivity analysis which provides us with insights to the dynamics in RD column. In addition, intermediate simulation results, which are obtained through all the generations, are demonstrated to produce informative distributed plots for the sensitivity analysis, as compared to the normalGA where the tournament-based selection method is used.

DOI： 10.1007/978-3-319-13545-8_18

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Publisher：Journal of the Japan Petroleum Institute  

A simulator for internally heat integrated distillation columns (HIDiC) with a rate-based model was developed. Using a mass transfer correlation for structured packings and the Chilton-Colburn analogy, heat transfer coefficients for the liquid phase were obtained. Based on the simulation results, the overall heat transfer coefficient U for the internal heat exchange in the HIDiC was estimated. Since the overall heat transfer coefficient obtained was similar to that obtained from the small experimental plant, the simulation with the rate-based model is useful to predict the overall heat transfer coefficient with the mass transfer correlation.

DOI： 10.1627/jpi.58.189

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SOC CHEMICAL ENG JAPAN  

In the present study, we investigate a framework for the application of genetic algorithm (GA) methods to reactive distillation (RD) process design. First, a computational method for hybrid simulation is proposed by linking a commercial process simulator with an in-house GA-based optimizer in order to accelerate the search for process designs showing high performance. When developing the hybrid simulation system, detailed methods for the GA operations of crossover, mutation, and selection were investigated to achieve a combination that maximizes the effectiveness of the simulation framework. Next, we investigate the designs obtained from the simulations for a case study, an RD process for acetyl acetate. The proposed GA method is shown to provide not only the lowest total annual cost (TAC) design, but also various alternative design solutions. Since the generation of alternative designs lets us consider many other factors, e. g., the distillate composition and the overall conversion of the product, we believe that the application of techniques such as multi-niche crowding (MNC) GA could be effective for searching simulataneously structural and operational conditions of multifunctional processes.

DOI： 10.1252/jcej.13we119

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：SOC CHEMICAL ENG JAPAN  

The effects of operating conditions such as reflux ratio and reboiler duty on the product composition and reaction performance were discussed based on a simulation model of reactive distillation with multiple steady states(MSS). The region of MSS, determined by bifurcation analysis, was found to shift toward higher reboiler duty along with increase of reflux ratio. Separation and reaction performance under the MSS condition was higher than that in the absence of an MSS region.

DOI： 10.1252/kakoronbunshu.40.244

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：SOC CHEMICAL ENG JAPAN  

Process dynamics of reactive distillation with multiple steady states (MSS) was investigated to provide a novel operation procedure. The existence of MSS was first clarified using a simulation model with bifurcation analysis. Dynamic simulations under MSS conditions were next performed and showed that the MSS had both stable and unstable solutions. The dynamic simulation results indicated the potential for operation using multiple steady-state conditions.

DOI： 10.1252/kakoronbunshu.40.240

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Publisher：Journal of Polymer Science, Part A: Polymer Chemistry  

Core crosslinked star (CCS)-polymers with water-soluble arms composed of poly(N-hydroxyethylacrylamide) (PHEAA) are described. N-Hydroxyethylacrylamide was polymerized by the atom transfer radical polymerization consisting of ethyl 2-chloropropionate, copper(I) chloride (CuCl), and tris[2-(dimethylamino)ethyl] amine in an ethanol/water mixed solvent at 20 °C. The obtained PHEAA-arms were subsequently coupled using N,N'-methylenebisacrylamide as the crosslinking agent and sodium L-ascorbic acid (AscNa) as the reaction activator. A total of 17 representative coupling reactions with diverse conditions are discussed together with the characterizations of the products mainly by size exclusion chromatograph equipped with the multiangle laser light scattering detector (SEC-MALS). Consequently, the coupling reactions provided CCS-polymers with PHEAA-arms (CCS-PHEAAs) having weight averaged-molecular weights determined by SEC-MALS (M w,MALS) ranging from 63.8 kg mol -1 to 832 kg mol -1, which corresponded to the average arm-number (N arm) ranging from 4.1 to 42, respectively. CCS-PHEAA with the M w,MALS of 250 kg mol -1 was isolated and characterized by small angle X-ray scattering measurements in 0.05 M NaNO 3 aq. at 25 °C, which was shown to possess a star-shaped structure and exist as single molecules with a radius of gyration at the infinite dilution condition (<R g2> z,01/2) of 74 ± 4 Å. Copyright © 2012 Wiley Periodicals, Inc.

