Boiling Point Distribution Research Articles

Catalytic hydrothermal liquefaction of Azolla filiculoides into hydrocarbon rich bio-oil over a nickel catalyst in supercritical ethanol

Hydrothermal liquefaction (HTL) is one of the most promising thermochemical techniques for converting wet biomass into crude oil-like products (bio-oil). In this study, Catalytic hydrothermal liquefaction of Azolla filiculoides (AZ) was performed over a various loading of nickel (Ni) on magnesium oxide (MgO) catalyst for the higher and quality bio-oil production. The key operating parameters such as temperature, reaction holding time, amount of Ni on MgO supports catalyst, and reaction solvents were investigated in the presence of a hydrogen environment. There was a 12.8 wt% increase in bio-oil yield and a 6.3 wt% decrease in biochar yield with addition of 15 wt% Ni catalysts compared to the non-catalytic reaction bio-oil yield (44.0 wt%). Results confirmed the highest total bio-oil yield of 56.8 wt% was attained at 280 °C with the catalyst amount of 15 wt% at a residence time of 45 min. Gas chromatography-mass spectrometry (GC-MS), FT-IR, CHNS, TGA, and NMR analyses were performed on the bio-oil, identifying 32.8 % long-chain hydrocarbons (C12-C16) along with small amounts of alcohols, alkanes, and esters. The boiling point distribution revealed that bio-oil produced using the Ni/MgO catalyst contained a significantly higher proportion of diesel-range hydrocarbons (42.4 %). Furthermore, the bio-oil yield under ethanol solvent and Ni catalysts showed higher heating value (HHV) 42.2 MJ/kg. Overall in the presence of Ni hydrogenation efficient catalysts on MgO in the liquefaction reaction promoted the deoxygenation and hydrogenation reaction.

Renewable diesel blends production from hydrothermal liquefaction of food waste: A novel approach coupling fractional distillation and emulsification

Hydrothermal liquefaction (HTL) is a promising approach for producing biocrude oil from wet biowaste, but the suboptimal properties of HTL biocrude hinder its direct utilization as transportation fuel. This study presents an innovative approach by integrating fractional distillation and emulsification to upgrade HTL biocrude derived from food waste into renewable diesel blends. Fractional distillation is effective in removing metals, heavy fractions, and impurities, thus improving the physicochemical properties of the biocrude. Subsequent emulsification of distillates (10–30 wt%) with diesel, using Atlox 4912 as the surfactant, ensures a homogeneous mixture. The solubility of biocrude in diesel increased from 34.80 wt% to 100 wt% after distillation. Compared to direct HTL biocrude emulsification, distillate emulsion exhibited a 17.22% and 20.89% reduction in oxygen and nitrogen content, respectively, as well as significant improvements in terms of higher heating value, carbon and energy recoveries, and reduction of metal elements. The resulting emulsion demonstrated comparable viscosity, molecular weight, and boiling point distributions to the commercial diesel. Moreover, the oxidation and thermal stability tests revealed superior performance of distillate emulsion, with no observable sedimentation during the storage period. In contrast, direct biocrude emulsion experienced 14.37 wt% of phase separation. The mechanism of emulsion aging was then investigated, providing the basis for obtaining emulsions with preferable yield and quality. The comparative evaluation in this study showed that the integrated approach of fractional distillation and emulsification enhances the feasibility and quality of producing renewable diesel blends from HTL biocrude.

Determination of boiling point distribution by TG using a novel crucible and comparison with true boiling point distillation and simulated distillation by GC–MS and Py-GC/MS

