Alumina Catalysts Research Articles

FeO–alumina catalyst for reforming waste polyethylene terephthalate (PET) pyrolyzed products: synthesis, characterization, and performance evaluation

FeO–alumina catalyst for reforming waste polyethylene terephthalate (PET) pyrolyzed products: synthesis, characterization, and performance evaluation

DLP 3D printing of alumina catalyst architectures: Design, kinetics and modeling of structure effects on catalyst performance

DLP 3D printing of alumina catalyst architectures: Design, kinetics and modeling of structure effects on catalyst performance

CFD modeling of DME synthesis based on methanol dehydration process by an adiabatic reactor: Characterization

Today, Dimethyl ether (DME) can be used as a fuel in various applications, including as a substitute for diesel fuel. Despite its advantages, there are some challenges associated with DME as a fuel. One of the main challenges is the limited availability of DME refueling stations and the need for dedicated storage facilities due to their different properties compared to traditional fuels. DME shows promise as a clean-burning alternative fuel with the potential to reduce emissions and dependence on fossil fuels, especially in the transportation and power generation sectors. Ongoing research and development efforts are focused on improving production methods, expanding infrastructure, and exploring new applications for DME as a fuel. DME is a colorless gas that can be used as a fuel or as a precursor for the production of other chemicals. The most common method for DME synthesis involves the dehydration of methanol. Methanol is first converted to dimethyl ether by removing a molecule of water. This reaction is typically catalyzed by acidic materials such as alumina or zeolites. In this work, to study the physical properties of the methanol dehydration reaction, CFD modeling of the adiabatic reactor has been accomplished. The researchers showed that the use of an alumina catalyst, which has selective mechanical properties and unique surface properties, is a suitable choice as a catalyst for DME synthesis. The results of this study indicate that laboratory data such as pressure, energy, and velocity in the adiabatic reactor satisfy the reaction conditions well. Also, temperature profile diagrams with changes in temperature, pressure, and velocity show that the reaction of methanol dehydration is strongly dependent on environmental factors and presents different results under the influence of other conditions.

CO-Free Fuel Processing of Water Gas Shift Feedstocks: Effect of Support on CuMn Spinel Performance

AbstractCleaning up carbon monoxide (CO) in water gas shift feedstocks is crucial for fuel cell applications. The catalytic transformation of CO in hydrogen-rich feeds poses a significant challenge in environmental catalysis. To address this issue, a range of Cu–Mn-based monometallic and bimetallic catalysts with diverse supports (such as alumina, silica, zirconia, and titania) were employed. Temperature programming techniques were utilised to observe the reduction and oxidation behaviours of these catalysts. The investigation involved testing CO oxidation at various temperatures over copper and manganese-based supported catalysts in the presence of H2O and CO2 (simulating realistic conditions). A positive impact of H2O on catalytic performance was noted, whereas CO2 had a suppressive effect. Furthermore, the specific support materials (Al2O3, SiO2, TiO2, and ZrO2) were studied to understand their roles in CO oxidation under realistic conditions. In the presence of water, alumina catalysts containing bimetallic metals (Cu–Mn) exhibited 100% CO conversion even at a lower temperature of 160 °C. Conversely, under the predominant influence of CO2, alumina catalyst (Cu–Mn) showed 55% CO conversion. The exceptional performance was attributed to CO preferential adsorption on highly active Cu–Mn sites and a small H2-oxidative atmosphere of the catalysts. The activity results highlighted the strong dependence of CO conversion on reaction temperatures, the presence of metals, and the types of supports. Overall, these findings suggest the potential use of these catalysts for H2 purification under realistic conditions. Graphical Abstract

Corrosion Behavior of Aluminum in Fossil Diesel Fuel and Biodiesel From Chicken Eggshell‐Alumina‐Catalyzed Waste Cooking Oil

