Microwave-Absorbing Catalysts in Catalytic Reactions of Biofuel Production
Abstract
:1. Introduction
2. Microwave Irradiation
2.1. Fundamentals of Microwave Irradiation
2.2. Mechanism of Microwave Irradiation
3. Catalysts Synthesis
4. Applications
4.1. Bio-Oil Production
4.2. Methanation
4.3. Methane Reforming
Process | Catalyst/ Absorbent | Textural Properties/ Composition | Yield | Remarks | Reference |
---|---|---|---|---|---|
Methane steam reforming | Ni/CeO2-Al2O3 on a SiC monolith | Average pore diameter: 4.6 µm Specific surface area: 10.0 m2/g SiC: 87.5 wt% Ni: 1.7 wt% Al2O3: 0.5 wt% CeO2: 10.8 wt% | Equilibrium in H2 yield and CH4 conversion @800 °C (GHSV: 3300 h−1) and 850 °C (GHSV: 5000 h−1) | Pressure: 1 bar S/C: 3 Energy efficiency: 55% @1300 W (Power of microwave) Energy consumption: 3.8 kW/Nm3H2 | [79] |
Methane steam reforming | Ni/CeO2-Al2O3 on a SiC monolith | Pore distribution with radius: 3 nm Thickness of catalytic layer: 200 µm | Equilibrium in H2 yield and CH4 conversion @750 °C (GHSV: 5000 h−1) | Pressure: 1 bar S/C: 3 Energy efficiency: 73% Power of microwave: 400 W Energy consumption: 2.5 kWh/Nm3H2 | [80] |
CO2 dry reforming of methane | Fe/SiC | Specific surface area: 32.118 m2/g (fresh) and 27.443 m2/g (after 50 h) Pore size: 5–8 nm and small amount of 0–2 nm micropores 1 C: 0.46; 22.16 1 O: 1.85; 35.29 1 Mg: 0; 2.88 1 Al: 3.36; 2.93 1 Si: 10.84; 33.87 1 Ca: 0.73; 0 1 Fe: 82.77; 0.22 | CH4 and CO2 conversions: 85% H2/CO ratio: ~1 | Specific microwave power: 72 W/g Durable stability for 50 h Carbon deposition: ~0.78 wt% | [45] |
Methane dry reforming | Fe-rich char from corn stalk | BET specific surface area: 150.46 m2/g (fresh) and 139.18 m2/g (during test) Total pore volume: 0.326 cm3/g (fresh) and 0.313 cm3/g (during test) Micropore volume: 0.309 cm3/g (fresh) and 0.269 cm3/g (during test) K: 0.956 wt% Fe: 7.126 wt% Ca: 0.443 wt% Mg: 1.523 wt% Al: 0.189 wt% Na: 0.367 wt% | CH4 conversion: 90.8% CO2 conversion: 95.2% | Fe2O3 addition of 10% Temperature: 800 °C Syngas content: 88.79% H2/CO ratio: 0.92 Durable stability for 160 min | [46] |
Methane dry reforming | Char from corn stalk | BET specific surface area: 30.86 m2/g (fresh) and 25.98 m2/g (during test) Total pore volume: 0.175 cm3/g (fresh) and 0.179 cm3/g (during test) Micropore volume: 0.137 cm3/g (fresh) and 0.116 cm3/g (during test) K: 0.740 wt% Fe: 0.052 wt% Ca: 0.505 wt% Mg: 1.606 wt% Al: 0.262 wt% Na: 0.030 wt% | CH4 conversion: ~57% CO2 conversion: ~80% | Temperature: 800 °C Syngas content: 88.79% H2/CO ratio: 0.87 Durable stability for 160 min | [46] |
Methane dry reforming | Ruthenium-doped SrTiO3 perovskite | SrTiO3 crystallite size: 29.8 nm Semi-quantitive weight percentage: 77.8 wt% BET specific surface area: 8 m2/g Total pore volume: 0.026 cm3/g | CH4 conversion: ~99.5% CO2 conversion: ~94% | 7 wt% of ruthenium doped H2/CO ratio: ~0.9 Temperature: ~940 °C CH4:CO2 vol.% feed ratio = 45:55 (maximized CH4 conversion) | [85] |
Dry reforming of methane | Ni/SiC | - | CH4 conversion: 80% CO2 conversion: 90% | Temperature: 800 °C Short-term stability test for 6 h | [76] |
