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In the alkaline system, the iron complex was used to absorb hydrogen sulfide to obtain sulfur, and the iron complex absorbent was oxidized and regenerated at the anode by electrolysis method for recycling, and hydrogen was obtained at the cathode. This process can recover both hydrogen and sulfur from hydrogen sulfide and avoid the harsh conditions of strong acidity. In this paper, SPE electrode is used in the oxidation and regeneration process of iron complex. The results show that the oxidation current density of iron complex at SPE electrodes are one order of magnitude higher than that of traditional electrodes, and the current efficiency is slightly lower than that of traditional electrode. The current efficiency of carbon cloth SPE electrode reaches 90% from 0.25 to 0.5V, the performance of complexed iron oxidation is better than that of the stainless-steel mesh SPE electrode, and the side reaction is mainly EDTA oxidation reaction.

High-resolution mass spectrometry enables molecular characterization of heavy petroleum fractions for petroleomics research. However, results from mass spectrometry are usually not quantitative. Th...

A high-sulfur (4.69 wt%) crude oil was discovered in the China Bohai Bay Basin which is known to contain low sulfur crude oil. The composition of this high sulfur crude oil and its geological origin are unknown. In this study, thiophenic and sulfidic sulfur compounds were isolated from the crude oil by methylation/demethylation and characterized using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and gas chromatography-mass spectrometry (GC–MS). Relatively high abundance of sulfur compounds with 30 carbon atoms and 5–7 double bond equivalence (DBE), which were assigned to sulfurated steranes with thiophene or tetrahydrothiophene moieties. Some of these compounds have not been reported in fossil fuels. In addition to commonly found sulfur compounds in petroleum feedstock, such as benzothiophenes and dibenzothiophenes, other structural sulfur compound types were detected: long-chain 2,5-di-n-alkylthiolanes, 2,5-di-n-alkylthianes, bicyclic terpenoid sulfides, isoprenoid thiophenes, and isoprenoid benzothiophenes. The presence of abundant biomarker sulfur compounds suggests that the sulfuration of the high sulfur crude oil was occurred in the early diagenesis stage instead of a thermochemical sulphate reduction (TSR) process.

A Canadian in situ oilsands bitumen-derived vacuum residue (VR) was subjected to supercritical fluid extraction and fractionation (SFEF) into 13 extractable fractions and an unextractable end-cut and characterized by positive- and negative-ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The results of negative-ion ESI FT-ICR MS showed that the N1 class species was the most abundant and the multifunctional group compounds, such as N1O1, N1O2, N1S1, N1S2, and N2 class species became abundant as the SFEF fraction became heavier. In positive-ion ESI mode, the relative abundance of N1 class species decreased gradually in the heavy SFEF fractions while that of multifunctional group compounds increased. The relative abundance of N4V1O1 increased dramatically in heavy fractions and the end-cut. The distributions of polar heteroatom species of VR derived from oilsands bitumen were similar with those of VR derived from the Venezuela Orinoco extra heavy oil.

Ruthenium-ion-catalyzed oxidation (RICO) is an approach for investigating the structure of heavy oils by selectively removing aromatic carbon from petroleum fractions, while leaving the structural ...

Recovery hydrogen from hydrogen sulfide is an effective way of utilizing exhaust gas. In this paper, removal of hydrogen sulfide by indirect electrochemical process was studied using acidic aqueous solution of Fe3+/Fe2+ as the electrochemical intermediate. Solid polymer electrolyte was applied to hydrogen production by indirect electrolysis of H2S, in which the anode was graphite cloth, the cathode was the platinized graphite cloth, and the membrane was proton exchange membrane. The results of electrolysis experiments showed the relationship of current density as a function of electrolytic voltage at constant flow rate of electrolyte, temperature, and electrolyte composition. The effect of the cathode liquid velocity on current density was small. When the flow rate of anode electrolyte was greater than 200 L/hr., the current density tended to be stable. When [Fe3+]>0.20 mol/L, the concentrations of Fe2+ and Fe3+ ions in the anode solution had no significant impact on the current density. The current density gradually increased with temperature. In the electrolytic process of hydrogen production, the Fe2+ ions diffused from the anode to the cathode. The amount of diffusing Fe2+ ions gradually increased with time. The effect of Fe2+ ions diffusion from anode to cathode on hydrogen production was discussed.