ABSTRACTTo curb environmental pollution emanating from the exhausts of engines using fossil diesel fuel (DF), studies on the use of biodiesel from renewable energy source are ongoing. However, engine components have been observed to corrode easily in biodiesels. In this study, a comparative study of the corrosion rate of aluminum coupon (AC) in biodiesel from waste cooking oil over chicken eggshell‐supported alumina catalyst (WCOB) and fossil DF was executed. Weight loss method was used to examine the corrosion rate. Highest corrosion rates of 0.0381 and 0.0052 mm year−1 were recorded for AC in WCOB and DF, respectively. The developed mathematical models proved effective for corrosion rate prediction. At optimum prediction, the minimum corrosion rates for the AC in WCOB and DF were 1.822 × 10−3 and 1.222 × 10−3 mm year, respectively. Characterization revealed pits formation and presence of oxygen and carbon on AC surface with loss of Al ions from the AC surface into WCOB and DF after corrosion. In conclusion, all results revealed high corrosion rates of AC in WCOB than DF.

Role of MgO in Al2O3‐supported Fe catalysts for hydrogen and carbon nanotubes formation during catalytic methane decomposition

AbstractCatalytic methane decomposition is a promising technology for reducing the reliance on fossil fuels and mitigating the effects of climate change by producing clean hydrogen and value‐added carbon without the emission of greenhouse gases. The aim of the study was to investigate the use of Al2O3‐modified MgO doped iron‐based catalysts for the catalytic decomposition of methane. The catalysts were synthesized using the impregnation method and characterized using various analysis techniques, including Brunauer, Emmett, and Teller, temperature programmed reduction, temperature programmed oxidation, X‐ray diffraction, thermal gravimetric analysis, Raman, scanning electron microscopy, and transmission electron microscopy. The activity of the synthesized catalysts was tested in a packed‐bed reactor with a gas flow rate of 20 mL/min at a temperature of 800°C. The investigation focuses on the influence of incorporating magnesium into alumina catalysts with MgO concentration ranging from (20%–70%), where higher magnesium levels improve catalytic activity by creating more active sites, positively impacting methane decomposition. Enhanced catalyst reducibility and increased particle dispersion lead to improved catalytic properties despite the reduced surface area. The FA70M and FA63M catalysts exhibited almost the same catalytic characteristics and the highest stability and methane conversion among the catalysts investigated, reaching 87% and 85% at 800°C for 120 min. Moreover, both catalysts showed hydrogen yields of 86% and 85%, respectively. The introduction of MgO further increased the total carbon yield from 103% with FA and 39% for FM to 114% and 120% for the respective catalysts (FA70M and FA63M). During the methane decomposition reaction, carbon nanotubes of varying diameters were produced. Higher iron loading resulted in a positive trend.

Effect of acidity of solid acid catalysts during non-oxidative thermal decomposition of LDPE

AbstractThermal decomposition of low-density polyethylene (LDPE) was monitored by thermogravimetry under N2 atmosphere in the presence of solid acid catalysts such as alumina (α-Al2O3, γ-Al2O3), crystalline silica-alumina (SA, molar ratio of Si/Al = 0.19) and amorphous silica-alumina catalysts (ASA, molar ratio of Si/Al = 4.9). Crystal structure and surface area of solid acid catalysts were measured by XRD and BET, respectively. The strength and distribution of acid sites of solid acid catalysts were estimated by NH3-TPD. It was observed that total acidity strength is in the order of ASA (1.77 μmmol NH3/g) > AS (1.42 μmol NH3/g) > γ-Al2O3 (1.06 μmol NH3/g) > α-Al2O3 (0.06 μmol NH3/g). Thermal degradation behavior of LDPE with and without solid acid catalyst was monitored by TGA, where heating rates (β) of 5, 10, and 20 °C/min were employed under an inert atmosphere, and their activation energies (Ea), onset temperatures (Tinitial), decomposition temperatures (Tdecomp) were calculated and compared. The activation energy (Ea) was evaluated using the Coats-Redfern method. Solid acid catalysts with stronger acidity and higher surface area showed a decrease in activation energy and onset temperature. Activation energy of LDPE over ASA catalyst is decreased to 97.3 kJ/mol from thermal decomposition of LDPE without catalyst of 117.2 kJ/mol under heating rate of 10 °C/min. The isothermal decomposition of LDPE was monitored at 300 °C for 3 h with a heating rate of 10 °C/min, where 13.1% and 24.2% wt. loss were observed over SA and ASA, respectively, while only 0.7% wt. loss was observed for LDPE without a solid acid catalyst. Graphical abstract Single step decomposition of LDPE Thermal degradation behavior of LDPE monitored by TGA, with different heating rates (β) of 5, 10, 20 °C/min.

