Design of a robust catalyst with high activity but the low cost for the hydrodeoxygenation(HDO) of biooils is of great importance to bring the biorefinery concept into reality.In this study,density functional theory(D...Design of a robust catalyst with high activity but the low cost for the hydrodeoxygenation(HDO) of biooils is of great importance to bring the biorefinery concept into reality.In this study,density functional theory(DFT) calculation was adopted to analyze the optimal location of Ni on MoO_(3-x) containing oxygen vacancy,and the corresponding result demonstrated that metallic Ni cluster located at the neighborhood of oxygen vacancies would significantly evoke HDO activity.Enlightened by DFT results,NiMoO_(4) was first hydrothermally synthesized and then employed to fabricate Ni-MoO_(3-x) catalyst via a low-temperature reduction,where Ni escaped from NiMoO_(4) and was reduced to its metallic state.Such an evolution of Ni species also induced the formation of oxygen vacancies around metallic Ni cluster.In the HDO of p-cresol,Ni-MoO_(3-x) exhibited high activity with a complete conversion and a methylcyclohexane selectivity of 99.4% at 150℃.Moreover,the catalyst showed good versatility in catalyzing HDO of diverse lignin-derived oxygenates and lignin oil.2D HSQC NMR,gas chromatograph and elemental analysis of the lignin oil demonstrated the high deoxygenation efficiency and saturation of the benzene ring over Ni-MoO_(3-x).In the upgrading of crude lignin oil,the deoxygenation degree was up to 99%,and the overall carbon yield of the naphthenes was as high as 69.4%.Importantly,the structures and carbon numbers of the naphthene products are similar to jet fuel-range cycloalka nes,which are expected to have a high density that can be blended into jet fuel to raise the range(or payload) of airplanes.This work demonstrates the feasibility for improving the targeted catalytic reactivity by rational tailoring the catalyst structure under the guidance of theoretical analysis,and provides an energy-efficient route for the upgrading of lignin crude oil into valuable naphthenes.展开更多
Biomarker and stable carbon isotope analyses are presented for the Garau Formation of the Cretaceous Age,an important source rock in western Iran,to reveal its potential as an oilprone source rock.The C_(28)/C_(29)ste...Biomarker and stable carbon isotope analyses are presented for the Garau Formation of the Cretaceous Age,an important source rock in western Iran,to reveal its potential as an oilprone source rock.The C_(28)/C_(29)sterane ratio value range(0.72 to 0.83)of bitumen samples from the formation suggests that they were likely formed during phytoplankton blooms.Sterane,hopane,and isoprenoid/n-alkane ratios indicate that the formation's organic matter predominantly consists of algae,and bacteria,accompanied by some reworked material derived from higher plants.Due to the predominance of anoxic conditions and the actions of sulfate-reducing bacteria,the bitumen present is enriched with sulfur compounds.The percentages of saturates,aromatics,and nitrogen-sulfuroxygen(NSO)fractions in the bitumen samples classify them as naphthenic oils.Isotope analysis reveals that biodegradation and water-washing have reduced the concentrations of some volatile saturates and low molecular weight aromatics in the bitumen samples.These actions have resulted in distinctiveδ^(13)C values for the formation's kerogen and bitumen fractions.The formation's organic matter has been subjected to high-temperature thermal regimes and has entered the oil-generation window at the sampled localities,with vitrinite reflectance(%R_(C))varying between 0.7%and 0.75%.展开更多
Naphthenic acids,NAs,are a major contaminant of concern and a focus of much research around remediation of oil sand process affected waters,OSPW.Using activated carbon adsorbents are an attractive option given their l...Naphthenic acids,NAs,are a major contaminant of concern and a focus of much research around remediation of oil sand process affected waters,OSPW.Using activated carbon adsorbents are an attractive option given their low cost of fabrication and implementation.A deeper evaluation of the effect NA structural differences have on uptake affinity is warranted.Here we provide an in-depth exploration of NA adsorption including many more model NA species than have been assessed previously with evaluation of adsorption kinetics and isotherms at the relevant alkaline pH of OSPW using several different carbon adsorbents with pH buffering to simulate the behaviour of real OSPW.Uptake for the NA varied considerably regardless of the activated carbon used,ranging from 350 mg/g to near zero highlighting recalcitrant NAs.The equilibrium data was explored to identify structural features of these species and key physiochemical properties that influence adsorption.We found that certainNAwill be resistant to adsorptionwhen hydrophobic adsorbents are used.Adsorption isotherm modelling helped explore interactions occurring at the interface between NA and adsorbent surfaces.We identified the importance of NA hydrophobicity for activated carbon uptake.Evidence is also presented that indicates favorable hydrogen bonding between certain NA and surface site hydroxyl groups,demonstrating the importance of adsorbent surface functionality for NA uptake.This research highlights the challenges associated with removing NAs from OSPW through adsorption and also identifies howadsorbent surface chemistry modification can be used to increase the removal efficiency of recalcitrant NA species.展开更多
Naphthenic acids (NAs) are complex mixtures of carboxylic acids that are responsible for the corrosivity of the crude oil with high total acid number(TAN).NAs are difficult to analyze due to their complexity and the l...Naphthenic acids (NAs) are complex mixtures of carboxylic acids that are responsible for the corrosivity of the crude oil with high total acid number(TAN).NAs are difficult to analyze due to their complexity and the lack of commercially available NA standards.This paper describes the use of negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) for the analysis of NAs in Liaohe heavy crude oil.FT-ICR MS resolves thousands of species in a single mass spectrum allowing for unambiguous determination of elemental composition.O2 classes (with two O heteroatoms in one molecule) and their carbon number (revealing the extent of alkylation) distribution were detailedly investigated.We find that 2-5 rings NAs is the dominate component of acidic compounds in Liaohe crude oil,espasically with a high abundance of steroid acids and hopanoic acids.Neg-ESI-FTMS is very well suited to the characterization of naphthenic acids within a crude oil sample.Determination of the nature of the naphthenic acids present provides vital information,such as the acids’ sizes and composition.展开更多