Dry and bi-reforming of methane | Co-Mo/TiO2 | BET specific surface area: 36.4 cm2/g Uniform size distribution: 50–100 nm | CH4 conversion: 81% CO2 conversion: 86% | H2/CO ratio: 0.9 Durable stability for >50 h | [86] |
Dry and bi-reforming of methane | Cu-Mo/TiO2 | - | CH4 conversion: 76% CO2 conversion: 62% | H2/CO ratio: 0.8 Durable stability for >60 h | [86] |
Methane dry reforming | Wood-derived activated carbon | BET specific surface area: 937.99 m2/g Specific micropore surface: 353.65 m2/g Specific pore volume: 0.61 cm3/g Specific micropore volume: 0.20 cm3/g | CH4 conversion: ~80.0% CO2 conversion: ~60.0% | Microwave power: 560 W CH4/CO2/N2 = 1:1:3 Total gas flow of H2/CO ratio: 250 mL/min H2/CO ratio: 1.3 | [47] |
4.4. Sugar Conversion to 5-Hydroxymethylfurfural (5-HMF)
Process | Feedstock | Catalyst/ Absorbent | Yield | Remarks | Reference |
---|---|---|---|---|---|
Biphasic systems with aqueous and organic phase | Fructose | 1 Acidic deep eutectic solvents | HMF yield: 91.0% | Using [Ch]Cl:CA Microwave heating: 2 min Temperature: 120 °C Solid/liquid ratio: 0.05 | [51] |
Direct conversion using ionic liquids | Corn stalk, rice straw and pine wood | CrCl3·6H2O | HMF yield: 45–52% Furfural yield: 23–31% | Irradiation time: 2–6 min | [52] |
Direct conversion | Fructose | TiO2 nanoparticles | HMF yield: 3.4% (commercial TiO2), 25–54% | Microwave power: 300 W Temperature: 120–140 °C Time: 5–20 min | [89] |
Direct conversion | Glucose | TiO2 nanoparticles | HMF yield: 22.1–37.2% | Temperature: 120–140 °C Time: 2 or 5 min | [89] |
Direct conversion | Sucrose | TiO2 nanoparticles | HMF yield: 12.0–21.0% | Temperature: 120–140 °C Time: 5 or 10 min | [89] |
Direct conversion | Cellobiose | TiO2 nanoparticles | HMF yield: 14.5–18.7% | Temperature: 120 °C or 140 °C Time: 5 min | [89] |
Direct conversion | Maltose | TiO2 nanoparticles | HMF yield: 10.7–14.1% | Temperature: 120 °C or 140 °C Time: 5 min | [89] |
Direct conversion in water | Fructose | Sulfonated carbon microsphere catalysts | HMF yield: 88.3 mol% | Power: 60 W Temperature: 186 °C Time: 10 min Energy efficiency: 0.147 mmol/kJ | [90] |
Direct conversion in DMSO-water | Chitin | Polyoxometalates: H4[SiW12O40] | HMF yield: 23.1% | Solvent: 67% DMSO-water Temperature: 200 °C Time: 3 min | [91] |
Direct conversion in ionic liquids | Cellulose | ZrCl4 | HMF yield: 51.4% | Time: 3.5 min Power: 400 W Ionic liquid: [Bmim]Cl | [53] |
Rapid catalytic conversion | Lignocellulosic Sunn hemp fibres | CuCl2 | HMF yield: 26.8% | Temperature: 160–200 °C Time: 46 min Ionic liquid: [Bmim]Cl | [92] |
Catalytic dehydration | Corn starch | AlCl3·6H2O | HMF yield: 59.8 wt% | Solvent used: DMSO/[Bmim]Cl Temperature: 150 °C Time: 20 min | [93] |
Direct conversion | Microcrystalline cellulose | Ionic liquid: [TMG]BF4 | HMF yield: 28.63% | Temperature: 132 °C Time: 48 min Catalyst loading: 0.44 mg/mg | [94] |
4.5. Ammonia Synthesis
5. Challenges and Future Prospect
6. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Categories | Interaction with Microwave | Material Characteristics | Type of Materials | Penetration |
---|---|---|---|---|
Reflector or Opaque | Conductor | Steel, aluminum, copper, silver | None as microwave are reflected and no energy transfer. | |