A novel decoupled triple-fluidized bed reaction system for polyvinyl chloride (PVC) disposal: (I) Thermodynamic simulation and experimental investigation

ABSTRACT In this work, a novel decoupled triple-fluidized bed reaction system was proposed to dispose of polyvinyl chloride (PVC). Thermodynamic simulation and thermogravimetric experiments were conducted to examine the dechlorination feasibility and analyze the effects of CaO and CaCl2 on PVC pyrolysis. Besides, the quantitative removal efficiency of HCl was investigated in a lab-scale bubbling fluidized bed. Results indicated that HCl hardly interacted with the silica−alumina catalyst and Fe2O3 adsorbent, while for Na2O and CaO adsorbents, HCl could convert into corresponding stable chlorides, demonstrating the theoretical feasibility of the system. Next, PVC pyrolysis was a multi-stage process, and CaO spontaneously reacted with the released HCl but simultaneously inhibited its alkylation reaction; moreover, CaCl2 could act as a catalyst to facilitate its HCl release and alkylation reaction. Finally, as the temperature rose, the dechlorination efficiency first increased and then decreased, reaching a peak value of 87.6% at 700°C in the N2 atmosphere. In addition, the dechlorination efficiency in the CO2 atmosphere was higher at 400–900°C.

Chromium-extracted aluminum catalyst for co-pyrolysis of cotton fabric waste and polypropylene plastic waste to bio-oil

Heterogeneous catalysts of chromium-extracted aluminum (CE) were prepared and used to produce bio-oil from the co-pyrolysis of cotton fabric waste (CFW) and polypropylene waste (PPW). The catalysts were synthesized via wet impregnation at 5–20 wt% catalyst loading and calcined at 600 °C for 5 h. The co-pyrolysis was conducted in a fixed-bed reactor at 500 °C for 1 h with 1:1 CWF/PPW ratio and 1:1 catalyst/feedstock ratio. The physical and chemical properties of the catalysts and bio-oil were characterized by several techniques such as Brunauer–Emmet–Teller, scanning electron microscopy, energy dispersive x-ray spectroscopy, x-ray diffraction, temperature-programmed desorption and gas chromatography-mass spectrometry. Investigations into the effects of metal loadings revealed that the 15CE catalyst was the most active, achieving a maximum bio-oil yield of 76.4 % and producing valuable chemical compounds like hydrocarbons, alcohols, phenols, and furans. The XRD of 15CE catalyst confirmed the presence of chromium oxide and assigned to the rhombohedral phase of the crystal lattice. BET indicated 15CE has the largest surface area (50.4 m2/g) among the CE catalysts which contributed to its high activity. The SEM revealed CE catalysts at different metal loadings contain irregular shapes and sizes with a rough surface texture. The NH3-TPD profiles indicated alterations in acid site distribution due to the interaction between the introduced Cr metal and EA. The 15CE catalyst also demonstrated significant reusability, maintaining performance after two regeneration cycles. These results confirm the potential of CE catalysts in enhancing bio-oil production from CFW and PPW.

Features of CO₂ Hydrogenation on MoO₃/Al₂O₃ and γ-Al₂O₃

The physicochemical and catalytic (CO₂ hydrogenation) characteristics of Mo-containing catalysts have been studied. Catalysts with an oxide content of Mo 8 and 15 wt% were prepared by impregnation with ammonium paramolybdate γ-Al₂O₃ followed by drying and calcining at 500°C. The introduction of Mo oxide reduces the pore volume of the support and increases their average size, which indicates the distribution of the deposited molybdenum oxide in the pores of the support. According to X-ray diffraction data, the calcined catalyst contains practically no crystalline MoO₃ phase. According to the Raman spectra, oxygen-containing formations are present on the catalyst surface, in which Mo atoms are tetrahedrally and octahedrally coordinated with respect to oxygen atoms. The impregnated MoO₃ oxide is partially reduced by hydrogen during linear heating starting from 320°C. Hydrogenation of CO₂ (gas of composition, vol.%: 30.7 CO₂, 68 H₂, rest. N2, sample 0.5 g) was studied in the mode of linear heating up to 400°C. The main reaction is the reverse reaction of CO steam reforming. The contribution of the methanation reaction to CO₂ hydrogenation is small. An increase in temperature and pressure has a positive effect on CO₂ conversion. With an increase in pressure from 1 to 5 MPa, the CO content increases approximately twofold. In the hydrogenation of CO₂, γ-Al₂O₃, preheated in a flow of H₂ to 400°C, also exhibits noticeable activity, although significantly lower compared to Mo-containing catalysts. With increasing pressure, the activity of aluminium oxide and Mo-containing catalysts, increases.