Highly acidic crude oil is thermally soaked to investigate how the temperature and time involved affect the removal of organic acid in feedstock. Experimental results indicate that thermal treatment is an effective a...Highly acidic crude oil is thermally soaked to investigate how the temperature and time involved affect the removal of organic acid in feedstock. Experimental results indicate that thermal treatment is an effective approach to decreasing acidity and the acid removal rate reaches 80%. Temperature is one of the main factors that determine the acid removal reaction. When the temperature ranges from 420oC to 440oC, the acid removal rate increases with the rise of the reaction temperature, but the increase slows down gradually. At the reaction temperature below 440oC, the long reaction time favors the acid removal. The cracking and polymerization of hydrocarbon molecules take place so that the properties of the crude oil change at the same time when the highly acidic crude is thermally treated.展开更多
Although naphthenes have long been identified as important feedstock components for the production of light olefins and aromatics in fluid catalytic cracking units,their cacking mechanism and microscopic reaction netw...Although naphthenes have long been identified as important feedstock components for the production of light olefins and aromatics in fluid catalytic cracking units,their cacking mechanism and microscopic reaction networks,such as activation modes,ring-opening paths,and the production of aromatics,remain debated.In this context,we reported experimental and computational work aimed at elucidating the reaction network of naphthenes in fluid catalytic cracking using cyclohexane as the model naphthene.First,the main reactions for the formation of highly selective and value-added products such as light olefins and aromatics were discussed.Then,the proportions of cyclohexane activation via(i)the non-classical carbonium mechanism and(ii)the classical carbenium mechanism were analyzed by data fitting methods,which revealed that around 32.6%of cyclohexane was initiated by path(i),and the remaining naphthene was activated by path(ii).Moreover,our DFT results showed that the ring opening of cyclohexane through pathway(i)was more difficult than that through path(ii),and ring opening followed by the ring contraction of cyclohexane carbenium ions was the most energetically favorable route among the different ring-opening ways.展开更多
To meet the requirements for high aromatic content and low polycyclic aromatic(PCA)concentration,eco-friendly aromatic-rich rubber extender oils are usually produced by two-stage solvent extraction processes with furf...To meet the requirements for high aromatic content and low polycyclic aromatic(PCA)concentration,eco-friendly aromatic-rich rubber extender oils are usually produced by two-stage solvent extraction processes with furfural.Among the different properties of rubber processing oils,density and refractive index are some of the most important properties related to their final quality.Two types of methods,including a pseudo-component approach by using mixing rules and several correlations,were used for calculation of density and refractive index at 20℃ of paraffinic furfural-extract oils and their secondary raffinates.Results indicated that similar accuracy was obtained for predicting the density and the refractive index of furfural+furfural-extract paraffinic oil systems.However,the quadratic correlation presents its advantage over the pseudo-component approach when the composition of oils is not available.Moreover,the quadratic correlation was also used for naphthenic lubricating oils during two-stage solvent extraction processes.The predictions showed much larger discrepancies with respect to experimental values than those of paraffinic lubricating oils,which indicated that the quadratic correlation was more suitable for paraffinic oils with a CN value of below 37%.展开更多
In this study,various nonionic surfactants(NS) with different ethylene oxide(EO) numbers and tail lengths and its binary blends with anionic surfactants(AS) were used as emulsifiers for naphthenic oil to form the micr...In this study,various nonionic surfactants(NS) with different ethylene oxide(EO) numbers and tail lengths and its binary blends with anionic surfactants(AS) were used as emulsifiers for naphthenic oil to form the microemulsion metalworking fluids(MWFs),and the effects of them on the stability of the emulsion system were investigated by formulation triangle method.The results indicated that binary complex surfactants of NS and AS as emulsifiers exhibited better emulsifying effect than that of single NS.NS with different EO numbers and tail lengths presented various emulsifying effects.NS(EO=10)exhibited the greatest number of stable formulations,especially the TX-10,but no linear relationship existed between the number of stable formulations and the tail length of NS.In addition,aromatic primary alcohol ethoxy late(APAE) series surfactants containing benzene groups similar to the cycloalkanes in the naphthenic oil so that presented the best emulsifying affect and the greatest number of stable formulations.The co-surfactant of sodium dodecyl benzene sulfonate(SDBS) binary blends with NS exerted the best synergistic effect,and the stable formulations numbers were ranged from 5 to 7,next sodium stearate(SS) comes last followed by sodium dodecyl sulfate(SDS-1) and sodium dodecyl sulfonate(SDS-2).展开更多