To effectively guide the processing and utilization of oils, their true boiling point distillation (TBPD) data must be determined accurately and simply. In this investigation, the experimental distillation of crude oil (RP), low-temperature coal tar (MT), and high-temperature coal tar (HT) were investigated by using the TBPD apparatus, simulated distillation based on gas chromatography-mass spectrometry (GC–MS) and Py (pyrolyzer)-GC/MS, and thermogravimetry with a self-modified crucible (TG-Distillation). GC–MS calibration curves were calibrated using alkane and aromatic external standards. Several parameters for simulated distillation were calibrated, and the dependence of alkane and aromatic components on column temperature was examined. An in-depth analysis and comparison were conducted on TBPD, GC–MS, Py-GC/MS, and TG-Distillation methods. The results show that the difference in TBPD between GC–MS and Py-GC/MS is less than 10 %. Aromatics have a stronger temperature-dependence than alkane components, and the column heating rate of 5 °C/min is better than 10 °C/min. The resolution of oils (especially aromatic-rich coal tar) by GC–MS and Py-GC/MS can be effectively improved by calibrating the components with multiple parameters. TG-Distillation can achieve good distillation and separation effects comparable to that of GC–MS after adjusting the reflux ratio. At the heating rate of 5 °C/min, the TG-Distillation effect is close to the results of TBPD, especially the RP, with a difference of less than 10 %. Adjusting the height of the crucible lid achieves a wider boiling point distribution examination. Additionally, a conversion method was employed to accurately convert TG linearizable data into data from other simulated distillation methods, and predict boiling point distribution up to 400 °C with a prediction deviation of less than 5 % (R2 > 0.98).

Understanding catalytic hydrotreating of hydrothermal liquefaction nitrogen-rich biocrude in a two-stage continuous hydrotreater

Hydrothermal liquefaction biocrude from non-lignocellulosic feedstocks often shows properties, such as a high presence of inorganics, oxygen and especially a high nitrogen content, which are challenging in view of hydroprocessing for the production of drop-in biofuels. In particular, nitrogen removal requires severe conditions, that might compromise continuous operations and affect the yield of the different hydrocarbon fractions. This work demonstrates the possibility of successful long-time continuous operations for microalgae biocrude, a feed with a high content of metals and nitrogen, thanks to a multi-stage approach with different sulfided catalysts. Whereas hydrodeoxygenation was achieved at relatively mild conditions, nitrogen removal was challenging. By using a number of advanced characterization techniques, among which FTICR-MS, it was possible to unveil how nitrogen removal takes place at different reaction severities, in terms of temperature, WHSV and pressure. High nitrogen removal needs high temperature (∼400 °C) and low space velocities and is associated with a high H2 consumption. This causes also a remarkable change in the boiling point distribution, which is shifted to products in the gasoline range, while the yields of middle distillates are marginally affected by hydrotreating severity. This seems to be a consequence of the denitrogenation mechanism, promoting the fragmentation of larger molecules in the heavy fractions of biocrude.

E-waste plastic liquefaction using supercritical Toluene: Evaluation of reaction parameters on liquid products

Solvothermal liquefaction (STL) is a thermochemical conversion technique that employs solvents other than water to transform waste plastics into valuable compounds. The objective of this study was to explore the potential use of supercritical toluene, a nonpolar solvent, for the depolymerization of four electrical waste (e-waste) thermoplastics, namely polyamide (PA), polycarbonate (PC), polyoxymethylene (POM), and polyether ether ketone (PEEK), into liquid products. Depolymerization experiments were carried out in batch reactors at three reaction temperatures (325, 350, and 375 °C), and three residence times (1, 3, and 6 h). The findings revealed that increasing STL temperature and extending the reaction time enhances the depolymerization of e-waste thermoplastics. The highest STL conversation (100 %) was observed for POM, and the lowest STL conversation (32.23 %) was observed for PEEK. Additionally, the ultimate analysis showed that the liquid product obtained from STL at 375 °C and 6 h exhibited higher heating values (HHV) within the range of 31.43 to 35.31 MJ/kg. Thermogravimetric analysis (TGA) demonstrated that the boiling point distributions of liquid products are highly dependent on thermoplastic type. Finally, the reaction mechanisms of STL for PA, PC, POM, and PEEK were proposed based on gas chromatography-mass spectrometry (GCMS) analysis.

Mechanistic insight into the coke formation tendency during upgradation of crude oil in slurry phase batch reactor using MoS2 and its various oil soluble catalysts

