吸附法脱除废气中羰基硫的研究进展

羰基硫(COS)广泛存在于黄磷尾气、电石炉尾气等矿热冶炼废气中,但因其结构较稳定,极性和酸性较弱难以直接脱除.本文综述了吸附法脱除COS常用的吸附剂以及吸附剂改性方法,对负载改性所涉及的活性组分进行详细介绍,并分析影响吸附效果的主要因素及吸附机理,对比不同吸附剂的再生方式及再生效果.最后,分析吸附法脱除COS存在的不足...     

Performance and Characterization of Bi-Metal Compound on Activated Carbon for Hydrogen Sulfide Removal in Biogas

This study reports on the synthesis of bi-metal compound (BMC) adsorbents based on commercial coconut activated carbon (CAC), surface-modified with metal acetate (ZnAc₂), metal oxide (ZnO), and the basic compounds potassium hydroxide (KOH) and sodium hydroxide (NaOH). The adsorbents were then characterized by scanning electron microscopy and elemental analysis, microporosity analysis through Brunauer–Emmett–Teller (BET) analysis, and thermal stability via thermogravimetric analysis. Adsorption–desorption test was conducted to determine the adsorption capacity of H₂S via 1 L adsorber and 1000 ppm H₂S balanced 49.95% for N₂ and CO₂. Characterization results revealed that the impregnated solution homogeneously covered the adsorbent surface, morphology, and properties. The adsorption test result reveals that the ZnAc₂/ZnO/CAC_B had a higher H₂S breakthrough adsorption capacity and performed at larger than 90% capability compared with a single modified adsorbent (ZnAc₂/CAC). Therefore, the synthesized BMC adsorbents have a high H₂S loading, and the abundance and low cost of CAC may lead to favorable adsorbents in H₂S captured.     

Copper Adsorption on Lignin for the Removal of Hydrogen Sulfide

Lignin is currently an underutilized part of biomass; thus, further research into lignin could benefit both scientific and commercial endeavors. The present study investigated the potential of kraft lignin as a support material for the removal of hydrogen sulfide (H₂S) from gaseous streams, such as biogas. The removal of H₂S was enabled by copper ions that were previously adsorbed on kraft lignin. Copper adsorption was based on two different strategies: either directly on lignin particles or by precipitating lignin from a solution in the presence of copper. The H₂S concentration after the adsorption column was studied using proton-transfer-reaction mass spectrometry, while the mechanisms involved in the H₂S adsorption were studied with X-ray photoelectron spectroscopy. It was determined that elemental sulfur was obtained during the H₂S adsorption in the presence of kraft lignin and the differences relative to the adsorption on porous silica as a control are discussed. For kraft lignin, only a relatively low removal capacity of 2 mg of H₂S per gram was identified, but certain possibilities to increase the removal capacity are discussed.     

Catalysis by Hydrogen Carbonate and Silicate Anions of the Oxidation of Diethyl Sulfide with Hydrogen Peroxide in Aqueous and Aqueous–Alcoholic Media

The kinetics of the oxidation of diethyl sulfide (Et₂S) with hydrogen peroxide, catalyzed by hydrogen carbonate and silicate anions, agree with the assumption that peroxymonocarbonate (HCO^– ₄) and peroxymonosilicate (HSiO^– ₄) anions are formed as intermediates. The rate of reaction of Et₂S with HCO^– ₄ is about 100 times as fast as with H₂O₂. Transfer to aqueous–alcoholic solutions leads to an increase in the solubility of Et₂S while retaining the catalytic effects.     

纳米分子筛的合成及硫化氢吸附性能

利用无模板水热法合成纳米尺寸的小孔SOD型和大孔X型分子筛, 并考察了其硫化氢脱除性能. 通过对比两种分子筛的硫化氢吸附性能, 证实分子筛对硫化氢的吸附主要集中于孔道内和可及的活性位. 考察了晶粒尺寸、 体积空速和吸附温度等因素对硫化氢吸附的影响, 发现纳米尺寸X型分子筛具有更大的硫容, 并且在低温和低空速下分子筛中的硫化氢分子易于脱除. 随后对纳米X型分子筛进行了金属离子交换改性, 发现Cu改性的分子筛硫容优于其它离子改性的吸附剂, 能达到20.6 mg/g. NaX-N和Cu-NaX-N再生后的硫容分别为新鲜分子筛的62.4%和78.5%.     

