Catalytic Hydropyrolysis of Lignin for the Preparation of Cyclic Hydrocarbon-Based Biofuels
Abstract
:1. Introduction
2. Lignin Depolymerization Methods
- (i).
- Lignin depolymerization in the presence of water medium at a suitable temperature (100–350 °C) is hydrolysis. The hydrolysis of lignin may occur using acid or base catalysts. Several acidic homogenous (H2SO4, HNO3, HCl, heteropoly acids, ionic liquids, etc.) and heterogeneous (acidic metal oxide, zeolites, acidic resins/clays, sulfonated carbon materials, etc.) catalysts were extensively reported for acid-catalyzed hydrolysis/depolymerization of lignin. Biphasic medium, water, along with organic solvent or supercritical fluids were also reported for better conversion of lignin. Phenol, alkylphenols, methoxyphenols, alkenylphenols, alkyl/methoxy-phenols, and alkenyl/methoxy-phenols are primarily observed during the lignin hydrolysis [24].
- (ii).
- Lignin depolymerization in the presence of a solvent or a mixture of solvents at suitable temperatures is known as solvolysis. The process minimizes the formation of char and usually forms low-oxygen-containing aromatic hydrocarbons. Several organic solvents such as alcohols (methanol, ethanol, propanol, iso-propanol), oxanes (dioxane), ketones (acetone), alkanes (dodecane), etc., and a mixture thereof with water were frequently used for lignin solvolysis. The supported metal (Pt, Ru, Rh, Pd, Ni, Mo, Cu, and Co) catalysts displayed good yields of biooil (80–95%) [25].
- (iii).
- Thermal decomposition at high temperatures (300–1000 °C) under an inert atmosphere is called pyrolysis. Lignin pyrolysis ended up with gases (hydrogen, methane, carbon monoxide, and carbon dioxide), liquids (oxygenated cyclic hydrocarbons, especially hydroxy, methoxy, and alkyl-substituted benzenes), condensable vapors, and solid char. The thermal decomposition at high temperatures under H2 atmosphere is known as hydropyrolysis. Several supported metal catalysts were reported for the hydropyrolysis of lignin and, within this, hydrogenation and hydrodeoxygenation reaction plays an important role in obtaining high yield of non-oxygenated aromatic compounds. Syringol and guaiacol type molecules (from hardwood), guaiacol type phenols (from softwood), and a mixture of phenol, guaiacol, and syringol type compounds (from herbaceous) were predominantly observed during the pyrolysis. The non-catalytic pyrolysis-derived concoction is associated with poor stability and undergoes repolymerization to produce sticky material. Thus, the catalytic pyrolysis process improves the yield of biooil, and catalytic depolymerization produces the most stable products where there is less possibility for repolymerization [26].
- (iv).
- Oxidative cleavage of lignin in the presence of oxidants is known as oxidative lignin depolymerization. Several oxidants, such as O2, KMnO4, H2O2, and peroxy acids, etc., were reported for this type of reaction. The oxidative cleavage of lignin generally produces oxygenated-aromatic hydrocarbons (hydroxyl, carbonyl, and carboxyl-substituted benzenes). The oxygen radical species, obtained from oxidants during the reaction, perform multiple cleavages of the lignin and this leads to the formation of several oxygenated aromatic compounds [24,27].
- (v).
- Gasification is usually referred to a process of oxygen-deficient thermal decomposition of carbonaceous substances such as coal, petroleum, or lignocellulosic biomass with a major objective of producing valuable gaseous products such as hydrogen or syngas. Lignin gasification provides an array of hydrocarbons (gas, liquid, and solid) depending upon on the gasification temperature. The C/O ratio of lignin is high as compared to lignocellulose and other biomass sources, and thus formation of solid/tar, i.e., high-molecular-weight condensable organic hydrocarbons, usually take place [28].