Absorber 1 | Lossy insulator | Water, charcoal, silicon carbide | Partial to total as the microwave are absorbed and exchange of electromagnetic energy takes place. | |
Transparent | Low loss insulator | Polytetrafluoroethylene (PTFE), alumina-based ceramics, corundum, fused quartz, Teflon, glass 2, alumina 2, silica 2, magnesium oxide 2 | Total where the transmittance of microwave occurs without energy transfer. |
Microwave-Assisted Heating | Conventional Heating |
---|---|
Rapid and uniform heating | Slow heating |
Shorter preparation time | Longer preparation time |
Lower thermal inertia | Higher thermal inertia |
Heat transferred through in-core volumetric heating at molecular level | Heat transferred by conduction, convection or radiation |
Application | Feed | Experimental Conditions | Method | Findings | Reference |
---|---|---|---|---|---|
Bio-oil | Switchgrass | Power: 750 W Temperature: 400 °C Catalyst: 10 wt% K3PO4 + 10 wt% Bentonite | Microwave-assisted catalytic pyrolysis | Reduced water content in bio-oil with increased BET surface area of biochar using microwave-assisted pyrolysis. Average heating rate: 141 °C/min Heating time: 2.83 min BET surface area: 76.29 m2/g Micropore area: 44.56 m2/g Pore volume: 0.0332 cm3/g | [36] |
Chlorella vulgaris and high-density polyethylene (HDPE) | Feedstock mixing ratio: 1:1 Absorbent addition: 40% activated carbon (AC) Power: 800 W | Microwave-assisted co-pyrolysis | The promotion of CO, H2O or CO2 was observed with the addition of AC. Oxygen/Nitrogen-containing compounds: 28.79%/20.8% Hydrocarbons content: 48.88% Alcohols: 14.6% | [37] | |
Algae | Feed-to-susceptor ratio: 1:1 Power: 450 W Catalyst: ZSM-5 Temperature: 600 °C | Microwave-assisted co-pyrolysis | Pyrolysis char used a susceptor and pyrolysis of algae was rich in phenolic derivatives. Hydrocarbons obtained were ranging from C6 to C30. Bio-oil yield: 45 wt% Gas yield: 35 wt% Biochar yield: 20 wt% | [38] | |
Switchgrass | Temperature: 400 °C Catalyst: 10 wt% K3PO4 + 10 wt% Bentonite | Conventional pyrolysis | Longer heating time to reach desired temperature with poor biochar properties. Average heating rate: 14 °C/min Heating time: 28.81 min BET surface area: 0.33 m2/g Micropore area: 2.01 m2/g Pore volume: 0.0068 cm3/g | [36] | |
Switchgrass | Temperature: 300 °C to 500 °C Heating rate: 10 °C/min Feed amount: 1 kg | Conventional pyrolysis | Bio-oil yield: ~28 wt% to ~32 wt% Gas yield: ~176 L to ~271 L Biochar yield: ~30 wt% to ~40 wt% | [39] | |
White ash | Temperature: 300 °C to 500 °C Heating rate: 10 °C/min Feed amount: 1 kg | Conventional pyrolysis | Bio-oil yield: ~38 wt% to ~43 wt% Gas yield: ~154 L to ~225 L Biochar yield: ~28 wt% to ~39 wt% | [39] | |
Methanation | CO2, H2, He | Temperature: 300 °C Molar ratio of CO2/H2/He: 1/4/5 Ni: 30 wt% Ce: 20 wt% | Microwave-assisted hydrothermal synthesis | Addition of Ce enhanced the catalyst activities and microwave promoted Ni dispersion on support. CH4 selectivity: 98.0% CO2 conversion: 52.9% | [40] |
CO2, H2, N2 | Temperature: 325 °C Ratio of CO2/H2/N2: 1/4/4 Flowrate: 70 mL/min Ni: 20 wt% | Microwave-assisted synthesis | Low temperature of H2 pretreatment allows more Ni active sites. CH4 selectivity was well-maintained from 200 °C to 400 °C. CH4 selectivity: 99.3% CO2 conversion: 91.6% | [41] | |