Forecasting of the gasoline demand is a key issue for refineries in China. Some international energy organizations (IEOs) and international oil companies have estimated the gasoline demand in China for the next 20 years. These organizations and companies used the assumptions that the technology of clean-energy vehicles do not gain significant progresses, and they do not consider the trends of policy changes of different provinces in China. So the forecast of IEOs (international energy organizations) may not reflect the real trend of gasoline demand in China. In this paper, we considered more stringent regional environmental regulations and the possibility of technological progress in clean-energy vehicles, using the bottom to up method to estimate the gasoline demand of all 30 provinces in China, adding them up, to gain the forecast of total gasoline demand in China for the next twenty years. The result shows that gasoline demand will increase slower and decrease faster than the estimation of some mean IEOs (international energy organizations).

Highly active Zn–Al composite oxides were synthesized via a hydrothermal process followed by thermal treatment and were used as supports to prepare Ni-based hydrogenation catalysts for catalytic deoxygenation of oleic acid, stearic acid, and 1-octadecanol. The results showed that increasing the temperature of hydrothermal synthesis changed the morphology of the Zn–Al composite oxides from sheet-like structures to spheroidal structures. High hydrothermal synthesis temperatures enhanced the interaction between Zn and Al atoms, resulting in more ZnAl2O4 spinel phase. This phase not only improved the chemical stability of the support but also supplied strong basic sites which efficiently inhibited the formation of by-products and increased the yield of heptadecane in the catalytic deoxygenation of oleic acid. Stearic acid and 1-octadecanol could be readily transformed to alkanes in the presence of metallic Ni and ZnAl2O4 phase. Decarbonylation of the octadecanal intermediate and dehydrogenation of 1-octadecanol were key reaction pathways to produce heptadecane, in which decarbonylation was catalyzed by metallic Ni, while the dehydrogenation was attributed to synergistic catalysis between metallic Ni and the strong basic sites of the support. Individual metallic Ni only catalyzed the cleavage of C–H bonds but did not affect the O–H bond of 1-octadecanol.

Electrochemical reduction desulfurization is a low cost, environmental friendly technology which is capable of achieving a high degree of automation. Electrochemical coupling reactions of organic sulfur hydrogenation and water electrolysis on the C/Nafion electrodes were performed. The electrochemical desulfurization was determined by cyclic voltammetry (CV), bulk electrolysis with coulometry (BEC) and electrochemical impedance spectroscopy (EIS) techniques. Thiophene and benzyl mercaptan were used as model organic sulfur compounds. The results of cyclic voltammetry showed that the electrochemical hydrogenation reduction reaction of thiophene occurred at about −0.35 V. The process included proceeding chemical reaction and electrochemical reaction. The currents generated from thiophene hydrogenation reactions increased with the reaction temperature and the H + concentration of the electrolyte acidity of anode. Under the same reaction conditions, the desulfurization efficiency of benzyl mercaptan was significantly higher than that of thiophene. From the products of electrolytic reactions, the mechanisms of electrochemical hydrogenation of thiophene were proposed, consisting of two pathways: ring opening followed by hydrogenation and directly hydrogenation followed by ring opening. The proposed reaction mechanisms were consistent with the EIS results, indicating the predominant reactions were ring opening followed by hydrogenation. The reaction products and EIS results suggested that the reaction mechanisms of electrochemical hydrogenation of benzyl mercaptan were by breaking C S bond to form H 2 S and toluene.

Sulfur compounds in deep hydrodesulfurization (HDS)-derived diesels were effectively separated into thiophenic and sulfidic fractions using the methylation/demethylation method and characterized by gas chromatography–mass spectrometry (GC–MS) and GC–sulfur chemiluminescence detector (SCD). Sulfidic fractions account for over 15 wt % of total residual sulfur, in which a series of refractory cyclic sulfidic compounds, 1,1-dimethylhexahydrodibenzothiophenes (1,1-DMH6DBTs) and 1,9b-dimethylhexahydrodibenzothiophenes (1,9b-DMH6DBTs), were found in the diesels, and larger molecular weight homologues were identified. Some homologue series of C1–C4 alkyl-substituted thiaadamantanes were detected in the HDS diesel. These cyclic sulfidic components are refractory to deep HDS, which require more prudent catalysis and reaction systems to achieve ultralow-sulfur diesel (ULSD) production.