This work intends to provide a deep insight on how can the MoS2 and its oil soluble analogues synthesized using various organic acid ligands (oleate, palmitic acid, lauric acid, stearic acid) efficiently fits well into the landscape of refinery and petrochemical integrations. The slurry phase hydroprocessing of crude oil has been efficiently carried out at 420 °C temperature and 120 bar H2 pressure. The hydroprocessing of crude oil presents the prominent results by increasing the lighter and more valuable fractions in the crude oil, as obtained from SARA analysis result, boiling point distribution, viscosity, sulfur and MCR data. The oil soluble MoS2 catalyst (MLT) synthesized from sodium oleate presented better hydroprocessing activity (65 % VR conversion) than other catalysts due to the small crystallite size, greater hydrophobic interaction, low stacking number and slab length. In this study, the comprehensive analysis of the solid coke obtained from both thermal and catalytic reactions are conducted using the XRD to get various structural parameters (average layer distance between two aromatic sheets (dm), average inter-chain layer distance (dλ), average perpendicular height of stack of aromatic sheets (Lc), average diameter of aromatic sheet (La), and average number of stacked aromatic sheets (M)) to elucidate the coke formation mechanism. These findings highlight the crucial role of catalysts in activating supplied hydrogen gas and promoting the hydrocracking reactions.

Storage stability of biocrude oil fractional distillates derived from the hydrothermal liquefaction of food waste

Biocrude oil produced via hydrothermal liquefaction (HTL) is a promising precursor for transportation fuels and biochemicals. Present studies have highlighted the inherent instability of the biocrude oil, which poses significant challenges for its subsequent storage, upgrading and transportation. On the other hand, biocrude oil distillates showed the potential to serve as a transportation fuel blendstock. To this end, this study aimed to investigate the influence of the distillation temperature (199–238 °C and 238–274 °C), storage atmosphere (air and nitrogen), temperature (25 °C and 55 °C), and time (0–16 weeks) on the physical, chemical, and boiling point distribution properties of the distillates. Results demonstrated that changes in the stored distillates due to different distillation temperature were drastically higher than that between different storage atmospheres and temperatures. Comparing with the raw distillate, the distribution of compounds with a molecular weight < 300 Da in low-temperature (199–238 °C) distillates (LD) and medium-temperature (238–274 °C) distillates (MD) was improved with the increasing storage time. In addition, storage led to a decrease in O:C ratio (21.6 % and 86.5 %), and an increase in the HHV (3.6 % and 12.3 %) in the LD and MD, respectively. Furthermore, only slight deviations were observed in the density (5.2 % and 7.4 %) and viscosity (5.2 % and 0.8 %) for LD and MD, respectively. In particular, the MD group exhibited comparable characteristics to transportation fuels with decreased acidity (1.8–2.8 mg KOH/g) and increased HHV (46.2–46.8 MJ/kg) after long-term storage. At last, the mechanism of superior distillates stability was discussed. This study indicated that distillation not only presents a potential approach for producing transportation fuel blendstock but also improves the stability of HTL biocrude oil.

Boiling point modeling for petroleum speciation data

An empirical model is presented for generating the boiling curve of a petroleum sample based on parameters that are experimentally available using typical speciation techniques. The approach estimates the boiling point distribution of the detected components and allows a comparison with the simulated distillation profile of the sample. The model is shown to predict the boiling behavior of the speciation-derived average components in crude oil distillation fractions, which match the measured average distillation temperature of the fractions. The model is then applied to generate boiling distributions, based on mass spectrometric and gas chromatographic speciation data, which match the measured simulated-distillation curves with less than 20 °C difference. The model is also applied to the isolated fraction of saturated compounds, where the modeled boiling profile matches well with the measured distillation profile of the entire sample. This confirms that the model, although built using Fourier transform ion cyclotron resonance mass spectrometry data of aromatic compounds, extends to data obtained using comprehensive 2-dimensional gas chromatography, and also describes the boiling behavior of saturated compounds speciated by field desorption time of flight mass spectrometry. Consequently, the modeled boiling distribution enables an assessment of how well a speciation measurement describes the sample, and provides an estimation of lower and higher-boiling portions that have been omitted in the data set.

Mineral Additives Based on Industrial Waste for Modifications of Bitumen Polymers

The increase in cost of carbonaceous materials, as well as significant costs of industrial waste, have prompted scientists to use alternative raw materials as components of the construction industry. This study investigated the suitability of waste products from the coke industry as modifying agents for polymer bitumen. The by-product of the coking industry reaches a high level of silicon and is called silicon-containing additive (SCA), the composition of which is similar to the mineral solutions for bitumen. In this article, the results of using SCA as standard additives for modified polyethylene terephthalate (PET) with bitumen waste is presented. Using the Simdist boiling point distribution method, simulated high temperature distillation by gas chromatography, differential thermal (DTA) analyzes, and other methods of physic- chemical properties of bitumen after adding of SCA were studied. It was revealed that the connection and consumption of additives occurs because of the content of aromatic components, as well as an increase in the consumption of bitumen characteristics. Thus, the presented method for obtaining road surfaces based on PET waste and coke production waste meet the requirements of sustainable development, which implements both a significant use of industrial waste as secondary products and their processing into a new product using an energy-saving technology that reduces the consumption of raw materials and resources.