Effect of S/N Ratio on the Removal of Hydrogen Sulfide from Biogas in Anoxic Bioreactors

Both biogas desulfurization and wastewater denitrification can be achieved simultaneously, when nitrate/nitrite is used as the electron acceptor for H₂S oxidation. The main objective of this study was to investigate the influence of the molar ratio of sulfide/nitrate (S/N) on biogas desulfurization performance in a biotrickling filter (BTF) and a biobubble column (BBC). The results show that with the decrease of the S/N ratios from 3.6 to 0.7, the removal efficiencies of H₂S increased from about 66 to 100 %, while the removal of nitrate decreased from 100 to 70 % in the two bioreactors. The BTF has a better and more stable desulfurization performance than the BBC does, which could be attributed to their different gas-liquid contacting modes. With the increase of the S/N ratios from 1.0 to 2.5 in the BTFs, the removal of H₂S in biogas was affected slightly, while the percentages of the produced sulfate decreased evidently. In addition, different supplying methods of nitrate wastewater, i.e., intermittent and continuous, did not affect the removal of H₂S significantly, while the intermittent addition of nitrate wastewater increased the percentages of sulfate and denitrification performance.     

In situ Removal of Hydrogen Sulfide During Biogas Fermentation at Microaerobic Condition

In this paper, rice straw was used as a raw material to produce biogas by anaerobic batch fermentation at 35 °C (mesophilic) or 55 °C (thermophilic). The hydrogen sulfide in biogas can be converted to S⁰ or sulfate and removed in-situ under micro-oxygen environment. Trace oxygen was conducted to the anaerobic fermentation tank in amount of 0.5, 1.0, 2.0, 3.0, 4.0, 5.0, or 10.0 times stoichiometric equivalence, respectively, and the control experiment without oxygen addition was carried out. The results showed that the initial H₂S concentrations of biogas are about 3235?±?185 mg/m³ (mesophilic) or 3394?±?126 mg/m³ (thermophilic), respectively. The desulfurization efficiency is 72.3 % (mesophilic) or 65.6 % (thermophilic), respectively, with oxygen addition by stoichiometric relation. When the oxygen feeded in amount of 2～4 times, theoretical quantity demanded the removal efficiency of hydrogen sulfide could be over 92 %, and the oxygen residue in biogas could be maintained less than 0.5 %, which fit the requirement of biogas used as vehicle fuel or combined to the grid. Though further more oxygen addition could promote the removal efficiency of hydrogen sulfide (about 93.6 %), the oxygen residue in biogas would be higher than the application limit concentration (0.5 %). Whether mesophilic or thermophilic fermentation with the extra addition of oxygen, there were no obvious changes in the gas production and methane concentration. In conclusion, in-situ desulfurization can be achieved in the anaerobic methane fermentation system under micro-oxygen environment. In addition, air could be used as a substitute oxygen resource on the situation without strict demand for the methane content of biogas.     

氦液滴中羰基硫分子的光解动力学

用时间切片速度成像方法研究了氦液滴中羰基硫(COS)分子的光解动力学. 从共振增强(2+1)电离的CO光谱中发现在氦液滴环境中解离产物CO的转动冷却比振动冷却更有效.利用速度成像采集到的CO (v=0)和CO (v=1)的影像在角分布上都呈现出各向同性的特点. 产物平动能分布的结果表明尽管大部分的平动能都被超流体环境所弛豫, 但振动激发态产物CO (v=1) 的平均平动能比振动基态产物CO (v=0) 的平均平动能高.对羰基硫分子在氦液滴中的光解动力学机理进行了讨论.     