CO, H2, N2 | Temperature: 300 °C Pressure: 1 MPa Ratio of CO/H2/N2: 1/1/3 Heating rate: 3 °C/min | Microwave-assisted solution combustion | Catalyst with large specific surface area and small Ni particles was obtained. CH4 selectivity: 96.2% CO2 conversion: 95.7% | [42] | |
CO2, H2, N2 | Temperature: 350 °C Ratio of CO2/H2/N2: 1/4/4 Flowrate: 70 mL/min Ni: 20 wt% | Impregnation | Low temperature of H2 pretreatment allows more Ni active sites. CH4 selectivity was well-maintained from 200 °C to 400 °C. CH4 selectivity: ~99% CO2 conversion: 84.3% | [41] | |
CO2, H2, He | Temperature: 50–200 °C Ratio of CO2/H2: 1/4 Catalyst amount: 200 mg Flowrate: 20 mL/min | Sol-gel, aerosol, impregnation | Low methanation production at 350 °C but maximum was achieved after annealing at 450 °C. CH4 selectivity: 100% @200 °C CH4 yield: 2.05 µmolCH4/gcat/s | [43] | |
CO2, H2, N2 | Temperature: 250–450 °C Molar ratio of H2/CO2/N2: 36/9/10 Catalyst amount: 0.1744 g Flowrate: 250 mL/min | Impregnation | Catalyst synthesized through impregnation has poorer performance due to the Ni0 size. CH4 selectivity: ~94% @450 °C CO2 conversion: 70.0% @450 °C | [44] | |
Methane reforming | CH4, CO2 | Specific power: 90 W/g Ratio of CH4/CO2/Ar: 1/1/2 Space velocity: 200 h−1 | Microwave dry reforming | Insignificant changes and negligible carbon deposition on catalyst after 50 h stability test. CH4 conversion: > 95% CO2 conversion: > 95% H2/CO ratio: ~1 | [45] |
CH4, CO2 | Temperature: 800 °C Molar ratio of CO2/CH4: 0.5, 1, 1.5, 2 N2 flowrate: 60 mL/min Volumetric hourly space velocity: 2.4 L/(g.h) | Microwave dry reforming | 10% of Fe2O3 addition led to maximum performance of dry reforming reaction with good catalyst stability. CH4 conversion: 90.8% CO2 conversion: 95.2% H2/CO ratio: 0.92 | [46] | |
CH4, CO2 | Power: 560 W Ratio of CH4/CO2/N2: 1/1/3 Gas flowrate: 250 mL/min | Microwave dry reforming | Decreasing CH4/CO2 ratio and increasing microwave power improve CH4 and CO2 conversions. CH4 conversion: ~80% CO2 conversion: ~60% H2/CO ratio: 1.3 | [47] | |
CH4, CO2 | Temperature: 800 °C GHSV: 33,000 mL/gcat.h Catalyst amount: 0.9 g | Conventional dry methane reforming | Energy efficiency using this method was lower by 10% compared to microwave heating reactors. CH4 conversion: ~65% CO2 conversion: ~70% H2/CO ratio: 0.85 | [48] | |
CH4, CO2 | Temperature: 800 °C Pressure: 1 atm | Dry methane reforming | The reaction can be improved by altering pressure and ratio of oxidant/methane. CH4 conversion: 85% CO2 conversion: 90% | [49] | |
CH4, CO2 | Temperature: 950 °C Gas hourly space velocity: 8570 h−1 Sample mass: 300 mg | Dry reforming of methane (magnetic induction) | Magnetic catalyst used to improve CH4 dry reforming. CH4 conversion: 70% CO2 conversion: 80% H2 yield: 75% CO yield: 85% | [50] | |
Sugar conversion | Fructose | Using [Ch]Cl:CA Microwave heating: 2 min Temperature: 120 °C Solid/liquid ratio: 0.05 | Biphasic systems with aqueous and organic phase assisted with microwave | The purity of 5-HMF remained after the repetition of 3 cycles process, reusing acidic deep eutectic solvents. HMF yield: 91.0% | [51] |