Delayed coking is an important petroleum resid conversion process. The processability of coking liquids is known to be dependent on the heteroatom compounds present in the coking liquids. Eight commercial delayed coking liquids were characterized by electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) and gas chromatographic techniques. High relatively abundant heteroatom compounds in the coking liquids were 1–4 aromatic-ring pyridinic nitrogen compounds, carbazoles, benzocarbazoles, phenols, mercaptans, benzothiophenes, dibenzothiophenes, and naphthobenzothiophenes. Coking liquids derived from various feeds had similar compound class types, molecular weight distribution ranges, and double bond equivalents (DBE). However, the concentration of individual compounds and the distribution of DBE versus carbon number of heteroatom compounds varied. A comparison of heteroatom compounds in coker feeds and products revealed the various reaction mechanism of heteroatom compounds occurred during the coking process. The results suggested that molecular-level process models can be developed for optimization of unit operation to obtain desirable products that meet the environmental specifications and quality requirements.

Catalytic deoxygenation of fatty acids to alkanes is an ideal route to produce biodiesel with high heating value. However, traditional transition-metal sulfide and noble metal catalysts are sulfide-contaminated, high cost, or easily poisoned. To overcome the above issues, this work developed a non-noble and sulfide-free reduced transition-metal composite NixNbyOz, which was effective to selectively hydrogenate stearic acid, a typical fatty acid model compound, to diesel-range alkanes. By using a simple slurry method, reduced NixNbyOz catalysts have been successfully prepared with an outstanding catalytic performance. The results showed that catalyst Ni0.5Nb0.5Oz effectively converted stearic acid to n-alkanes with nearly 100% conversion and >99% n-alkanes selectivity at mild conditions (513 K and 3.5 MPa of H2 pressure). Appropriate Nb species improved the dispersion of Ni species, which may supply more hydrogenation active sites. Two possible reaction routes of stearic acid were proposed, and the hydrogenolysis of stearyl stearate was confirmed as the rate-determining step based on the kinetics experiments. Because of moderate acidity of Nb species, the ratio of C17/C18 alkane was not markedly affected by reaction conditions when the conversion of stearic acid was higher than 99%. Moreover, catalyst Ni0.5Nb0.5Oz showed a high recycle ability and compatibility for other long-chain fatty acids, demonstrating that catalyst Ni0.5Nb0.5Oz is a promising green catalyst for producing biodiesel from fatty acids.

Delayed coking is a common resid conversion process used in refining operations. A large amount of oil-containing wastewater is produced during the hydraulic decoking process. The coking wastewater contains emulsions which are difficult to process in water treatment plants, especially when the coker is fed with feedstocks have high content of heteroatoms. This study examined the molecular composition of emulsified oil and dissolved organic matter (DOM) in coking wastewater. The emulsification agents in coking wastewater were identified. The emulsified oil and DOM were separated and enriched by liquid–liquid extraction, solid phase extraction, and adsorption chromatography, and then characterized by gas chromatography-mass spectrometry and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry analyses. The results showed that the emulsified oil and DOM in coking wastewater contained highly condensed molecules with a large number of nitrogen and oxygen heteroatomic compounds. The OxSy surfactants and their derivatives, polyoxyethylene ether, and the strong polar oxygen-, nitrogen-, and sulfur-containing compounds are likely the oil–water emulsification agents.

Co-Mo sulfide catalysts with different particle size and structures were prepared in ethanol-water mixed solvent followed by a low-temperature sulfurization process, and were tested in dibenzothiophene hydrodesulfurization. The effects of the ethanol/water ratio on the particle size of precursors, active phase composition, active site number, morphology, and hydrodesulfurization activity of the final catalysts were investigated. The atomic ratio of Co/Mo and active phase morphology of catalysts closely relate to the dielectric constant of ethanol-water mixed solvent. Appropriate dielectric constant favors the formation of (Co)MoS2 slabs with shorter length (∼ 5.0 nm) and higher stacking number (∼ 4.3 layers), resulting in more coordinatively unsaturated sites, especially in the corner sites. The catalytic activity not only depends on the active sites of CoMoS phase, but also on that of Co9S8 and MoS2 phases because of synergistic effect. For MoS2 and CoMoS phases, the corner sites show higher direct desulfurization activity than the edge sites.

Dissolved organic matter (DOM) in oil refinery process water was fractionated by XAD-8 resin techniques into four subfractions: hydrophobic acid (HOA), hydrophobic base (HOB), hydrophobic neutral (HON), and hydrophilic substance (HIS) fractions. Negative and positive electrospray ion (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to characterize the composition of DOM and its subfractions. Compounds with multi-oxygen atoms were found to be predominant in DOM by either negative or positive ESI analysis, which are similar in composition to most other treated water samples. The DOM in the HOA fraction had a similar molecular composition to that of raw process water by negative ESI analysis. The DOM in the HOB fraction had a low molecular weight (MW) when analyzed by positive ESI, and basic nitrogen compounds, such as N1 class species, were found to be predominant. The DOM in the HON fraction was predominantly O2 class species. The DOM in the HIS fraction had a relative...