DOI： 10.1002/pola.26139

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Publisher：Journal of Chemical Engineering of Japan  

Internally heat integrated distillation columns (HIDiCs) have attracted industrial attention since HIDiCs are expected to have a strong impact on energy savings in chemical industries. Particularly in Japan, large national research projects for HIDiCs have been conducted, and a HIDiC pilot plant has been constructed. The pilot HIDiC has shown energy savings of more than 60% compared to a conventional distillation column in the separation example of a twelve-component hydrocarbon mixture. In addition, several research projects on HIDiCs have been carried out also in Europe. In this paper, the overview and recent advances in HIDiC technologies of Japan and Europe are introduced. © 2012 The Society of Chemical Engineers, Japan.

DOI： 10.1252/jcej.11we127

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Language：English   Publishing type：Research paper (scientific journal)  

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Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：Italian Association of Chemical Engineering - AIDIC  

In this paper, the controllability of reactive distillation (RD) on the multiple steady states (MSS) was analysed. We used the RD column for tert-amyl methyl ether (TAME) synthesis for a case study. The model was prepared five PI controllers which control liquid level, feed flow rate, pressure of column overhead and bottom product composition. Initial conditions of dynamic simulation were chose three cases each of upper, middle and lower branches on the MSS. Product composition was controlled for the ±10 % disturbances of feed flow rate and reflux ratio. However, pressure disturbance was failed to keep the set point. These phenomena are able to explain the bifurcation diagrams. Copyright © 2012, AIDIC Servizi S.r.l.

DOI： 10.3303/CET1229038

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Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：Italian Association of Chemical Engineering - AIDIC  

A model for an internally heat-integrated batch distillation column (Batch or Semi-batch HIDiC) was developed, and the separation of a benzene-toluene binary mixture was simulated. The applicability of the model was examined by using the commercial process simulator Aspen Plus Dynamics® to evaluate energy-saving performance and process time against the compression ratio and reflux ratio. The batch or semi-batch HIDiC model results were compared with the conventional batch distillation model. It was found that with the semi-batch HIDiC, the model has the potential to reduce process time and energy consumption more precisely than the conventional batch distillation model. Copyright © 2012, AIDIC Servizi S.r.l.

DOI： 10.3303/CET1229047

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Language：English  

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Publisher：Journal of Chemical Engineering of Japan  

This paper addresses the addition of internal heat integration to the pressure-swing distillation (PSD) process used in the separation of binary pressure-sensitive azeotropes. The primary step in the process design is to determine the pressure elevation from the low-to high-pressure distillation columns, followed by the design of internal heat integration between the two distillation columns. A general procedure is suggested and illustrated through the separation of an acetonitrile-water binary mixture, which forms pressure-sensitive minimum-boiling azeotropes. Comparisons are made between the conventional and the internally heat integrated PSD processes. It is demonstrated that breaking pressure-sensitive azeotropic mixtures can be made more economical than the current practice with conventional PSD processes. However, the degree of cost reduction is strongly dependent upon the properties of the mixtures to be separated. © 2011 The Society of Chemical Engineers, Japan.

DOI： 10.1252/jcej.11we064

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Publisher：Chemistry Letters  

Manganese oxide nanoparticles can be obtained simply by mixing surfactant/water/oil ternary systems containing dialkyldimethylammonium chloride, manganese(II) nitrate hexahydrate, and n-hexane. This finding is valuable in the design of a one-pot synthesis of nanoparticles from microemulsion systems. © 2011 The Chemical Society of Japan.

DOI： 10.1246/cl.2011.1262

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Publisher：Chemistry Letters  

We have developed a simple scheme for preparation of silver nanoparticle film. This scheme includes the reaction between octanethiol in the toluene and silver ion in water at toluenewater interface. The electric conductive films would be produced by sintering the coated films of the prepared silver nanoparticles below 200 °C. © 2011 The Chemical Society of Japan.

DOI： 10.1246/cl.2011.1260

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Publisher：Kagaku Kogaku Ronbunshu  

A model for an internally heat-integrated batch distillation column (Batch or Semi-batch HIDiC) was developed, and the separation of a benzene-toluene binary mixture was simulated. The applicability of the model was examined by using the commercial process simulator Aspen Plus Dynamics® to evaluate energy-saving performance and process time against the compression ratio and reflux ratio. The batch or semi-batch HIDiC model results were compared with the conventional batch distillation model. It was found that with the semi-batch HIDiC, the model has the potential to reduce process time and energy consumption more precisely than the conventional batch distillation model. © 2011 The Society of Chemical Engineers, Japan.