Corn stalk, rice straw and pine wood | Irradiation time: 2–6 min | Direct conversion using ionic liquids assisted with microwave | The yield of products obtained within 3 min of processing time, very efficient process. HMF yield: 45–52% | [52] | |
Cellulose | Time: 3.5 min Power: 400 W Ionic liquid: [Bmim]Cl | Direct conversion in ionic liquids assisted with microwave | Microwave was proven to have synergetic effects on the cellulose conversion. HMF yield: 51.4% | [53] | |
Glucose | Time: 10 min Temperature: 200 °C Medium: 50:50 w/w% 1-hexyl-3-methyl imidazolium chloride-water mixture | Direct conversion in ionic liquids-water mixture | Synergistic effect was observed through the addition of protic solvents. HMF yield: 53% | [54] | |
Glucose | Temperature: 100 °C Catalyst amount: 0.5 g Time: 6 h | Direct conversion in ionic liquids | The catalyst porosity has to be optimized according to the medium used for maximum production. HMF yield: 64% | [55] | |
Fructose | Medium: 3:1 of methylisobutylketone: 2-butanol Feed amount: 1 g Time: 6 h | Direct conversion in solvents | Good yield obtained using similar experimental condition for waste potato biomass too. HMF yield: 50 wt% | [56] | |
Ammonia synthesis | H2, N2 | Temperature: 260 °C Ambient pressure Catalyst amount: 1.2 g | Microwave-assisted catalytic synthesis | Low temperature and pressure required for this method are energy-saving compared to Haber-Bosch process. NH3 production rate: 1313 µmolNH3/gcat.h | [57] |
H2, N2 | Temperature: 320 °C Pressure: 0.65 MPa H2/N2 ratio: 1 Time: 11 min | Microwave-assisted catalytic synthesis | Quick catalyst recovery compared to Haber-Bosch technology. NH3 production rate: 0.04 g/gcat.h | [58] | |
H2, N2 | Temperature: ~260 °C Pressure: 0.1 MPa | Microwave-assisted catalytic synthesis | Ce-promoted catalyst enhances production and microwave activates stable molecules. NH3 production rate: 1.18 mmol/h.gcat | [59] | |
H2, N2 | Temperature: 300 °C Pressure: 10 bar | Catalytic synthesis | Efficient synthesis rate obtained through Co-Mg-O solid solution supported LiH catalyst, with Co nanoparticles. NH3 production rate: 19 mmol/g/h | [60] | |
H2, N2 | Temperature: 350 °C Pressure: 7 atm Molar ratio of H2/N2: 1/1 | Catalytic synthesis | The ammonia synthesis rate altered according to the composition of catalyst. NH3 production rate: 0.397 mmol/gcat.h | [61] |
Process | Feedstock | Catalyst/ Absorbent | Properties/Composition | Yield | Remarks | Reference |
---|---|---|---|---|---|---|
Catalytic pyrolysis | Switchgrass | 30 wt% clinoptilolite | pH: 4.19 Water content: 21.77 wt% Viscosity (40 °C): 6.11 cP | 36.2 wt% | BET surface area (biochar): 76.3 m2/g | [36] |
Catalytic pyrolysis | Cellulose | Fe/Modified HZSM-5 | Phenols: 6.23% Oxiranes: 5.45% HCs: 0% Esters: 5.21% Ketones: 12.79% CAs: 25.50% Furans: 23.06% SCs: 21.76% | 54.85 wt% | Biochar yield: 14.46 wt% Biogas yield: 23.78 wt% Coke yield: 6.91 wt% | [64] |
Catalytic pyrolysis | Cellulose | Fe-Ni/Modified HZSM-5 | Phenols: 20.86% Oxiranes: 14.15% HCs: 3.96% Esters: 0.73% Ketones: 11.94% CAs: 26.96% Furans: 21.40% SCs: 0% | 51.86 wt% | Biochar yield: 14.46 wt% Biogas yield: 26.33 wt% Coke yield: 7.35 wt% | [64] |
