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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2025 · IF 3.9

Efficient Electrophotochemical Microreactor for Direct Green Production of Phenol from Benzene

Zhiming Ding,Danfeng Wang,Gang Wang,Runjuan Du,Chuanting Fan,Yaheng Zhang,Jie Zhang,Zhiyong Tang

Electrophotocatalysis, a burgeoning and sustainable technique in the field of organic synthesis, faces challenges in practical implementation due to technological and equipment limitations. This work introduces the design and engineering of an electrophotocatalytic flow microreactor for efficient synthesis of phenol from benzene in one step. The study explored the effects of microreactor configuration and various parameters, such as applied voltage, light intensity, and the concentrations of oxidant DDQ and electrolyte TBABF4. The innovative microreactor, characterized by a compact electrode gap and an expansive optical window, achieved a high phenol yield of 21.2% within a short residence time of 10 min, a significant improvement over the 14.3% yield obtained by a batch reactor in 6 h. The microreactor delivered a remarkable phenol productivity of 116.8 mmol h–1 L–1, outperforming all previous electrophotocatalytic synthesis records. Furthermore, a techno-economic analysis demonstrated that small-scale electrophotocatalytic synthesis of phenol reduced the per-unit production cost, displaying economic advantages competitive with the traditional cumene method. This work provides valuable insights into the engineering of flow microreactors for electrophotocatalysis and offers guidance for the potential industrial-scale application of electrophotocatalytic flow reactions.

CAS / MDL: 64-19-7
研究领域: 有机合成 · 化学工程 · 可持续技术
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2018 · IF 3.909

DNA-directed trypsin immobilization on a polyamidoamine dendrimer-modified capillary to form a renewable immobilized enzyme microreactor

Nan Wu,Siming Wang,Ye Yang,Jiayi Song,Ping Su,Yi Yang

A novel type of trypsin capillary microreactor was developed based on a DNA-directed immobilization (DDI) technique applied to a fused-silica capillary modified with polyamidoamine (PAMAM) dendrimers. Trypsin binding to the inner wall of the capillary was confirmed by confocal laser scanning microscopy. The properties of the trypsin–DNA conjugated, PAMAM-modified capillary microreactor were investigated by monitoring hydrolysis of N α-benzoyl- L -arginine ethyl ester. Through the hybridization and dehybridization of the DNA, the inner wall of the capillary functionalized with trypsin can be regenerated, thus indicating the renewability of this enzyme microreactor. In addition, these results demonstrated that introduction of PAMAM enabled higher amounts of trypsin to be immobilized, markedly improving the enzymolysis efficiency, compared with traditional modified capillaries. The digestion performance of the trypsin capillary microreactor was further evaluated by digesting cytochrome C, and a peptide numbers of 8, and a sequence coverage of 59% were obtained. This renewable and efficient immobilized trypsin capillary microreactor combines advantages of both DDI technology and PAMAM, and is potentially adaptable to high-throughput enzyme assays in biochemical and clinical research.

研究领域: 生物化学 · 酶学 · 分析化学 · 生物医学工程
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Journal of Flow Chemistry · 2018 ·Vol. 8 ·期 3 ·139-146 · IF 1.658

Continuous diazotization of aromatic amines with high acid and sodium nitrite concentrations in microreactors

Liu Yang,Zeng Changfeng,Wang Chongqing,Zhang Lixiong

We design a new continuous diazotization microreaction process in which concentrated acid and sodium nitrite solutions are used. We form oil in water (O/W) microdroplets by mixing amine with sodium nitrite aqueous solution, which react with mineral acid to make the diazotization. In this way, the formed particles are dispersed in the aqueous phase, which can flow with the main stream, and consequently are consumed. Then the fluid can smoothly flow without clogging in the microchannels and we can achieve continuous operation. We use aniline, o-methylaniline, m-methylaniline, and o-ethylaniline as the raw materials, 6 M HCl and 6.5 M H 2 SO 4 as the acid as well as sodium nitrite to demonstrate the feasibility. The resulting diazonium salts are converted to iodo-substitute aromatic compounds to measure the yield. The results show that, SIMM-V2 micromixer is efficient to form the emulsion. Mixing the microdroplets with acid in a co-axial flow way can prevent clogging. In hydrochloric acid medium, high reaction yield can be obtained when the reaction temperature is 4 °C and the residence time is 13–15 s. In sulfuric acid medium, high conversion of aromatic amine of up to 99% and yield of approximately 90% can be achieved at the reaction temperature of 9 °C and the residence time of 14–16 s. This process provides efficient continuous diazotization reactions using concentrated acid and sodium nitrite solutions, minimizing the production of waste water.