Detailed characterization of petroleum derived sulfur compounds has been challenging, due to the complex composition of the hydrocarbon matrix. A novel method was developed for selective separation of thiophenic and sulfidic compounds from petroleum. Sulfur compounds were methylated to sulfonium salts by AgBF4 and CH3I, then the polar salts were separated by precipitation from petroleum matrix. The thiophenic and sulfidic sulfonium salts were sequentially demethylated with 7-azaindole and 4-dimethylaminopyridine, obtaining original thiophenic and sulfidic compounds, respectively. The method was validated by model compounds, and applied to a diesel and a vacuum distillation petroleum fraction. Sulfur fractions were characterized by gas chromatography (GC) coupled with a sulfur chemiluminescence detector (SCD) and quadrupole mass spectrometry (MS), and high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The technique was effective to selectively obtain high-purity thiophenic and sulfidic compounds and showed rare discrimination among sulfur compounds with ranging molecular weights and degrees of unsaturation. The method would facilitate multifaceted detailed characterization of sulfur compounds in an organic complex matrix.

Venezuela Orinoco extra-heavy-crude-oil-derived vacuum resid (VR) was subjected to supercritical fluid extraction and fractionation (SFEF) to prepare multiple narrow fractions. The SFEF fractions were analyzed by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with various ionization techniques, including positive-ion electrospray ionization (ESI), negative-ion ESI, positive-ion atmospheric pressure photoionization (APPI), and sulfur methylation followed by positive-ion ESI. The results showed that the SFEF separates the VR species by their molecular weights and degrees of molecular condensation. The mass ranges of compounds determined by various ionization techniques were comparable. The FT-ICR MS data were in agreement with the elemental analysis and molecular weight determined by gel permeation chromatography (GPC) and vapor pressure osmometry (VPO) for the extractable fractions. The molecular compositions of SFEF fractions determined by FT-ICR MS provide important clues for the...

Apodization is a generally applied signal processing method in FT-ICR MS (Fourier transform ion cyclotron resonance mass spectrometry) analysis for complex petroleum samples that is used to lower the spectral leakage and smoothen the spectrum line shape. Present study evaluates the effect of apodization on the FT-ICR MS results through a systematic examination on both simulated and actual heavy petroleum signals. The result shows that the resolving power, instead of the dynamic range, is the key factor for heavy petroleum FT-ICR MS analysis due to the severe peak overlapping. Window functions with high dynamic range will reduce the resolving power so that many of the species cannot be detected. The improvement on accuracy of apodization with peak intensity is negligible and all the window functions have similar intensity error. Low dynamic range window functions perform better for FT-ICR MS analysis since they have less resolving power reduction and the spectral leakage is eliminated to ensure correct peak selection. Sine-bell and low beta value Kaiser window functions are recommended for complex mixtures.

The hindered stepwise aggregation (HSA) model was used to elucidate the molecular aggregation in heavy petroleum fractions which were derived from supercritical fluid extraction fractionation (SFEF) of Venezuela Orinoco vacuum residue (VR). The SFEF fractions consisted of multiple extractable narrow fractions and a nonextractable end-cut. The SFEF fractions were diluted with toluene, and their number-average molecular weights (MWs) were determined using vapor pressure osmometry (VPO). The initial molecular association constants (K1) and aggregation hindrance factors (H) of the HSA model for each SFEF fraction were calculated from the VPO MWs at various SFEF solution concentrations. The results showed that the HSA model fit well with VPO MW data and the parameters of the HSA model are physically significant. The values of MW and K1 increased as the SFEF fraction became heavier. The SFEF end-cut had the highest K1 and lowest H value, in which the aggregates were 2 to 8 monomers. Except for the initial fract...

Au/Nafion/Pt electrodes were used in the coupled reaction system of benzene hydrogenation and water electrolysis for hydrogen production and storage. Au/Nafion/Pt electrodes with the short electrode spacing reduce hydrogen evolution and increase current density and current efficiency. The morphology of metal layer surface of electrodes and electrochemistry hydrogenation reactions were studied. The results showed that the morphology and conductivity of metal layer surface of electrodes were related to the reduction reaction rate of metal complex in the electrode preparation process. The Au complex reduction reaction rate and Au deposition rate were lower than Pt complex reduction reaction rate, yielding a dense smooth Au surface which had low resistance and was not conducive to the diffusion of H + . Benzene hydrogenation reaction rate increased and current efficiency decreased with increased electrode potential. The effect of electrode potential on current efficiency was similar for all electrodes tested. Au/Nafion/Pt electrodes had the highest current efficiency and current density among the electrodes tested; the current density of benzene hydrogenation was higher than 100 mA/cm 2 and 90% current efficiency.