Removal of Thiram from Aqueous Solutions

In this study activated carbon was used for the removal of thiram from aqueous solutions. Adsorption experiments were carried out as a function of time, initial thiram concentration and temperature. Equilibrium data fitted well to the Freundlich and Langmuir equilibrium models in the studied concentration range. Adsorption kinetics followed a pseudo second‐order kinetic model rather than pseudo first‐order model. The results from kinetic experiments were used to describe the adsorption mechanism. Both boundary layer and intraparticle diffusion played important role in the adsorption mechanism of thiram. Thermodynamic parameters (ΔG₀, ΔH₀, and ΔS₀) were determined and the adsorption process was found to be an endothermic one. The negative values of ΔG⁰ at different temperatures were indicative of the spontaneity of the adsorption process.     

Colorimetric Carbonyl Sulfide (COS)/Hydrogen Sulfide (H2S) Donation from γ‐Ketothiocarbamate Donor Motifs

Hydrogen sulfide (H₂S) is a biologically active molecule that exhibits protective effects in a variety of physiological and pathological processes. Although several H₂S‐related biological effects have been discovered by using H₂S donors, knowing how much H₂S has been released from donors under different conditions remains challenging. Now, a series of γ‐ketothiocarbamate (γ‐KetoTCM) compounds that provide the first examples of colorimetric H₂S donors and enable direct quantification of H₂S release, were reported. These compounds are activated through a pH‐dependent deprotonation/β‐elimination sequence to release carbonyl sulfide (COS), which is quickly converted into H₂S by carbonic anhydrase. The p‐nitroaniline released upon donor activation provides an optical readout that correlates directly to COS/H₂S release, thus enabling colorimetric measurement of H₂S donation.     

Kinetics of Cadmium Sulfide Precipitation from Aqueous Thiourea Solutions

Kinetics of cadmium sulfide precipitation with thiourea from solutions of cadmium(II) ammine complexes under conditions of spontaneous nucleation of the solid phase in the bulk of solution was studied.     

化学滴定法测定丙烯中微量羰基硫

羰基硫是丙烯中极其有害的杂质之一,它使丙烯聚合反应的链终止;当总硫含量(包括羰基硫)在7×10-6以上时,聚合反应明显受影响,催化剂活性下降,粉料中出现塑化块[1]。独山子石化公司乙烯厂70kt/a聚丙烯装置采用Himont公司的Spheripol环管反应器液相本体聚合工艺,该工艺要求精制后丙烯中羰基硫(COS)含量不大于0.02×10-6mol·L-1。可见,准确、及时地测定丙烯中微量基羰基硫非常重要。本文用化学滴定法测定丙烯中微量羰基硫含量[2],经过在现场生产实践中的应用,效果良好。1　试验部分1.1　仪器与试剂乙二胺:使用前需蒸馏EDTA溶液:0.1mol…     

纳米零价铁去除水体中砷的效能与机理

全球超过一亿人受到高毒性、难处理的砷污染引发的饮用水安全的威胁,解决砷污染问题迫在眉睫而又任重道远。纳米零价铁(nZVI)能高效去除重(类)金属、硝酸盐、磷酸盐、高氯酸盐、卤代物、多环芳烃、偶氮染料和苯酚等污染物,成为广泛应用的工程纳米材料之一,在全球已有近60例的环境原位修复和废水处理工程案例。其独特的纳米级核壳结构和表面性质使其能够通过吸附、还原和沉淀等多种作用高效去砷。本文综述了近年来nZVI及其改性材料去除水中砷的研究进展,探讨了nZVI去除水中As(Ⅲ)和As(Ⅴ)的反应机理,归纳了不同反应条件(初始pH值、反应时间、nZVI投加量、砷初始浓度、共存离子和有机质)对去除效果的影响,总结了nZVI改性材料(多孔材料负载改性nZVI、金属掺杂改性nZVI、表面稳定剂改性nZVI和绿色合成nZVI)对砷的去除效率,展望了纳米零价铁去除砷的发展方向和所面临的挑战。     

Convenient,Mild Catalytic Deprotection of Oximes to Carbonyl Compounds with Hydrogen Peroxide and Iodine Catalyst in Aqueous Acetonitrile

A clean, mild, and efficient catalytic deoximation procedure compatible with several common functional groups has been developed using 30% hydrogen peroxide activated by iodine catalyst in aqueous acetonitrile under essentially neutral conditions. The mechanistic features of an iodonium ion–driven nucleophilic cleavage of oximic C[dbnd]N have been revealed.     