3. Lignocellulose-Based Emerging Biofuels
4. Lignin Conversion in the Presence of H2
- Alkene chain double hydrogenation, hydrodemethoxylation (hydrogenolysis of C–OCH3) to 4-propylphenol; reaction conditions: Ni/SBA-15, 260 °C, 30 bar H2 [41].
- Alkene chain double hydrogenation, hydrodealkylation (hydrogenolysis of C–C) to guaiacol; reaction conditions: Pt/γ-Al2O3, 300 °C, H2 [44].
- Alkene chain double hydrogenation, hydrodealkylation (hydrogenolysis of C–C), hydrodemethoxylation (hydrogenolysis of C–OCH3) to phenol; reaction conditions: Pt/γ-Al2O3, 300 °C, H2 [44].
- Alkene chain double hydrogenation, hydrodealkylation (hydrogenolysis of C–C), hydrodehydroxylation (hydrogenolysis of C–OH) to anisole; reaction conditions: Pt/HY, 250 °C, 40 bar H2 [45].
- Alkene chain double hydrogenation, hydrodealkylation (hydrogenolysis of C–C), hydrodemethoxylation (hydrogenolysis of C–OCH3), hydrodehydroxylation (hydrogenolysis of C–OH) to benzene; reaction conditions: Ni/HZSM-5, 350 °C, 20 bar H2 [46].
- Alkene chain double hydrogenation, aromatic ring hydrogenation to 2-methoxy-4-propylcyclohexanol; reaction conditions: Pd/C, 250 °C, 30 bar H2 [47].
- Alkene chain double hydrogenation, aromatic ring hydrogenation, hydrodehydroxylation (hydrogenolysis of C–OH) to 1-methoxy-3-propylcyclohexane; reaction conditions: Ni/MCM-4+HZSM-5, 200 °C, 50 bar H2 [51].
- Alkene chain double hydrogenation, aromatic ring hydrogenation, hydrodemethoxylation (hydrogenolysis of C–OCH3), hydrodehydroxylation (hydrogenolysis of C–OH) to propylcyclohexane; reaction conditions: Ru/CNT, 220 °C, 50 bar H2 [52].
5. Hydropyrolysis of Lignin into Cyclic Hydrocarbons
- Chemical treatment: a. dilute acid (HCl, HNO3, and H2SO4) treatment minimizes the ash content and removes the elements (Na, K, S, P, Si, Cl, Mg, Fe, Al, etc.); b. base treatment isolates the lignin from lignocellulose biomass and improves the quality of the oil. Moreover, chemical pre-treatment weakens the linkages in the lignocellulose biomass, which easily breaks down during pyrolysis and hydrodeoxygenation processes.
- The physical treatment such as size reduction using milling or grinding of biomass usually provides a high yield of biooil. Also, heat and mass transfer are high in this case which leads to good cleavage capacity.
- The pretreatment of biomass with the hydrothermal process using a Soxhlet extractor to remove the colorants, pectin, dust particles, and elements, etc., the treated biomass provide with good-quality and low-viscosity biooil.
- Biological pretreatment is also one of the gateways to produce highly selective biooil; for example, the white-rot-fungus-treated biomass forms selectively aromatic hydrocarbons and suppresses the coke yield. In fact, the white-rot fungus has the capability to disconnect the refractory cell walls of lignocellulose.
