Density functional theory study of B- and Si-doped carbons and their adsorption interactions with sulfur compounds

Understanding the adsorption interactions between carbon materials and sulfur compounds has far-reaching impacts,in addition to their well-known important role in energy storage and conversion,such as lithium-ion batteries.In this paper,properties of intrinsic B or Si single-atom doped,and B-Si codoped graphene(GR)and graphdiyne(GDY)were investigated by using density functional theory-based calculations,in which the optimal doping configurations were explored for potential applications in adsorbing sulfur compounds.Results showed that both B or Si single-atom doping and B-Si codoping could substantially enhance the electron transport properties of GR and GDY,improving their surface activity.Notably,B and Si atoms displayed synergistic effects for the codoped configurations,where B-Si codoped GR/GDY exhibited much better performance in the adsorption of sulfurcontaining chemicals than single-atom doped systems.In addition,results demonstrated that,after B-Si codoping,the adsorption energy and charge transfer amounts of GDY with sulfur compounds were much larger than those of GR,indicating that B-Si codoped GDY might be a favorable material for more effectively interacting with sulfur reagents.

Identification and Characterization of Sulfur Compounds in Straight-Run Diesel Using Comprehensive Two-Dimensional GC Coupled with TOF MS

The solid-phase extraction using Pd-Al2O3 as the stationary phase was employed to pre-separate the sulfur compounds in straight-run diesel. The isolating effect was evaluated quantitatively by gas chromatography with a sulfur chemiluminescence detector to harvest a satisfactory result. The identification of the structure of sulfur compounds by comprehensive two-dimensional gas chromatography coupled with the time-of-flight mass spectrometry indicated that cyclo-sulfides, benzothiophenes, dibenzothiophenes, dihydro-benzothiophenes and tetrahydro-dibenzothiophenes were included in straightrun diesel obtained from the Arab medium crude(AM). A total of 259 individual compounds were detected and their molecular structures were identified. The analytical method was approved as an effective way to characterize the composition of sulfur compounds, which reduced the interference of other compounds, facilitated the data presentation and provided more detailed information about molecular composition of sulfur compounds.

Ultra-deep adsorptive removal of thiophenic sulfur compounds from FCC gasoline over the specific active sites of CeHY zeolite

Adsorption desulfurization performance of Na Y,HY and Ce HY zeolites is evaluated in a miniature fixedbed flow by model gasoline containing with thiophene,tetrahydrothiophene,2-methylthiophene,benzothiophene or mixed sulfur compounds.The structural properties of adsorbents are characterized by XRD,N2-adsorption and XPS techniques.Adsorption desulfurization mechanisms of these sulfur compounds over the specific active sites of adsorbents as a major focus of this work,have been systematically investigated by using in situ FT-IR spectroscopy with single and double probing molecules.Desulfurization experimental results show that the Ce HY adsorbent exhibits superior adsorption sulfur capacity at breakthrough point of zero sulfur for ultra-deep removal of each thiophenic sulfur compound,especially in the capture of aromatic 2-methylthiophene(about ca.28.6 mgS/gadsorbent).The results of in situ FT-IR with single probing molecule demonstrate an important finding that high oligomerization ability of thiophene or 2-methylthiophene on the CeHY can promote the breakthrough adsorption sulfur capacity,mainly resulting from the synergy between Br?nsted acid sites and Ce(III)hydroxylated species active sites located in the supercages of Ce HY.Meanwhile,the result of in situ FT-IR with double probing molecules further reveals the essence of oligomerization reactions of thiophene and 2-methylthiophene molecules on those specific active sites.By contrast,the oligomerization reaction of benzothiophene molecules on the active sites of Ce HY cannot occur due to the restriction of cavity size of supercages,but they can be adsorbed on the Br?nsted acid sites via protonation,and on Ce(III)hydroxylated species and extra-framework aluminum hydroxyls species via direct"S-M"bonding interaction.As to the tetrahydrothiophene,adsorption mechanism is similar to that of benzothiophene,except in the absence of protonation.The paper can provide a new design idea of specific adsorption active sites in excellent desulfurization adsorbents for elevating higher quality of FCC gasoline in the future.