研究领域: 化学工程 · 有机合成
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FUEL PROCESSING TECHNOLOGY · 2022 · IF 8.129

Noncatalytic hydropyrolysis of lignin in a high pressure micro-pyrolyzer

Huiyuan Wang,Tan Li,Jing Su,Kai Miao,Kaige Wang

Lignin hydropyrolysis was investigated in a high-pressure micro-reactor with on-line analysis characterization of products. The influences of atmosphere, pressure, and temperature on product formation during lignin pyrolysis were quantitatively discussed. The presence of hydrogen, elevated pressure and temperature favored the production of condensable vapors and permanent gas while inhibited the formation of char. High-pressure hydrogen boosted the conversion of methoxy phenolics to non-methoxy phenolics, and facilitated the generation of hydrocarbon condensable vapors and hydrocarbon gases. Non-methoxy phenolics were major condensable vapor from lignin hydropyrolysis. Yield of non-methoxy phenolics reached 19.68C% at 3 MPa and 500 °C. The monocyclic and polycyclic aromatic hydrocarbons as well as condensable aliphatic hydrocarbons were observed from lignin hydropyrolysis. Methane was the most abundant gas product from lignin hydropyrolysis, yield of which was 10.27C% at 2 MPa and 600 °C. The formation mechanisms of typical products were proposed and verified with experiments using model compounds. The formation of non-methoxy phenolics, monocyclic aromatic hydrocarbons and aliphatic hydrocarbons is related to the substitution of methoxy (and its methyls) and phenolic hydroxyl groups on benzene rings by alkyls, alkenyls and hydrogen radicals, as well as the hydrogenation of π bonds .

CAS / MDL: 2785-87-7
研究领域: 化学工程 · 能源科学
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CHEMICAL ENGINEERING SCIENCE · 2024 · IF 4.1

Development of an electrophotochemical flow microreactor for efficient electrophotocatalytic C-H hydroxylation of benzene to phenol

Zhiming Ding,Yaheng Zhang,Jian Ruan,Chuanting Fan,Runjuan Du,Jie Zhang,Zhiyong Tang

Electrophotocatalytic C-H hydroxylation of benzene is an emerging green technology with high potential for producing phenol in one step. However, it is still limited by efficiency and scale-up challenges in batch process. In this study, a novel electrophotochemical flow microreactor was designed and manufactured using 3D printing technology. Static mixers were incorporated to enhance the mixing. The effect of various parameters, such as electrode materials, reaction time, potential, and reactant concentration, etc., on the continuous synthesis of phenol in the as-developed microreactor was investigated. Furthermore, machine learning (ML) algorithms were employed to explore the impact of these parameters on the reaction efficiency. With cost-effective electrodes, higher phenol productivity was achieved in the present flow microreactor when comparing with batch counterpart and literature value. This study offers insights into the optimization of electrophotochemical microreactor for the hydroxylation of benzene, and provides guidance for exploring sustainable electrophotocatalytic organic synthesis in flow.

CAS / MDL: 64-19-7
研究领域: 化学工程 · 环境科学 · 材料科学
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Catalysts · 2018 ·Vol. 8 ·期 6 ·249 · IF 3.465

Enzymatic Synthesis of Thioesters from Thiols and Vinyl Esters in a Continuous-Flow Microreactor

Nani Zhou,Le Shen,Zhen Dong,Jiahong Shen,Lihua Du,Xiping Luo

The preparation of thioesters through the lipase-catalysed transesterification reaction of thiols with vinyl carboxyl esters is described. The reactions were carried out by Lipase TL IM fromThermomyces lanuginosusas a catalyst and performed under a continuous flow microreactor. We first found that lipase TL IM can be used in the reaction of thioester synthesis with high efficiency. Various reaction parameters were investigated including substrate molar ratio, reaction time, and temperature. Maximum conversion (96%) was obtained under the optimal condition of a substrate molar ratio of 1:2 (4-methylbenzyl mercaptan:vinyl esters) at 50 °C for about 30 min. Compared with other methods, the salient features of this work include mild reaction conditions (50 °C), short reaction times (30 min), high yields, and environment-friendliness.Keywords:enzymatic synthesis;thioester synthesis;flow chemistry;microreactor

