Development of Heterogeneous Catalysts for Thermo-Chemical Conversion of Lignocellulosic Biomass
Abstract
:1. Introduction
2. The Role of Catalysts in Bio-Oil Production
2.1. Application of Zeolites and Mesoporous Materials
2.2. Modification of Zeolites and Mesoporous Materials by the Addition of Metals
2.3. Application of Metal Oxides and Supported Catalysts
2.4. Bio-Oil Upgrading via Hydrodeoxygenation (HDO)
3. Catalysts for the Production of a Hydrogen-Rich Gas from Lignocellulosic Biomass
4. Summary
5. Perspectives on the High-Temperature Conversion of Lignocellulosic Feedstock
Author Contributions
Conflicts of Interest
References
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No. | Catalyst | Feedstock | Products and Remarks Regarding Influence of Catalyst | Conditions of Pyrolysis Process | Reference |
---|---|---|---|---|---|
1 | ZSM-5 | Cellulose, hemicelluloses, lignin | Carbon yields of aromatics from cellulose, hemicelluloses and lignin were 28.8%, 19.4 and 7.4%, respectively. | Micro-furnace pyrolyzer equipped with an autoshot sampler at 400 °C–800 °C, analysis of products by GCMS (Gas Chromatograph coupled with Mass Spectrometer) | [7] |
2 | ZSM-5 | Pine, corncob and straw cellulose, hemicellulose and lignin | Fast pyrolysis, the highest yield of aromatics (38.4% for cellulose and 25.4% for pine) was obtained in the presence of catalyst. | Py-GCMS, residence time and heating rate were fixed to 600 °C, 50 s and 20,000 °C/s, catalyst to feedstock weight ratio = 9 | [15] |
3 | desilicated ZSM-5 | Beech wood | Fast pyrolysis, desilicated ZSM-5 more active towards production of aromatics than unmodified material (26.2% and 30.2%, respectively) and slightly limits coke formation (from 41.2% to 39.9%). | Py-GCMS, maximal temperature, residence time and heating rate were fixed to 650 °C, 60 s and 20,000 °C/s, catalyst to feedstock weight ratio = 10 | [16] |
4 | ZSM-5 | Cellulose | 32% of aromatics in the presence of ZSM-5 with optimized structure | Micro-pyrolyzer (equipped with an autoshot sampler) at 700 °C, catalyst to biomass weight ratio = 20, analysis of products by GCMS | [17] |
5 | ZSM-5 | Spent coffee grounds | Considerable increase in the amount of aromatic hydrocarbons in comparison to non-catalyzed process | (a) Py-GCMS and (b) fixed bed reactor (a)—maximal temperature, residence time and heating rate were fixed to 490 °C–590 °C, 10 s and 2000 °C/s, catalyst to feedstock weight ratio = 1 (b)—temperature—490 °C–590 °C, residence time in thermal bed 1.5 s and 2.5 s in catalytic bed, catalyst to feedstock weight ratio = 1 | [19] |
6 | ZSM-5 | Corn stalk and food waste | Co-pyrolysis, relative content of aromatics about 30% | Py-GCMS, maximal temperature, residence time and heating rate were fixed to 500 °C–700 °C, 20 s and 20,000 °C/s, catalyst to feedstock weight ratio = 1 | [20] |
7 | HZSM-5 | Citrus unshiu peel | Ex situ catalytic pyrolysis, yield of aromatics about 7% | Tandem micro-reactor consisting of two sequential furnaces coupled to GCMS, pyrolysis—500 °C, upgrading—400 °C–600 °C, catalyst to feedstock weight ratio = 1 | [22] |
8 | HZSM-5 | Beech wood, cellulose, microalgae | The relative yield of total BTX (benzene, toluene, xylene) was the highest for beech wood among studied feedstocks | Tandem micro-reactor consisting of two sequential furnaces coupled to GCMS, temperature 400 °C–600 °C, catalyst to feedstock weight ratio = 5–20 | [23] |
9 | ZSM-5 | Beech wood | Investigations of the influence of various metals contamination on the efficiency of in situ catalytic pyrolysis of biomass | Bubbling fluidized bed pyrolysis reactor, temperature 500 °C, catalyst 150 g, biomass 100 g (fed to the reactor at a rate of 5 g/min) | [24] |