Petroleum is an ultra-complex hydrocarbon system. Characterization of petroleum has been challenging for the analytical chemistry community. The recent development of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) enables the characterization of petroleum molecular composition. This new technique provides new insights on petroleum chemistry which can result in technological breakthroughs in petroleum and petrochemical industries. In this paper, the mass resolving power and ionization techniques required in mass spectrometry for petroleum analysis are summarized, the advances in FT-ICR MS for petroleum analysis are discussed, and the technique challenges and the further research issues are discussed. Whats more, the prospective of using FT-ICR MS technique for petroleum characterization and its application to petroleum research are also included.

Heavy petroleum fractions, which have distinct chemical and physical properties, are becoming important refinery feedstocks. In comparison to aromatic and heteroatom-containing compounds, the saturate compounds in heavy petroleum fractions have rarely been analyzed using recent advanced mass spectrometry methods. In this work, the compositions of saturate fractions derived from six vacuum residua (VR) of different geological origins were determined and compared. Saturate fractions were subjected to ruthenium-ion-catalyzed oxidation (RICO) derivatization and characterized with negative-ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The results showed that the VR-derived saturates consisted of n-paraffins, isoparaffins, and naphthenes with 1–10 rings. The maximum double bond equivalent (DBE) values of species in various VR-derived saturates were similar. The maximum carbon number of VR-derived saturates was up to 100. The maximum carbon numbers of ...

Life cycle cost (LCC) analysis was performed for a 1.6 million tons per year (30,000 BPD) delayed coking unit. The results show that the LCC of coke production is higher than the price of coke and profits are obtained at the expense of environmental costs. The feedstock cost accounts for a majority of LCC. The variability impacts of processing expenses and carbon dioxide (CO2) price on LCC are relative similar. This suggests that if a higher CO2 price is imposed on coke production, it is unlikely that the producer will make any effort to reduce the CO2 emissions either by improving the efficiency of coking process or implement CO2 remediation initiatives. The CO2 price increase will be considered as a processing cost increase. The green factor (GF) is predominantly dependent on coke price; an increased coke price improves the GF significantly. Increased CO2 price has a negative impact on GF, but the relative incremental impact of CO2 price on GF is less at high CO2 prices. Hence, there is little can be done to improve the GF of coke production, since the coke price is beyond the control of coke producer.

Negative-ion electrospray ionization (ESI) enabled the direct mass spectrographic analysis of phenols, naphthenic acids, and neutral nitrogen compounds in petroleum fractions without prefractionation; however, ESI results provide few quantitative and structural information about the analytes: the composition of acidic compounds in heavy oil, such as distillate resid, is still unclear. In this study, extrography was used to fractionate oilsands bitumen-derived vacuum-topped bitumen (VTB) and its maltene and asphaltene fractions into multiple subfractions. The molecular compositions of acidic functional compounds in the VTB and its subfractions were analyzed by negative-ion ESI Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Extrographic separation was a necessary step to isolate acidic compounds of various acidities and/or polarities in vacuum resid fractions to achieve a systematic analysis. The results showed that the O2 class species in VTB were highly condensed phenols and carb...

This paper examined the bond dissociation behavior and aromatic ring architecture of basic nitrogen compounds in Sudan heavy petroleum fraction. Both broadband and quadrupole isolation modes positive-ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) coupled with collision induced dissociation (CID) techniques were used to characterize a low sulfur crude oil derived vacuum residuum (VR). The appropriate CID operating condition was selected by comparing the molecular weight distributions of the basic nitrogen compounds under various CID operating conditions. Both odd- and even-electron fragment ions were observed from the mass spectrum, indicating that the heterolytic and homolytic bond cleavages occurred simultaneously during the CID process. The odd-electron fragment ions were predominant in each class species, indicating preferential heterolytic bond cleavages. At the optimal CID condition, the alkyl groups decomposed deeply and just left the aromatic cores of the nitrogen compounds. No significant variation in double bond equivalent (DBE) value was observed between the fragment and parent ions, revealing that the domination of single core structure.