Effect of Olefins on Formation of Sulfur Compounds in FCC Gasoline

The effect of olefins on formation of sulfur compounds in FCC gasoline was studied in a small-scale fixed fluidized bed （FFB） unit at temperatures ranging from 400℃ to 500℃, a weight hourly space velocity （WHSV） of 10 h-1, and a catalyst/oil ratio of 6. The results showed that C4--C6 olefins contained in the FCC gasoline could react with HzS to form predominantly thiophenes, alkyl-thiophenes as well as a fractional amount of thiols, while large molecular olefins such as heptene could react with hydrogen sulfide to form benzothiophenes. The amount of sulfur compounds formed at different tem- peratures over different catalysts were in proportion to the mass fractions of olefins in the feedstock, with the amount of sulfur compounds formed over REUSY catalyst exceeding those formed over the shape selective zeolite catalyst owing to the effect of catalyst performance and the impact of catalyst on the degree of olefin conversion. The amount of sulfur compounds generated and their increase reached a maximum at 450℃ and a minimum at 400℃ because of the influence of temperature on the thermodynamic and kinetic constants for formation of sulfur compound as well as on the olefin conversion degree. Based on the above-mentioned study, a reaction network and a model for prediction of sulfur compounds generated upon reaction of olefins in FCC gasoline with HES were established.

Removal of Heteroaromatic Sulfur Compounds by a Non-noble Metal Fe Single-atom Adsorbent

Sulfur-containing compounds(SCCs)must be removed from fuels before use.In this study,a novel non-noble metal Fe single-atom adsorbent(SA-Fe/CN)was synthesized using a core-shell strategy and applied for the adsorptive removal of benzothiophene(BT)and dibenzothiophene(DBT).The adsorption isotherms,thermodynamics,kinetics,and adsorption-regeneration cycles of DBT and BT on SA-Fe/CN were studied.SA-Fe/CN exhibited a significant capacity to adsorb DBT,and the isothermal equilibrium was well described by the Langmuir isotherm.The Gibbs free energy values were negative(ΔG^(0)<0),indicating that the adsorption of DBT and BT was favored and spontaneous.The adsorption process conformed to the pseudo-second-order kinetic model with high R^(2) values(0.9994,0.9987).The adsorption capacity of SA-Fe/CN for DBT and BT reached 163.21 mg/g and 90.35 mg/g,respectively,due to the highly active sites of the single atom and electrostatic interaction with the sulfide.Therefore,SA-Fe/CN may be a promising adsorbent for SCC removal.

RELATIONSHIP OF POLYCYCLIC AROMATIC SULFUR COMPOUNDS AND GOLD ENRICHMENT IN THE KUPFERSCHIEFER FROM POLAND AND GERMANY

The contents of polycyclic aromatic sulfur compounds (PASCs) in the Kupferschiefer varied from sample to sample. Twenty PASCs were determined in the Kupferschiefer from Poland and Germany. Gold enrichment was only observed in samples with higher PASC contents. At the same time, all the samples with gold enrichment originated from areas close to the redox boundary (the front section of Rote Fule) that was formed by oxidizing brines in contact with the reducing Kupferschiefer. It is proposed that the gold-bearing solutions encountered PASCs in the Kupferschiefer. PASCs could easily displace chloride ions from aurous chloride complexes to form stable gold S-chelates. Subsequent oxidation of these gold organic compounds could destroy the organic components and lead to the formation of metallic gold.