DOI： 10.1252/kakoronbunshu.37.241

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Publisher：Kagaku Kogaku Ronbunshu  

Continuous preparation of Mn-doped ZnS nanocrystals, which exhibit photoluminescence properties, by the hot-soap method was conducted in a thin tube flow reactor. The hot-soap method is a reactive crystallization from organometallic reagents dissolved in hot surfactant (tri-n-octylphosphine oxide : TOPO). While rapid mixing is generally essential for reactive crystallization, in the case of laminar flow in a thin tube reactor, diffusion-based slow mixing is expected to be dominant in the reaction field. In this study, the effect of introducing gasliquid slug flow into the thin tube reactor was examined, with the expectation that the mixing performance would be improved by the internal circulating in the liquid slug. As the result, the reaction period (residence time) was found to be reduced compared to that without slug flow. © 2011 The Society of Chemical Engineers, Japan.

DOI： 10.1252/kakoronbunshu.37.96

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Publisher：Kagaku Kogaku Ronbunshu  

The present work proposes a method for process intensification of the reaction-separation process. A model of the reactive distillation (RD) system involving a prereactor was developed by use of an equilibrium stage model, and the reaction-separation of a multicomponent mixture was simulated by use of a simulator that was capable of predicting steady-state conditions. The developed model was applied to an RD system with multi-feed, and the reaction-separation and operation performance were examined. As a result, the RD system was found to be usable for reaction-separation interaction phenomena. This process improved the function and performance of conventional reaction-separation process and could be miniaturized. © 2011 The Society of Chemical Engineers, Japan.

DOI： 10.1252/kakoronbunshu.37.104

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Publisher：Kagaku Kogaku Ronbunshu  

The present work discusses a method for process intensification of the distillation process of separation. A model of an internally heat-integrated distillation column (HIDiC) of concentric type was developed using a rate-based model, and the separation of a binary mixture was simulated in a simulator which is capable of predicting steady-state conditions. The developed model was applied to a concentric-type HIDiC, and the heat transfer and operation performances were compared. This process improved the function and performance of conventional distillation separation process and could be miniaturized. In addition, the HIDiC showed highly energy saving performance compared with the conventional distillation processes. © 2011 The Society of Chemical Engineers, Japan.

DOI： 10.1252/kakoronbunshu.37.100

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Language：Japanese   Publishing type：Research paper (scientific journal)  

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：SOC CHEMICAL ENG JAPAN  

A model for an internally heat-integrated batch distillation column (Batch or Semi-batch HIDiC) was developed, and the separation of a benzene-toluene binary mixture was simulated. The applicability of the model was examined by using the commercial process simulator Aspen Plus Dynamics (R) to evaluate energy-saving performance and process time against the compression ratio and reflux ratio. The batch or semi-batch HIDiC model results were compared with the conventional batch distillation model. It was found that with the semi-batch HIDiC, the model has the potential to reduce process time and energy consumption more precisely than the conventional batch distillation model.

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：SOC CHEMICAL ENG JAPAN  

The present work discusses a method for process intensification of the distillation process of separation. A model of an internally heat-integrated distillation column (HIDiC) of concentric type was developed using a rate-based model, and the separation of a binary mixture was simulated in a simulator which is capable of predicting steady-state conditions. The developed model was applied to a concentric-type HIDiC, and the heat transfer and operation performances were compared. This process improved the function and performance of conventional distillation separation process and could be miniaturized. In addition, the HIDiC showed highly energy saving performance compared with the conventional distillation processes.

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：SOC CHEMICAL ENG JAPAN  

The present work proposes a method for process intensification of the reaction-separation process. A model of the reactive distillation (RD) system involving a prereactor was developed by use of an equilibrium stage model, and the reaction-separation of a multicomponent mixture was simulated by use of a simulator that was capable of predicting steady-state conditions. The developed model was applied to an RD system with multi-feed, and the reaction-separation and operation performance were examined. As a result, the RD system was found to be usable for reaction-separation interaction phenomena. This process improved the function and performance of conventional reaction-separation process and could be miniaturized.