研究领域: 生物化学 · 有机化学
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RSC Advances · 2017 ·Vol. 7 ·期 20 ·12283-12291 · IF 3.108

Polydopamine-mediated preparation of an enzyme-immobilized microreactor for the rapid production of wax ester

Yicheng Bi,Hua Zhou,Honghua Jia,Ping Wei

In our study, a polytetrafluoroethylene (PTFE) open-tubular enzyme-immobilized microreactor has been successfully prepared using dopamine polymerization and multi-layer deposition. The polydopamine layer was utilized as a primer layer in the microchannel to provide PTFE surface reactable groups, and polyethylenimine and Candida antarctica lipase B were alternatively adsorbed on the PTFE surface by the layer-by-layer method. The lipase loading kept increasing as the number of layers increased and reached a plateau at the 8th layer. The formation of multilayers and increase of enzyme loading were described and explained by the water contact angle measurement, Fourier transform infrared spectroscopy (FI-IR), and X-ray photoelectron spectroscopy, while the morphological characteristics were observed using Atomic Force Microscopy (AFM) and field emission scanning electron microscopy (FE-SEM). Preparation of a wax ester using the microreactor had much better production efficiency (35 minutes to reach 95% yield) than that using traditional reactors (over 4 hours to complete the reaction). Very excellent stability can be achieved by the microreactor, which could be used for 144 hours with the residual activity remaining at 83% of the initial activity.

研究领域: 生物化学 · 材料科学 · 酶工程
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Visible-light-driven direct decarboxylative carbonylation of carboxylic acids using acridine photocatalysis in oxygen-liquid flow

Qiang Chen,Yujun Wang,Guangsheng Luo

Photocatalytic direct decarboxylative carbonylation of ubiquitous carboxylic acids is a promising strategy to obtain highly versatile ketone building blocks, but metal-free and efficient conversions are still lacking. Here, density functional theory calculations are used to guide the experimental screening of catalysts, highlighting the potential influence of frontier molecular orbital energy levels on the catalytic process and revealing an acridine photocatalyst capable of realizing value-added conversion of carboxylic acid at room temperature under visible light with excellent performance. The possible mechanism for this conversion was elucidated in depth by combining study of the excited state behavior of the photosensitizer and the results of detection experiments for radicals. Theoretical calculations and mechanistic studies further disclose the kinetically rate-limiting role of oxygen, including its participation in the formation of superoxide radicals for carbonylation and as an electron trapping agent for catalyst cycling. Based on these findings, a flow microreactor platform was ingeniously built to achieve previously inaccessible photocatalytic decarboxylative carbonylation promoted by acridine in concert with oxygen. Interestingly, the gas–liquid segmented microflow is found to enable a significant acceleration (from 14 to 2 h) and higher yield compared to the batch counterpart, resulting in a high space–time yield of 137.4 g/L d -1 for this transformation, which far exceeds the reported values. This study underscores the feasibility of broadening the competence of acridine photocatalysis through the involvement of kinetically adapted oxygen, thus enabling substitution of metal-dependent photocatalysis and even more efficient and high-yield decarboxylative carbonylation of carboxylic acids.

研究领域: 有机化学 · 催化化学
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Materials Science & Engineering C-Materials for Biological Applications · 2017 · IF 4.164

Efficient synthesis of highly fluorescent carbon dots by microreactor method and their application in Fe3 + ion detection

Longshi Rao,Yong Tang,Zongtao Li,Xinrui Ding,Guanwei Liang,Hanguang Lu,Caiman Yan,Kairui Tang,Binhai Yu

Rapidly obtaining strong photoluminescence (PL) of carbon dots with high stability is crucial in all practical applications of carbon dots, such as cell imaging and biological detection. In this study, we proposed a rapid, continuous carbon dots synthesis technique by using a microreactor method. By taking advantage of the microreactor, we were able to rapidly synthesized CDs at a large scale in less than 5   min, and a high quantum yield of 60.1% was achieved. This method is faster and more efficient than most of the previously reported methods. To explore the relationship between the microreactor structure and CDs PL properties, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) were carried out. The results show the surface functional groups and element contents influence the PL emission. Subsequent ion detection experiments indicated that CDs are very suitable for use as nanoprobes for Fe 3   + ion detection, and the lowest detection limit for Fe 3   + is 0.239   μM, which is superior to many other research studies. This rapid and simple synthesis method will not only aid the development of the quantum dots industrialization but also provide a powerful and portable tool for the rapid and continuous online synthesis of quantum dots supporting their application in cell imaging and safety detection.