Iron Fertilization with Enhanced Phytoplankton Productivity under Minimal Sulfur Compounds and Grazing Control Analysis in HNLC Region

The present study investigated quantitatively the significance of HNLC (high-nutrient low-chlorophyll) regions and its grazing control with the improved iron fertilization for climate change. The limitation of iron (Fe) for phytoplankton growth in HNLC regions was confirmed by sulfur compounds (S) such as volcanic ash and hydrogen sulfide (H2S) in batch cultures, whose chemical sediment of Fe3S4 showed 4.06 wt%. The technologies developed for iron fertilization since 1993 till now were not practical to provide sufficient amounts of bioavailable iron due to sedimentary iron sulfides induced by undersea volcanic sulfur compounds. The proposed technology for iron fertilization was improved to enhance the bioavailable iron to phytoplankton by keeping minimal sulfur compounds in HNLC regions. The low productivity of phytoplankton by grazing control in HNLC regions was 6% diatoms whose 52% was grazed by copepods and 42% by krill on the basis of data analysis in 2000 EisenEx Experiment at boundary of Antarctic and African tectonic plates. All of the previous iron fertilization experiments were conducted at volcanic sulfur compounds enriched HNLC regions. The present study revealed that the enhanced phytoplankton productivity in batch culture without sedimentary iron sulfides can be possible only if sulfur compounds are minimal, as is in Shag Rocks (53°S, 42°W) of South Georgia in Scotia Sea in the Southern Ocean.

Sulfur-containing amino acid methionine as the precursor of volatile organic sulfur compounds in algea-induced black bloom

After the application of methionine, a progressive and significant increase occurred in five volatile organic sulfur compounds （VOSCs）： methanethiol （MESH）, dimethyl sulfide （DMS）, dime^yl disulfide （DMDS）, dimethyl trisulfide （DMTS） and dimethyl tetrasulfide （DMTeS）. Even in the untreated control without a methionine addition, methionine and its catabolites （VOSCs, mainly DMDS） were found in considerable amounts that were high enough to account for the water＇s offensive odor. However, blackening only occurred in two methionine-amended treatments. The VOSCs production was observed to precede black color development, and the reaching of a peak value for total VOSCs was often followed by water blackening. The presence of glucose stimulated the degradation of methionine while postponing the occurrence of the black color and inhibiting the production of VOSCs. In addition, DMDS was found to be the most abundant species produced after the addition of methionine alone, and DMTeS appeared to be the most important compound produced after the addition of methionine＋glucose. These results suggest that methionine acted as an important precursor of the VOSCs in lakes suffering from algea-induced black bloom. The existence of glucose may change the transformation pathway of methionine into VOSCs to form larger molecular weight compounds, such as DMTS and DMTeS.

Integration of cryogenic trap to gas chromatography-sulfur chemiluminescent detection for online analysis of hydrogen gas for volatile sulfur compounds

Hydrogen fuel cells are among the promising energy sources worldwide,which could accomplish cyclic production of energy and avoid the emission of green-house or contaminative byproducts.However,sulfur compounds(SCs)even at trace level(nmol/mol)are usually involved in cell construction and further H_(2)production,which would cause degradation of the catalysts and shorten the lifetime of the fuel cells.Moreover,the highly reactive SCs could cause varied species and concentrations of them in complex matrices,so online rather than offline analysis of SCs in H_(2)would be preferred.In this context,we developed a new system combining online cryogenic preconcentration of nine SCs and subsequent determination by GC-SCD(sulfur chemiluminescent detector),with the correlation coefficients of the calibration curves higher than 0.999,calculated limits of detection no higher than 0.050 nmol/mol,analytical time around 30 min per sample,and satisfactory precision and accuracy(RSD<5%and SD<15%).The analytical performance was much better than or at least comparable to the previously reported and the developed system was successfully applied for real sample analysis.