Asphaltenes-free vacuum resid derived deasphalted oils (DAOs) from Chinese Liaohe (LDAO) and Venezuela Orinoco (VDAO) were subjected to catalytic hydrotreating. Electrospray ionization (ESI) Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) analyses were performed on LDAO and VDAO before and after hydrotreating to determine the structural composition transformation of nitrogen-containing compounds as a result of hydrotreating. The results showed that the basic nitrogen contents of the two DAO before and after hydrotreating were relatively constant. However, the neutral nitrogen contents of hydrotreated LDAO and VDAO were dramatically reduced. The LDAO had a higher neutral nitrogen conversion than VDAO, even though LDAO had a higher neutral nitrogen content than VDAO prior to hydrotreating. The significant difference in nitrogen removal for the DAOs was due to the structural variation of the neutral nitrogen compounds. By plotting the double bond equivalent (DBE) value as a function o...

Venezuela Orinoco heavy crude oil was fractionated into diesel, vacuum gas oil (VGO), vacuum residue (VR), and asphaltene fractions, which were subjected to molecular weight (MW) measurement by vapor pressure osmometry (VPO). The VPO is known to overestimate the average molecular weight (MW) of heavy hydrocarbons, because of molecular aggregation. This paper proposes a hindered stepwise aggregation (HSA) model to simulate the molecular aggregation and used the model to estimate the true MW of heavy petroleum fractions. A data regression procedure was developed to determine the model parameters, aggregation equilibrium constant, and aggregate distribution, using a fast simulated annealing (FSA) algorithm based on the VPO data. This data analysis method is self-tuned to fit the VPO data to the HSA models of various petroleum fractions using the optimized solution of the FSA algorithm. The results showed that the VPO data of heavy petroleum fractions at various solution concentrations were in good agreement ...

Although the progress of high resolution mass spectrometry in the past decade has enabled the molecular characterization of dissolved organic matter (DOM) in water as a whole, fractionation of DOM is necessary for a comprehensive characterization due to its super-complex nature. Here we proposed a method for the fractionation of DOM in a wastewater based on solubility and acidic-basic properties. Solid phase extraction (SPE) cartridges with reversed phase retention and ion-exchange adsorption capacities, namely MAX and MCX, were used in succession to fractionate a petroleum refinery wastewater into four fractions: hydrophobic acid (HOA), hydrophobic neutral (HON), hydrophobic base (HOB), and hydrophilic substance (HIS) fractions. According to the total organic carbon (TOC) analysis, 72.6% (in term of TOC) of DOM was extracted in hydrophobic fractions, in which HON was the most abundant. Hydrophobic extracts were characterized by negative and positive ion electrospray (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), respectively. Compounds with multiple oxygen atoms were predominant in the HOA, which were responded strongly in the negative ESI MS. Nitrogen containing compounds were the major detected species by positive ion ESI in all hydrophobic fractions. The molecular composition of the DOM were discussed based on the FT-ICR MS results. The fractionation provided salt free samples which enables the direct analysis of the fractions by ESI and a deep insight into the molecular composition of DOM in the wastewater. The method is potential for routine evaluation of DOM in industry wastewaters, as well as environmental water samples.

Coal tar has been considered as a potential energy alternative because of dwindling supplies of petroleum. To determine if the coal tar could be refined and upgraded to produce clean transportation fuels, detailed investigation of its composition is necessary, particularly for identifying the acidic components that account for about one-quarter of the weight of the coal tar. A middle-temperature coal tar (MTCT) and its fractions were characterized by gas chromatography–mass spectrometry (GC–MS) and negative-ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with different ion transmission modes for high- and low-mass ions. Analytical results of narrow distillation fractions from FT-ICR MS agreed reasonably well with those from GC–MS, although each technique has its own advantages and disadvantages. In this work, FT-ICR MS was demonstrated to be capable of characterizing small molecules of

A Venezuela Orinoco petroleum vacuum residue (VR) was subjected to supercritical fluid extraction fractionation (SFEF) and separated into 13 extractable fractions and an unextractable end-cut. Detailed molecular composition of polar heteroatom species in the SFEF subfractions were determined by electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The SFEF subfractions were also subjected to high-temperature gas chromatography (GC) for their simulated distillation analysis, gel permeation chromatography (GPC) for their molecular distributions, and open column liquid chromatography for their saturates, aromatics, resins, and asphaltenes (SARA) compositions. In ESI FT-ICR analysis, the mass spectra showed that the mass range and maximum peak of the SFEF subfraction increased as the SFEF subfraction became heavier. Multifunctional group compounds, such as N1S1, N1S2, N1O1, and N2, show high relative abundance in heavier subfractions. The double bond equivalenc...