Catalytic pyrolysis | Corn stover | 10–30% Na2CO3 | Water content: 53.09–61.49% pH: 3.92–4.62 Dynamic viscosity: 3.31–4.05 mPa.s (for 500 and 700 W) Phenols: 33.26% Furans: 14.11% Acids: 4.77% Guaiacols: 7.05% | 41 wt% | Microwave: 700 W for compositions and yield. | [65] |
Catalytic pyrolysis | Waste cooking oil | CaO from crab shell | Total aromatics relative content: 54.89% Cycloalkenes relative content > 4.07% | 67 wt% | Biogas yield: 30 wt% CH4 and H2 formation being promoted. | [66] |
Catalytic pyrolysis | Torrefied corn cob | Fe modified biochar (from rice husk) | Phenol: 0.455–0.704 mg/mL bio-oil (~0.16–0.24 mg/g biomass) Cresol: 0.09–0.239 mg/mL bio-oil (~0.03–0.08 mg/g biomass) | ~33–35 wt% | The yield varies according to Fe amount | [67] |
Co-pyrolysis | Microalgae and HDPE | Activated carbon | HCs: 48.88% Alcohols: 14.6% Amines: 7.16% Acids/esters: 5.74% Ketones: 0.42% Nitriles: 6.02% Phenols: 0% Others: 17.18% | - | 31.02% of C7-C12, 22.3% of C16, 18.4% of > C18 hydrocarbons were obtained. | [37] |
Co-pyrolysis | Microalgae and waste cooking oil | Phosphorus-doped biochar | C5-C16 aliphatics: 30.58% C16+ aliphatics: 2.62% Mono-aromatics: 52.35% Poly-aromatics: 6% Nitriles: 3.38% Alcohols: 5.17% | 47.63% | No n-heterocyclics, amides, esters, phenols in bio-oil, but these components presented in the bio-oil produced using biochar. | [68] |
Catalytic pyrolysis | Microalgae | Fe2O3 with graphite | Phenol: 3% Ketone: 23% Aromatic compounds: 3% Esters: 9% Acids: 14% Nitrogen-cont. compound: 23% Alcohol: 8% | 24.9% | Optimal ratio for Fe2O3 with graphite is 3:7 | [69] |
Catalytic pyrolysis | Microalgae | ZMS-5 with graphite | Phenol: 4% Ketone: 14.5% Aromatic compounds: 10% Esters: 5% Acids: 14% Nitrogen-cont. compound: 11.5% Alcohol: 3% | 23.8% | Optimal ratio for Fe2O3 with graphite is 5:5 | [69] |
Catalytic pyrolysis | Peanut shells | Mixture of peanut shells and activated carbon | Other HCs: 18.85% Aromatic HCs: 15.08% Alcohols: 12.14% Phenols: 51.19% Ketones: 10.73% | 25.97% | Ratio of catalysts to peanut shells: 12.5% Biochar: 34.5% Syngas: 39.53% | [70] |
Catalytic co-pyrolysis | Mixture of waste polyethylene and algae | ZSM-5 catalyst | Aliphatic HC: 27% Cyclic aliphatic HC: 10% Aliphatic oxygenates: 22% Monoaromatic HC: 27% Polyaromatic HC: 8.6% Phenolics: 5% | 40 wt% | Char surface area: 125 m2/g | [38] |
Catalytic co-pyrolysis | Mixture of waste polypropylene and algae | ZSM-5 catalyst | Aliphatic HC: 30% Cyclic aliphatic HC: 13% Aliphatic oxygenates: 44% Monoaromatic HC: 5.8% Polyaromatic HC: 2.7% Phenolics: 5% | 45 wt% | Char surface area: 121 m2/g | [38] |
Catalytic co-pyrolysis | Mixture of waste expanded polystyrene | ZSM-5 catalyst | Aliphatic HC: 32% Cyclic aliphatic HC: 12% Aliphatic oxygenates: 43% Monoaromatic HC: 5.1% Polyaromatic HC: 0.8% Phenolics: 7% | 65 wt% | Char surface area: 118 m2/g | [38] |
Catalyst Synthesized | Process | Textural Properties/ Composition | Yield | Remarks | Reference |
---|---|---|---|---|---|
Ni/Al2O3 | Microwave | O: 40.50 wt% Al: 39.93 wt% Ni: 19.57 wt% Ni particle size: 10 nm Ni reduction degree: 90.4% Ni dispersion: 25.3% | CO2 conversion: 91.6% CH4 selectivity: 99.3% | Temperature: 325 °C Durable stability for 72 h Reduced by H2 at 450 °C Surfactant: Polyvinyl pyrrolidone (PVP) | [41] |
