Continuous Flow Reactor Research Articles

Process intensification in flow chemistry using micro and millidevices: Numerical simulations of the syntheses of three different intermediate API compounds for diabetes mellitus drug production

Microreactor Technology (MRT) appears as an interesting alternative for process intensification, including the development of continuous synthesis of fine chemicals and Active Pharmaceutical Ingredients (API). The inherent proposal of MRT is to reduce the scale-up time by simply increasing the number of microreactors in parallel, the numbering-up concept using optimal designed micro or millidevices. Among the API, rosiglitazone and lobeglitazone are derivatives of thiazolidine-2,4-dione (TZD), which is used as a building block, for molecules with biological activity, sensitive to insulin and, thus, with its administration the body makes better use of the insulin it produces, being an important structural element in medicinal chemistry, especially for type 2 diabetes mellitus, one of the biggest concerns in the health area worldwide, affecting nowadays more than 180 million people. The numerical assessment of MRT for various API synthesis related to type 2 diabetes mellitus drugs indicates its comparable or superior performance compared to traditional batch process. Specifically, proposed micromixer designs facilitate successful scale-up to milliscale while maintaining microscale performance, with significantly lower pressure drops than commercial Asia microreactors. The proposed flow distributors offer good performance in ensuring uniform distribution across outlets due to their conical shape design and laminar flow regime, with low pressure drops. The flow distributor with eights outlet is preferred for higher flow rates due to its superior performance, minimizing the pressure drops. Efficient flow rate and molar concentration control at each reactor unit can be ensured by using one distributor for each reactant's feed stream. This approach guarantees accurate concentration, flow rate control and ideal residence time, ultimately facilitating higher total throughput for scale-up. The potential use of micromixer actuators lies in its ability to maintain or enhance performance while transitioning from micro to milli-scale, offering promising alternatives for process intensification and scale-up in pharmaceutical synthesis, particularly for medications targeting type 2 diabetes mellitus.

Magnetic Induction Heating-Driven Flow Chemistry Enabling Uniform and Continuous Growth of Metal–Organic Frameworks in Confined Microchannels of Wood

Magnetic Induction Heating-Driven Flow Chemistry Enabling Uniform and Continuous Growth of Metal–Organic Frameworks in Confined Microchannels of Wood

Florfenicol removal from veterinary pharmaceutical effluents: Tri-metallic zeolite 5A° for electrochemical oxidation and catalytic ceramic membrane separation

Contaminants of emerging concern, including pharmaceuticals, are commonly found in wastewater from households, farms, and healthcare facilities. When active pharmaceutical ingredients enter water sources, they contaminate the waterways and cause potential hazard effects on the aquatic environment and human populations. This concern is especially critical with antibiotics, due to the development of antibiotic-resistant bacterial strains. However, Florfenicol, a bacteriostatic antibiotic widely used in veterinary medicine, poses a significant risk of water pollution when discharged into waterways. In the present study and its practical application, removal of targeted pollutant namely antibiotic florfenicol by ozonation was investigated by measuring chemical oxidation demand (COD), biochemical oxygen demand (BOD), and turbidity for pharmaceutical wastewater in the batch reactor, while optimizing feeding electro flocculation voltage, O3 flow rate, O3 dosage and ceramic membrane filtration. Due to the production of hydroxyl radicals with strong oxidation properties, pollutants in wastewater can be effectively degraded via heterogeneous catalytic ozonation. It was examined whether the regenerated catalyst exhibited good catalytic activity after three cycles of washing with Milli-Q water and ethanol. The results show that the effluent concentration of antibiotic Florfenicol is about 99% alongside residual values for 91%, 79%, and 89% for COD, BOD, and turbidity, respectively (Time: 30 min, pH: 7.5). Meanwhile, the wastewater's degradability capacity (BOD5/COD ratio) increased from 0.37 to 0.53, rendering it more readily biodegradable for further treatment. These results indicate that the process of hybrid electro flocculation and catalytic ozonation with ceramic membrane has a high treatment efficiency for veterinary antibiotics, and a continuous-flow reactor can be utilized more practically for a full-scale industrial application.