Lubricating oils are usually produced by solvent extraction to separate aromatics in order to achieve the desired specifications and better quality products.Among the different properties of lubricating oils,density a...Lubricating oils are usually produced by solvent extraction to separate aromatics in order to achieve the desired specifications and better quality products.Among the different properties of lubricating oils,density and refractive index are some of the most important properties which can both be used for petroleum fluid characterization.Predictions of density and refractive index for naphthenic oils during solvent extraction by DMSO obtained by the pseudo-component approach and the quadratic correlation were both examined.The pseudo-component approach is a method to predict density and refractive index from composition while the latter merely relates density to refractive index.Results indicated that the predictions yielded by the pseudo-component method were in good agreement with experimental data for naphthenic oils.And the use of a function of refractive index(FRI_(20))as a pseudo-component property remarkably improved n_(20)predictions for the naphthenic mixtures.However,the density and refractive index predictions obtained by the quadratic correlation exhibited significantly higher de-viations for naphthenic oils than those for paraffinic oils.Thus a new modified correlation of the same functional form was proposed for naphthenic oils.The modification significantly improved predictions for naphthenic oils,which presented similar accuracy as the pseudo-component approach.And the previous correlation was still used for paraffinic oils.Additionally,effect of temperature on density and refractive index of naphthenic oils was examined.Results showed that the modified quadratic correlation was accurate for describing the relationship between density and refractive index of naphthenic oils at 20-90℃.The temperature dependence of density and refractive index for the raffinates and the extracts could be accurately described by the thermal coefficients for saturates and aromatics,respectively.Regarding the refractive index variation of the extracts with temperature,the empirical equation was proved to be a better option compared with the method using the thermal coefficient for aromatics.展开更多
Three high-acidity crudes, Dar, SZ36-1, and QHD326, were separated through distillation into several fractions, including diesel distillates, and VGOs. Samples were characterized by negative-ion ESI FT-ICR MS. The O2 ...Three high-acidity crudes, Dar, SZ36-1, and QHD326, were separated through distillation into several fractions, including diesel distillates, and VGOs. Samples were characterized by negative-ion ESI FT-ICR MS. The O2 class species （petroleum carboxylic acids）, which have a close relationship with corrosion of equipment caused by high-acidity crudes, were put in the focus of attention and were discussed in this paper. Monocyclic, bicyclic, and tricyclic naphthenic acids are the main types of petroleum carboxylic acids in naphthenic-base crudes （SZ36-1 and QHD326）. But the main types of petroleum carboxylic acids in paraffinic-base crude （Dar） are aliphatic acids and monocyclic naphthenic acids. The O2 class species in SZ36-1 and QHD326 are distributed in a wider range and have bigger DBE value （double-bond equivalence value） and carbon number than Dar. Bicyclic naphthenic acids have the highest proportion among petroleum carboxylie acids in diesel distillates, but monocyclic and tricyclic naphthenic acids also occupy a high proportion. Particularly, aliphatic acids in the diesel distillate of Dar still have high proportion among petroleum carboxylic acids. The distribution of petroleum carboxylic acids in VGO is basically identical. The bicyclic naphthenic acids assume the first place （about 25 m%）, while the monocyclic and tricyclic naphthenic acids take the next place. The comparison of petroleum carboxylic acids in diesel distillates and VGOs has revealed that the molecules of carboxylic acids in VGOs are not only bigger but also more complicated.展开更多
The removal of acid compounds （naphthenates） from acidic oil with ionic liquids was systematically investigated. [BMIM]Br-AlCl3 was used to investigate the effect on deacidification of oil. Experimental results show...The removal of acid compounds （naphthenates） from acidic oil with ionic liquids was systematically investigated. [BMIM]Br-AlCl3 was used to investigate the effect on deacidification of oil. Experimental results showed that at a temperature of 323K with a molar ratio of AlCl3 to [BM1M]Br-AlCl3 of 0.2, and a mass ratio of IL to white oil of 4%, the deacidification rate could reach 75.9%. And a reaction time of 4 h was sufficient to achieve the goal. The study on reproducibility of catalytic performance of [BMIM]Br-AlCl3 showed the possibility of using the ionic liquid in the continuous catalytic reaction.展开更多
This work was mainly concentrated on the removal of naphthenic acids(NAs) from dewaxed vacuum gas oil(VGO) by adsorption using a commercial grade activated clay(AC) adsorption during lube base oil refining. The NAs in...This work was mainly concentrated on the removal of naphthenic acids(NAs) from dewaxed vacuum gas oil(VGO) by adsorption using a commercial grade activated clay(AC) adsorption during lube base oil refining. The NAs in dewaxed VGO cut-4 were identified by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry(ESI FT-ICR MS). The AC sample from a refinery was characterized by XRD, BET, TG/DTA, and SEM. A series of experiments were carried out to investigate the performance of NAs adsorption by AC using a batch adsorption technique, in which some key experimental parameters such as temperature, contact time, initial concentration of NA in oil sample as well as the dosage of adsorbent were investigated. Equilibrium isotherms were analyzed using the Langmuir, Freundlich, Tempkin and Dubinin-Radushkevich(D-R) adsorption models. The pseudo-first order, the pseudo-second order, and intraparticle diffusion models were employed to describe the kinetics data. The results revealed that the D-R isotherm provided a better fit to the experimental data than other isotherms, and the adsorption kinetics followed the pseudo-first order kinetic equation. The thermodynamic data indicated that the adsorption process was feasible and spontaneous as an endothermic process. The results could provide a clear understanding of the NAs adsorption by AC during lube base oil processing at refineries.展开更多