10 | HZSM-5 | Corn stover | Microwave-assisted catalytic fast pyrolysis conducted with the presence of HZSM-5 (H form of Zeolite Socony Mobil-5) modified by chemical vapor deposition with TEOS (tetraethyl orthosilicate), relative content of aromatics 38%–39% | Microwave oven containing semi-continuous biomass feeder, temperature 500 °C, HZSM-5 was mixed with SiC particles (used as the microwave absorbent) | [25] |
11 | HZSM-5, sulfated zirconia, Al–MSU–S alumnosilicate and bauxite waste | Poplar | High selectivity of HZSM-5 towards aromatics, in the case of mesoporous catalysts their mesoporosity, high pore volume and acidity facilitated cracking of pyrolysis intermediates which led to the production of higher amount of permanent gases and coke | Py-GCMS, maximal temperature, residence time and heating rate were fixed to 650 °C, 20 s and 1000 °C/s, catalyst to feedstock weight ratio = 5 | [26] |
12 | HZSM-5, H-Y | Woody biomass (LIGNOCEL) | Flash pyrolysis, HZSM-5 allowed for the more efficient decrease in the contribution of acid fraction and production of considerably higher amount of phenolics in comparison to H-Y | Continuous bench scale unit, temperature 450 °C–550 °C, residence time 2–4 s, catalyst to feedstock weight ratio = 0.1–0.5 | [27] |
13 | waste FCC catalyst and H-Y | Wild reed | H-Y zeolite allows for the formation of higher amount of aromatics and a decrease in the content of oxygenates in comparison to regenerated FCC catalyst | Batch-type reactor, temperature 500 °C, residence time 14–20 s, catalyst to feedstock weight ratio = 1–10 | [28] |
14 | Al-MCM-41, Al-SBA-15 Al-MSU-J and HZSM-5 | Lignin | Al-MCM-41 (Mobil Composition of Matter No. 41) possessing large pore volume and allowing for enhanced mass transfer enabled formation of similar amount of aromatics to that obtained in the case of H-ZSM-5 having noticeably higher acidity | 650 °C at heating rate 20,000 °C/s, reaction time 20 s, catalyst to feedstock weight ratio = 4 | [29] |
No. | Catalyst | Feedstock | Products and Remarks Regarding Influence of Catalyst | Conditions of Pyrolysis Process | Reference |
---|---|---|---|---|---|
1 | HZSM-5 modified by Fe, Zr and Co | Pine sawdust | Zr/HZSM-5 and Fe/HZSM-5 catalysts promoted formation of aromatic hydrocarbons, the content of aromatics observed for these two materials was noticeably higher (43%–45%) in comparison to that obtained in the presence of Co/HZSM-5 and unmodified HZSM-5 (23% and 33%, respectively). | Two-stage fixed-bed pyrolysis system with continuous feeding, temperature 550 °C, catalyst to feedstock weight ratio = 0.5 | [30] |
2 | HZSM-5 modified by Fe | Cellulose, cellobiose, lignin, and switchgrass | Fe/HZSM-5 catalyst favored formation of benzene and naphthalene and inhibited production of p-xylene, ethylbenzene and trimethylbenzene in comparison to unmodified zeolite. | Py-GCMS, maximal temperature and residence time were fixed to 500 °C, 30 s, catalyst to feedstock weight ratio = 5–10 | [31] |
3 | Fe/ZSM-5 | Wood sawdust | Fe/ZSM-5 increased efficiency of the production of monocyclic aromatic hydrocarbons and decreased the amount of the formed polycyclic aromatic hydrocarbons in comparison to ZSM-5. | Py-GCMS, maximal temperature, residence time and heating rate were fixed to 600 °C, 25 s and 20,000 °C/s, catalyst to feedstock weight ratio = 10 | [33] |
4 | ZSM-5 modified by Ni, Mg, Cu < Ga and Sn | Woody biomass | Ni-ZSM-5 and Ga-ZSM-5 materials led to the formation of the highest amount of haromatics. | Fixed bed reactor, temperature 450 °C | [34] |
5 | Ni/ZSM-5 | Pine | Modification of ZSM-5 by Ni resulted in the increase in the amount of aromatics and enhanced conversion of oxygenates in comparison to unmodified material. | Bench-scale, semi-batch reactor system, temperature 500 °C, 35.5 mg of biomass per 2.5 min was inserted into the pyrolysis zone containing 500 mg of catalyst | [35] |