Molecular characterization of sulfur compounds in some special sulfur-rich Chinese crude oils by FT-ICR MS

Routine GC/MS analysis may apply to the volatilized Low-Molecular-Weight compounds in saturate and aromatic hydrocarbon fractions;thus,relative studies using this technique inevitably bring about some limitations on distribution of miscellaneous sulfur atom.In this article,Fourier Transform Ion Cyclotron Resonance Mass Spectrometry(FT-ICR MS)with high resolution is employed to investigate the distribution of organic sulfur compounds(OSCs)in the crude oil typically derived from the Eogene carbonate-evaporite sediments with further chemical compositional characterization in molecular level by miscellaneous atomic type,carbon number,and double bond equivalent(DBE).A variety of miscellaneous atomic types with S1,S2,S3,OS,OS2,O2S,O2S2,NS,and NOS etc.(S1 means those OSCs with one sulfur atom in a molecule)were identified in OSCs in these oil samples.High levels of alkyl thioether series compounds with one ring structure were presented mainly in the crude oil in the Jianghan Basin whereas high amounts of benzothiophene,dibenzothiophene etc.compounds with higher values in DBE and carbon number range occurred in the sulfur-rich heavy oil in the Jinxian Sag.Although carbonate-evaporite sediments deposited in the saline lacustrine facies in the Eogene basin both occurred in the Jinxian Sag and Jianghan Basin,obviously,they possess different chemical diagenetic pathway of sulfur under various microbial reactions,leading to diverse distributional characteristics on biomarkers,OSCs,and even different hydrocarbon generation mechanism of immature crude oil.

QSPR Study on the Boiling Points of Some Oxygenand Sulfur-containing Organic Compounds

Structural and thermodynamic parameters of 56 oxygen-containing and 56 sulfur- containing organic compounds were computed at the B3LPY/6-311G＊＊ level using density functional theory （DFT） method. Furthermore,the dependent equations between the experimental data of boiling points （Tb） and theoretical parameters were proposed with SPSS12.0 for windows software,whose correlation coefficients R2 are 0.933 and 0.945. These dependent equations were validated by cross-validation method （q2 are 0.923 and 0.929,respectively）. VIF （variance inflation factors） and t-value methods were also used to verify the significance and self-correlationship of each variable. Results indicate that our dependent equation exhibits good prediction ability,and molecular polarizability （α） is the main factor affecting the Tb of oxygen- and sulfur-containing organic compounds. To our interest,obvious dependence could also be found among the oxygen- and sulfur-containing organic compounds＇ experimental data of boiling points （Tb） with R^2 of 0.857.

Reconstitution activity of partial metallocluster-deficient molybdenum-iron protein of nitrogenase with a series of molybdenum-sulfur compounds

RECENTLY,the structure of MoFe protein from Azotobacter vinelandii has been deter-mined,and based on this,the structural models of FeMo-co and P-clusters in MoFe proteinhave been proposed.According to the model,FeMo-co consists of two clusters,Fe4S3 andMoFe3S3 with a homocitrate ligand coordinated to Mo atom,bridged by three nonprotein lig-ands,two of which are inorganic sulfur atoms and the other is nitrogen- or

An Innovative Method for the Determination of Sulfur-containing Compounds by Vapor Molecular Absorption Spectrometry

Since the most sensitive resonance lines of nonmetallic elements are situated in vacuum ultraviolet region （below 190 nm）, they can not be directly determined with a common AAS instrument covering the spectral range from 190 to 700 nm. The molecular absorption spectrometry is often used for the determination of nonmetallic elements. Syty et al. used vapor molecular absorption spectrometry（VMAS） to determine the sulfur dioxide and sulfide, in which a hydrogen hollow cathode lamp was used as a continuum source to determine SO;at 210 nm and a deuterium arc

Silica sulfuric acid:A versatile reagent for oxathioacetalyzation of carbonyl compounds and deprotection of 1,3-oxathiolanes

Oxathioacetalyzation of carbonyl compounds with 2-mercaptoethanol and deprotection of the obtained 1,3-oxathiolanes is easily performed in the presence of silica sulfuric acid （SSA）. All reactions were performed under mild and completely heterogeneous reaction conditions in good to high yields.