5.1. Non-Catalytic Hydropyrolysis of Lignin
5.2. Catalytic Hydropyrolysis of Lignin
5.2.1. Acid-catalyzed Hydropyrolysis of Lignin
S. No | Source | Catalyst | Reaction Conditions | Yield of Biooil(%) | Ref. |
---|---|---|---|---|---|
1 | Poplar wood-derived lignin | HZSM-5 (Si/Al-30) | Pyrolysis at 600 °C, 20 s, He, catalyst to lignin ratio (2:1) | 35.7 mg/g of aromatic hydrocarbon | [12] |
2 | Kraft lignin | 1. Natural zeolite 2. HZSM-5 | Pyrolysis in two stage-reactor 1. 500 °C, N2, catalyst to lignin ratio (1:1) 2. 600 °C, N2 | 30–35% of biooil with mixture of oxygenated and non-oxygenated aromatic compounds | [68] |
3 | Acid-treated lignin (derived from peanut shells) | HZSM-5 | Pyrolysis at 600 °C, N2, catalyst to lignin (1:2) | 43–45% of biooil (50% sel. of aromatic hydrocarbons) | [20] |
4 | Kraft lignin | HZSM-5 | Pyrolysis at 600 °C, 10 min, N2, catalyst to lignin (1:1) | Yield of biooil is not reported but selectivity towards the methoxy/alkyl aromatics hydrocarbons (50% sel.) | [10] |
5 | Kraft lignin | HZSM-5 | Hydropyrolysis at 450 °C, 10 bar H2 for 60 min. | 47% yield of biooil (50 wt.% of aromatic hydrocarbons) | [11] |
6 | Kraft lignin | HY and FeReOx/ZrO2 | Hydropyrolysis (using HY) followed by hydrodeoxygenation (using FeReOx/ZrO2) | 75% selectivity towards phenolic compounds | [77] |
5.2.2. Supported Metal Catalyzed Hydropyrolysisof Lignin
- I.
- Disclosed hydropyrolysis of pyrolytic lignin using Ru/C at 400 °C, 4 h, 100 bar H2, which resulted in high liquid product yield, i.e., 75%, of which monomeric compounds comprise 50% (Table 2, entry 3). Several products, including 18–20% phenolic compounds (phenol, cresols, methoxyphenols, alkylphenols), 14–15% aromatic hydrocarbons (benzene alkylbenzenes, xylenes, naphthalene, and methylnaphthalene), and 6–7% cycloalkanes (cyclohecane, alkylcyclohexanes, alkylcyclopentanes), were identified as the major products in this work [35].
- II.
- Screened various catalysts (Ru/C, Ru/Al2O3, Ru/TiO2, Pd/C, Pd/Al2O3, Cu/ZrO2) for the hydrotreatment of Alcell lignin at 400 °C and 100 bar H2. From the studied catalysts, the Ru/TiO2 showed a high yield of biooil (78%), comprising alkylphenolics (9 wt.%), aromatic hydrocarbons (2.5 wt.%), and hydroxyphenols (3.5 wt.%) (Table 2, entry 4) [84].
- III.
- Reported hydropyrolysis of Kraft lignin with NiMo and CoMo metallic catalysts on different supports: acidic (Al2O3 and ZSM-5), neutral (activated carbon), and basic (MgO-La2O3). The hydropyrolysis was carried out at 350 °C, 100 bar H2 for 4 h. The basic sulfide NiMo/MgO-La2O3 catalyst showed high catalytic activity to obtain greater monomeric cyclic hydrocarbon yield (26 wt.%), consisting majorly of alkyl-phenolic compounds (Table 2, entry 5). The neutral activated carbon supported metal catalysts showed moderate conversion of lignin, and acidic supports (Al2O3 and ZSM-5) were found to be less active in the conversion because in the presence of acidic support re-condensation between reaction intermediates is initiated, which results in the solid residue [15].
- IV.
- Low-priced catalysts, i.e., Limonite ((FeO(OH)·nH2O)),were investigated for the conversion of Kraft lignin at 450 °C, 100 bar H2 for 4 h. The catalyst resulted in ~34% of low-molecular-weight aromatic hydrocarbons (phenol, alkylphenols and alkylbenzenes, alkylnaphthalenes, and alkyl anthracene) and a trace amount of cycloalkanes. The recycled Limonite catalyst (after the first run) was pre-treated at 450 °C and used for the second cycle, which showed a good yield of aromatic hydrocarbons with 25% yield. The authors concluded that Limonite is a cheap and potential catalyst for making bio-based phenolics and aromatics from lignin through the hydrodeoxygenation reaction [85].
- V.
- Investigated catalytic (Ru/C, CoMo/alumina, phosphided NiMO/C) hydrodeoxygenation of Kraft lignin in two-step hydropyrolysis, and as they observed a high yield of monomeric phenolic compounds (alkylphenols) as compared with single pyrolysis [86].