6 | Ni/ZSM-5 | Miscanthus | Hydropyrolysis, both hydrogen pressure and the presence of catalyst leaded to the increase in the amount of saturated hydrocarbons. | Py-GCMS, maximal temperature, residence time and heating rate were fixed to 600 °C, 20 s and 20,000 °C/s, catalyst to feedstock weight ratio = 3.3 | [36] |
7 | ZSM-5, Ni/ZSM-5, MCM-41, Ni/MCM-41 | Miscanthus, scots pine, mahogany | Fast pyrolysis of biomass pyrolysis vapors, the presence of catalysts increased content of aromatics and lighter phenols. | Py-GCMS, maximal temperature, residence time and heating rate were fixed to 600 °C, 20 s and 20,000 °C/s, catalyst to feedstock weight ratio = 3.3 | [37] |
8 | ZSM-5 modified by Ni/P | Pine and low-density polyethylene | Co-pyrolysis, modification of zeolite results in the production of increased amount of olefins and valuable aromatics. Moreover, increased hydrothermal stability of the catalyst and resistance against carbon deposit formation is observed. | Py-GCMS, maximal temperature, residence time and heating rate were fixed to 650 °C, 60 s, catalyst to feedstock weight ratio = 15 | [38] |
9 | B-zeolite modified by Cu | Japanese knotweed | Introduction of copper promoted selectivity to hydrocarbons. | Down-draft fixed bed reactor, temperature 600 °C, heating rate 80 °C/min, duration 30 min, catalyst to feedstock weight ratio = 3.3 | [39] |
10 | Cu/MCM-41 and Cu/KIT-6 | Cedar wood | Catalysts prepared by cyclodextrin-assisted co-impregnation method were more active than the materials synthesized via impregnation. Cu/KIT-6 catalyst was more active in the formation of monocyclic aromatic compounds than Cu/MCM-41 sample. | Fixed bed reactor, reaction temperature, reaction time, and heating rate were fixed at 565 °C, 4 min, and 1000 °C/min, catalyst to feedstock weight ratio = 6 | [40] |
11 | V-MCM-41 | Commercial cellulose, xylan kraft lignin and levoglucosan | Ex-situ catalytic pyrolysis, H-V-MCM-41 showed highest catalytic activity for the production of valuable furanic compounds. | Py-GCMS for 3 min at 500 °C, catalyst to feedstock weight ratio = 1 | [41] |
12 | Mo/KIT-5 | Pine, lignin and cellulose | Fast pyrolysis, catalyst highly selective for the production of furans. | Horizontal quartz annular flow reactor, temperature 500 °C | [42] |
No. | Catalyst | Feedstock | Products and Remarks Regarding Influence of Catalyst | Conditions of Pyrolysis Process | Reference |
---|---|---|---|---|---|
1 | Na2CO3/Al2O3 and Pt/Na2CO3/Al2O3 | Pine | Hydropyrolysis—dual-bed system consisting of two separate units containing Na2CO3/Al2O3 and Pt/Al2O3 allowed for a noticeable improvement in the quality of bio-oil | Horizontal quartz annular flow reactor consists of two beds, the catalysts in this study were applied using single-bed and dual-bed modes, temperature 500 °C, vapor residence time 2 s, catalyst to feedstock weight ratio = 0.5 | [46] |
2 | Cu, Fe and Zn supported on Al2O3 and SiO2 | Ultrasonically pretreated cedar | The highest yield of hydrocarbons was achieved in the presence of Zn/Al2O3, the largest fraction of aromatic hydrocarbon was produced with the use of Fe/Al2O3 | Fixed bed reactor, reaction temperature, reaction time and heating rate were fixed at 500 °C, 30 min and 20 °C/min, catalyst to feedstock weight ratio = 3.3 | [47] |
3 | Cu and Fe supported on mesoporous rod-like Al2O3 | Sunflower stalks | Application of mesoporous Al2O3 with a larger pore size resulted in the formation of more polycyclic aromatic hydrocarbons | Fixed bed reactor, reaction temperature, reaction time and heating rate were fixed at 565 °C, 4 min and 1000 °C/min, catalyst to feedstock weight ratio = 8 | [48] |
4 | TiO2, CeO2, CeOx-TiO2, ZrO2 and MgO | Sugar maple, cellulose | CeO2-based catalysts were the most effective in the production of a wide group ketones from oxygenated reaction intermediates | Py-GCMS, temperature 550 °C, residence time 20 s, catalyst to feedstock weight ratio = 8 | [49] |