SCD/FPD检测器-气相色谱法测定天然气中的硫化合物

利用硫化学发光检测器(SCD)和火焰光度检测器(FPD)两种不同检测器的气相色谱法对天然气中的硫化合物含量进行分析,并进行定性分析和分离度评价、检出限测定、精密度和准确性检测。实验结果表明,两种方法对硫化合物的分离度良好,测定结果的相对标准偏差最大为1.12%,GC-FPD检测回收率为100.2%~100.8%,GC-SCD检测回收率为99.6%~100.6%,表明两种方法所测结果的重复性和准确度良好,再现性满足国标要求。

添加剂对堆肥过程中挥发性有机物(VOCs)的减排效果

为明确添加剂对堆肥挥发性有机物(Volatile organic compounds,VOCs)排放的减排效果和影响因素,通过文献筛选出吸附类添加剂(活性炭和沸石)与有机酸类添加剂(柠檬酸和草酸)开展实验研究。在鸡粪-玉米秸秆堆肥实验中,设置5个处理,分别为对照(CK)、添加活性炭、添加沸石、添加柠檬酸和添加草酸处理。研究对象包括115种VOCs、三甲胺和6种含硫有机挥发气体(二甲硫醚、二甲基二硫醚、二甲基三硫醚、甲硫醇、乙硫醇、乙硫醚)。结果表明:在28 d的好氧发酵中,所有处理均达到50℃并维持7 d,满足无害化标准。检出110种VOCs、三甲胺和3种含硫有机挥发气体(二甲硫醚、二甲基二硫醚,二甲基三硫醚)。VOCs的排放集中在前9 d,在第3天时VOCs达到峰值。5个处理在堆肥第3天检测到的VOCs浓度范围为169.22~548.26 mg·m^(-3)。4种添加剂对各类VOCs均有减排效果。在第3天,活性炭、沸石、柠檬酸和草酸对烷烃类的减排效率分别为79%、26%、77%和46%,对卤烃类的减排效率分别为96%、38%、93%和97%,对芳香烃类的减排效率分别为28%、11%、24%和53%。从堆肥第6天开始只有沸石对各类VOCs有减排效果,最高减排效率为30%。针对含硫有机挥发气体减排,减排效果依次是草酸>柠檬酸>沸石>活性炭。4种添加剂对含硫有机挥发气体均有减排效果,但是对三甲胺没有减排效果。综合堆肥前9 d VOCs的减排情况,4种添加剂中沸石对各类VOCs减排效果最好。堆肥过程中添加沸石有利于VOCs和其他气体的协同减排,并且对土壤和农作物不存在风险,所以沸石在堆肥工程中有广阔的应用前景。

6种武陵酱香型白酒中挥发性含硫化合物差异分析

挥发性含硫化合物由于具有香气特征强、阈值低的特点,对食品风味具有十分重要的影响。然而大多数挥发性含硫化合物在食品中的含量低于气相色谱-质谱联用(G C-MS)分析技术的检出限,难以被鉴定和识别。酱香型是我国白酒的主要香型,产于湖南的武陵酱香型白酒是酱香型白酒的重要代表之一。为深入探究我国酱香型白酒中重要的痕量挥发性含硫化合物的组成,研究采用顶空固相微萃取结合全二维气相色谱-硫化学发光检测(GC×G C-SCD)技术,以6种不同类型武陵酱香型白酒为研究对象,对其中的含硫化合物进行了分析。研究共定性鉴定出27种含硫化合物,其中共有含硫化合物19种,非共有含硫化合物8种,主要包括4种硫醇、6种硫酯、5种多硫醚、5种噻唑、6种噻吩、1种噻烷;对其中信噪比大于100的23种含硫化合物,采用外标曲线法进行了定量分析。依据定量分析结果,采用主成分分析和正交偏最小二乘判别分析,研究确定了6种不同类型武陵酱香型白酒中挥发性含硫化合物含量的差异;14种变量投影值大于1的含硫化合物,可作为区分6种不同类型武陵酱香型白酒风味特征的差异组分。希望研究可为酱香型白酒的调配提供数据参考,为白酒企业调控生产过程、提高产品质量提供帮助。