Ni-Ce/metakaolin | Hydrothermal | Ni: 26.57 wt% NiO crystallite size: 24 nm BET surface area: 31.18 m2/g Pore volume: 0.1532 cm3/g Average pore size: 19.65 nm | CO2 conversion: 52.9% CH4 selectivity: 98% CH4 yield: 51.9% | Temperature: 300 °C Ce-promoted in catalyst synthesizing Durable stability for 48 h | [40] |
Mesoporous silica KCC-1 | Microemulsion coupled with hydrothermal | BET surface area: 773 m2/g Total pore volume: 1.2195 cm3/g Pore distribution: 4–6 nm and 20–25 nm Particle size: 200–400 nm Basic sites concentration: 586 | CO2 conversion: 48.7% CH4 selectivity: 98% CH4 yield: 38.9% | Temperature: 449.85 °C Durable stability for 90 h | [73] |
Ni/mesocellular silica foam | One-pot for mesocellular silica foam; incipient wetness impregnation for Ni | Surface area of support: 913 m2/g Pore volume of support: 0.98 cm3/g Ni particle size: 4.5 nm Si/O: 0.56 Ni/Si: 0.014 Ni: 5 wt% | CO2 conversion: 62–77% CH4 selectivity: 94–97% | Synthesized from rice husk ashes Cyclohexane as swelling agent Temperature: 350 °C Durable stability for 20 h | [74] |
Ni/La-Sm-CeO2 | Sol-gel | Ni particle size: 12.3 nm Ni dispersion: 7.9% Pore volume: 0.08 cm3/g CeO2 crystalline size: 7.2 nm BET surface area: 40.3 m2/g Ni: 12.1% Ce: 14.4% O: 61.8% C: 7.0% Na: 0.9% La: 1.0% Sm: 2.8% | CO2 conversion: 53% CO selectivity: 5% @500 °C (0 at 300 °C) CH4 selectivity: 100% CH4 yield: 59.9–61.6% | Temperature: 300 °C Durable stability for 20 h | [75] |
Ni/La-Pr-CeO2 | Sol-gel | Ni particle size: 10.1 nm Ni dispersion: 9.6% Pore volume: 0.09 cm3/g CeO2 crystalline size: 8.0 nm BET surface area: 45.8 m2/g Ni: 11.3% Ce: 13.6% O: 61.7% C: 7.6% Na: 1.4% La: 1.0% Pr: 3.4% | CO2 conversion: 55% CO selectivity: 2.5% @500 °C (0 at 300 °C) CH4 selectivity: 100% CH4 yield: 62.0–63.4% | Temperature: 300 °C Durable stability For 20 h | [75] |
Ni/La-Mg-CeO2 | Sol-gel | Ni particle size: 9.1 nm Ni dispersion: 10.7% Pore volume: 0.07 cm3/g CeO2 crystalline size: 7.5 nm BET surface area: 38.8 m2/g Ni: 14.3% Ce: 13.4% O: 62.5% C: 6.4% Na: 0.2% La: 1.1% Mg: 2.1% | CO2 conversion: 49% CO selectivity: 4.5% @500 °C (0 at 300 °C) CH4 selectivity: 100% CH4 yield: 58.2–61.8% | Temperature: 300 °C Durable stability for 20 h | [75] |
Ni-Al2O3 | Combustion with urea (fuel) | BET surface area: 186.1 m2/g Average pore diameter: 3.6 nm Dispersion: 5.2% Maximum Ni surface area: 34.6 m2/g | CO conversion: 95.7% CH4 selectivity: 96.2% | Temperature: 300 °C Lifetime test: 200 h | [42] |
Catalyst Synthesized | Process | Textural Properties/ Composition | Yield | Remarks | Reference |
---|---|---|---|---|---|
Pt/CeO2 | Wetness impregnation | BET specific surface area: 39.58 m2/g Average particle size: 21 nm Carbon formation: 1.75 mmol/g | CH4 conversion: 71.4% | 10% of Pt was doped Durable stability for 6 h | [78] |
NiCo-MgAl2O4 | Two-step combustion | BET specific surface area: 35 m2/g (fresh) and 33.5 m2/g (used) Mean pore diameter: 28.45 nm (fresh) and 24.60 nm (used) Total pore volume: 0.26 cm3/g (fresh) and 0.21 cm3/g (used) Metal crystallite size: 19 nm (fresh) and 22 nm (used) Ni dispersion: 5.30% Lattice strain: 0.19 Mg: 20.87 wt% Al: 53.65 wt% Ni: 18.9 wt% Co: 7.08 wt% | CH4 conversion: 99.3% | Temperature: 750 °C Microwave power: 800 W CH4:H2O feed ratio = 1:1.12 Low carbon deposition (0.09% weight loss) after 15 h 0.0035 mg lamentous carbon deposited | [24] |
