A density functional theory study on the decomposition of aliphatic hydrocarbons and cycloalkanes during coal pyrolysis in hydrogen plasma

To get deep understanding of the reaction mechanism of coal pyrolysis in hydrogen plasma, the decomposition reaction pathways of aliphatic hydrocarbons and cycloalkanes, which are two main components in volatiles from coal, were investigated. Methane and cyclohexane were chosen as the model compounds. Density functional theory was employed, and many reaction pathways were involved. Calculations were carried out in Gaussian 09 at the B3LYP/6-31G（d,p） level of the theory. The results indicate that the main pyrolysis products of methane and cyclohexane in hydrogen plasma are both hydrogen and acetylene, and the participation of active hydrogen atoms makes dehydrogenation reactions more favorable. H2 mainly comes from dehydrogenation process, while many reaction pathways are responsible for acetylene formation. During coal pyrolysis in hydrogen plasma, three main components in volatiles like aliphatic hydrocarbons, cycloalkanes and aromatic hydrocarbons lead to the formation of hydrogen and acetylene, but their contributions to products distribution are different.

Hyperbranched polymer hollow-fiber-composite membranes for pervaporation separation of aromatic/aliphatic hydrocarbon mixtures

The separation of aromatic/aliphatic hydrocarbon mixtures is crucial in the petrochemical industry.Pervaporation is regarded as a promising approach for the separation of aromatic compounds from alkanes. Developing membrane materials with efficient separation performance is still the main task since the membrane should provide chemical stability, high permeation flux, and selectivity. In this study, the hyperbranched polymer(HBP) was deposited on the outer surface of a polyvinylidene fluoride(PVDF)hollow-fiber ultrafiltration membrane by a facile dip-coating method. The dip-coating rate, HBP concentration, and thermal cross-linking temperature were regulated to optimize the membrane structure.The obtained HBP/PVDF hollow-fiber-composite membrane had a good separation performance for aromatic/aliphatic hydrocarbon mixtures. For the 50%/50%(mass) toluene/n-heptane mixture, the permeation flux of optimized composite membranes could reach 1766 g·m^(-2)·h^(-1), with a separation factor of 4.1 at 60℃. Therefore, the HBP/PVDF hollow-fiber-composite membrane has great application prospects in the pervaporation separation of aromatic/aliphatic hydrocarbon mixtures.

A Technique for Carbon and Chlorine Isotope Analyses of Chlorinated Aliphatic Hydrocarbons in Groundwater

Chlorinated aliphatic hydrocarbons （CAHs）, significant contaminants in groundwater, can be characterized by stable isotopic compositions of carbon and chlorine. Previously published methods were of low analytical sensitivity or not ideal for natural samples with low concentrations of CAHs. This method is reported here to carry out simultaneously carbon and chlorine isotope analyses for mieromolar concentrations of dissolved CAHs. It was executed by extracting and converting CAHs to carbon dioxide and methyl chloride （CH3CI）. Specially, a continuous-flow interface GasBench Ⅱ was used to extract CH3CI for online chlorine isotope analysis. As a result, it greatly enhances the efficiency for isotope analysis by eliminating procedures for offline CH3CI preparation and separation. Sample size requirement was reduced to approximately 11 pmol chlorine. The standard deviation of δ^＋3C and δ^37CI for both TCE solvents and water samples was better than 0.30‰ and 0.20%0 （1σ）, respectively.Carbon and chlorine isotope analyses can be used as an important tool to study the sources of organic contaminants in groundwater and their behaviors in the aquifers. The method is applicable to manufacturers＇ products as well as a sample from a polluted site in principle, which will be validated in our field studies.

Highly selective extraction of aromatics from aliphatics by using metal chloride-based ionic liquids

The separation of aromatics from aliphatics is essential for achieving maximum exploitation of oil resources in the petrochemical industry.In this study,a series of metal chloride-based ionic liquids were prepared and their performances in the separation of 1,2,3,4-tetrahydronaphthalene(tetralin)/dodecane and tetralin/decalin systems were studied.Among these ionic liquids,1-ethyl-3-methylimidazolium tetrachloroferrate([EMIM][FeCl_(4)])with the highest selectivity was used as the extractant.Density functional theory calculations showed that[EMIM][FeCl_(4)]interacted more strongly with tetralin than with dodecane and decalin.Energy decomposition analysis of[EMIM][FeCl_(4)]-tetralin indicated that electrostatics and dispersion played essential roles,and induction cannot be neglected.The van der Waals forces was a main effect in[EMIM][FeCl_(4)]-tetralin by independent gradient model analysis.The tetralin distribution coefficient and selectivity were 0.8 and 110,respectively,with 10%(mol)tetralin in the initial tetralin/dodecane system,and 0.67 and 19.5,respectively,with 10%(mol)tetralin in the initial tetralin/decalin system.The selectivity increased with decreasing alkyl chain length of the extractant.The influence of the extraction temperature,extractant dosage,and initial concentrations of the system components on the separation performance were studied.Recycling experiments showed that the regenerated[EMIM][FeCl_(4)]could be used repeatedly.