天然气原位再生型液体复合脱硫剂研制

针对油气井钻井完井测试期间作业时间短、搬迁频繁,现有的干法或湿法脱硫工艺需要的设备繁多、工艺复杂、建安周期长及其操作困难的情况,利用自氧化、自还原的特种化合物与变价金属离子催化剂相结合,研制了一种原位再生型液体复合脱硫剂,通过对该脱硫剂的催化剂浓度、pH值、二氧化碳及温度等指标,对脱硫效果的影响进行了实验研究。结果表明:pH值在8~13间的硫容不低于330 g/L,在脱硫剂中金属离子催化剂质量浓度不低于500 mg/L时,脱硫效率大于99.9%,二氧化碳含量小于27%时,对硫容质量分数的影响小于3%;该脱硫剂具有反应快、硫容大、适应性强、选择性强和装填方便的特点,为油气井钻井完井测试期间天然气脱硫提供了一种新手段,为天然气原位再生型液体复合脱硫剂推广应用奠定了基础。

炸鸡翅营养组分变化及关键香气成分分析

将鸡翅裹面并采用棕榈油炸,分析炸制前后鸡翅中脂肪酸和氨基酸组成变化及炸鸡翅的关键香气成分。研究发现,油炸后鸡翅肉中脂肪酸和氨基酸总含量均升高,尤其必需氨基酸与总氨基酸的比值及必需氨基酸与非必需氨基酸的比值达到了43.23%和76.16%,营养指标提高。以二氯甲烷为溶剂,采用溶剂辅助蒸发提取炸鸡翅样品中的挥发性风味物质,结合气相色谱-质谱分析鉴定出80种挥发性化合物,频率法气相色谱-嗅闻分析鉴定出51种风味物质是油炸鸡翅的气味活性化合物,G C-O检测的强势气味化合物(NIF≥55%)为2,5-二甲基-吡嗪、己醛、3-甲硫基丙醛、3-乙基-2,5-二甲基-吡嗪、2-甲基丁醛、(E)-2-壬烯醛、γ-丁内酯等36种,对这些化合物计算OAV值,确定炸鸡翅关键香气化合物(OAV≥1)25种,分别为2-甲基-3-呋喃硫醇、双(2-甲基-3-呋喃基)二硫、(E,E)-2,4-癸二烯醛、2-乙基-3,5-二甲基-吡嗪、1-辛烯-3-酮、(E)-2-癸烯醛、(E,E)-2,4-壬二烯醛、2-甲基丁醛、(E)-2-壬烯醛、3-乙基-2,5-二甲基-吡嗪、3-甲硫基丙醛、糠醛、己醛、辛醛、二甲基二硫醚、壬醛、癸醛、苯乙醛、2-戊基呋喃、2-丁酮、2,5-二甲基-吡嗪、(E)-2-庚烯醛、2,3,5-三甲基-吡嗪、2-甲基-吡嗪、乙偶姻25种。希望研究结果可为鸡肉的烹饪加工和肉味香精的研制提供理论参考。

二氧化硫调节乙醇代谢对葡萄采后香气的影响

为研究葡萄采后SO_(2)处理对葡萄贮藏过程中香气合成途径的影响,该研究采用气相色谱-质谱联用技术测定香气物质,并通过测定乙醇代谢途径中底物含量、酶活性及基因表达,明确SO_(2)处理通过调节乙醇代谢对葡萄采后香气的影响。结果表明,采用1000μL/L SO_(2)处理时,果实中SO_(2)残留量符合欧美发达国家鲜食葡萄进出口食品标准。SO_(2)处理有效提高了葡萄采后酯类香气物质的含量。同时,SO_(2)处理还提高了丙酮酸、乙醛和乙醇的含量,提高了丙酮酸脱羧酶、乙醇脱氢酶和醇酰基转移酶活性,上调了VvPDC1、VvADH1、VvADH2、VvADH3、VvADH6、VvADH7和VvAAT的表达,下调了VvPDC 2的表达水平。这些结果表明,SO_(2)处理通过激活乙醇代谢途径,加快了葡萄采后香气物质的合成。