Conversion of Waste Cooking Oil into Bio-Fuel via Pyrolysis Using Activated Carbon as a Catalyst.

The utilization of activated carbon (AC) as a catalyst for a lab-scale pyrolysis process to convert waste cooking oil (WCO) into more valuable hydrocarbon fuels is described. The pyrolysis process was performed with WCO and AC in an oxygen-free batch reactor at room pressure. The effects of process temperature and activated carbon dosage (the AC to WCO ratio) on the yield and composition are discussed systematically. The direct pyrolysis experimental results showed that WCO pyrolyzed at 425 °C yielded 81.7 wt.% bio-oil. When AC was used as a catalyst, a temperature of 400 °C and 1:40 AC:WCO ratio were the optimum conditions for the maximum hydrocarbon bio-oil yield of 83.5 and diesel-like fuel of 45 wt.%, investigated by boiling point distribution. Compared to bio-diesel and diesel properties, bio-oil has a high calorific value (40.20 kJ/g) and a density of 899 kg/m3, which are within the bio-diesel standard range, thus demonstrating its potential use as a liquid bio-fuel after certain upgradation processes. The study revealed that the optimum AC dosage promoted the thermal cracking of WCO at a reduced process temperature with a higher yield and improved quality compared to noncatalytic bio-oil.

Effects of temperature, reaction time, atmosphere, and catalyst on hydrothermal liquefaction of Chlorella

AbstractHydrothermal liquefaction (HTL) is the direct conversion of wet biomass into bio‐oil at high temperature (200–400°C) and high pressure (10–25 MPa). In this work, we investigated HTL with 4.5 g of Chlorella and 45 ml of water/ethanol (1:1 vol. ratio) in a 100 ml reactor. Bio‐oils produced are characterized via elemental analysis, thermogravimetric analysis, and gas chromatography–mass spectrometry (GC–MS). HTL of Chlorella was investigated at 240 and 250°C for 0 and 15 min under an air or H2 atmosphere and with and without 5% zeolite Y. Temperature increased the bio‐oil yield from 38.75% at 240°C to 43.04% at 250°C for 15 min reaction time. Longer reaction time increased the bio‐oil yield at 250°C from 39.14% for 0 min to 43.04% for 15 min. The H2 atmosphere had a significant effect for HTL at 240°C. Zeolite Y increased the bio‐oil yield significantly from 32.03% to 43.06% at 250°C for 0 min. The carbon content of bio‐oil increased with the temperature while the oxygen content decreased. The boiling point distribution of bio‐oils in the range of 110–300°C varies with temperature, and atmosphere. At 240°C for 15 min, the 110–300°C range increased from 31.19% in air (240‐15‐air) to 39.25% in H2 (240‐15‐H2). The H2 atmosphere increased the content of hydrocarbons, alcohols, and esters from 69.61% in air (240‐0‐air) to 82.83% in H2 (240‐0‐H2). Overall, temperature, reaction time, atmosphere, and catalyst all significantly influenced the yield and/or quality of bio‐oils from HTL of Chlorella.

Effect of Acidic Hydrochar on Plastic Crude Oil Produced from Hydrothermal Liquefaction of Waste PVC

In this study, the effect of hydrothermal liquefaction (HTL) of waste PVC was investigated in the presence of acidic hydrochar. The hydrochar was prepared by hydrothermal carbonization of pineapple waste at 250 °C and at 1 h in the presence of citric acid. Hydrochar was acidic, stable, and porous and contained acidic functional groups. Hydrochar was co-fed with PVC during HTL to enhance HTL conversion and quality of the plastic crude oil. HTL experiments were performed at 300–350 °C, 0.25–4 h of reaction times, and 0–20 wt% hydrochar-to-PVC ratio. The plastic crude oil was separated from the solid residue to evaluate HTL conversion and to analyze elemental compositions, boiling point distribution, alteration of chemical bonds, and chemical compositions. The results showed that acidic hydrochar enhances HTL conversion with a maximum value of 28.75 at 5 wt% hydrochar content at 350 °C and 0.5 h. Furthermore, plastic crude oils contained no chloride but contained significantly high carbon and hydrogen, resulting in a higher heating value of up to 36.43 MJ/kg. The major component of the plastic crude oil was 3, 5 dimethylphenol produced ranging from 61.4 to 86.4% (percentage of total identified area) according to gas chromatography mass spectroscopy (GCMS) data.