CAS / MDL: 64-17-5 77-92-9 107-15-3
研究领域: 材料科学 · 分析化学 · 生物医学工程
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Catalysts · 2022 ·Vol. 12 ·期 3 ·339 · IF 4.501

Continuous Flow Biocatalysis: Synthesis of Coumarin Carboxamide Derivatives by Lipase TL IM from Thermomyces lanuginosus

Li-Hua Du,Meng-Jie Yang,Yue Pan,Ling-Yan Zheng,Shi-Yi Zhang,Zhi-Kai Sheng,Ping-Feng Chen,Xi-Ping Luo

Coumarin carboxamide derivatives are important building blocks for organic synthesis and chemical biology due to their excellent biopharmaceutical properties. In this paper, we demonstrate for the first time a two-step enzymatic synthesis of coumarin carboxamide derivatives. Salicylaldehyde and dimethyl malonate were reacted to obtain coumarin carboxylate methyl derivatives, which were then reacted with various amines under the catalysis of lipase TL IM fromThermomyces lanuginosusto obtain coumarin carboxamide derivatives in continuous flow reactors. We studied various reaction parameters on the yields. The important features of this method include mild reaction conditions, a short reaction time (40 min), reduced environmental pollution, higher productivity (STY = 31.2941 g L−1h−1) and enzymes being relatively easy to obtain.Keywords:enzymatic synthesis;microreactor;coumarin carboxamide derivatives

研究领域: 有机化学 · 生物催化 · 药物化学
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ORGANIC PROCESS RESEARCH & DEVELOPMENT · 2023 · IF 3.4

Study on Continuous Flow Nitration of Naphthalene

Feng Xu,Zhiquan Chen,Lei Ni,Gang Fu,Jian Liu,Juncheng Jiang

In this work, the continuous flow nitration of naphthalene to 1-nitronaphthalene was systematically studied from the microreactor to mesoscale flow reactor and the safety issues during the reaction process were investigated. The effect of the molar ratio of nitric acid to naphthalene, residence time, reaction temperature, and sulfuric acid strength on the reaction process was comprehensively investigated in the microreactor. Under optimal conditions, the reaction yield could reach 94.96%. Due to the rapid exothermic characteristics of nitration, a quick heat transfer assessment was proposed to obtain the temperature profile during optimal conditions. It was found that the maximum overtemperature during the reaction was only 3.78 °C, which was consistent with the high yield under the optimal conditions. Then a scale-up of the microreactor to production was realized by a dimension-enlarging strategy. In the mesoscale flow reactor, the influence of volumetric flow rates was investigated. The annual output of the flow reactor could reach 2643 kg·a–1 while the highest overtemperature inside the reactor channel well exceeded 17.1 °C. In addition, a conventional semibatch experiment was carried out in the batch calorimeter RC1e to explore the reaction’s exothermic characteristics. Finally, the performances of the two reactors were compared, showing that the continuous flow reactor had more advantages than the batch reactor in economic benefit and inherent safety.

研究领域: 化学工程 · 安全科学
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Chemical Engineering and Processing-Process Intensification · 2019 · IF 3.031

Separation of Zn(II) from Zn-Ni-Co sulphate solution by di-(2-ethylhexyl)phosphoric acid (D2EHPA) using a slug flow microreactor

Wenbin Xie,Libo Zhang,Jianyu Yang,Lihua Zhang,Shaohua Ju,Yaoyao Luo

Separation of Zn 2+ from sulphate solution containing Ni 2+ and Co 2+ using di-(2-ethylhexyl)phosphoric acid (D2EHPA) has been carried out in capillary microreactors. Well-defined slug flows are formed at total flow rates of 0.1–4 mL/min, and the slugs size and specific interfacial area are determined. The effects of saponification degree of D2EHPA, extractant concentration, and residence time on extraction and separation of these three metal ions are investigated. Meanwhile, conventional batch experiments at 94 s and equilibrium experiments at 8 h are also done in parallel at different extractant concentrations. Compared with conventional batch experiments, better extraction and separation performance, e.g. 2.7–38.9 times higher of β Zn/Ni and 3.9–34.9 times higher of β Zn/Co , is obtained in the slug flow microreactor. In addition, the overall volumetric mass transfer coefficient k L a and overall mass transfer coefficient k L are measured. Compared with other microreactors and the batch mixer-settler, the used slug flow microreactor shows higher k L a values of Zn.

研究领域: 化学工程 · 材料科学
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