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SOC CHEMICAL ENG JAPAN  

This paper addresses the addition of internal heat integration to the pressure-swing distillation ( PSD) process used in the separation of binary pressure-sensitive azeotropes. The primary step in the process design is to determine the pressure elevation from the low-to high-pressure distillation columns, followed by the design of internal heat integration between the two distillation columns. A general procedure is suggested and illustrated through the separation of an acetonitrile-water binary mixture, which forms pressure-sensitive minimum-boiling azeotropes. Comparisons are made between the conventional and the internally heat integrated PSD processes. It is demonstrated that breaking pressure-sensitive azeotropic mixtures can be made more economical than the current practice with conventional PSD processes. However, the degree of cost reduction is strongly dependent upon the properties of the mixtures to be separated.

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：The Materials Research Society of Japan  

A simple technique has been developed to surface modification from liquid solution by the solvent evaporation method. Using this technique, the preparation of lithium manganese oxide, LiMn₂O₄, which are the most promising cathode materials for lithium secondary battery, has been carried out for various operating conditions. The as-prepared samples exhibited a monophobic cubic spinel structure (fd3m) without any impurities in the XRD patterns, and the chemical composition of as-prepared powders showed in a good agreement with the one of precursor solution.<br>The as-prepared sample was used as cathode active materials for lithium secondary battery and their charge/discharge properties have been investigated. Test experiments in the electro chemical cell Li|1M LiPF6 in EC with DEC|LiMn2O4 demonstrated that the sample, prepared by the solvent evaporation method, was a promising cathode material for 4V lithium secondary batteries.

DOI： 10.14723/tmrsj.35.833

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：The Materials Research Society of Japan  

Copper particles were synthesized in a batch reactor and concentric microreactor by the reduction-precipitation method. The products were observed by scanning electron microscopy, and their composition and crystal structure were measured by energy dispersive X-ray spectroscopy elemental analysis and powder X-ray diffraction (XRD), respectively. Spherical copper nanoparticles were prepared using a concentric microreactor. It was found that these particles had diameter less than 100 nm and contained copper and cuprous oxide. In addition, polyhedral particles were prepared in the batch reactor. Cubic particles could also be synthesized under certain conditions, and the size of the polyhedral and cubic particles was about 1 μm. Compared with the microreactor, the batch reactor produced particles that were larger and more varied in shape. However, the crystal structure of the particles prepared in each type of reactor was similar, as determined by XRD. The oxygen content changed with reaction time and the molar ratio of the reactants.

DOI： 10.14723/tmrsj.35.837

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Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：AIDIC SERVIZI SRL  

This paper reports the analysis of the energy saving for design of an internally heat integrated distillation column (HIDiC) conducted in the second-phase of Japanese national research project for energy conservation in multicomponent petroleum distillation. The practical commercial scale distillation column separating cyclopentane from a multicomponent mixture consisting of mainly C5 hydrocarbons was selected as a target of the application of HIDiC technology. By choosing the compression ratio, the number of the theoretical stages, and the heat transfer rate as design and operating variables, temperature, pressure, flow rates, and composition profiles were computed as well as the reboiler heat duty of the HIDiC by Pro/II. The energy consumption of the HIDiC was compared with that of the practical conventional distillation column operated at the minimal reflux ratio. It was confirmed that at least 25 % of energy saving can be achieved by means of the HIDiC system. A pilot plant of the HIDiC was designed based on the results obtained in this study. It was constructed and has been in operation since 2005. The pilot HIDiC shows more than 50 % of energy savings compared to the conventional distillation column, validating the analysis of this study.

DOI： 10.3303/CET1021022

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Publisher：Journal of Chemical Engineering of Japan  

Internally heat-integrated distillation columns (HIDiCs) are one of the most attractive alternatives for the conventional distillation columns (CDiCs) since HIDiCs have very high potential to separate a mixture with smaller energy consumption compared to CDiCs. In order to prove the energy saving characteristics of HIDiCs, a pilot plant of HIDiC was constructed for the separation of multicomponent hydrocarbon mixture. The HIDiC pilot plant was operated at zero external reflux condition, and achieved more than 50% reduction in the energy consumption compared to the simulation results of the existent CDiC. Copyright © 2008 The Society of Chemical Engineers, Japan.