- VI.
- Reported several metal (Ni. Mo, W, NiMo, NiW) phosphide catalysts supported on activated carbon for the hydropyrolysis of Kraft lignin at 400–500 °C, 100 bar H2 for 4 h. The 10NiMoP/AC catalyst showed a 71% yield of biooil (with 100% mass balance) as compared with other catalysts. Moreover, the catalyst yielded (45.7 wt.%) high monomeric aromatic hydrocarbons such as alkylphenols and alkyl aromatics. The authors did not observe corresponding peaks of methoxy groups and C–O–C linkages of biooil (obtained via hydrotreating of the Kraft lignin using the NiMoP/AC catalyst), suggesting that common ether linkages were broken, leading to the formation of monomeric aromatic hydrocarbons [61].
- VII.
- Phosphided NiMo on different supports were reported for hydropyrolysis of lignin at 400 °C, 100 bar H2 for 2 h. The catalytic supports used in this work are activated carbon, SiO2-Al2O3, SiO2, MgO-Al2O3, and TiO2. Among them, the NiMoP supported on SiO2 produced a high yield (68%) of biooil, 52% monomeric compounds including 31% alkylphenols, 8% aliphatic compounds, and 5.7% aromatic compounds, etc. The SiO2 support consists of medium acidity which produced a higher yield than the basic- (MgO-Al2O3) and high-acid supports (SiO2-Al2O3). However, a reason behind the high activity of NiMoP/SiO2 is not reported [2].
S. No | Source | Catalyst | Reaction Conditions | Yield of Biooil (%) | Ref. |
---|---|---|---|---|---|
1 | Kraft and Organosolv lignin | Pd/C and Ni-Mo/aluminosilica | Hydropyrolysis at 350–450 °C, 120 bar H2 | 81% (using Pd/C) and 66% (using Ni-Mo/aluminosilica) yield of biooil | [81,82] |
2 | Lignin derived from hybrid poplar | Pd/HZSM-5 | Hydropyrolysis at 650 °C and 17 bar H2, catalyst-to-lignin ratio of 20:1 | 45% yield of aromatic hydrocarbons | [83] |
3 | Pyrolytic lignin | Ru/C | Hydropyrolysis at 400 °C, 100 bar H2 for 4 h | 75% yield of biooil (50 wt.% of monomeric compounds) | [35] |
4 | Alcelllignin | Ru/TiO2 | Hydropyrolysis at 400 °C, 100 bar H2 for 4 h | 78% yield of biooil | [84] |
5 | Kraft lignin | NiMo/MgO-La2O3 | Hydropyrolysis at 350 °C, 100 bar H2 for 4 h | 26% yield of monomeric cyclic hydrocarbon | [15] |
6 | Kraft lignin | Limonite (FeO(OH)·nH2O) | Hydropyrolysis at 450 °C, 100 bar H2 for 4 h | 34% yield of aromatic hydrocarbons | [85] |
7 | Kraft lignin | 10NiMoP/AC | Hydropyrolysis at 400–500 °C, 100 bar H2 for 4 h | 71% yield of biooil | [61] |
8 | Kraft lignin | NiMoP/SiO2 | Hydropyrolysis at 400 °C, 100 bar H2 for 2 h | 68% yield of biooil, (52% sel. of monomeric compounds and 31% sel. of alkylphenols) | [2] |
9 | Pinewood | W2C/γ-Al2O3 | Hydropyrolysis at 500 °C, H2 ambience for 30 s | 17% BTX, 18% alkyl benzenes, 15–17% of naphthalenes | [87] |
10 | Lignin extracted from Chinese fir | NixMo/ZrO2 | Hydropyrolysis at 400 °C under atmospheric H2 | 18–19% yield of aromatics and 6% cycloalkanes | [88] |
11 | Industrial (Etek) lignin | Fe/ZrO2 | Hydropyrolysis at 400 °C under atmospheric H2 | 65–67% Sel. of non-oxygenated aromatics (BTX) | [89] |
12 | Stem wood | Pt/TiO2 | Hydropyrolysis at 600 °C under H2 | 35–37% yield of biooil | [90] |
13 | Kraft lignin | Y zeolite | Hydropyrolysis at 400 °C, 35 bar H2 for 5 h | 21% yield of biooil | [91] |
14 | Kraft lignin | NiMo/Y zeolite | Hydropyrolysis at 400 °C, 35 bar H2 for 5 h | 31% yield of biooil | [91] |
15 | Pine sawdust | NiMo/HZSM-5 | Hydropyrolysis at 320 °C and 50 bar H2 | 24 wt.% of yield w.r.t dried biomass | [92] |
6. Key Observations of Lignin Hydropyrolysis
- Hydropyrolysis is an industry-relevant process, it does not require solvent/medium which leads to low operation costs, and it is techno-economically viable.