Low-temperature viscosity of lube oils mixed with paraffinic base oil and naphthenic base oil at different mass ratios has been tested by experiments. The influence of paraffinic base oil on the performance of naphthe...Low-temperature viscosity of lube oils mixed with paraffinic base oil and naphthenic base oil at different mass ratios has been tested by experiments. The influence of paraffinic base oil on the performance of naphthenic base oil was investigated by studying the low-temperature viscosity of tested oils. The viscosity of lube oils increased with an increasing content of high-viscosity paraffinic base oil in the oil mixture. And the low-temperature viscosity was less influenced when the content of paraffinic base oil in the mixture was insignificant. In order to reduce the cost for formulating lubricating oil, a small fraction of paraffinic base oil can be added into naphthenic base oil as far as the property of lubricating oil can meet the specification. According to the study on low-temperature viscosity of the oil mixed with paraffinic base oil and naphthenic base oil, a basic rule was worked out for the preparation of qualified lubricating oils.展开更多
In present research, a novel extractant system (D2EHPA + naphthenic acid + pyridine- ester) was used to purify cobalt anolyte and a simulated industrial production were carried out. This novel extraction system can ex...In present research, a novel extractant system (D2EHPA + naphthenic acid + pyridine- ester) was used to purify cobalt anolyte and a simulated industrial production were carried out. This novel extraction system can extract Cu and/or Ni against Co from chloride medium solutions at pH range of 2.5-4.5. About 2g/l nickel and 0.2g/l copper were removed from the cobalt chloride anolyte containing about 100g/l cobalt and 200g/l chloride ions respectively, the raffinate contains nickel and copper less than 0.03g/l and 0.0003g/l respectively and can be used to electrolyze high-purity cobalt. About 5.5t cobalt anolyte was purified in the simulation industrial experiment and kilogram quantities of cobalt of 99.98% purity and about 95% recovery have been produced.展开更多
High resolution tandem mass spectrometry has been applied to obtain the structure information of petroleumsamples. Here, we report a mefflod for structural characterization of crude oil molecules by the collision-indu...High resolution tandem mass spectrometry has been applied to obtain the structure information of petroleumsamples. Here, we report a mefflod for structural characterization of crude oil molecules by the collision-induced dissocia-tion （CID） technology coupled wiffl the high-field Fourier transform ion cyclotron resonmlce mass spectrometry （FT-ICRMS）. The ion isolation window was narrowed down to 1 Da to distinguish file complex homologues contained in petroleum.Aromatic model compounds and crude oil samples were measured by CID FT-ICR MS at different collision energy levels.The fragmentation of model compounds wiffl alkyl side-chains was found to be related to the size of file aromatic rings. Thefragmentation of model compounds wiffl archipelago structures depended on file lengffl of file bridge alkylene chain. Theprevalent reaction pafflway of model compounds with naphthenic rings was mainly determined by the position of naphfflen-ic rings in file molecules. On file basis of file fragmentation pathways, the structure differences of two crude oils were recog-nized as different content of naphthenic rings by CID technology with 1 Da isolation window. The NMR analysis was alsoapplied to confirm file CID results. This study exhibits the great potential of CID FT-ICR MS wiffl narrow isolation windowin file smlctural characterization of crude oil molecules.展开更多
N-alkyl imidazolium carbonate ionic liquids were employed to separate and recover naphthenic acid from model oils.The effects of the cationic and anionic structures of ionic liquids and operating conditions on the dea...N-alkyl imidazolium carbonate ionic liquids were employed to separate and recover naphthenic acid from model oils.The effects of the cationic and anionic structures of ionic liquids and operating conditions on the deacidification performance were investigated.The deacidification performance of traditional organic solvents was also investigated for comparison.The results indicated that the naphthenic acid could be completely removed from the model oil with a small mass ratio of ionic liquid to oil.The extracted naphthenic acid was regenerated with a recovery of up to 92%.In addition,imidazolium carbonate ionic liquids could be successfully regenerated and recycled.The mechanism of interaction between imidazole ionic liquids and the naphthenic acid molecules were explained by Gauss calculation.展开更多
Most heavy crude oils underwent biodegradation and generated a significant amount of naphthenic acids. Naphthenic acids are polar compounds with the carboxylic group and are considered as a major factor affecting the ...Most heavy crude oils underwent biodegradation and generated a significant amount of naphthenic acids. Naphthenic acids are polar compounds with the carboxylic group and are considered as a major factor affecting the oil viscosity. However, the relationship between the molecular composition of naphthenic acids and oil viscosity is not well understood. This study examined a “clean” heavy oil with low contents of heteroatoms but had a high content of naphthenic acids. Naphthenic acids were fractionated by distillation and caustic extraction. The molecular composition was characterized by high-resolution Orbitrap mass spectrometry. It was found that the 2- and 3-ring naphthenic monoacids with 15–35 carbon atoms are dominant components of the acid fractions;the caustic extraction is capable of isolating naphthenic acids with less than 35 carbons, which is equivalent to the upper limit of the distillable components, but not those in the residue fraction;the total acid number of the heavy distillates is higher than that of the residue fraction;the viscosity of the distillation fraction increases exponentially with an increased boiling point of the distillates. Blending experiments indicates that there is a strong correlation between the oil viscosity and acids content, although the acid content is only a few percent of the total oil.展开更多