DOI： 10.1252/jcej.08we017

Scopus

Publisher：Kagaku Kogaku Ronbunshu  

Optimum operation, energy saving, carbon-dioxide emission and cost estimation of a pilot plant of an internally heat-integrated distillation column (HIDiC) separating a twelve-component hydrocarbon mixture to obtain residue-product of crude cyclopentane were studied. From the operation results of the HIDiC at zero external reflux and reboiler free operation, the reduction in CO2 emission by the HIDiC was 56.6 kg/h (453 t/y), which is 63.5% of the total CO2 emission of the conventional distillation column. The HIDiC pilot plant is expected to be reasonable in view of the inflation of the steam cost. The cost estimation results were also compared with those obtained from the conventional column, which showed that the HIDiC pilot plant can provide a strikingly shorter payback time. Copyright © 2008 The Society of Chemical Engineers.

DOI： 10.1252/kakoronbunshu.34.444

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：SOC CHEMICAL ENG JAPAN  

Optimum operation, energy saving, carbon-dioxide emission and cost estimation of a pilot plant of ail internally heat-integrated distillation column (HIDiC) separating a twelve-component hydrocarbon mixture to obtain residue-product of crude cyclopentane were studied. From the operation results of the HIDiC at zero external reflux and reboiler free operation, the reduction in CO(2) emission by the HIDiC was 56.6 kg/h (453 t/y), which is 63.5% of the total CO(2) emission of the conventional distillation column. The HIDiC pilot plant is expected to be reasonable in view of the inflation of the steam cost. The cost estimation results were also compared with those obtained from the conventional column, which showed that the HIDiC pilot plant can provide a strikingly shorter payback time.

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Publisher：Kagaku Kogaku Ronbunshu  

To analyze the effect of the maldistribution of vapor and liquid flows among tube units of an internally heat-integrated distillation column (HIDiC) on its separation performance, a simulator was developed with an equilibrium stage model. The simulation study indicated that the maldistribution of vapor and liquid flows among tube units would influence the top product specification. From the simulation results, the acceptable difference between the maximum and the minimum liquid flow rates was determined to be less than 3%. The design strategy for the high performance liquid distributor for the pilot-scale HIDiC with seven tube units was discussed. The distribution system developed was validated by experiments. Furthermore, the distributor was applied to the pilot HIDiC. Since there is no temperature distribution between tube units, the distributor seems to achieve a maldistribution rate of less than 2.5%. Copyright © 2008 The Society of Chemical Engineers.

DOI： 10.1252/kakoronbunshu.34.224

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Publisher：Hydrocarbon Processing  

Scopus

Publisher：Kagaku Kogaku Ronbunshu  

Operation and energy savings in the separation of a twelve-component hydrocarbon mixture by the pilot plant of an internally heat-integrated distillation column (HIDiC) were studied. Based on the operation results, a HIDiC simulator was developed using the commercial process-simulation software. The operation and simulation results showed that zero external reflux and zero reboiler heat duty operation were the most economical operation conditions, and that energy reduction of 62% compared to the conventional distillation column is achievable under these conditions. With the HIDiC simulator developed, a process flow involving heat exchange between the overhead vapor and the feed was studied, and the possibility of further energy-saving operation of the HIDiC was suggested. Copyright © 2008 The Society of Chemical Engineers.

DOI： 10.1252/kakoronbunshu.34.70

Scopus

Publisher：Kagaku Kogaku Ronbunshu  

The present work discusses a method for process intensification of the distillation process of separation. A model of an internally heat-integrated distillation column (HIDiC) with concentric and compact heat exchanger types was developed using a rate-based model and the separation of multicomponent mixture was simulated in a simulator which is capable of predicting steady-state conditions. The developed model was applied to concentric and compact heat exchanger types of HIDiC, and their separation and operation performances were compared. It was found that the HIDiC compact heat exchanger process can also be used for zero reflux and/or no reboil operation. This process improved the function and performance of conventional distillation separation process and could be miniaturized. In addition, the HIDiC compact heat exchanger showed highly energy saving performance compared with the conventional distillation processes. Copyright © 2008 The Society of Chemical Engineers.

DOI： 10.1252/kakoronbunshu.34.64

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Language：Japanese   Publishing type：Research paper (scientific journal)  

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Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1627/jpi.50.162

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Publisher：Journal of Chemical Engineering of Japan  

Exergy analysis of an ideal heat-integrated distillation column is conducted in this paper. It is found that the process is most favourable to the separation of binary close-boiling mixtures. Pressure elevation from stripping section to rectifying section appears to be a critical design variable that can affect the thermodynamic efficiency of the process. Feed composition presents almost no effect upon internal heat integration between the rectifying section and the stripping section. Although an implicit limitation has been imposed on the process throughput, it can be obviated through a careful trade-off between capital investment and operating cost during process development. Comparison against a conventional distillation column is also conducted, which shows the great potential of internal beat integration between the rectifying section and the stripping section. Copyright © 2006 The Society of Chemical Engineers, Japan.