Highly Selective Regeneration of Carbonyl Compounds from Their Oximes and Semicarbazones in Aqueous Medium

Abstract

Chemoselective regeneration of aryl alkyl ketone, α‐tetralone, and cycloalkanone by hydrolysis of their oximes and semicarbazones has been accomplished using aqueous phosphoric acid without involvement of any organic cosolvent in the reaction medium, where the similar derivatives of aryl aldehyde, diaryl ketone, aliphatic acyclic aldehyde and ketone remain mostly inert.     

Oxidative Cracking of Propane in the Presence of Hydrogen

Russian Journal of Applied Chemistry - An effect of hydrogen additions to the initial mixture on the parameters of the oxidative cracking of propane at atmospheric pressure, temperatures of...     

硫化纳米零价铁对水中U(VI)的高效去除研究

近年来, 放射性污染物铀(U(VI))在水环境中的排放对生态环境和生物健康造成严重的威胁. 本研究采用液相还原法制备了硫化纳米零价铁(S-NZVI)材料, 并将其用于水中U(VI)的去除. 首先, 我们采取了一系列的微观表征技术探究了S-NZVI的表面特征及材料特性. 结果表明, 相比于纳米零价铁(NZVI), S-NZVI颗粒不易团聚, 性质更加稳定. 随后, 通过宏观实验探究了反应时间、温度、pH、背景离子浓度等因素对S-NZVI去除U(VI)的影响. 结果表明, S-NZVI对U(VI)的最大去除量高达562.5 mg•g^-1, 且在100 min内达到反应平衡. 宏观实验和X射线光电子能谱(XPS)分析表明S-NZVI对U(VI)的去除机理是吸附和氧化还原协同作用的结果. 此外, S-NZVI可以通过外加磁场从水中快速地进行分离, 便于材料再回收与利用. 综上, 本研究构筑了一种制备简单、便于回收且高效的U(VI)净化材料, 未来可能会在放射性核素的处理处置等相关工作中起到重要作用.     

Investigation the Effects of Green-Synthesized Copper Nanoparticles on the Performance of Activated Carbon-Chitosan-Alginate for the Removal of Cr(VI) from Aqueous Solution

In the present investigation, green nano-zerovalent copper (GnZVCu), activated carbon (AC), chitosan (CS) and alginate (ALG) nanocomposites were produced and used for the elimination of chromium (VI) from a polluted solution. The nanocomposites GnZVCu/AC-CS-alginate and AC-CS-alginate were prepared. Analysis and characterization were performed by the following techniques: X-ray diffraction, energy dispersive X-ray spectroscopy, scanning electron microscopy, transmission electron microscopy and Fourier transform infrared spectroscopy. The SEM analysis revealed that the nanocomposites are extremely mesoporous, which leads to the greatest adsorption of Cr⁺⁶ (i.e., 97.5% and 95%) for GnZVCu/AC-CS-alginate and AC-CS-alginate, respectively. The adsorption efficiency was enhanced by coupling GnZVCu with AC-CS-alginate with a contact time of 40 min. The maximum elimination of Cr⁺⁶ with the two nanocomposites was achieved at pH 2. The isotherm model, Freundlich adsorption isotherm and kinetics model and P.S.O.R kinetic models were discovered to be better suited to describe the exclusion of Cr⁺⁶ by the nanocomposites. The results suggested that the synthesized nanocomposites are promising for the segregation of Cr⁺⁶ from polluted solutions, specially the GnZVCu/AC-CS-alginate nanocomposite.     

实验与教具

为了配合高中化学迎考总复习,本刊特邀请了北京市海淀区教师进修学校卞学诚同志、北京四中的胡晓萍同志、北京123中学的夏枚同志,撰写了这组有助于培养思维能力的实验稿。