- Generally, the non-catalytic pyrolysis resulted in oxygenated aromatic compounds including alkenyl-, aldo-, keto-, and carboxy-substituted compounds.
- In the acid-catalyzed hydropyrolysis of lignin, the HZSM-5 showed good activity for the biooil, which consists of a mixture of compounds such as phenols, alkyl-phenols, methoxyphenols, and non-oxygenated aromatics.
- The addition of base to acid-catalyzed lignin hydropyrolysis improves the cleavage of methoxy groups in the methoxyphenolic compounds and reveals a high amount of non-oxygenated compounds. Moreover, the additional base suppressed the condensation/polymerization (in between formed monomeric aromatics during acid-catalyzed hydropyrolysis) reaction and avoids the solid/char/polyaromatics formation.
- The Pd/C catalyst showed a high yield of biooil (81%), consisting of alkyl-cyclohexanones as major components. However, the Pd-containing bimetallic catalysts such as Pd-Fe and Pd-Co catalysts showed a high quantity of non-oxygenated aromatics, predominantly benzene and alkyl benzenes.
- The Ru-based catalysts showed a high yield (75–78%) of biooil, consisting of alkyl/hydroxyl phenols, non-oxygenated aromatic compounds (alkyl-substituted benzenes, benzene, toluene, xylenes, naphthalenes), and cycloalkanes.
- The Ni-containing bimetallic catalysts extensively reported for hydropyrolysis of lignin and the catalytic system’s synergetic effect play important roles. For example, in the Ni-Mo bimetallic catalytic system, the Mo metal initiates the cleavage of methoxy moieties in the methoxyphenolics, and the Ni metal promotes the cleavage of hydroxyl moieties in the phenolic compounds and also initiates the hydrogenation of the benzene ring. The combined properties of bimetallic catalyst provided a good yield of monomeric non-oxygen-containing aromatic/alicyclic hydrocarbons.
- The oxophilicity character of metal (for example, Mo and Fe) interacts with oxygenated aromatic compounds, which leads to the closer distance between the catalyst active sites and the oxygenated reactant. Thus, the strategy enhances the hydrodeoxygenation capacity of lignin-oxygenates.
7. Conclusions
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Gundekari, S.; Karmee, S.K. Catalytic Hydropyrolysis of Lignin for the Preparation of Cyclic Hydrocarbon-Based Biofuels. Catalysts 2022, 12, 1651. https://doi.org/10.3390/catal12121651
Gundekari S, Karmee SK. Catalytic Hydropyrolysis of Lignin for the Preparation of Cyclic Hydrocarbon-Based Biofuels. Catalysts. 2022; 12(12):1651. https://doi.org/10.3390/catal12121651
Chicago/Turabian StyleGundekari, Sreedhar, and Sanjib Kumar Karmee. 2022. "Catalytic Hydropyrolysis of Lignin for the Preparation of Cyclic Hydrocarbon-Based Biofuels" Catalysts 12, no. 12: 1651. https://doi.org/10.3390/catal12121651