5 | Ni supported on Al2O3, SiO2, MgO, CeO2, ZrO2 and CaO-ZrO2 | Cellulose | Fast pyrolysis, Ni/Al2O3 and Ni/ZrO2 favored formation of hydrocarbons, while Ni/CeO2 and Ni/SiO2 were less effective, the last two catalysts were not capable to the efficient decrease in the amount of carboxylic acids | Py-GCMS, maximal temperature, residence time and heating rate were fixed to 600 °C, 20 s and 2000 °C/s, catalyst to feedstock weight ratio = 5 | [50] |
6 | Ni supported on CeO2, ZrO2 and CeO2-ZrO2 | Cellulose | Fast pyrolysis, introduction of ceria to the support structure resulted in the formation of larger amount of olefins and paraffins in comparison to the catalyst supported on monoxide zirconia. Simultaneously, the production of a higher yield of carboxylic acids was also observed. | Py-GCMS, temperature, residence time and heating rate were fixed to 400 °C–600 °C, 20 s and 2000 °C/s, catalyst to feedstock weight ratio = 5 | [51] |
7 | Pt/C, Pd/C, ZSM-5, MCM-41 | Wheat bran | Pt/C and Pd/C catalysts efficient in the removal of oxygen from the produced bio-oil and formation of aromatic hydrocarbons | Thermogravimetric analyzer coupled to FTIR spectrometer, dry biomass samples were heated to 700 °C with heating rate of 100 °C/min, catalyst to feedstock weight ratio = 1 | [52] |
No. | Catalyst | Feedstock | Process, Products and Remarks Regarding Influence of Catalyst | Reaction Conditions | Reference |
---|---|---|---|---|---|
1 | Ni, Ni-Ce supported on olivine | White oak submitted to thermal pretreatment | Gasification with the use of fluidized bed, Ni facilitated the production H2 and reduced the formation of CH4 and tars. | Inconel 800 reactor operated at 800 °C, gas residence time at a fluidizing steam flow rate of 0.8 kg/h was calculated to be 8.6 s | [72] |
2 | Commercial Ni/Al2O3 | Pine sawdust | Fast pyrolysis followed by steam reforming process, highest H2 yield observed at 600 °C. | Conical spouted bed reactor followed by in-line steam reforming of formed vapors in a fluidized bed reactor (temperature 500 °C–700 °C), steam biomass ratio 2–5, space time 2–25 gcat/min·g | [73] |
3 | Commercial Ni powder | Coconut shells mixed with HDPE | Integrated catalytic gasification and tar cracking, enhanced syngas and hydrogen production. | Bench scale setup consists of two cylindrical reactors with both the fluidized and fixed bed gasifiers, temperature of fluidized bed 650 °C–870 °C, temperature of fixed bed 600 °C | [74] |
4 | Ni-Mg-Al-Ca | Wood sawdust mixed with polypropylene | Ca addition responsible for enhancement of in situ adsorption of carbon dioxide and limitation of growth of filamentous carbon. | Two-stage stainless tube reactor, pyrolysis was carried out in the first stage and evolved volatiles were passed directly to the second stage reactor where steam gasification of pyrolysis gases took place, gasification and pyrolysis temperature 800 °C and 600 °C, respectively | [75] |
5 | Ni/CaAlOx | Wood sawdust | Pyrolysis-steam reforming, presence of calcium resulted in growth of selectivity to carbon oxide and reduction of carbon dioxide content, change of Ca content allowed for control of ratio between hydrogen and carbon oxide in the formed gaseous mixture. | Fixed bed two-stage reaction system, the first stage involved pyrolysis of feedstock and pyrolysis gases were passed directly to the second stage where catalytic reforming took place, temperature of the first unit 500 °C and the second 800 °C | [76] |
6 | NiZnAlOx | Wood sawdust | Pyrolysis and subsequent steam reforming reactions, H2 yield increased more than twice while amount of introduced Ni on the catalyst surface changed from 5% to 35%, presence of ZnO protect against the agglomeration of nickel particles and formation of coke deposit. | Two-stage fixed bed reactor, in the first reactor biomass was decomposed into pyrolysis vapors, which were passed to the second reactor for catalytic steam reforming, temperature of the first unit 535 °C and the second 800 °C | [77] |