SolvX: Solvothermal conversion of mixed waste plastics in supercritical toluene in presence of Pd/C catalyst

As the world's ability to cope with the fast-rising output of disposable plastic products is limited, plastic pollution has emerged as one of the most important environmental challenges. Catalytic solvothermal conversion (SolvX) could potentially utilize mixed waste plastics (MWPs) for sustainable fuels and chemical production. In this study, the effect of SolvX reaction time (1 – 5 h), Pd/C catalyst loading (0 – 10 wt%), and hydrogen loading (0–75 bar) on MWPs were investigated using supercritical toluene as solvent at temperature 350 °C. Four major waste plastics including low-density polyethylene (#4), polypropylene (#5), polystyrene (#6), and polyurethane (#7) were used as feedstock for this study. Along with SolvX conversion, the liquid products (crude oils) were characterized for elemental composition changes using ultimate analysis, boiling point distribution via thermogravimetric analysis, functional groups alteration using Fourier transform infrared spectroscopy, and product identification via gas chromatography-mass spectrometry. The results showed that the addition of catalyst and hydrogen have positive effects on the SolvX conversion. According to the elemental analysis, the SolvX crude oils' higher heating values (HHV) range from 32 to 38 MJ/Kg. The range of boiling points demonstrates that Pd/C increases the formation of lighter hydrocarbons. Additionally, a proposed catalytic SolvX reaction mechanism shows that the aromaticity raised with the increment of residence time and Pd/C enhances hydrodenitrogenation and deoxygenation at higher hydrogen loading.

Elucidating the Maillard Reaction Mechanism in the Hydrothermal Liquefaction of Binary Model Compound Mixtures and Spirulina

Hydrothermal liquefaction (HTL) transforms wet biomass and biowaste feedstock into water-insoluble biocrude and valuable water-soluble organic products. HTL takes advantage of the exceptional properties of water near the critical point to break bio-macromolecule linkages, and as a reaction medium, subcritical water ions allow the reaction and recondensation of intermediates into various structures and product phases. Among the different reaction mechanisms involved in the hydrothermal conversion, the synergetic interaction between protein and carbohydrate intermediates, known as the Maillard reactions, can boost the renewable biocrude yield up to 25% higher than solely free fatty acid hydrolysis from lipids. However, the reaction mechanisms and the effect of biomass composition are not fully understood. In this study, the Maillard reactions have been investigated with a central composite design to validate the impact of mass ratio (carbohydrate/protein) over temperature and residence time, via product response analysis, including product yields, boiling point distribution, aqueous tests, elemental, and chemical compositions. Then, the gas chromatography–mass spectrometry data is used to propose a potential pathway, followed by levulinic acid from carbohydrates as a candidate, to produce proline via Maillard interactions before amino acid condensation into piperazinediones and reduction into pyrazines among other complex degradations. The understanding of Maillard interactions under HTL conditions could lead to more robust compositional models, and the present results showed that a protein-to-carbohydrate mass ratio 2:1 would maximize the volatile fraction, elemental carbon, and higher heating value in the renewable crude, with a 90–95% of the maximum crude yield being obtained. The HTL experiments were run with glucose and soy protein as model compounds and spirulina in a batch reactor at 300 °C temperature, 20 min residence time, and 50% mass ratio as a central point, with an alpha (α) of 20 °C, at 10 min, and a 25% mass ratio.