Synthesis of Deuterated Compounds by Flow Chemistry.

Development of the efficient and practical method for the synthesis of deuterated compounds which occupies the broadest area among stable isotopes is one of the most essential issues toward the industrial advance and building a sustainable society. This review describes recent advances in deuteration reactions, where the continuous flow chemistry plays pivotal roles for the successful installation of deuterium atom into diverse organic frameworks, opening new fields of isotope-based synthetic chemistry.

Pilot–scale vertical continuous–flow reactors applied to treat rural domestic wastewater at low temperature via aerobic granular sludge

A pilot–scale vertical–flow continuous flow reactors (VF–CFR) was investigated for the treatment of rural domestic wastewater in the cold areas of Northeast China. VF–CFR helps in the creating of aerobic granular sludge (AGS), which improves the sludge concentration and removal efficiency of pollutants. VF–CFR achieved a high removal efficiency of Chemical Oxygen Demand (COD), Ammonia Nitrogen (NH3−N), Total Nitrogen (TN) and Total Phosphorus (TP) with 90 %, 94 %, 75 % and 93 % under the condition of sharp fluctuation of influent quality and temperature. The high–throughput sequencing analysis of the AGS revealed that Flavobacterium was a functional bacterium in the AGS process that had the function of heterotrophic nitrification and denitrification. The field–scale experiment confirmed the superiority of VF–CFR in wastewater treatment efficacy and stability. During the experiment, the concentrations of COD, TP and NH3–N in effluent at different temperatures were well met with the first–class A discharge standard of China (GB 18596–2001). However, there was a risk of exceedance exists in the reduction of TN removal under low temperature conditions.

An improved immersed boundary method with local flow pattern reconstruction and its validation

This study introduces an immersed boundary (IB) method based on coefficient array transformations of discrete equations for local cells and local flow pattern reconstruction, for the simulation of turbulent flow and combustion chemistry inside combustors with complex structure. This IB method is combined with a geometric scanning algorithm that traverses each fluid grid point in the vicinity of the wall, and based on the exact wall positions and normal vectors obtained from the scanning, the coefficient matrices of the individual grid points and their discrete forms of the governing equations are transformed, and the boundary conditions are added implicitly and exactly. The effectiveness of the method is validated through simulations of a cylinder, a gas turbine model combustor [Meier et al., “Spray and flame structure of a generic injector at aeroengine conditions,” in Proceedings of the ASME 2011 Turbo Expo: Power for Land, Sea, and Air (American Society of Mechanical Engineers, 2011), pp. 61–72 and Freitag et al., “Measurement of initial conditions of a kerosene spray from a generic aeroengine injector at elevated pressure,” Atomization Sprays 21, 521 (2011)], and a specific aero-engine combustor, demonstrating precision comparable to traditional body-fitted mesh approaches, especially for complex combustor structures. The simulation demonstrates that the IB method achieves accuracy comparable to a fitted grid when it provides boundary information of similar quality and detail for control equations. The locally reconstructed IB method introduced in this paper successfully delivers high-precision boundary conditions, making it valuable for practical engineering applications.

A compact 3D printed magnetically stirred tank reactor cascade coupled with a free impinging jet for continuous production of colloidal nanoparticles