7 | Ni supported on ZrO2, Al2O3, SiO2, CeO2, TiO2 and MgO | Cellulose | Pyrolysis, zirconia the most promising material among the investigated oxides. | Stirred batch reactor at 700 °С for 4 h, 5 g of biomass and 0.2 g of catalyst were used | [78] |
8 | Ni supported on ZrO2 prepared by different methods | Cellulose | Pyrolysis, catalyst containing ZrO2 prepared from ZrOCl2 by precipitation with NaOH was the most active in the conversion of cellulose to gaseous products, especially hydrogen. | Stirred batch reactor at 700 °С for 4 h, 5 g of biomass and 0.2 g of catalyst were used | [79] |
9 | Ni/CeO2-ZrO2 | Cellulose | Pyrolysis, introduction of Ni on surface of CeO2-ZrO2 synthesized by sol-gel or impregnation allowed for the production of the highest hydrogen yield. | Stirred batch reactor at 700 °С for 4 h, 5 g of biomass and 0.2 g of catalyst were used | [80] |
10 | Ni/MexO-ZrO2 (M e = Ca, Mg, Na and K) | Cellulose | Pyrolysis, alkali metals allows for the formation of oxygen vacancies responsible for the removal of the carbon deposit, enhanced adsorption of CO2 shifts an equilibrium of the reactions of thermal treatment of cellulose. | Stirred batch reactor at 700 °С for 4 h, 5 g of biomass and 0.2 g of catalyst were used | [82] |
11 | Ni/CaO-ZrO2 | Cellulose and pretreated beech, birch, poplar and pine | Upgrading of pyrolysis vapors, higher resistance against coke formation, decrease in the production of permanent gases in the case of real biomass samples. | Quartz fixed bed two step reactor, biomass decomposition (500 °C) was separated from the catalyst bed (700 °C), 0.4 g of biomass and 0.1 g of the catalyst were used | [83] |
12 | Ni supported on SBA-15, SBA-16, KIT-6 and MCM-41 | Cellulose | Pyrolysis, the use of Ni/SBA-15 and Ni/KIT-6 results in the increase in the efficiency in H2 production in comparison to Ni/SiO2 sample | Stirred batch reactor at 700 °С for 4 h, 5 g of biomass and 0.2 g of catalyst were used | [71] |
13 | Ni-Co/Mg-Al Ni supported onAl2O3, activated carbon, TiO2, ZrO2, MgO Ni/biomass Ru/C | Lignin, cellulose, wheat straw, timothy grass, canola meal pine wood, fruit pulp | Subcritical and supercritical water gasification of various kinds of lignocellulosic biomass | [ 70,71,72]—batch supercritical water reactor, temperature and pressure—650 °C, 260 atm, water to biomass mass ratio = 5 [73]—batch reactor, temperature 300 °C–500 °C, pressure 230-250 atm, residence time 15–45 min, water to biomass mass ratio = 5–10 [74]—batch reactor, temperature 400 °C–600 °C, reaction time up to 60 min | [84,85,86,87,88] |
14 | Fe-Zn/Al2O3 | Wood sawdust | Steam reforming of volatiles from pyrolysis of wood sawdust, hydrogen production increased with the increase of Zn content, catalysts showed high stability in the reaction conditions | Fixed bed two-stage reaction system, the first stage involved pyrolysis of feedstock and pyrolysis gases were passed directly to the second stage where catalytic steam reforming took place, temperature of the first unit 500 °C and the second 800 °C | [89] |
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Grams, J.; Ruppert, A.M. Development of Heterogeneous Catalysts for Thermo-Chemical Conversion of Lignocellulosic Biomass. Energies 2017, 10, 545. https://doi.org/10.3390/en10040545
Grams J, Ruppert AM. Development of Heterogeneous Catalysts for Thermo-Chemical Conversion of Lignocellulosic Biomass. Energies. 2017; 10(4):545. https://doi.org/10.3390/en10040545
Chicago/Turabian StyleGrams, Jacek, and Agnieszka M. Ruppert. 2017. "Development of Heterogeneous Catalysts for Thermo-Chemical Conversion of Lignocellulosic Biomass" Energies 10, no. 4: 545. https://doi.org/10.3390/en10040545