Molecular reconstruction of vacuum gas oils using a general molecule library through entropy maximization

Vacuum gas oil (VGO) is the most important feedstock for hydrocracking processes in refineries, but its molecular composition cannot be fully acquired by current analysis techniques owing to its complexity. In order to build an accurate and reliable molecular-level kinetic model for reactor design and process optimization, the molecular composition of VGO has to be reconstructed based on limited measurements. In this study, a modified stochastic reconstruction-entropy maximization (SR-REM) algorithm was applied to reconstruct VGOs, with generation of a general molecule library once and for all via the SR method at the first step and adjustment of the molecular abundance of various VGOs via the REM method at the second step. The universality of the molecule library and the effectiveness of the modified SR-REM method were validated by fifteen VGOs (three from the literature) from different geographic regions of the world and with different properties. The simulated properties (density, elemental composition, paraffin-naphthene-aromatics distribution, boiling point distribution, detailed composition of naphthenes and aromatics in terms of ring number as well as composition of S-heterocycles) are in good agreement with the measured counterparts, showing average absolute relative errors of below 10% for each property.

Hydrotreatment of solvent-extracted biocrude from hydrothermal liquefaction of municipal sewage sludge

The objective of this research was to investigate the influence of four solvents on hydrotreatment of hydrothermal liquefaction (HTL) biocrude derived from municipal sewage sludge. HTL of sludge was performed at 350 °C in a 1.8 L batch reactor. The biocrude was then extracted from the reaction mixture using dichloromethane (DCM), hexane, toluene, and acetone as solvents. Solvent extraction using DCM, hexane, toluene, and acetone resulted in 38%, 12%, 18%, and 10% biocrude yields (dry-ash-free basis), respectively. Hydrotreatment of four biocrude samples was studied using Ni/SiO2-Al2O3 catalyst at 350 °C in a 100 ml batch reactor. Physicochemical properties of biocrude samples and hydrotreated oils were determined using 2D-NMR, GC–MS, bomb calorimeter, viscometer, TAN and CHNS-O analyzers, and simulated distillation. The hydrotreatment of DCM-extracted biocrude was quite challenging due to catalyst deactivation, polymerization of biocrude, and equipment corrosion. The challenge was mainly attributed to high chloride content in DCM-extracted biocrude. However, the upgraded oil was produced at 86%, 60%, and 47% liquid yield from hexane-, toluene-, and acetone-extracted biocrudes. Most nitrogen-containing compounds were recovered using acetone. Among these three solvents, hexane produced the highest quality oil in terms of fuel properties such as acid number, heating value, boiling point distribution, and elemental composition.

Geochemistry of oils and condensates from the lower Eagle Ford formation, south Texas. Part 1: Crude assay measurements and SimDist modeling

Fifty-five oils and condensates produced from unconventional reservoirs in lower Eagle Ford Shale were characterized. Most of the samples are from the play area east of the Maverick Basin and west of the San Marcos Arch, while five samples are from wells east of the Arch. Crude assay measurements (API gravity, wt% sulfur, wt% nitrogen, viscosity at 25 and 40 °C, pour point, simulated distillation [SimDist] and C15+ chemical group-type fractionation) were conducted on dead oil samples using standard methods. All bulk properties were found to correlate well with each other. Relationships between crude assay measurement and production depth suggest that thermal maturation accounts for most of the variance in composition; however, different depth trends are observed in oils from the Karnes Trough area compared to locations west of that region.Refinery valuation and process models rely heavily on the fractional composition of crude feedstock defined by boiling point distribution. We constructed a model using seven crude assay parameters (API gravity, % S, % N, viscosity at 40 °C, and % C15+ saturates, % C15+ aromatics and % C15+ resins) as inputs for predicting SimDist boiling point curves. Using optimized parameters derived from this model, we found that SimDist curves can be modeled with nearly the same degree of accuracy using only API gravity and %S because of their strong correlation with the other bulk properties. This offers the prospect for refiners to identify wells producing specific grades of crude across the entire lower Eagle Ford play. The ability to construct a SimDist predictive model based only on the most basic assay measurements suggest that the compositional variations are due mostly to thermal maturity and the heterogeneity in source facies is insignificant in the lower Eagle Ford west of the San Marcos Arch. The SimDist predictive model is specific to the Eagle Ford shale oils and condensates, but the methodology could be used to construct formation specific models in other unconventional plays.