The catalytic esterification reaction was used to decrease total acid number(TAN) of crude oil by converting naphthenic acids to naphthenic acid esters in the presence of Zn-Al hydrotalcite used as the catalyst and gl...The catalytic esterification reaction was used to decrease total acid number(TAN) of crude oil by converting naphthenic acids to naphthenic acid esters in the presence of Zn-Al hydrotalcite used as the catalyst and glycol used as the reactant. The crude oil and its corresponding esterified oil were characterized by the negative-ion electrospray ionization(ESI) Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS). Six acidic class species, O_2, O_1, N_1, N_2, N_1O_1 and N_1O_2 were assigned in the negative-ion spectrum both in the crude oil and its esterified oil. Among the identified acidic compounds, the O2 class was dominant. The relative abundance of O_2 class species was much higher than other acidic class species in crude oil, while it was significantly decreased after esterification. The most abundant O_2 class species had a carbon number of 30-34 and a double-bond equivalence(DBE) value of 5 before and after esterification. It could be concluded that the naphthenic acids in crude oil can be esterified to lower its TAN value, and each of them seems to exhibit identical esterification efficiency approximately due to the similar DBE versus the-carbon number distribution before and after esterification.展开更多
基金supported by the National Key R&D Program of China (2022YFB3805401, 2019YFC1905300)the National Natural Science Foundation of China (22178297)+1 种基金the Hunan Provincial Natural Science Foundation (2022JJ40425, 2022JJ40432)the Process Intensification and Green Chemical Engineering Innovation Team of Hunan Province。
文摘Design of a robust catalyst with high activity but the low cost for the hydrodeoxygenation(HDO) of biooils is of great importance to bring the biorefinery concept into reality.In this study,density functional theory(DFT) calculation was adopted to analyze the optimal location of Ni on MoO_(3-x) containing oxygen vacancy,and the corresponding result demonstrated that metallic Ni cluster located at the neighborhood of oxygen vacancies would significantly evoke HDO activity.Enlightened by DFT results,NiMoO_(4) was first hydrothermally synthesized and then employed to fabricate Ni-MoO_(3-x) catalyst via a low-temperature reduction,where Ni escaped from NiMoO_(4) and was reduced to its metallic state.Such an evolution of Ni species also induced the formation of oxygen vacancies around metallic Ni cluster.In the HDO of p-cresol,Ni-MoO_(3-x) exhibited high activity with a complete conversion and a methylcyclohexane selectivity of 99.4% at 150℃.Moreover,the catalyst showed good versatility in catalyzing HDO of diverse lignin-derived oxygenates and lignin oil.2D HSQC NMR,gas chromatograph and elemental analysis of the lignin oil demonstrated the high deoxygenation efficiency and saturation of the benzene ring over Ni-MoO_(3-x).In the upgrading of crude lignin oil,the deoxygenation degree was up to 99%,and the overall carbon yield of the naphthenes was as high as 69.4%.Importantly,the structures and carbon numbers of the naphthene products are similar to jet fuel-range cycloalka nes,which are expected to have a high density that can be blended into jet fuel to raise the range(or payload) of airplanes.This work demonstrates the feasibility for improving the targeted catalytic reactivity by rational tailoring the catalyst structure under the guidance of theoretical analysis,and provides an energy-efficient route for the upgrading of lignin crude oil into valuable naphthenes.
文摘Biomarker and stable carbon isotope analyses are presented for the Garau Formation of the Cretaceous Age,an important source rock in western Iran,to reveal its potential as an oilprone source rock.The C_(28)/C_(29)sterane ratio value range(0.72 to 0.83)of bitumen samples from the formation suggests that they were likely formed during phytoplankton blooms.Sterane,hopane,and isoprenoid/n-alkane ratios indicate that the formation's organic matter predominantly consists of algae,and bacteria,accompanied by some reworked material derived from higher plants.Due to the predominance of anoxic conditions and the actions of sulfate-reducing bacteria,the bitumen present is enriched with sulfur compounds.The percentages of saturates,aromatics,and nitrogen-sulfuroxygen(NSO)fractions in the bitumen samples classify them as naphthenic oils.Isotope analysis reveals that biodegradation and water-washing have reduced the concentrations of some volatile saturates and low molecular weight aromatics in the bitumen samples.These actions have resulted in distinctiveδ^(13)C values for the formation's kerogen and bitumen fractions.The formation's organic matter has been subjected to high-temperature thermal regimes and has entered the oil-generation window at the sampled localities,with vitrinite reflectance(%R_(C))varying between 0.7%and 0.75%.
文摘Naphthenic acids,NAs,are a major contaminant of concern and a focus of much research around remediation of oil sand process affected waters,OSPW.Using activated carbon adsorbents are an attractive option given their low cost of fabrication and implementation.A deeper evaluation of the effect NA structural differences have on uptake affinity is warranted.Here we provide an in-depth exploration of NA adsorption including many more model NA species than have been assessed previously with evaluation of adsorption kinetics and isotherms at the relevant alkaline pH of OSPW using several different carbon adsorbents with pH buffering to simulate the behaviour of real OSPW.Uptake for the NA varied considerably regardless of the activated carbon used,ranging from 350 mg/g to near zero highlighting recalcitrant NAs.The equilibrium data was explored to identify structural features of these species and key physiochemical properties that influence adsorption.We found that certainNAwill be resistant to adsorptionwhen hydrophobic adsorbents are used.Adsorption isotherm modelling helped explore interactions occurring at the interface between NA and adsorbent surfaces.We identified the importance of NA hydrophobicity for activated carbon uptake.Evidence is also presented that indicates favorable hydrogen bonding between certain NA and surface site hydroxyl groups,demonstrating the importance of adsorbent surface functionality for NA uptake.This research highlights the challenges associated with removing NAs from OSPW through adsorption and also identifies howadsorbent surface chemistry modification can be used to increase the removal efficiency of recalcitrant NA species.