Effect of Contact Time on Carbon Deposition and Catalytic Activity of Nickel Alumina Catalysts for Dry Reforming of Methane

AbstractDry reforming of methane (DRM) reaction is advantageous in producing syngas with a low H2/CO, relevant to many industries. Effect of contact time on catalytic activity and carbon deposition is studied for DRM using Ni−Al catalysts, along with the effect of metal loading, reaction temperature, and reactant partial pressure (CO2/CH4). Maximum CH4 conversion (58 %) and CO2 (59 %) were achieved at a higher contact time of 4.009 kg‐cat . h/kgCH4. A maximum of 46 % CH4 conversion was achieved at 1023 K with a contact time of 0.134 kg‐cat . h/kgCH4. Higher CH4 and CO2 conversion were achieved with an excellent H2 and CO yield due to the RWGS reaction with increased metal (Ni) loading (10–30 wt . %). When the reactant partial pressure (CO2) changed from 0.1–0.3, the CH4 conversion increased whereas CO2 conversion decreased. FESEM images revealed the formation of whisker‐like carbon fibers for all loadings. For the best syngas output and stability in a Ni‐based catalyst, a combination of a basic support (alumina) at a higher contact time (~4.009 kg‐cat . h/kgCH4) and a CO2/CH4 ratio of 1–1.5 at a moderate temperature of 873 K may provide best CO2 adsorption with minimal coking.

Identification of suitable catalyst among HZSM-5, HY and γ-Al2O3 to obtain upgraded pyrolysis oil with augmented liquid oil yield

This study examines catalytic ability of various zeolite materials in converting discarded tire pyrolyzed oil by employing a moderate sized pyrolysis plant of a 10 L working volume. The study revealed that the yield of liquid fractions using γ-Al2O3 was greater than that of HZSM-5 and HY, while the yield of condensates were limited in the absence of catalyst. The tire waste pyrolysis oil catalytcially enhanced by alumina catalyst analyzed using Fourier transform infrared spectroscopy exhibited the stretching bands corresponding to aromatic and non-aromatic compounds. The GC MS analysis revealed that the cyclic unsaturated fragment percentages in liquids were decreased by the catalysts to 53.9% with HY, 59.0% with γ-Al2O3, and 62.2% with HZSM-5, which in turn was converted into aromatic chemicals. Nitrogen adsorption desorption analysis revealed that γ-Al2O3 has an enhanced surface area of 635 m2/g which improved its catalytic performance. The cracked liquid oil had viscosity (10.36 cSt), values of pour and flash temperatures of −2.2 °C and 41 °C respectively, analogous to petroleum diesel. The upgraded pyrolysis oil (10%) is blended with gasoline (90%), and emission analysis was performed. Moreover, liquid oil needs post treatment (refining) for its use as energy source in transportation application. The novelty of this research is in its comparative analysis of multiple catalysts under controlled conditions using a small pilot-scale pyrolysis reactor, which provides insights into optimizing the pyrolysis process for industrial applications.