Most colloidal nanoparticle production processes involve more than one step, such as particle nucleation, growth and stabilisation, that often take place at different time scales. Flow chemistry offers an attractive platform for nanoparticle synthesis, as it can provide excellent control of conditions for each individual step. In this work, a free impinging jet reactor (FIJR), known for its rapid mixing capability and fouling-proof operation, is followed by a cascade of 5 miniaturised (3 ml) continuous stirred tank reactors (mCSTR) that provides longer residence time and efficient temperature control for subsequent synthesis steps, while still being resistant to clogging due to active mixing. The small (0.1 mm) diameter nozzle design allowed the FIJR to provide excellent mixing even at relatively low flowrates (2 ml/min/jet). The mCSTR cascade was arranged in a vertical configuration (one tank on top of another), offering a compact design that is simple to use and requiring only one magnetic stirrer. It provided near-ideal macromixing with limited dead volumes and interconnections, as reflected by a residence time distribution comparable with the theoretical one for a CSTR cascade. Most parts of the reactor system were 3D printed with features that facilitated the assembly. The proposed FIJR design overcomes the accuracy limitations of 3D printing by combining it with micromilling to achieve one of the smallest FIJR reported and by allowing for rotation of the nozzles to easily resolve issues with jet alignment. The reactor system was employed for the synthesis of colloidal (∼10 nm size) silver nanoparticles via NaBH4 reduction of AgNO3, in a 0.06 g/day scale for 50 min continuous operation and (∼6 nm core size) iron oxide nanoparticles via co-precipitation of Fe3+/Fe2+, producing colloidally stable nanoparticles in a 16.1 g/day scale for over 2 h continuous operation.

General, Modular Access toward Immobilized Chiral Phosphoric Acid Catalysts and Their Application in Flow Chemistry.

Chiral phosphoric acids (CPAs) are among the most frequently used organocatalysts, with an ever-increasing number of applications. However, these catalysts are only obtained in a multistep synthesis and are poorly recyclable, which significantly deteriorates their environmental and economic performance. We herein report a conceptually different, general strategy for the direct immobilization of CPAs on a broad scope of solid supports including silica, polystyrene, and aluminum oxide. Solid-state catalysts were obtained in high yields and thoroughly characterized with elemental analysis by inductively coupled plasma-optical emission spectrometry (ICP-OES), nitrogen sorption measurements, thermogravimetric analysis, scanning transmission electron microscopy/energy-dispersive X-ray spectroscopy (STEM/EDX) images, and solid-state NMR spectroscopy. Further, the immobilized catalysts were applied to a variety of synthetically valuable, highly stereoselective transformations under batch and flow conditions including transfer hydrogenations, a Friedländer condensation/transfer hydrogenation sequence, and Mannich reactions under cryogenic flow conditions. Generally, high yields and stereoselectivities were observed along with robust catalyst stability and reusability. After being used for 10 runs under batch conditions, no loss of selectivity or catalytic activity was observed. Under continuous-flow conditions, the heterogeneous system was in operation for 19 h and the high enantioselectivity remained unchanged throughout the entire process. We expect our approach to extend the applicability of CPAs to a higher level, with a focus on flow chemistry and a more environmentally friendly and resource-efficient use of these powerful catalysts.

Microfluidic controllable production and morphology-independent phase-change heat transfer of boehmite nanofluids

Enhanced boiling heat transfer through nanofluids represents a significant approach to improving the cooling performance of electronic devices. However, the preparation of nanofluids poses challenges regarding production efficiency, morphology control, and structural stability. In addition, the underlying mechanism of flow boiling heat transfer enhancement of nanofluids, particularly changes in vapor behavior, remains a limited understanding. This study presents a facile and straightforward microfluidic strategy for the controllable synthesis of nanofluids toward efficient heat transfer enhancement. The microfluidic flow synthesis approach effectively enhances mixing efficiency at various flow rates, enabling continuous and high-throughput synthesis of boehmite nanofluids with different morphologies. The synthesized nanofluids exhibit long-term stability (>50 days) at room temperature. Both rod- and sphere-shaped nanofluids under equivalent concentrations can significantly improve critical heat flux (CHF) and maximum heat transfer coefficient (HTC) across various operating parameters, but with similar enhancement characteristics. Analysis of the period of bubble growth and burst, bubble size distributions, number of bubbles, and vapor phase fractions reveals that rod- and sphere-shaped nanofluids could shorten the period, enhance surface wetting, increase nucleation sites, and reduce bubble size efficiently and similarly. Furthermore, the effect of the concentration of nanofluid on phase-change heat transfer performance is systematically explored. 0.01 wt% nanofluid behaves the most remarkable enhancement, CHF and maximum HTC are improved by 24 % and 14.4 %, respectively. These findings not only shed new light on the controllable synthesis of functional nanomaterials but also provide important guidelines for the rational design of nanofluids for efficient two-phase cooling of electronic devices.