文摘Naphthenic acids (NAs) are complex mixtures of carboxylic acids that are responsible for the corrosivity of the crude oil with high total acid number(TAN).NAs are difficult to analyze due to their complexity and the lack of commercially available NA standards.This paper describes the use of negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) for the analysis of NAs in Liaohe heavy crude oil.FT-ICR MS resolves thousands of species in a single mass spectrum allowing for unambiguous determination of elemental composition.O2 classes (with two O heteroatoms in one molecule) and their carbon number (revealing the extent of alkylation) distribution were detailedly investigated.We find that 2-5 rings NAs is the dominate component of acidic compounds in Liaohe crude oil,espasically with a high abundance of steroid acids and hopanoic acids.Neg-ESI-FTMS is very well suited to the characterization of naphthenic acids within a crude oil sample.Determination of the nature of the naphthenic acids present provides vital information,such as the acids’ sizes and composition.
文摘Highly acidic crude oil is thermally soaked to investigate how the temperature and time involved affect the removal of organic acid in feedstock. Experimental results indicate that thermal treatment is an effective approach to decreasing acidity and the acid removal rate reaches 80%. Temperature is one of the main factors that determine the acid removal reaction. When the temperature ranges from 420oC to 440oC, the acid removal rate increases with the rise of the reaction temperature, but the increase slows down gradually. At the reaction temperature below 440oC, the long reaction time favors the acid removal. The cracking and polymerization of hydrocarbon molecules take place so that the properties of the crude oil change at the same time when the highly acidic crude is thermally treated.
基金This work was performed with the financial support of Sinopec Research Institute of Petroleum Processing(RIPP,Proj.R17022).
文摘Although naphthenes have long been identified as important feedstock components for the production of light olefins and aromatics in fluid catalytic cracking units,their cacking mechanism and microscopic reaction networks,such as activation modes,ring-opening paths,and the production of aromatics,remain debated.In this context,we reported experimental and computational work aimed at elucidating the reaction network of naphthenes in fluid catalytic cracking using cyclohexane as the model naphthene.First,the main reactions for the formation of highly selective and value-added products such as light olefins and aromatics were discussed.Then,the proportions of cyclohexane activation via(i)the non-classical carbonium mechanism and(ii)the classical carbenium mechanism were analyzed by data fitting methods,which revealed that around 32.6%of cyclohexane was initiated by path(i),and the remaining naphthene was activated by path(ii).Moreover,our DFT results showed that the ring opening of cyclohexane through pathway(i)was more difficult than that through path(ii),and ring opening followed by the ring contraction of cyclohexane carbenium ions was the most energetically favorable route among the different ring-opening ways.
文摘To meet the requirements for high aromatic content and low polycyclic aromatic(PCA)concentration,eco-friendly aromatic-rich rubber extender oils are usually produced by two-stage solvent extraction processes with furfural.Among the different properties of rubber processing oils,density and refractive index are some of the most important properties related to their final quality.Two types of methods,including a pseudo-component approach by using mixing rules and several correlations,were used for calculation of density and refractive index at 20℃ of paraffinic furfural-extract oils and their secondary raffinates.Results indicated that similar accuracy was obtained for predicting the density and the refractive index of furfural+furfural-extract paraffinic oil systems.However,the quadratic correlation presents its advantage over the pseudo-component approach when the composition of oils is not available.Moreover,the quadratic correlation was also used for naphthenic lubricating oils during two-stage solvent extraction processes.The predictions showed much larger discrepancies with respect to experimental values than those of paraffinic lubricating oils,which indicated that the quadratic correlation was more suitable for paraffinic oils with a CN value of below 37%.
基金supported from the Shanghai Association for Science and Technology Achievements Transformation Alliance Program(No.LM201851)the National Natural Science Foundation of China(Nos.21878188,21606151 and 21707092)+2 种基金Shanghai Excellent Technology Leaders Program(No.17XD1424900)"Chenguang Program"from Shanghai Education Development FoundationShanghai Municipal Education Commission(No.18CGB12)。
文摘In this study,various nonionic surfactants(NS) with different ethylene oxide(EO) numbers and tail lengths and its binary blends with anionic surfactants(AS) were used as emulsifiers for naphthenic oil to form the microemulsion metalworking fluids(MWFs),and the effects of them on the stability of the emulsion system were investigated by formulation triangle method.The results indicated that binary complex surfactants of NS and AS as emulsifiers exhibited better emulsifying effect than that of single NS.NS with different EO numbers and tail lengths presented various emulsifying effects.NS(EO=10)exhibited the greatest number of stable formulations,especially the TX-10,but no linear relationship existed between the number of stable formulations and the tail length of NS.In addition,aromatic primary alcohol ethoxy late(APAE) series surfactants containing benzene groups similar to the cycloalkanes in the naphthenic oil so that presented the best emulsifying affect and the greatest number of stable formulations.The co-surfactant of sodium dodecyl benzene sulfonate(SDBS) binary blends with NS exerted the best synergistic effect,and the stable formulations numbers were ranged from 5 to 7,next sodium stearate(SS) comes last followed by sodium dodecyl sulfate(SDS-1) and sodium dodecyl sulfonate(SDS-2).
