An overview on the analytical methods for characterization of biocrudes and their blends with petroleum

Badoga, Sandeep; Gieleciak, Rafał; Alvarez‐Majmutov, Anton; Xing, Tingyong; Chen, Jinwen

doi:10.1016/j.fuel.2022.124608

Cited by 9 publications

(10 citation statements)

References 161 publications

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“…In a preliminary phase of this study, 10 solvents with varying degrees of polarity were screened based on their ability to reject contaminants in biocrude. 38 The solvents included n-pentane, nheptane, toluene, dichloromethane, tetrahydrofuran, chloroform, ethyl acetate, methyl ethyl ketone, acetone, and methanol. In a typical test, ∼2 g of biocrude were mixed with ∼125 mL of solvent at room temperature.…”

Section: Methodsmentioning

confidence: 99%

Upgrading of Hydrothermal Liquefaction Biocrude from Forest Residues Using Solvents and Mild Hydrotreating for Use as Co-processing Feed in a Refinery

Badoga,

Alvarez-Majmutov,

Rodriguez

et al. 2023

Energy Fuels

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The presence of a variety of reactive oxygen compounds in biocrudes derived from thermochemical conversion of biomass creates challenges for their co-processing with petroleum in a refinery. In this work, we explore two different technology approaches to upgrade a biocrude produced by hydrothermal liquefaction of forest residues, to the level at which it becomes compatible for co-processing in a refinery. The first approach consisted of using solvents to reject petroleum-insoluble oxygen components in the biocrude, whereas the second one was catalytic hydrotreating under relatively mild conditions. The biocrude had 11.3 wt % oxygen and was completely immiscible in the reference petroleum feedstock (vacuum gas oil). Upgrading using solvents (toluene, dichloromethane, ethyl acetate, and npentane) resulted in the rejection of high boiling components, but the concentration of oxygen components in the resulting extract did not change significantly. While the biocrudes treated with n-pentane and toluene were miscible in the reference petroleum feedstock, the mass rejected by these solvents from the biocrude was significant (>35%). Hydrotreating the biocrude was effective at reducing oxygen content down to 2.9 wt % and converting high boiling fractions, while preserving more than 90% of the biocrude's mass as the liquid product. At this level of deoxygenation, the biocrude was fully miscible in the reference petroleum feedstock and the blend was stable over 7 days. NMR spectroscopy provided insights into the structural changes taking place upon hydrotreating the biocrude. In general, it was found that after hydrotreating the biocrude became more saturated in nature and thus more miscible in petroleum.

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Section: Methodsmentioning

confidence: 99%

Upgrading of Hydrothermal Liquefaction Biocrude from Forest Residues Using Solvents and Mild Hydrotreating for Use as Co-processing Feed in a Refinery

Badoga,

Alvarez-Majmutov,

Rodriguez

et al. 2023

Energy Fuels

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“…These studies have demonstrated that Orbitrap MS is steadily becoming a reliable tool for petroleum characterization. 10 High-performance liquid chromatography is an effective method for studying complex mixtures, 1 of liquid chromatography and Orbitrap MS is beneficial for analyzing crude oil composition from multiple dimensions. 11 Yang et al 12 employed liquid chromatography−high-resolution Orbitrap MS to detect the characteristic distribution of naphthenic acids in various crude oils and refined petroleum products.…”

Section: Introductionmentioning

confidence: 99%

“…Petroleum serves as a crucial source of energy and chemical raw materials. In the realm of oil exploration and development, chemical analysis plays a pivotal role in completing oil source screening . Petroleum features a diverse and complex range of hydrocarbons and heteroatom-containing analogues, including sulfides and thiophenes, basic and non-basic nitrogen compounds, and carboxylic acids.…”

Section: Introductionmentioning

confidence: 99%

“…In the realm of oil exploration and development, chemical analysis plays a pivotal role in completing oil source screening. 1 Petroleum features a diverse and complex range of hydrocarbons and heteroatom-containing analogues, including sulfides and thiophenes, basic and non-basic nitrogen compounds, and carboxylic acids. While the proportion of heteroatom compounds in crude oil is relatively small, it can adversely impact critical processes such as petroleum refining, processing, transportation, and storage.…”

Section: Introductionmentioning

confidence: 99%

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Characterization of Differential Markers among Crude Oil Samples Using UPLC-QE-MS/MS and Multivariate Statistical Analysis

