| 11. |
- Nejadmoghadam, Elham, 1984, et al.
(författare)
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Stabilization of bio-oil from simulated pyrolysis oil using sulfided NiMo/Al 2 O 3 catalyst
- 2023
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Ingår i: Fuel. - 0016-2361. ; 353
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Tidskriftsartikel (refereegranskat)abstract
- Pyrolysis oil comprises compounds with a broad range of functional groups making its thermal/catalytic upgrading challenging due to the formation of undesired char. In this context, the current contribution addresses the thermal and catalytic hydrotreatment of a simulated pyrolysis oil containing all the representative groups of compounds under bio-oil stabilization conditions (180–300 °C, 60 bar, 4 h) using sulfided NiMo/Al2O3. The effect of reaction conditions and different oxygenated organic compounds on the yields and properties of products was compared thoroughly. Interestingly, a correlation between the presence/absence of oxygenated furan and sugar compounds was found to significantly affect the yield of liquid product containing stabilized compounds. The presence of such compound groups significantly enhances the solid formation via oligomerization and polymerization reactions. To gain further insight, the solid products were analyzed/characterized in detail to elucidate their characteristics by extracting them into a dimethyl sulfoxide (DMSO) soluble and insoluble solid fraction. It was found that in the presence of NiMo/Al2O3, increasing temperature from 180 to 300 °C enhances the formation of liquid product due to transformation of some of the soluble solids, while for experiments without the catalyst, the formation of solids was significantly higher. Oppositely, during heating up to 180 °C, no solids were found in the case without the catalyst, however the presence of the catalyst during heating resulted in solid formation due to various catalytic reactions that promoted char formation. Analysis of solids revealed that the structure of soluble solids at lower temperatures (180 °C) using the catalyst was closely related to sugar derivatives, whereas the corresponding insoluble solids with higher molecular weight were not fully char-like developed. However, at higher temperatures, the soluble and insoluble solid compositions were found to contain aliphatic compounds and fully developed char, respectively. Therefore, the stabilization of furan particularly with attached carbonyl groups and sugars derivatives in pyrolysis oil is of great importance to improve upgrading efficiency.
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| 12. |
- Nejadmoghadam, Elham, 1984, et al.
(författare)
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Stabilization of fresh and aged simulated pyrolysis oil through mild hydrotreatment using noble metal catalysts
- 2024
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Ingår i: Energy Conversion and Management. - 0196-8904. ; 313
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Tidskriftsartikel (refereegranskat)abstract
- The nature and reactivity of the oxygenates, containing different functional chemical groups, and especially carbonyl compounds, render pyrolysis oil unstable. Alterations in physical and chemical properties of pyrolysis oil during storage and the catalytic stabilization of this oil is therefore critical and is the objective of the current work. In this study, Pd/Al2O3, Pt/Al2O3, Rh/Al2O3, Re/Al2O3 and sulphided NiMo/Al2O3 catalysts were employed in the hydrotreatment (180 °C, 60 bar H2, 4 h) of simulated pyrolysis oil to examine their effect on stabilization and potential polymerization routes. Of all the catalysts used, Pd/Al2O3 with well-dispersed metal particles, and a high char-suppressing potential was the most effective catalyst. It had the highest bio-liquid yield and the highest selectivity to low molecular weight stabilized oxygenates and deoxygenated products. In addition, the acidity in the light fraction was low and a very low solid product formation was found that consisted mainly of soluble polymers composed predominantly of aliphatic compounds and sugars, whereas insoluble polymers were not fully developed char. The solid yield increased in the following order: Pd (3.3 wt%) < Rh (13.3 wt%) < NiMo (13.6 wt%) < Pt (21.5 wt%) < Re (25.8 wt%) < Blank (27.4 wt%). This trend was also accompanied by an enhanced yield of heavy oligomers in the corresponding liquid phase abundant in phenolic compounds compared to carboxylic acids and aliphatic compounds based on GPC and P-NMR analyses. The Pd loading necessary to obtain a high-quality product was also assessed, and the lower carbon loss when using catalysts with smaller contents of metal was revealed. Based on the results a detailed reaction network was proposed regarding the reactions during stabilization of sugars, aldehydes, ketones, furans, acids and phenols present in pyrolysis oil. To delve deeper into the simulated pyrolysis oil properties, it was subjected to accelerated aging. Interestingly as much as 79 % of the feed was converted during aging. According to GC/MS analysis only large oligomers were formed that could not be detected. When removing the most reactive components from the feed, i.e. the sugar and furan, the conversion was lowered to 53 %. Catalytic stabilization was conducted on the aged oil and compared with stabilization followed by aging. The results showed that the solid formation increased from 5.1 to 9.1 % when the pyrolysis oil was first aged, followed by stabilization. A suggested reason for this is the large amount of oligomers that were formed during the aging. Thus, aging before stabilization is very negative for an industrial process.
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| 13. |
- Olsson Månsson, Emma, 1992, et al.