Accumulation of petroleum hydrocarbons and heavy metals in clams (Ruditapes philippinarum) in Jiaozhou Bay,China

Accumulation and distributions of aliphatic and polyaromatic hydrocarbons (PAHs) and heavy metals were measured in tissues of the clam Ruditapes philippinarum collected from 5 sites in Jiaozhou Bay,Qingdao,China.The concentrations of total aliphatic hydrocarbon and PAHs ranged from 570 to 2 574 ng/gdw (gram dry weight) and from 276 to 939 ng/gdw,in the most and least polluted sites,respectively.The bio-accumulation of hydrocarbons and PAHs in the clams appeared to be selective.Aliphatic hydrocarbons were predominantly represented by short chain (<nC23) n-alkanes,suggesting that petroleum hydrocarbons were likely the major contamination source.The selective uptake of 3 and 4 ring PAHs,such as naphthalene,fluorene,phenanthrene,fluoranthene and pyrene,by the clams was probably related to the physiological and bio-kinetic processes that were energetically favorable for uptake of compounds with fewer rings.Accumulation of the metals Cd,Cu,Zn,Pb,Cr,Hg,and As in the clam tissues also showed high variability,ranging from 0.043 to 87 μg/gdw.Among the 7 detected metals,Zn,Cd,Cu,and As had a particularly high potential of accumulation in R.philippinarum.In general,a positive correlation was found between the tissue concentrations and sediment concentrations of hydrocarbons and of some metals.Our study suggests that moderate contamination with polyaromatic hydrocarbons,and low to moderate contamination with metals,currently exists for clam R.philippinarum in Jiaozhou Bay,in comparison with other regional studies.A long-term monitoring program is certainly needed for assessment of the potential ecological influence and toxicity of these contaminants of R.philippinarum in Jiaozhou Bay.

Membrane materials in the pervaporation separation of aromatic/aliphatic hydrocarbon mixtures—A review

The separation of aromatic/aliphatic hydrocarbon mixtures is a significant process in chemical industry, but challenged in some cases. Compared with conventional separation technologies, pervaporation is quite promising in terms of its economical, energy-saving, and eco-friendly advantages. However, this technique has not been used in industry for separating aromatic/aliphatic mixtures yet. One of the main reasons is that the separation performance of existed pervaporation membranes is unsatisfactory. Membrane material is an important factor that affects the separation performance. This review provides an overview on the advances in studying membrane materials for the pervaporation separation of aromatic/aliphatic mixtures over the past decade. Explored pristine polymers and their hybrid materials(as hybrid membranes) are summarized to highlight their nature and separation performance. We anticipate that this review could provide some guidance in the development of new materials for the aromatic/aliphatic pervaporation separation.

ATR-FTIR Analysis on Aliphatic Hydrocarbon Bond(C-H)For­mation and Carboxyl Content during the Ageing of DC Air Plasma Treated Cotton Cellulose and Its Impact on Hydrophilicity

The surface of the cotton fabric was modified using a direct current(DC)air plasma treatment and hence enhances its hydrophilicity.The Box-Behnken approach(design expert software)was used to optimise the input process parameters.The sample prepared under optimized condition is subjected to ATR-FTIR and Field Emission Scanning Electron Microscopy(FESEM)studies in order to determine the changes in hydrogen bond energies(EH),Total Crystallinity Index(TCI),Hydrogen Bond Intensity(HBI),Lateral Order Index(LOI),functionalization,lattice parameters(a,b,c&β),degree of crystallinity(in%)and surface etching.The ageing of this sample has been studied by comparing the values of carboxyl content and AC-C/AC-O-C ratio calculated using data extracted from ATR-FTIR spectra of the sample recorded periodically for one month.

Aliphatic Halogenated Hydrocarbons: Report and Analysis of Liver Injury in 60 Patients

Background and Aims:Intoxications by aliphatic halogenated hydrocarbons(AHH),used as effective solvents,are rare and may cause life-threatening liver injury.Patients with acute intoxications by AHH received an innovative treatment.Methods:Analyzed were data of 60 patients intoxicated by AHH,such as dichloromethane(n=3),chloroform(n=2),carbon tetrachloride(n=12),1,2-dichloroethane(n=18),1,1,2-trichloroethane(n=2),trichloroethylene(n=2),tetrachloroethylene(n=13)or mixed AHH chemicals(n=8),who received a new treatment consisting of CO2-induced hyperventilation to accelerate toxin removal via the lungs.Results:Added to the inspiration air at a flow rate of 2-3 Liter min-1,CO2 increased the respiratory volume up to 25-30 Liter min-1,ensuring forced AHH exhalation.This CO2-induced hyperventilation therapy was commonly well tolerated by the 60 patients and lasted for 106.0±10.5 hours.In most cases,initially increased liver test results of aminotransferases normalized quickly under the therapy,and liver histology obtained at completion of the therapy revealed,in the majority of patients,normal findings or fatty changes,and rarely severe single cell necrosis but no confluent liver cell necrosis.Despite therapy,clinical outcome was unfavorable for 4/60 patients(6.7%)of the study cohort,due to single or combined risk factors.These included late initiation of the CO2-induced hyperventilation therapy,intentional intoxication,uptake of high amounts of AHH,concomitant ingestion of overdosed drugs,consumption of high amounts of alcohol,and history of alcohol abuse.Conclusions:For intoxications by AHH,effective therapy approaches including forced hyperventilation to increase toxin removal via the lungs are available and require prompt initiation.