Utilizing anaerobic substrate distribution for growth of aerobic granular sludge in continuous-flow reactors

The development of continuous flow reactors (CFRs) employing aerobic granular sludge (AGS) for the retrofit of existing wastewater treatment plants (WWTPs) using a continuous-flow activated sludge (CFAS) system has garnered increasing interest. This follows the worldwide adoption of AGS technology in sequencing batch reactors (SBRs). The better settleability of AGS compared to AS allows for process intensification of existing wastewater treatment plants without the difficult conversion of often relatively shallow CFRs to deeper AGS-SBRs.To retrofit existing CFAS systems with AGS, achieving both increased hydraulic capacity and enhanced biological nutrient removal necessitates the formation of granular sludge based on the same selective pressures applied in AGS-SBRs. Previous efforts have focussed mainly on the selective wasting of flocculent sludge and retaining granular sludge to drive aerobic granulation.In this study a pilot-scale CFR was developed to best mimic the implementation of the granulation mechanisms of full-scale AGS-SBRs. The pilot-scale reactor was fed with pre-settled municipal wastewater. We established metrics to assess the degree to which the proposed mechanisms were implemented in the pilot-scale CFR and compared them to data from full-scale AGS-SBRs, specifically with respect to the anaerobic distribution of granule forming substrates (GFS). The selective pressures for granular sludge formation were implemented through inclusion of anaerobic upflow selectors with a water depth of 2.5 meters, which yielded a sludge with properties similar to AGS from full-scale SBRs. In comparison to the CFAS system at Harnaschpolder WWTP treating the same pre-settled wastewater, a more than twofold increase in volumetric removal capacity for both phosphorus and nitrogen was achieved. The use of a completely mixed anaerobic selector, as opposed to an anaerobic upflow selector, caused a shift in EBPR activity from the largest towards the smallest size class, while nitrification was majorly unaffected. Anaerobic selective feeding via bottom-feeding is, therefore, favorable for the long-term stability of AGS, especially for less acidified wastewater. The research underlines the potential of AGS for enhancing the hydraulic and biological treatment capacity of existing CFAS systems.

One-step synthesis of 1,4-butanediol from maleic anhydride by gas-phase selective hydrogenation over xRe/CuZnZr catalysts

Producing 1,4-butanediol with selective hydrogenation of maleic anhydride has significant financial benefits. This work reported a “green” one-step method for preparing 1,4-butanediol from maleic anhydride in a gas-phase fixed bed continuous flow reactor over an efficient 2Re/CuZnZr catalyst for the first time. In this paper, CuZnZr composite metal oxides were synthesized using the co-precipitation technique, followed by impregnation of Re to produce xRe/CuZnZr catalysts. The study aimed to investigate the effects of including Re on the catalyst's structure and performance. The results obtained from the characterization indicate that the presence of Re in the system restricts the growth of Cu0 grains. In addition, the inclusion of Re facilitated the utilization of ZnO as an effective spacer, reducing the size and quantity of Cu species agglomerates and enhancing active metal dispersion. This phenomenon may be attributed to being the primary factor responsible for the observed enhancement in the activity of the maleic anhydride hydrogenation reaction. Meanwhile, Re facilitated the transformation of γ-butyrolactone, an intermediate resulting from the hydrogenation of maleic anhydride into 1,4-butanediol. The 2Re/CuZnZr catalyst exhibited favorable catalytic activity under the conditions of 190 °C and 6 MPa, resulting in the complete conversion of maleic anhydride and a selectivity of 85 % towards 1,4-butanediol. The catalyst showed consistent catalytic performance throughout the 200 h. The finding about the impact of Re promoter on Cu-based catalysts has the potential to yield a highly efficient catalytic system for alcohol generation.