(författare)
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Removal of Inorganic Impurities in the Fast Pyrolysis Bio-oil Using Sorbents at Ambient Temperature
- 2024
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Ingår i: Energy & Fuels. - 1520-5029 .- 0887-0624. ; 38:1, s. 414-4254
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Tidskriftsartikel (refereegranskat)abstract
- Fast pyrolysis bio-oil (FPBO) sourced from residual biomass waste (such as sawdust) is a promising feedstock that may be used for biofuel production. Their inorganic elements may, however, vary and cause deactivation of the catalysts in the hydrodeoxygenation (HDO) upgrading biorefinery unit. It was found that the use of zeolite Y and strong acidic ion-exchange resins as adsorbents was almost equally efficient in lowering the concentrations of Ca from <10 to <1 ppm and of Fe, K, and Mg to <0.3 ppm in FPBO at 30 °C, atmospheric pressure, and 4 h adsorption time. The removal efficiency of zeolite and resins exceeded 85–98% (detection limit) of these particular elements. For the first time for the FPBO, phosphorus was reported as being successfully targeted by aluminum oxide, being lowered from 1 ppm to <0.1 ppm, which is a reduction of at least 90%. Characterization of the oil and sorbents suggests that the surface acidity affects the removal efficiency of these elements from FPBO. Organic compounds in the pyrolysis oil, including isopropanol, lactic acid, hydroxy acetone, furfural, guaiacol, and levoglucosan, were semiquantified using two-dimensional gas chromatography coupled with mass spectrometry (GCxGC-MS). Compared to the fresh oil, the compositions and contents of these organic compounds were not impacted significantly by the sorbents under these mild operating conditions. This research indicates that inorganic impurities present in bio-oils can be removed, and thus, they may be considered feedstocks for producing biofuels with less deactivation of HDO catalysts.
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| 14. |
- Salam, Muhammad Abdus, 1983, et al.
(författare)
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Elucidating the role of NiMoS-USY during the hydrotreatment of Kraft lignin
- 2022
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Ingår i: Chemical Engineering Journal. - : Elsevier BV. - 1385-8947. ; 442
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Tidskriftsartikel (refereegranskat)abstract
- Major hurdles in Kraft lignin valorization require selective cleavage of etheric and C–C linkages and subsequent stabilization of the fragments to suppress repolymerization reactions to yield higher monomeric fractions. In this regard, we report the development of efficient NiMo sulfides and ultra-stable Y zeolites for the reductive liquefaction and hydrodeoxygenation of Kraft lignin in a Parr autoclave reactor at 400 °C and 35 bar of H2 (@25 °C). Comparing the activity test without/with catalyst, it is revealed that NiMo sulfides over ultra-stable Y zeolites (silica/alumina = 30) achieved a significant reduction (∼50 %) of the re-polymerized solid residue fraction leading to a detectable liquid product yield of 30.5 wt% with a notable monocyclic and alkylbenzenes selectivity (∼61 wt%). A physical mixture counterpart, consisting of hydrothermally synthesized unsupported NiMoS and Y30, on the other hand, shows lower selectivity for such fractions but higher stabilization of the lignin fragments due to enhanced access to the active sites. Moreover, an extended reaction time with higher catalyst loading of the impregnated NiMoY30 facilitated a remarkable alkylbenzene (72 wt%) selectivity with an increased liquid yield of 38.9 wt% and a reduced solid residue of 16.4 wt%. The reason for the high yield and selectivity over NiMoY30, according to the catalyst characterization (H2-TPR, XPS, TEM) can be ascribed to enhanced stabilization of depolymerized fragments via H2-activation at a lower temperature and high hydrodeoxygenation ability. In addition, the better proximity of the acidic and deoxygenation sites in NiMoY30 was beneficial for suppressing the formation of polycyclic aromatics.
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| 15. |
- Shafaghat, Hoda, et al.
(författare)
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Customized Atmospheric Catalytic Hydropyrolysis of Biomass to High-Quality Bio-Oil Suitable for Coprocessing in Refining Units
- 2024
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Ingår i: Energy & Fuels. - : American Chemical Society. - 0887-0624 .- 1520-5029. ; 38:6, s. 5288-5302
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Tidskriftsartikel (refereegranskat)abstract
- This study aimed to investigate the critical elements of the biomass ex situ catalytic hydropyrolysis (CHP) concept to improve the quality of fast pyrolysis bio-oil (FPBO) for further coprocessing in a fluid catalytic cracking (FCC) refining unit. Generally, the high oxygen and low hydrogen contents of biomass result in a bio-oil with low quality, necessitating its upgrading, which can be performed as integrated in the pyrolysis process via in situ or ex situ configuration. In this work, the quality of stem wood-derived pyrolyzates (520 °C) was improved via ex situ CHP (400 °C) using a continuous bench-scale drop tube pyrolyzer (60 g h-1), and then the produced FPBO was coprocessed with vacuum gas oil (VGO) fossil oil using a lab-scale FCC unit (525 °C). CHP of stem wood was carried out using different metal-acid catalysts such as Ni/HZSM-5, Ni/HBeta, Mo/TiO2, and Pt/TiO2 at atmospheric pressure. FCC runs were performed using an equilibrium FCC catalyst and conventional fossil FCC feedstock cofed with 20 wt % stem wood-derived bio-oil in a fluidized bed reactor. Cofeeding the nonupgraded FPBO with fossil oil into the FCC unit decreased the generation of hydrocarbons in the range of gasoline and naphtha, indicating that bio-oil needs to be upgraded for further coprocessing in the FCC unit. Experimental results showed that different catalysts significantly affected the product composition and yield; Ni-based catalysts were strongly active tending to generate a high yield of gas, while Mo- and Pt-based catalysts seemed better for production of liquid with improved quality. The quality of FPBO was improved by reducing the formation of reactive oxygenates through the atmospheric CHP process. The composition of oil obtained from hydropyrolysis also showed that the yields of phenols and aromatic hydrocarbons were enhanced. © 2024 The Authors.
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