The use of hydrogen in benzene–water system which combines water electrolysis and hydrogenation in a polymer electrolyte cell was carried out as a means for seasonal storage of electricity. Gas diffusion electrodes were effective in improving coupled reactions of electrochemical benzene hydrogenation and water electrolysis. The reaction kinetics for the electrochemical hydrogenation process using gas diffusion electrodes was investigated by evaluating current efficiency and reaction rate. The results showed that the rate of hydrogen evolution was higher than the rate of benzene hydrogenation and the apparent activation energy of hydrogen evolution was lower than that of benzene hydrogenation. As the electrode potential increased, the hydrogen evolution rate increased. The benzene hydrogenation reaction rate reached a maximum at −0.8 V electrode potential, then decreased slightly. The current efficiency, however, reached its maximum at −0.7 V. Modifying electrodes by adding 0.2 wt% polyethylene glycol (PEG6000) reduced the mass transfer resistance of organic phase (cyclohexane/benzene) and improved the hydrogenation reaction rate.

A middle-temperature coal tar (MTCT) was distilled into multiple narrow boiling point fractions. The MTCT and its distillate fractions were subjected to bulk property analysis and molecular composi...

A red pine fast pyrolysis bio-oil was subjected to sequential solvent fractionation into n-hexane soluble (HS), ether soluble (ES), ether insoluble (EIS), dichloromethane soluble (DS), and methanol soluble (MeS) fractions. The volatile components of bio-oil were analyzed by gas chromatography–mass spectrometry (GC–MS), indicating the presence of acids, aldehydes, ketones, alcohols, phenols, and anhydromonosaccharides, which consisted of methoxy, hydroxy, and carbonyl functional groups. These results imply that the bio-oil was similar to the most reported fast pyrolysis bio-oil samples in molecular composition. The bio-oil and its five subfractions were analyzed by negative-ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The predominant compounds in bio-oil were O2–O17 class species with 1–22 double-bond equivalent (DBE) values and 4–39 carbon numbers. The most abundant class species in biocrude oil, HS, ES, EIS, DS, and MeS subfractions were O7, O...

A commercial lignite gasification-derived middle-temperature coal tar (MTCT) was subjected to acid–base extraction to obtain acidic, basic, and neutral fractions. The neutral fraction was characterized by mass spectrometry (MS) for hydrocarbon-group-type analysis and further fractionated by extrography into six subfractions, which were characterized by gas chromatography–mass spectrometry (GC–MS). Saturate, aromatic, and resin fractions of the neutral fraction accounted for 16.4, 47.6, and 36.0 wt %, respectively. The GC–MS analysis showed that the first neutral subfraction (15.7 wt %) contained alkanes, alkenes, and cycloalkanes; the second subfraction (52.0 wt %) contained 1–6-ring aromatics; the third subfraction (4.6 wt %) contained neutral nitrogen compounds, such as indoles, carbazoles, and benzocarbazoles; the fourth subfraction (8.2 wt %) contained neutral polar compounds, such as C8–C28 alkyl nitriles and aliphatic and aromatic ketones, such as 4-, 5-, and 6-ketones and phenyl ketones, derived fr...

A novel technique was developed for characterization of saturated hydrocarbons. Linear alkanes were selectively oxidized to ketones by ruthenium ion catalyzed oxidation (RICO). Branched and cyclic alkanes were oxidized to alcohols and ketones. The ketones were then reduced to alcohols by lithium aluminum hydride (LiAlH(4)). The monohydric alcohols (O(1)) in the products obtained from the RICO and RICO-LiAlH(4) reduction reactions were characterized using negative-ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) for identification of iso-paraffins, acyclic paraffins and cyclic paraffins. Various model saturated compounds were used to determine the RICO reaction and ionization selectivity. The results from the FTICR MS analysis on the petroleum distillates derived saturated fraction were in agreement with those from field ionization gas chromatography time-of-flight mass spectrometry (FI GC-TOF MS) analysis. The technique was also used to characterize a petroleum vacuum residue (VR) derived saturates. The results showed that the saturated molecules in the VR contained up to 11 cyclic rings, and the maximum carbon number was up to 92.