Engineering acidic and Pt sites on WO3- doped H-mordenite supported Pt catalyst for hydrogenation of γ -valerolactone to methyl tetra hydrofuran

The selective hydrogenation of gamma valerolactone (herein after GVL) into 2-methyl tetra hydrofuran (herein after MTHF) was studied over the different tungsten oxide-loaded Pt-doped H-Mordenite catalysts in a vapour phase continuous flow reactor. These catalysts were characterized by XRD, N2 adsorption-desorption analysis, SEM, TEM, FT-IR, Raman, XPS, TPR, NH3-TPD and pyridine adsorbed FT-IR analysis. XRD analysis result suggests that the tungsten oxide was well dispersed at low tungsten oxide loadings and, the tungsten oxide crystallites were formed at higher tungsten oxide loadings and the crystalline structure related to H-mordenite was retained for all the synthesised samples. The nitrogen adsorption-desorption analysis supported this result well. The TEM analysis confirms nano-sized platinum and tungsten oxide formation at 2Pt/10W-HM samples. The ammonia TPD analysis results suggested that all the samples possess weak and strong acidic sites and the amount and strength of acidic sites varies among the samples. The Pyridine adsorbed FT-IR results suggested that all the sample possesses mainly lewis acidic sites. These catalysts were evaluated for synthesising MTHF from GVL under different reaction conditions. Among the various synthesised catalysts studied, the 2 wt% Pt/10W-HM catalyst was identified as an effective catalyst with the 97 % conversion of GVL and the 98 % selectivity of MTHF. The higher catalytic performance depended on the distribution of surface tungsten oxide species along with the suitable acidic properties of the supported system.

4-Ketovalero lactone (KVL): A gateway molecule for diversification of the furanic platform

Diversification of the furanic platform has been developed from 4-ketovalerolactone (KVL), a platform molecule readily available from furfuryl alcohol. A halogen-free synthetic route to δ-aminolevulinic acid is reported alongside a further exploration of KVL in the synthesis of important 5-hyrdoxy levulinic acid esters. Flow chemistry approaches have been implemented for the synthesis of short- and long-chain esters that may find applications as biorenewable fuel oxygenates and lubricants, respectively.

Chemo-enzymatic flow synthesis of nature-inspired phenolic carbonates and carbamates as antiradical and antimicrobial agents

A series of carbonate and carbamate derivatives of natural phenols, tyrosol and hydroxytyrosol, were synthetized through a chemo-enzymatic flow approach. First, the chemoselective synthesis of tyrosol and hydroxytyrosol carbonates was performed using immobilized lipase B from Candida antarctica as catalyst in tert-amyl alcohol, a non-conventional green solvent. Then, two selected carbonates were reacted in flow with the appropriate amine to obtain the desired carbamates. All the compounds were isolated in moderate to good yields. The carbonate and carbamate derivatives showed increased lipophilicity compared to the natural parent compounds, while maintaining similar radical scavenger properties. Moreover, their antimicrobial activity against four selected bacterial strains was evaluated and they showed improved activity in comparison with tyrosol and hydroxytyrosol.

A novel continuous-flow photocatalytic device for antibiotic degradation

The presence of antibiotic contaminants in water reservoirs and aquatic environments poses considerable risks to public and ecosystem health. Despite its high mineralization efficiency and environmental friendliness, photocatalytic technology has limited practical applications due to low energy efficiency, intermittent operation, and inconvenient catalyst recovery. Here, we developed a continuous-flow photocatalytic device (CFP-D) with outstanding activity, stability, and university towards antibiotic wastewater degradation. Complete removal of total organic carbon was achieved for multiple antibiotic wastewaters using CFP-D in a continuous flow process. The unique combination of continuous-flow reactor and highly photo-permeable F-Ti-SiO2 aerogel with abundant TiO5 active sites overcomes the limitations of conventional photocatalytic devices. This study provides new insights for the design of highly efficient monolithic catalysts and continuous flow reaction devices, and showcases the immense potential of CFP-D in medical and organic wastewater treatment.