Towards solvothermal upcycling of mixed plastic wastes: Depolymerization pathways of waste plastics in sub- and supercritical toluene

Solvothermal liquefaction (STL) is a thermochemical conversion process, where a waste feedstock is treated with sub-and supercritical solvents. The key objective of the study was to investigate how a one-step STL using toluene as a solvent can degrade hard-to-recycle waste plastics (#5–#7). Three different plastic wastes namely, polypropylene (#5), polystyrene (#6), and polyurethane (#7), and their equal mixture (by weight, also referred here as mixed plastic wastes) were solvothermally liquefied by toluene in a 7 mL pressure bomb at 300, 350, and 400 °C for 3, 6, and 9 h in order to determine the effect of temperature and time, respectively. The liquid products were separated from the solid residue and further analyzed in terms of the STL conversion, change in elemental compositions via ultimate analysis, boiling point distribution via thermogravimetric analyzer (TGA), alteration of chemical bonds via proton nuclear magnetic resonance spectroscopy (1H NMR), and degradation products via gas chromatography mass spectroscopy (GCMS). The results showed that the STL conversion increase with the increase of reaction temperature and time. From the elemental analysis, it can be predicted that the higher heating values of the crude products are between 30 and 45 MJ/kg. Boiling point distribution showed that the production of lower hydrocarbon (C8–C20) increased significantly from about 10% at 300 °C to 80% at 400 °C. Additionally, product distribution showed that the aromaticity increased with the increase of residence time where the main products are benzene and styrene like products. Overall, it was observed that mixed plastic wastes have a synergistic effect on the degradation products.

Petroleum Hydrocarbon Quarterly Boiling Range Distribution of Iraqi Crude Oil by Simulated Distillation Method

This study includes analysis of different crude oil stock for various field Iraqi oil by gas chromatography instrument, using simulated distillation technique for determining the initial and final boiling point distribution and specified compound distillation information (normal paraffins) (Recovery W/W) for (nC5 – nC44), ASTM-D5307 becomes the analytical method. This method need tow samples; the first one spiked with internal standard and the second without internal standard. This analysis for quantitative and qualitative oil characterization which is often useful for evaluating the range of hydrocarbons in crude oil using Simulated Distillation. The study was performed using:&#x0D; &#x0D; Quarterly analysis of SIMDIS GC Distillation for three field (East Baghdad, Badra, Amara)&#x0D; Comparison of analyzes of SIMDIS GC Distillation with Different API (light, intermediate, heavy) with Initial boiling point (IBP).&#x0D; Finding experimental relationship between API and Initial boiling point (IBP):&#x0D; &#x0D; &#x0D; The result of this study shows that the boiling point increase as the number of carbon is increase, the values of n-Pentane (nC5) to n- Tetratetracontane (nC44) (w/w) changes from winter and summer (difference in temperatures), Positive correlation between C6 and C5 with API, where their percentages increase with increasing API for crude oil and C6 and C5 are lower in summer than in winter due to the evaporation of light components of the samples in summer. Initial boiling point increase as the API is decrease that mean in crude oil have heavy component increases and light component decrease (inverse relationship).

Production of upgraded biocrude from hydrothermal liquefaction using clays as in situ catalysts

Hydrothermal liquefaction (HTL) is a thermochemical process that converts biomass into biocrude. HTL suffers from low yields of water-insoluble biocrude with high oxygen contents and low heating values. Inexpensive clay minerals including montmorillonite, dolomite, kaolinite and sand were used to upgrade HTL biocrude as in situ acid-base catalysts. Batch tests were performed using starch with 5 wt% clay minerals at 300 °C for 1 h. Bio-oil was fractionated into water-soluble and water-insoluble parts to explore potential catalytic mechanisms by analyzing the fractional distribution, elemental composition and chemical composition. Higher carbon recoveries in the bio-oil fraction (approaching 60%) occurred with clay-catalyzed HTL. Energy recovery of both bio-oil fractions increased by approximately 22% for all clays. A base-catalyzed pathway inhibits char formation from catalytic HTL, with dolomite approaching a char yield as low as 3%. Chromatographic analysis of heavy and light oils from both fractions showed that dolomite and montmorillonite play a catalytic effect via base and acid pathways on upgrading biocrude. Clay-catalyzed HTL modified the boiling point distributions by producing more 100–300 °C middle temperature distillates. Overall, catalytic HTL with clay minerals enhanced the heating value and energy recovery of bio-oils.