Crude oil was subjected to extrography to obtain various acid compounds in multiple subfractions. Negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) and gas chromatography–mass spectrometry (GC–MS) were used to determine the acid compounds in the crude oil subfractions. Isoprenoidyl phenols with molecular formulas of C27H48O and C28H50O, which were previously deduced as sterol-type compounds, were highly enriched in a subfraction and confirmed by GC–MS. The mass peak with a molecular formula of C27H46O2 was identified as δ-tocopherol. The eluting sequence of the various compounds in crude oil was N1 carbazoles, followed by O1 class acid compounds, then O2 class acid compounds, and finally, N1O2, O3, and O4 class acid compounds. The results show that extrography is an adequate separation technique for partitioning crude oil acid compounds into various subfractions.

Detailed elemental composition and distribution of sulfides and thiophenic compounds in four subfractions of Kazakhstan vacuum gas oil (VGO) were determined by positive ion electrospray (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The sulfides in VGO subfractions were selectively oxidized into sulfoxides using tetrabutylammonium periodate (TBAPI). The sulfur compounds in the oxidized VGO subfractions were reacted by methylation to form methylsulfonium salts and were then characterized. Elemental composition and distribution of sulfides and thiophenic compounds in the VGO subfractions were characterized by their double bond equivalents (DBE) values and carbon numbers before and after the oxidation reactions. The results showed that the S1 class species with DBE values of 6 and greater are likely thiophenic compounds, while those with DBE values less than 6 are sulfides. As boiling point of VGO increased, the abundance of thiophenic compounds increased. DBE value and carbon...

Granulation is an effectual method to deal with huge amounts of deoiled asphalt (DOA) produced in the residue selective asphaltene extraction (SELEX-Asp) process, and the softening point of DOA plays an important role in asphalt particle production. In this paper, the variation of the softening point under different operation conditions and its influence on asphalt granulation behavior were studied with various solvents and feedstocks. Moreover, properties and structures of five C7 asphaltenes were analyzed with 13C nuclear magnetic resonance (NMR) and X-ray diffraction (XRD) measurements to examine the reasons of asphalt softening point differences for various residues under the same operation conditions. Ordered degree index (OI) and softening point index (SI) were proposed to investigate the influence of asphalt ordered aromatic sheets on the softening point. High softening point asphalt could be obtained with lower temperatures and higher pressures of the extractor, a larger mass ratio of solvent to f...

Detailed characterization of oil sludge obtained from an electric dehydrator was performed using various analytical techniques and compared with that of its parent crude oil. The findings showed that the oil sludge was a stable emulsion consisting of oil, water, solids, and polyethers, which are chemical additives commonly used in the oilfield and refinery operations. Spectral peaks derived from positive-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) were assigned to sodium adducts [M + Na]+ for four types of polyethers that are nonionic surfactants. The Na1Ox class species found in the sludge at the bottom section of an electric dehydrator were likely due to their low solubility in oil as the number of oxygen atoms in these compounds increased. Polyethers were likely involved in the formation of oil sludge in the electric dehydrator. Sodium adducts, such as [M – 2H + Na]−, [M – 3H + 2Na]−, and [M – 4H + 3Na]−, of both C80 and C60+ ARN acids found i...

A coker heavy gas oil (CHGO) was separated into saturates, aromatics, resins, and asphaltenes (SARA) fractions. The resin fraction was separated into six subfractions by high-performance liquid chromatography (HPLC). The CHGO and its subfractions were characterized by electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The mass spectra showed that the mass range of basic and neutral nitrogen compounds was 200−450 and 160−400 Da, respectively. Five nitrogen class species, N1, N2, N1O1, N1O2, and N1S1, were assigned in the positive-ion spectrum. Six nitrogen class species, N1, N2, N1O1, N1O2, N2O1, and N1S1, were assigned in the negative-ion spectrum. Among the identified nitrogen compounds, the N1 class species was dominant. The N1 class species were enriched in the resin fraction. The N2 class species are likely amphoteric molecules and were enriched in the asphaltene fraction. The composition of nitrogen compounds in the resin subfractions varied signifi...

Neutral nitrogen compounds have been used as molecular markers for tracking secondary oil migration in geochemistry. However, the distribution of neutral nitrogen compounds in the separation process is not well-characterized because the conventional analytical technique, such as gas chromatography−mass spectrometry (GC−MS), is non-selective for neutral nitrogen and not capable of detecting non-volatile high-molecular-weight compounds. In this paper, a crude oil was subjected to the traditional two-step open-column liquid chromatography (LC) technique to prepare subfractions, which were characterized for their molecular composition of neutral nitrogen compounds by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). The results showed that the two-step LC technique produced a low yield of carbazole in the neutral nitrogen fraction. The neutral nitrogen fraction was enriched with low-molecular-weight neutral nitrogen compounds. Most N1 class speci...