DOI： 10.1252/jcej.39.963

Scopus

Publisher：Journal of the Chinese Institute of Chemical Engineers  

The proposed of the present work is to develop a method for rigorous prediction of separation performance of the HIDiC. A process simulator (gPROMS) for prediction of performance of the HIDiC with random packing is developed by rate-based model using Maxwell-Stefan equations. The vapor and liquid flow rates of HIDiC increased from the bottom to the top in the stripping section. In the rectifying section, however, the flow rates decreased from the bottom to the top. Evaporation of liquid in the stripping section and the condensation of vapor in the rectifying section take place. Comparison was made observed data from a bench-scale separation (benzene-toluene system) HIDiC plant, about 16 m in height and 254 mm in diameter (concentric R&A sections) and simulation results. The energy-saving ratio shows a good agreement with observed data. The bench HIDiC showed about 40% reduction of energy consumption compared with the conventional distillation column. The effect of nonequilibrium of temperature in the HIDiC is also discussed.

Scopus

Publisher：Journal of Chemical Engineering of Japan  

Seeking internal heat integration between the whole rectifying section and the whole stripping section gives rise to two alternatives for the arrangement of a reboiler in an internally heat-integrated distillation column. One is to locate it at the bottom of the process (scheme A) and the other on the pipeline of the feed flow (scheme B). Although the former appears to be less thermodynamically efficient than the latter, it is generally preferable to scheme B from the viewpoint of process dynamics and operation. A detailed simulation study justifies the conclusion. Copyright © 2006 The Society of Chemical Engineers, Japan.

DOI： 10.1252/jcej.39.818

Scopus

Publisher：Journal of Chemical Engineering of Japan  

With the aid of the McCabe-Thiele diagram, heuristic synthesis of an internally heat-integrated distillation column is addressed in this work. A new scheme for internal heat integration between a rectifying section and a stripping section is derived with the introduction of double-feed arrangement. The process configuration is characterized by its high thermodynamic efficiency and strong resilience to changes in operating conditions. Separation of a binary close-boiling mixture is conducted and the results obtained corroborate the advantages. Copyright © 2006 The Society of Chemical Engineers, Japan.

DOI： 10.1252/jcej.39.703

Scopus

Publisher：AIChE Journal  

A novel technique has been developed to directly produce fine ceramic powders from liquid solution using a spray pyrolysis and fluidized bed hybrid system. Using this technique, the preparation of lithium manganese oxides LiMn2O4, which are the most promising cathode materials for lithium-ion batteries, has been carried out for various superficial gas velocities U0 = 0.30-0.91 m/s, static bed heights Ls = 50-150 mm, and medium particle sizes dpm,g = 294-498 μm. The resulting powders had spherical nano-structured particles that comprised primary particles with a few tens of nanometer in size, and they exhibited a pure cubic spinel structure without any impurities in the XRD patterns. Moreover, the as-prepared powders showed better crystallinity and smaller specific surface area than those by conventional spray pyrolysis. The effects of process parameters on powder properties, such as specific surface area and crystallinity, were investigated for a wide range of superficial gas velocities and static bed heights. An as-prepared sample was used as cathode active materials for lithium-ion batteries and the cell performance has been investigated. Test experiments in the electrochemical cell Li/1M LiClO 4 in PC/LiMn2O4 demonstrated that the sample prepared by the present technique was superior to that by the conventional spray pyrolysis and solid-state reaction method. © 2006 American Institute of Chemical Engineers.

DOI： 10.1002/aic.10841

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SOC CHEMICAL ENG JAPAN  

In this paper, the static and dynamic influences of pressure distribution are examined on an ideal heat-integrated distillation column. In the aspect of process design, pressure distribution is found to have an effect upon the thermodynamic efficiency and it appears beneficial to explore an optimum pressure distribution during process development. From the viewpoint of process operation, the dynamics of pressure distribution may give rise to a severe deterioration on process controllability. Therefore, it should be taken into account in control system design for an ideal HIDiC.