Liquid-liquid interfacial tension of equilibrated mixtures of ionic liquids and hydrocarbons

Ionic liquids are possible alternative solvents for the separation of aromatic and aliphatic hydrocarbons by liquid-liquid extrac- tion. Interfacial tension is an important property to consider in the design of liquid-liquid extraction processes. In this work, the liquid-liquid interfacial tension and the mutual solubility at 25 ℃ have been measured for a series of biphasic, equilibrated mixtures of an ionic liquid and a hydrocarbon. In particular, the ionic liquids 1-alkyl-3-methylimidazolium bis（trifluorome- thanesulfonyl）imide （with the alkyl substituent being ethyl, hexyl or decyl）, 1-ethyl-3-methylimidazolium ethylsulfate, and 1-ethyl-3-methylimidazolium methanesulfonate have been selected, as well as the hydrocarbons benzene, hexane, ethylben- zene, and octane. The selected sets of ionic liquids and hydrocarbons allow the analysis of the influence of a series of effects on the interfacial tension. For example, the interfacial tension decreases with an increase in the length of the alkyl substituent chain of the cation or with an increase of the degree of charge delocalisation in the anion of the ionic liquid. Also, the interfa- cial tension with the aromatic hydrocarbons is markedly lower than that with the aliphatic hydrocarbons. A smaller effect is caused by variation of the size of the hydrocarbon. Some of the observed trends can be explained from the mutual solubility of the hydrocarbon and the ionic liquid.

Tetrachloroethane(TeCA)removal through sequential graphite-mixed metal oxide electrodes in a bioelectrochemical reactor

Electro-bioremediation offers a promising approach for eliminating persistent pollutants from groundwater since allows the stimulation of biological dechlorinating activity,utilizing renewable electricity for process operation and avoiding the injection of chemicals into aquifers.In this study,a two-chamber microbial electrolysis cell has been utilized to achieve both reductive and oxidative degradation of tetrachloroethane(TeCA).By polarizing the graphite granules cathodic chamber at650 mV vs the standard hydrogen electrode and employing a mixed metal oxide(MMO)counter electrode for oxygen production,the reductive and oxidative environment necessary for TeCA removal has been established.Continuous experiments were conducted using two feeding solutions:an optimized mineral medium for dechlorinating microorganisms,and synthetic groundwater containing sulphate and nitrate anions to investigate potential side reactions.The bioelectrochemical process efficiently reduced TeCA to a mixture of trans-dichloroethylene,vinyl chloride,and ethylene,which were subsequently oxidized in the anodic chamber with removal efficiencies of 37±2%,100±4%,and 100±5%,respectively.The introduction of synthetic groundwater with nitrate and sulphate stimulated reductions in these ions in the cathodic chamber,leading to a 17%decrease in the reductive dechlorination rate and the appearance of other chlorinated by-products,including cis-dichloroethylene and 1,2-dichloroethane(1,2-DCA),in the cathode effluent.Notably,despite the lower reductive dechlorination rate during synthetic groundwater operation,aerobic dechlorinating microorganisms within the anodic chamber completely removed VC and 1,2-DCA.This study represents the first demonstration of a sequential reductive and oxidative bioelectrochemical process for TeCA mineralization in a synthetic solution simulating contaminated groundwater.

Characterization of contamination, source and degradation of petroleum between upland and paddy fields based on geochemical characteristics and phospholipid fatty acids

To evaluate contamination caused by petroleum, surface soil samples were collected from both upland and paddy fields along the irrigation canals in the Hunpu wastewater irrigation region in northeast China. N-alkanes, terpanes, steranes, and phospholipid fatty acids （PLFA） in the surface soil samples were analyzed. The aliphatic hydrocarbon concentration was highest in the samples obtained from the upland field near an operational oil well; it was lowest at I-3P where wastewater irrigation promoted the downward movement of hydrocarbons. The Hunpu region was found contaminated by heavy petroleum from oxic lacustrine fresh water or marine deltaic source rocks. Geochemical parameters also indicated significantly heavier contamination and degradation in the upland fields compared with the paddy fields. Principal component analysis based on PLFA showed various microbial communities between petroleum contaminated upland and paddy fields. Gram-negative bacteria indicated by 15：0, 3OH 12：0, and 16：1（9） were significantly higher in the paddy fields, whereas Gram-positive bacteria indicated by i16：0 and 18：1（9）c were significantly higher in the upland fields （p 〈 0.05）. These PLFAs were related to petroleum contamination. Poly-unsaturated PLFA （18：2ω6, 9; indicative of hydrocarbon- degrading bacteria and fungi） was also significantly elevated in the upland fields. This paper recommends more sensitive indicators of contamination and degradation of petroleum in soil. The results also provide guidelines on soil pollution control and remediation in the Hunpu region and other similar regions.