Stable continuous flow CANDAN process transitioning from anammox UASB reactor by facilitating indigenous nitrite-producing denitrification community

The emerging nitrogen removal process known as CANDAN (Complete Ammonium and Nitrate removal via Denitratation-Anammox over Nitrite) has been developed in Sequencing Batch Reactors (SBRs). Yet, starting up and maintaining stability in continuous-flow reactors remain challenging. This study explores the feasibility of transitioning the CANDAN process from an anammox-dominated process by introducing appropriate external organics to facilitate indigenous nitrite-producing denitrification community in an Upflow Anaerobic Sludge Blanket (UASB) reactor. 150-day operation results indicate that under feeding rates of domestic wastewater at 0.54 L/h and nitrate-containing wastewater at 1.08 L/h, excellent N removal was achieved, with effluent TN below 10.0 mg N/L. Adding external sodium acetate at a COD/NO3−-N = 2.0 triggered denitratation, ex-situ denitrification activity tests showed increased nitrite production rates, maintaining the nitrate-to-nitrite transformation ratio (NTR) above 90 %. Consequently, anammox activity was consistently maintained, dominating Total Nitrogen (TN) removal with a contribution as high as 78.3 ± 8.0 %. Anammox functional bacteria, Brocadia and Kuenenia were identified and showed no decrease throughout the operation, indicating the robustness of the anammox process. Notably, the troublesome of sludge flotation, did not occur, also contributing to sustained outstanding performance. In conclusion, this study advances our understanding of the synergistic interplay between anammox and denitrifying bacteria in the Anammox-UASB system, offering technical insights for establishing a stable continuous-flow CANDAN process for simultaneous ammonium and nitrate removal.

Aerobic granulation in a continuous-flow simultaneous nitrification, endogenous denitrification, and phosphorus removal system fed with low-strength wastewater: Granulation mechanism and microbial succession

The culture of aerobic granular sludge (AGS) in continuous-flow system for treating low-strength municipal wastewater is still a challenge for its widespread application. This study developed a continuous-flow reactor based on metabolic and hydraulic selection pressure to explore the feasibility of culturing AGS in conventional continuous-flow mode. The results showed that aerobic granulation was successfully achieved with a mean particle size of 373 μm and almost all granules (95.6 %) were larger than 200 μm. An obvious three-stages granulation process comprised of initial adhesion, the formation of early aggregates that acted as nuclei of granules, and the final AGS maturation, was observed in this work. The selective enrichment of slow-growing bacteria in alternating feast/famine condition played a critical role in the aerobic granulation. The analysis results of extracellular polymeric substances revealed that β-polysaccharides and proteins distributed uniformly within the mature granules, while α-polysaccharides were found mainly concentrated around the granules, which was believed to enhance the mechanical strength of granules. The continuous-flow AGS system exhibited an excellent simultaneous carbon, nitrogen, and phosphorus removal performance with high removal efficiencies of NH4+-N (97.6 %), TIN (91.0 %), COD (93.7 %), and TP (94.8 %). Moreover, a low sludge yield of 0.1 gMLSS/gCOD was obtained for dramatic in situ sludge reduction. Illumina MiSeq sequencing results confirmed the outstanding accumulation of GAOs (Candidatus_Competibacter) and PAOs (Rhodocyclaceae) in the system, which were responsible for simultaneous C, N, P removal and sludge reduction. Overall, this study demonstrated the feasibility of aerobic granulation in conventional continuous-flow mode and offered insights into the granulation mechanism, providing implications and references for the application of AGS technology in existing wastewater treatment plants.