Toyobo GS Catalyst, an eco-friendly aluminum catalyst for polyester polymerization, receives recognition for APR Design for Recyclability

Toyobo GS Catalyst, an eco-friendly aluminum catalyst for polyester polymerization, receives recognition for APR Design for Recyclability

Hydroprocessing of Gasoline on Modified Alumina Catalysts

The hydroprocessing of gasoline on modified alumina catalysts makes it possible to obtain high-octane products. The implementation and development of the process have largely become possible due to the development of modified alumina catalysts that do not contain noble metals and exhibit special catalytic properties. This article discusses topical issues of petrochemistry, namely the creation of catalysts with improved characteristics for the production of high-octane gasoline with low sulfur content. New catalytic systems based on alumina and other carriers modified with transition metals, lanthanum and phosphorus were synthesized. By physico-chemical methods of analysis TPD of ammonia, TEM and XRD, we studied the acid–base and structural characteristics of the developed catalysts. The activity of the developed catalysts in the studied process of hydrotreating gasoline fractions depends on the structure and condition of the active centers. The process of hydrotreating straight-run gasoline in the presence of synthesized catalysts was carried out on a laboratory flow unit. It was shown that, during the hydrotreating of straight-run gasoline on the NiO-MoO3-La-P-HZSM-HY-Al2O3 catalyst, the octane number in the final product increased to 88.6, and the sulfur content decreased from 0.0088 to 0.001%. It was found that the minimum sulfur content in the gasoline hydrotreating product of 0.0005% was achieved on the catalyst CoO-WO3-La-P-HZSM-HY-Al2O3, which is significantly lower than for other studied catalytic systems. The obtained results of the sulfur content in the hydrotreating products fully comply with the Euro-5 standard. Thus, the efficiency of hydrotreating the gasoline fractions studied in this work was mainly determined by the nature of the carriers and modifiers used for the synthesis of catalysts and the technological parameters of the process. The synthesized catalysts showed high activity and selectivity, resulting in high-octane gasoline with a low sulfur content that meets international quality standards.

Kinetic Resolution Polymerization Enabled Chemical Synthesis of Perfectly Isotactic Polythioesters.

Isotactic polythioesters (PTEs) that are thioester analogs to natural polyhydroxyalkanoates (PHAs) have attracted growing attention due to their distinct properties. However, the development of chemically synthetic methods for preparing isotactic PTEs has long been an intricate endeavour. Herein, we report the successful synthesis of perfectly isotactic PTEs via stereocontrolled ring-opening polymerization. This binaphthalene-salen aluminium (SalBinam-Al) catalyst promoted a robust polymerization of rac-α-substituted-β-propiothiolactones (rac-BTL and rac-PTL) with highly kinetic resolution, affording perfectly isotactic P(BTL) and P(PTL) with Mn up to 276 kDa. Impressively, the isotactic P(BTL) formed a supramolecular stereocomplex with improved thermal property (Tm=204 °C). Ultimately, this kinetic resolution polymerization enabled the facile isolation of enantiopure (S)-BTL, which could efficiently convert to an important pharmaceutical building block (S)-2-benzyl-3-mercapto-propanoic acid. Isotactic P(PTL) served as a tough and ductile material comparable to the commercialized polyolefins. This synthetic system allowed to access of isotactic PTEs, establishing a powerful platform for the discovery of sustainable plastics.

Kinetic Resolution Polymerization Enabled Chemical Synthesis of Perfectly Isotactic Polythioesters

AbstractIsotactic polythioesters (PTEs) that are thioester analogs to natural polyhydroxyalkanoates (PHAs) have attracted growing attention due to their distinct properties. However, the development of chemically synthetic methods for preparing isotactic PTEs has long been an intricate endeavour. Herein, we report the successful synthesis of perfectly isotactic PTEs via stereocontrolled ring‐opening polymerization. This binaphthalene‐salen aluminium (SalBinam‐Al) catalyst promoted a robust polymerization of rac‐α‐substituted‐β‐propiothiolactones (rac‐BTL and rac‐PTL) with highly kinetic resolution, affording perfectly isotactic P(BTL) and P(PTL) with Mn up to 276 kDa. Impressively, the isotactic P(BTL) formed a supramolecular stereocomplex with improved thermal property (Tm=204 °C). Ultimately, this kinetic resolution polymerization enabled the facile isolation of enantiopure (S)‐BTL, which could efficiently convert to an important pharmaceutical building block (S)‐2‐benzyl‐3‐mercapto‐propanoic acid. Isotactic P(PTL) served as a tough and ductile material comparable to the commercialized polyolefins. This synthetic system allowed to access of isotactic PTEs, establishing a powerful platform for the discovery of sustainable plastics.