Wang

Zuo

Gao³

et al. 2023

Energy Fuels

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In this study, we utilized ultra-high-performance liquid chromatography–Q Exactive plus Orbitrap mass spectrometry (to analyze the compounds in crude oil samples from two different reservoirs and proposed a novel analytical approach. The new method encompasses three-dimensional visualization of mass spectrometry (MS) data, various multivariate statistical analyses, and a combination of multivariate statistical and conventional analytical methods. The results revealed that the differential markers of the two groups of crude oil samples were primarily concentrated in N1, N1O1, and N1O1S1 compounds, with four-ring alkaline nitrogen-containing compounds such as benzacridines and highly condensed alkaline nitrogen-containing compounds serving as the best differential markers for distinguishing the two groups of crude oil samples. Furthermore, we discussed the application value of this method in petroleum-contaminated groundwater. This method demonstrates the potential and application value of multivariate statistical methods in the analysis of high-resolution MS data of crude oil.

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“…Dependent upon the feedstock, the biocrudes produced from the HTL process also contain a considerable amount of heteroatom content other than oxygen [i.e., nitrogen (∼0.1–7 wt % N) and sulfur (∼0–2 wt % S)] ,,, and also a high inorganic content (∼0.1–0.6 wt %). , Overall, this makes HTL biocrude a highly complex mixture, containing phenols, alcohols, fatty acids, carbonyls, and other oxygenated compounds of a diverse nature (O x , O x N x , O x S x , etc. species). − Inevitably, this entails high viscosity/density, high total acid number (up to ∼100 mg of KOH/g TAN), high microcarbon residue (MCR), low H/C atomic ratio, low calorific value, immiscibility with fossil products, and poor chemical/thermal stability of biocrudes and incorporates undesirable fuel properties in refinery context. − Therefore, raw biocrudes are intermediate energy carriers and require further refining to enhance physicochemical properties, drop-in fuel potential, and co-feeding compatibility in an existing refinery infrastructure. ,, In recent years, because of low capital investment, the co-processing of renewable feedstocks (e.g., HTL biocrudes) is of high interest and a ready-to-use approach for refineries. ,, Because most of the studies in the literature represent the stand-alone hydroprocessing of biocrudes, ,, therefore, in co-processing, the main concern is the limited scientific results covering the insertion point of biocrudes in already existing refineries.…”

Section: Introductionmentioning

confidence: 99%

Understanding the Miscibility and Co-feeding Potential of Hydrothermal Liquefaction Biocrude in Refinery Streams: Role of Hydrodeoxygenation

et al. 2022

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Co-processing of hydrothermal liquefaction biocrudes in existing refineries is attracting tremendous attention for large-scale commercialization of sustainable biofuels. As a result of the higher oxygen content, these biocrudes are not compatible with refinery streams; therefore, co-processing requires an essential (stand-alone) prior mild hydrotreating step. Therefore, Spirulina biocrude and mild hydrotreated samples (200, 250, 300, and 340 °C) were comprehensively investigated for their compatibility and solubility behavior with straight-run gas oil (SRGO) and rapeseed oil (RO). In total, 245 solubility tests were performed in 35 different solvents, and these tests provide the basis for theoretical predictions made by Hansen solubility parameters (HSPs) and three-dimensional Hansen double-sphere solubility plots. The compatibility of biocrude samples with SRGO and RO was verified by the overlapping area in their Hansen double-sphere plots and center-to-center distances (D cc). All of these values were found to be in direct relation with the degree of hydrodeoxygenation (HDO), meaning that higher compatibility is strongly dependent upon higher oxygen removal. Experimental miscibility studies confirmed the theoretical predictions and exhibited that severe HDO (93.4%) is needed to achieve the complete miscibility of the biocrude sample (mildly hydrotreated at 340 °C) in SRGO and RO. 13C nuclear magnetic resonance spectroscopy was used to effectively study the functional groups, and the obtained spectra corroborated with the results obtained from theoretical and experimental studies. The finding that HSPs can predict compatibilities of complex biocrudes very close to experimental results and a severe HDO (>90%) is essential to enhance solubility will pave a way in assessing the co-processing scenario.

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An overview on the analytical methods for characterization of biocrudes and their blends with petroleum

Cited by 9 publications

References 161 publications

Upgrading of Hydrothermal Liquefaction Biocrude from Forest Residues Using Solvents and Mild Hydrotreating for Use as Co-processing Feed in a Refinery

Upgrading of Hydrothermal Liquefaction Biocrude from Forest Residues Using Solvents and Mild Hydrotreating for Use as Co-processing Feed in a Refinery

Characterization of Differential Markers among Crude Oil Samples Using UPLC-QE-MS/MS and Multivariate Statistical Analysis

Understanding the Miscibility and Co-feeding Potential of Hydrothermal Liquefaction Biocrude in Refinery Streams: Role of Hydrodeoxygenation

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