Operational mode and powdered activated carbon promoting syntrophic propionate oxidation during anaerobic digestion of complex organic substances

Operational mode and powdered activated carbon (PAC) are key factors facilitating microbial syntrophy and interspecies electron transfer during anaerobic digestion, consequently benefiting process stability and efficient methanogenesis. In this study, continuous-flow reactor (CFR) and sequencing batch reactor (SBR), with and without the addition of PAC, respectively, were operated to examine their effects on system performance and methanogenic activity. Based on the cycle-test result, the PAC-amended CFR (CFRPAC) recorded both the highest methane yield (690.1 mL/L) and the maximum CH4 production rate (28.8 mL/(L·h)), while SBRs exhibited slow methanogenic rates. However, activity assays indicated that SBRs were beneficial for organics removal in batch experiments fed with peptone. Taxonomic and functional analysis confirmed that CFRs were optimal for proliferating oligotrophs (e.g., Geobacter) and SBRs were more suitable for copiotrophs (e.g., Desulfobulbus). Metagenomic analysis revealed that CFRs had efficient acetate metabolic pathways from propionate and ethanol, whereas SBRs did not, resulting in the buildup of propionate. Furthermore, Methanobacterium and Methanothrix were acclimated to the different operational conditions, while acetoclastic Methanosarcina and hydrogenotrophic Methanolinea were acclimated in SBRs (5.1–13.4%) and CFRs (0.3–1.7%), respectively. This study confirmed the enhancement of microbial syntrophy by the addition of PAC as well as the acclimation of electroactive bacteria (e.g., Geobacter) with complex organic substances.

Study of the influence of the gas circulation ratio on the production of C5–C18 alkenes in the Fischer–Tropsch synthesis

The process of producing C5+ hydrocarbons, including unsaturated ones, on a zeolite-containing catalyst Сo-Al2O3 /SiO2 /ZSM-5/Al2O3 in flow and flow-circulation modes of operation at a temperature of 250 °C, a pressure of 2.0 MPa, GHSV 1000 h–1 has been studied , H2 /CO ratio = 1.70 in the source gas and circulation ratios of 4, 8 and 16. It was determined that the process indicators (selectivity and productivity for C5+ products) pass through a maximum at a circulation ratio of 8. The use of gas circulation in comparison with flow synthesis mode allows you to regulate the composition of products. An increase in the circulation ratio in the range of 4–16 leads to an increase in the proportion of formed olefins with a hydrocarbon chain length containing 5–20 carbon atoms, from 53.9 wt.% up to 65.7 wt.%. The use of a zeolite-containing catalyst intensifies the formation of C8–C12 alkenes in comparison with the Co-Al2O3 /SiO2 catalyst by 3,3 times – the content increases from 13,5 wt.% up to 44.2 wt.% at similar values of circulation ratio, pressure and H2 /CO ratio = 1.70 in the source gas. It was found that as the circulation ratio increases, the rate of deactivation of the zeolite-containing catalyst decreases, which may be caused by a decrease in the partial pressure of water in the reaction volume.

Efficient synthesis of ethanol and propanediol from glucose via a noble metal promoted CuWO4 catalyst

Biomass is the most promising carbon feedstock for producing chemicals and fuels as substitutes for fossil resources. In this work, hydrogenolysis of glucose to ethanol (EtOH) and 1,3-propanediol (1,3-PDO) were carried out over multi-function noble metal promoted CuWO4 (0.1 wt% Ru, Pt and Pd) catalysts using a continuous-flow fixed-bed reactor. Amazingly, the Ru/CuWO4 catalyst presented the best catalytic performance with 84.3% glucose conversion, 63.2% EtOH and 21.2% 1,3-PDO selectivities over 40 h reaction. An array of characterization techniques, including XPS, Cu LMM AES, in-situ CO-DRIFTS, NH3-TPD, Py-FTIR, and operando EG-DRIFTS, were applied to reveal the nature of converting glucose into EtOH and 1,3-PDO. It is discovered that the added small amount of Ru tuned the chemical states of W and Cu, resulting in forming the highest content of W5+ and Cu0 on the Ru-promoted catalyst, which improves the glucose hydrogenolysis to EtOH. Besides, the strong Brønsted acid sites (BASs) derived from W6+ contribute to relatively high 1,3-PDO selectivity on Pt/CuWO4 catalyst.