Ni-MgAl2O3 | Two-step combustion | BET specific surface area: 41.69 m2/g (fresh) and 36.2 m2/g (used) Mean pore diameter: 23.11 nm (fresh) and 21.08 nm (used) Total pore volume: 0.24 cm3/g (fresh) and 0.191 cm3/g (used) Metal crystallite size: 29 nm (fresh) and 32 nm (used) Ni dispersion: 3.50% Lattice strain: 0.77 Mg: 20.84 wt% Al: 59.96 wt% Ni: 19.19 wt% | CH4 conversion: 97.4% | Temperature: 750 °C Microwave power: 800 W 0.0059 mg lamentous carbon deposited | [24] |
Ni-Co/MFI zeolite | Hydrothermal | BET specific surface area: 380 m2/g Specific micropore surface: 379 m2/g Total pore volume: 0.194 cm3/g | CH4 conversion: 97.0% CO2 conversion: 99.0% H2 yield: 98.0% CO yield: 94.0% | Temperature: 950 °C | [81] |
* Biochar | Pyrolysis | BET specific surface area: 39 m2/g Microporous specific surface area: 26.18 m2/g Total pore volume: 0.129 cm3/g Micropore volume: 0.021 cm3/g Average pore size: 1.322 nm K: 1.351 wt% Fe: 0.234 wt% Ca: 1.237 wt% Mg: 3.107 wt% Al: 0.244 wt% Na: 0.431 wt% | CH4 conversion: ~100% CO2 conversion: ~100% | Temperature: 800 °C Energy efficiency: 49.2% | [82] |
Process | Catalyst | Yield | Remarks | Reference |
---|---|---|---|---|
Catalytic synthesis | Cs promoted Ru/CeO2 | NH3 production rate: 1.18 mmol/h.gcat | Temperature: ~260 °C Pressure: 0.1 MPa | [59] |
Synthesis using non-plasma microwave system | Fe/Al2O3 | NH3 production rate: 128 µmol/g/h | Power: 300 W Temperature: 300 °C Ambient pressure 20 wt% of Fe is used | [97] |
Synthesis using fixed microwave frequency | Ru/MgO | NH3 production rate: 0.25 gamm/gcat/day | Temperature: 320 °C Time: 11 min Microwave frequency: 2.45 GHz Ambient pressure 10 wt% of Ru is used | [58] |
Catalytic synthesis | Cs-Ru/CeO2 | NH3 production rate: 1313 µmolNH3/gcat.h | Temperature: 260 °C Ambient pressure 2 wt% of Cs and 4 wt% of Ru are used | [57] |
Catalytic synthesis | Cs-Ru/CeO2 | NH3 production rate: 0.04 g/gcat.h | Temperature: 320 °C Pressure: 0.65 MPa H2/N2 ratio: 1 Stable for 6 cycles of startup-shutdown operation | [98] |
Catalytic synthesis | Fe promoted Co/γAl2O3 | NH3 production rate: 53.9 g−1 s−1 Total NH3 production: 441.5 mol | Temperature: 600 °C Pressure: 1 atm 0.5 wt% of Fe is used as promoter | [99] |
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Chia, S.R.; Nomanbhay, S.; Milano, J.; Chew, K.W.; Tan, C.-H.; Khoo, K.S. Microwave-Absorbing Catalysts in Catalytic Reactions of Biofuel Production. Energies 2022, 15, 7984. https://doi.org/10.3390/en15217984
Chia SR, Nomanbhay S, Milano J, Chew KW, Tan C-H, Khoo KS. Microwave-Absorbing Catalysts in Catalytic Reactions of Biofuel Production. Energies. 2022; 15(21):7984. https://doi.org/10.3390/en15217984
Chicago/Turabian StyleChia, Shir Reen, Saifuddin Nomanbhay, Jassinnee Milano, Kit Wayne Chew, Chung-Hong Tan, and Kuan Shiong Khoo. 2022. "Microwave-Absorbing Catalysts in Catalytic Reactions of Biofuel Production" Energies 15, no. 21: 7984. https://doi.org/10.3390/en15217984