基金sponsored by the Natural Science Foundation of Xinjiang Uygur Autonomous Region(No.2022D01F37).
文摘Lubricating oils are usually produced by solvent extraction to separate aromatics in order to achieve the desired specifications and better quality products.Among the different properties of lubricating oils,density and refractive index are some of the most important properties which can both be used for petroleum fluid characterization.Predictions of density and refractive index for naphthenic oils during solvent extraction by DMSO obtained by the pseudo-component approach and the quadratic correlation were both examined.The pseudo-component approach is a method to predict density and refractive index from composition while the latter merely relates density to refractive index.Results indicated that the predictions yielded by the pseudo-component method were in good agreement with experimental data for naphthenic oils.And the use of a function of refractive index(FRI_(20))as a pseudo-component property remarkably improved n_(20)predictions for the naphthenic mixtures.However,the density and refractive index predictions obtained by the quadratic correlation exhibited significantly higher de-viations for naphthenic oils than those for paraffinic oils.Thus a new modified correlation of the same functional form was proposed for naphthenic oils.The modification significantly improved predictions for naphthenic oils,which presented similar accuracy as the pseudo-component approach.And the previous correlation was still used for paraffinic oils.Additionally,effect of temperature on density and refractive index of naphthenic oils was examined.Results showed that the modified quadratic correlation was accurate for describing the relationship between density and refractive index of naphthenic oils at 20-90℃.The temperature dependence of density and refractive index for the raffinates and the extracts could be accurately described by the thermal coefficients for saturates and aromatics,respectively.Regarding the refractive index variation of the extracts with temperature,the empirical equation was proved to be a better option compared with the method using the thermal coefficient for aromatics.
文摘Three high-acidity crudes, Dar, SZ36-1, and QHD326, were separated through distillation into several fractions, including diesel distillates, and VGOs. Samples were characterized by negative-ion ESI FT-ICR MS. The O2 class species （petroleum carboxylic acids）, which have a close relationship with corrosion of equipment caused by high-acidity crudes, were put in the focus of attention and were discussed in this paper. Monocyclic, bicyclic, and tricyclic naphthenic acids are the main types of petroleum carboxylic acids in naphthenic-base crudes （SZ36-1 and QHD326）. But the main types of petroleum carboxylic acids in paraffinic-base crude （Dar） are aliphatic acids and monocyclic naphthenic acids. The O2 class species in SZ36-1 and QHD326 are distributed in a wider range and have bigger DBE value （double-bond equivalence value） and carbon number than Dar. Bicyclic naphthenic acids have the highest proportion among petroleum carboxylie acids in diesel distillates, but monocyclic and tricyclic naphthenic acids also occupy a high proportion. Particularly, aliphatic acids in the diesel distillate of Dar still have high proportion among petroleum carboxylic acids. The distribution of petroleum carboxylic acids in VGO is basically identical. The bicyclic naphthenic acids assume the first place （about 25 m%）, while the monocyclic and tricyclic naphthenic acids take the next place. The comparison of petroleum carboxylic acids in diesel distillates and VGOs has revealed that the molecules of carboxylic acids in VGOs are not only bigger but also more complicated.
文摘The removal of acid compounds （naphthenates） from acidic oil with ionic liquids was systematically investigated. [BMIM]Br-AlCl3 was used to investigate the effect on deacidification of oil. Experimental results showed that at a temperature of 323K with a molar ratio of AlCl3 to [BM1M]Br-AlCl3 of 0.2, and a mass ratio of IL to white oil of 4%, the deacidification rate could reach 75.9%. And a reaction time of 4 h was sufficient to achieve the goal. The study on reproducibility of catalytic performance of [BMIM]Br-AlCl3 showed the possibility of using the ionic liquid in the continuous catalytic reaction.
基金supported by the Young Talent Fund of University Association for Science and Technology in Shaanxi, China (No. 20160222)
文摘This work was mainly concentrated on the removal of naphthenic acids(NAs) from dewaxed vacuum gas oil(VGO) by adsorption using a commercial grade activated clay(AC) adsorption during lube base oil refining. The NAs in dewaxed VGO cut-4 were identified by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry(ESI FT-ICR MS). The AC sample from a refinery was characterized by XRD, BET, TG/DTA, and SEM. A series of experiments were carried out to investigate the performance of NAs adsorption by AC using a batch adsorption technique, in which some key experimental parameters such as temperature, contact time, initial concentration of NA in oil sample as well as the dosage of adsorbent were investigated. Equilibrium isotherms were analyzed using the Langmuir, Freundlich, Tempkin and Dubinin-Radushkevich(D-R) adsorption models. The pseudo-first order, the pseudo-second order, and intraparticle diffusion models were employed to describe the kinetics data. The results revealed that the D-R isotherm provided a better fit to the experimental data than other isotherms, and the adsorption kinetics followed the pseudo-first order kinetic equation. The thermodynamic data indicated that the adsorption process was feasible and spontaneous as an endothermic process. The results could provide a clear understanding of the NAs adsorption by AC during lube base oil processing at refineries.