A New Class of Chiral Polyethers and Polyesters Based on the [2.2]Paracyclophane Scaffold.

Over the past decades, the research on optically active polymers (OAPs) has significantly grown, and extensive studies have been carried out on their syntheses, conformations, and applications. The most commonly used OAPs are based on natural products such as sugars or amino acids, which limits their scope. A broader range of applications can be achieved by synthesizing lab-tailored monomers, which allow precise control over structure and properties. This research developed a four-step synthetic route to a previously unreported chiral [2.2]paracyclophane-based epoxide monomer. An aluminum catalyst and an alkylammonium initiating system were applied and optimized for its polymerization to provide access to a novel class of chiral polyethers. Furthermore, we demonstrated the copolymerization viability of the (4-[2.2]paracyclophanyl)oxirane monomer using phthalic anhydride.

Copolymerization of β-Butyrolactones into Functionalized Polyhydroxyalkanoates Using Aluminum Catalysts: Influence of the Initiator in the Ring-Opening Polymerization Mechanism.

Within bioplastics, natural poly(3-hydroxybutyrate) (PHB) stands out as fully biocompatible and biodegradable, even in marine environments; however, its high isotacticity and crystallinity limits its mechanical properties and hence its applications. PHB can also be synthesized with different tacticities via a catalytic ring-opening polymerization (ROP) of rac-β-butyrolactone (BBL), paving the way to PHB with better thermomechanical and processability properties. In this work, the catalyst family is extended based on aluminum phenoxy-imine methyl catalyst [AlMeL2], that reveals efficient in the ROP of BBL, to the halogeno analogous complex [AlClL2]. As well, the impact on the ROP mechanism of different initiators is further explored with a particular focus in dimethylaminopyridine (DMAP), a hardly studied initiator for the ROP of BBL. A thorough mechanistic study is performed that evidences the presence of two concomitant DMAP-mediated mechanisms, that lead to either a DMAP or a crotonate end-capping group. Besides, in order to increase the possibilities of PHB post-polymerization functionalization, the introduction of a side-chain functionality is explored, establishing the copolymerization of BBL with β-allyloxymethylene propiolactone (BPLOAll), resulting in well-defined P(BBL-co-BPLOAll) copolymers.

A Synthetic Approach to Synthesize Furan‐2‐Carboxylate Derivatives by Using a Magnetic Sodium Aluminate Catalyst

AbstractA novel and efficient procedure has been developed to synthesize furan‐2‐carboxylate derivatives through a one‐pot condensation of chloroacetate derivatives, 1,3‐diketones, and chloroform in the presence of magnetic sodium aluminate 40 wt. % (Aluminate NP‐40). The synthesized heterogeneous catalyst can be easily recovered from the reaction mixture by applying an external magnetic field. Magnetic aluminate NP catalysts provide a sustainable, environmentally friendly, and cost‐effective method for synthesizing furan‐2‐carboxylate derivatives. Additionally, the catalyst is stable and can be reused multiple times without losing its catalytic properties. High product yields in a short experimental time and easy workup are other advantages of the present method. All synthesized compounds were characterized by NMR spectroscopy.

Effect of calcination temperature on the performance of K-Co/Al2O3 catalyst for oxidative coupling of methane

The oxidative coupling of methane (OCM) involves directly converting methane to C2+ hydrocarbons (such as ethylene and ethane) via a reaction with oxygen. This study elucidated the effect of the calcination temperature on the structure and catalytic performance of potassium-doped-cobalt oxide supported on an alumina (K-Co/Al2O3) catalyst for the OCM reaction. The catalyst was highly active at relatively low reactor temperatures (500–640 °C). Four calcination temperatures (400, 500, 600, and 700 °C) were investigated, with the results showing that the calcination temperature strongly affected catalytic properties, such as the crystalline phases, elemental distribution, physical properties, and catalytic basicity, leading to a wide range in catalytic performances. The catalyst calcined at 400 °C was superior among the catalysts, with 8.3 % C2+ yield, 24.8 % C2+ selectivity, and 33.6 % CH4 conversion at 640 °C. Furthermore, the catalyst was robust over 24 h of testing.