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Publisher：Journal of Chemical Engineering of Japan  

Process asymmetry often introduces severe difficulties to process modeling and worsens control system performance. In this work, a simple modeling framework is proposed, which can effectively tradeoff the difference between positive and negative process dynamics. It is characterized by small modeling effort in the consideration of process asymmetry. Modeling and control of a nonlinear high-purity ideal heat-integrated distillation column is conducted and the results obtained demonstrate the effectiveness of the modeling method proposed. Copyright © 2006 The Society of Chemical Engineers, Japan.

DOI： 10.1252/jcej.39.448

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Language：English   Publishing type：Research paper (scientific journal)  

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Language：English   Publishing type：Research paper (scientific journal)  

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Language：English   Publishing type：Research paper (scientific journal)  

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Language：Japanese   Publishing type：Doctoral thesis  

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Publisher：Journal of Power Sources  

Spinel LiMn2O4 particles were successfully synthesized by an ultrasonic spray pyrolysis method from the precursor solutions; various combinations of nitrate, acetates or formats of lithium and manganese were stoichiometrically dissolved in distilled water. The product characteristics, such as crystallinity, specific surface area, particle morphology and interior structure of particles, were examined with X-ray diffraction (XRD), the Brunauer-Emmet-Teller (BET) method, field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). All the samples exhibited a pure cubic spinel structure without any impurities in the XRD patterns, while the surface morphology of as-prepared powders was classified into four patterns and the interior structure three patterns. The as-prepared samples were then used as cathode active materials for lithium-ion battery, and electrochemical studies were carried out on the charge/discharge characteristics of the Li/LiMn2O4 cells. The effect of LiMn2O4 particle properties such as crystallite size, specific surface area and particle morphology on the electrochemical properties were also discussed in details. © 2004 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.jpowsour.2004.01.019

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Publisher：Kagaku Kogaku Ronbunshu  

Spinel lithium manganese oxide powders were prepared directly by a continuous droplet-to-particle conversion process using an ultrasonic spray pyrolysis method. Nine kinds of precursor solutions were used to synthesize LiMn2O4 powders. The aqueous precursor solutions were made from various combinations of Li-salt, such as Li(HCOO) · H2O, Li(CH3COO) · 2 H20, Li(NO3), were Mn(HCOO)2·2 H20, Mn (CH3COO)2·4 H2O or Mn(NO3) · 6 H2O. The total concentration of metal ion is 0.54 mol/dm3. The particle properties of as-prepared LiMn204 powders were examined by X-ray diffraction (XRD), the Brunauer-Emmet-Teller (BET) method, transmission electron microscopy (TEM) and field emission scanning electron microscopy (FE-SEM). The chemical composition of the powders was determined by inductively coupled plasma spectroscopy (ICP). As the results, the powders were identified as single-phase spinel LiMn2O4, and the observed chemical compositions showed, good agreement with the stoichiometry one of LiMn2O4 for all samples. However, the particle morphology could be classified into four patterns depending on the original salts. The as-prepared particles were then used as cathode active materials for lithium-ion batteies and their charge/discharge properties were investigated. Their electrochemical properties in terms of cycle performance were also examined.

DOI： 10.1252/kakoronbunshu.29.232

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Geothermal heat is a huge amount of thermal energy obtained from the inside of the earth and emits a small amount of greenhouse effect gas (GHG) when used as energy. In addition, unlike other natural energies such as solar or wind, geothermal power is not affected by weather. Therefore, it is put to a variety of applications from power generation to heat downcycling as a clean energy source. Geothermal power generation is largely divided into two types: steam power generation based on a heat source of about 200 AC and the other binary generation based on a heat source of about 100 AC. Recently, more attention is drawn to binary power generation that uses a lower-temperature heat source. This chapter discusses the road map of geothermal-based power generation system and application of binary power generation technology.

DOI： 10.1007/978-4-431-55951-1_18

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Total pages：iv, 155p   Language：Japanese

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Language：Japanese Book type：Scholarly book

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Total pages：viii, 228p   Language：Japanese

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Language：Japanese   Publishing type：Article, review, commentary, editorial, etc. (scientific journal)   Publisher：分離技術会  

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Language：Japanese   Publishing type：Article, review, commentary, editorial, etc. (scientific journal)   Publisher：日本工業出版  

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Language：Japanese   Publishing type：Article, review, commentary, editorial, etc. (scientific journal)   Publisher：化学工業社  

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Event date： 2006.11

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