文摘Low-temperature viscosity of lube oils mixed with paraffinic base oil and naphthenic base oil at different mass ratios has been tested by experiments. The influence of paraffinic base oil on the performance of naphthenic base oil was investigated by studying the low-temperature viscosity of tested oils. The viscosity of lube oils increased with an increasing content of high-viscosity paraffinic base oil in the oil mixture. And the low-temperature viscosity was less influenced when the content of paraffinic base oil in the mixture was insignificant. In order to reduce the cost for formulating lubricating oil, a small fraction of paraffinic base oil can be added into naphthenic base oil as far as the property of lubricating oil can meet the specification. According to the study on low-temperature viscosity of the oil mixed with paraffinic base oil and naphthenic base oil, a basic rule was worked out for the preparation of qualified lubricating oils.
文摘In present research, a novel extractant system (D2EHPA + naphthenic acid + pyridine- ester) was used to purify cobalt anolyte and a simulated industrial production were carried out. This novel extraction system can extract Cu and/or Ni against Co from chloride medium solutions at pH range of 2.5-4.5. About 2g/l nickel and 0.2g/l copper were removed from the cobalt chloride anolyte containing about 100g/l cobalt and 200g/l chloride ions respectively, the raffinate contains nickel and copper less than 0.03g/l and 0.0003g/l respectively and can be used to electrolyze high-purity cobalt. About 5.5t cobalt anolyte was purified in the simulation industrial experiment and kilogram quantities of cobalt of 99.98% purity and about 95% recovery have been produced.
基金supported by the Key Laboratory of SINOPEC (KL17010)the research project of Research Institute of Petroleum Processing(R16075)
文摘High resolution tandem mass spectrometry has been applied to obtain the structure information of petroleumsamples. Here, we report a mefflod for structural characterization of crude oil molecules by the collision-induced dissocia-tion （CID） technology coupled wiffl the high-field Fourier transform ion cyclotron resonmlce mass spectrometry （FT-ICRMS）. The ion isolation window was narrowed down to 1 Da to distinguish file complex homologues contained in petroleum.Aromatic model compounds and crude oil samples were measured by CID FT-ICR MS at different collision energy levels.The fragmentation of model compounds wiffl alkyl side-chains was found to be related to the size of file aromatic rings. Thefragmentation of model compounds wiffl archipelago structures depended on file lengffl of file bridge alkylene chain. Theprevalent reaction pafflway of model compounds with naphthenic rings was mainly determined by the position of naphfflen-ic rings in file molecules. On file basis of file fragmentation pathways, the structure differences of two crude oils were recog-nized as different content of naphthenic rings by CID technology with 1 Da isolation window. The NMR analysis was alsoapplied to confirm file CID results. This study exhibits the great potential of CID FT-ICR MS wiffl narrow isolation windowin file smlctural characterization of crude oil molecules.
基金support of the National Natural Science Foundation of China(22078359,21276275).
文摘N-alkyl imidazolium carbonate ionic liquids were employed to separate and recover naphthenic acid from model oils.The effects of the cationic and anionic structures of ionic liquids and operating conditions on the deacidification performance were investigated.The deacidification performance of traditional organic solvents was also investigated for comparison.The results indicated that the naphthenic acid could be completely removed from the model oil with a small mass ratio of ionic liquid to oil.The extracted naphthenic acid was regenerated with a recovery of up to 92%.In addition,imidazolium carbonate ionic liquids could be successfully regenerated and recycled.The mechanism of interaction between imidazole ionic liquids and the naphthenic acid molecules were explained by Gauss calculation.
基金supported by the National Key R&D Program of China(2018YFA0702400)Science Foundation of China University of Petroleum,Beijing(ZX20210029).
文摘Most heavy crude oils underwent biodegradation and generated a significant amount of naphthenic acids. Naphthenic acids are polar compounds with the carboxylic group and are considered as a major factor affecting the oil viscosity. However, the relationship between the molecular composition of naphthenic acids and oil viscosity is not well understood. This study examined a “clean” heavy oil with low contents of heteroatoms but had a high content of naphthenic acids. Naphthenic acids were fractionated by distillation and caustic extraction. The molecular composition was characterized by high-resolution Orbitrap mass spectrometry. It was found that the 2- and 3-ring naphthenic monoacids with 15–35 carbon atoms are dominant components of the acid fractions;the caustic extraction is capable of isolating naphthenic acids with less than 35 carbons, which is equivalent to the upper limit of the distillable components, but not those in the residue fraction;the total acid number of the heavy distillates is higher than that of the residue fraction;the viscosity of the distillation fraction increases exponentially with an increased boiling point of the distillates. Blending experiments indicates that there is a strong correlation between the oil viscosity and acids content, although the acid content is only a few percent of the total oil.
基金financially supported by the National Natural Science Foundation of China (No. 21206194)
文摘The catalytic esterification reaction was used to decrease total acid number(TAN) of crude oil by converting naphthenic acids to naphthenic acid esters in the presence of Zn-Al hydrotalcite used as the catalyst and glycol used as the reactant. The crude oil and its corresponding esterified oil were characterized by the negative-ion electrospray ionization(ESI) Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS). Six acidic class species, O_2, O_1, N_1, N_2, N_1O_1 and N_1O_2 were assigned in the negative-ion spectrum both in the crude oil and its esterified oil. Among the identified acidic compounds, the O2 class was dominant. The relative abundance of O_2 class species was much higher than other acidic class species in crude oil, while it was significantly decreased after esterification. The most abundant O_2 class species had a carbon number of 30-34 and a double-bond equivalence(DBE) value of 5 before and after esterification. It could be concluded that the naphthenic acids in crude oil can be esterified to lower its TAN value, and each of them seems to exhibit identical esterification efficiency approximately due to the similar DBE versus the-carbon number distribution before and after esterification.
