Oxidative Desulfurization of Diesel Oil Using Mesoporous Phosphotungstic Acid/SiO2 as Catalyst

Ordered mesoporous phosphotungstic acid/SiO₂ (HPW/SiO₂) with Keggin‐type heteropolyacids (HPAs) encapsulated into a SiO₂ framework has been synthesized and used as the catalyst for oxidative desulfurization of diesel fuel. The sulfur compounds in diesel were oxidized and removed at a temperature range of 50–80 °C with H₂O₂ as the oxidant and acetonitrile as the extraction agent. The sulfur content in diesel was reduced to as low as 48–86 μg/g from the initial level of 438 μg/g. The loss in catalytic activity was negligible even after five cycles of use, and the reduction of the sulfur content was enhanced with increasing the immobilized phosphotungstic acid (HPW) concentration. Oxidation of model compounds showed that in the heterogeneous system both the electron density and the steric hindrance affected the reactivity of these sulfur compounds. The reactivities of these sulfur compounds studied in this work followed the order of dibenzothiophene > 4,6‐dimethydibenzothiophene > benzothiophene.     

MoO3/介孔Al2O3催化氧化脱除模拟油中的硫

以环己烷为溶剂,二苯并噻吩（DBT）、苯并噻吩（BT）、4,6-二甲基二苯并噻吩（4,6-DMDBT）、噻吩（Th）作为模型含硫化合物配制成模拟油,在MoO3/介孔Al2O3-H2O2体系中对模拟油催化氧化脱硫进行了研究. 考察了MoO3负载量、氧化剂用量、催化剂用量、氧化反应温度及反应时间对DBT脱除效果的影响. 实验结果表明：在MoO3负载量为20%,催化剂用量为1.5%,氧化剂H2O2与模拟油中硫的摩尔比为4,反应温度为60℃,反应时间为40分钟时DBT脱除率最高,达99.4%,几乎可以被完全脱除;在此条件下模型化合物的氧化反应活性顺序为：DBT > 4,6-DMDBT >BT>Th.     

Ti-HMS催化氧化脱除模拟燃料中的硫化物

 将噻吩、苯并噻吩、二苯并噻吩和4,6-二甲基二苯并噻吩(DMDBT)分别溶于正辛烷配成模拟燃料,以Ti-HMS为催化剂,以H2O2为氧化剂,对模拟燃料的氧化脱硫进行了研究,考察了Ti-HMS的催化活性及硅/钛比和结晶度对催化剂活性的影响. 结果表明,在Ti-HMS上硫化物氧化的难易顺序是由噻吩环上硫原子的电子云密度和硫化物分子的空间位阻共同决定的; 氧化反应发生在分子筛孔道内,骨架钛原子为活性中心; DMDBT在Ti-HMS上的氧化脱除效果比在TS-1,Ti-β或Ti-MCM-41上好. 随着Ti-HMS中硅/钛比的增大,DMDBT的脱除率降低; 随着Ti-HMS分子筛结晶度的升高,DMDBT的脱除率升高.     

超声方法条件下Ce4+对柴油的氧化脱硫

首次超声条件下使用Ce4 氧化柴油中的硫化物(主要为苯并噻吩类),并把这类硫化物氧化成砜类化合物,再选用合适的溶剂(DMF)将这些砜类化合物通过萃取方法除去,使柴油中的总硫含量从554mg/L降到25mg/L,达到了95.5%的高脱硫率。处理后的柴油总硫含量符合世界燃料规范Ⅲ柴油质量标准(不大于30mg/L)。同时,Ce4 氧化媒质可以通过电化学方法再生循环利用,DMF也可以循环利用,无三废排放、具有最佳的经济效益比,并且这种脱硫方法符合绿色化学发展的要求。最佳的操作条件:反应温度为70℃,溶液的pH=0.69,反应时间为50min;V(油):V(水)=1:9。Ce4 氧化媒质的再生条件:Pb电极为阳极,石墨电极为阴极,反应中需要的槽压为3.1V,再生后Ce4 氧化媒质仍具有很好的脱硫效果。     

直馏柴油NOx-空气催化氧化脱硫研究

 柴油氧化法脱硫技术具有操作条件温和,无需氢源以及工艺投资和操作费用低等优点,是取代直馏柴油加氢脱硫技术较为理想的工艺. 但是,该法仍存在H2O2氧化剂价格昂贵和不能再生,以及含硫废水排放等问题. 为克服这些缺点,采用NOx和空气作为氧化催化剂,采用冰乙酸作为助催化剂对直馏柴油进行了脱硫研究. 结果表明,加入冰乙酸的原料柴油,在60 ℃下用NOx和空气氧化70 min后,柴油中的硫含量从1?039降至299 μg/g; 用N,N-二甲基甲酰胺萃取柴油中的氧化产物,在剂油比为0.2的条件下萃取4次,脱硫柴油中的硫含量降至152 μg/g,脱硫效率高达85.4%,柴油收率高达93.7%,符合欧洲Ⅱ#柴油硫含量标准.     

超声与微波条件下Ce4+对柴油氧化脱硫的比较研究

分别在超声和微波条件下使用Ce4 把柴油中的硫化物(主要为苯并噻吩类)氧化成砜类化合物后,再用DMF把它萃取除去。超声条件下的氧化脱硫得到95.5%的高脱硫率,达到世界燃料规范Ⅲ柴油质量标准。微波条件下的氧化脱硫得到82.7%的脱硫率。Ce4 氧化媒质可以经电化学方法再生循环利用,DMF也可以循环利用,无三废排放,具有优化的经济效益比,符合绿色化学发展的趋势。     

氧化-温控双功能离子液体催化O2氧化模拟柴油脱硫

将温控结构单元聚醚链和催化氧化基团磷钨酸根共同引入到离子液体的结构中, 合成出一系列不同聚合度的十八胺类氧化-温控双功能离子液体, 并将其应用于催化O₂氧化模拟柴油的脱硫反应过程, 实现了反应分离一体化, 并取得了良好的脱硫效果和催化剂循环使用效果. 该类离子液体在甲苯/正十二烷混合溶剂中具有良好的温控性能. 筛选出活性较高的离子液体催化剂, 其聚合度n=111以及烷基碳链为C₁₂. 考察了反应温度、反应时间和氧气压力等因素对脱硫效果的影响. 在优化的反应条件(V(甲苯):V(模拟油)=1:1, T=100 ℃, t=2 h, p(O₂)=2.0 MPa)下, DMF萃取一次, 脱硫率接近100%. 催化剂循环使用11次, 脱硫率仍可达到95%以上.     

Vanadium(V) Sorption by Organosilicon Polymers

Features of vanadium(V) sorption by cross-linked organosilicon polymers-polyorganylsilsesquioxanes containing acetamide, phthalamide, malondiamide, and thiourea dioxide functional substituents, were studied.     

Vanadium(V) as an oxidant for thiol compounds

Vanadium(V) is shown to oxidize a number of thiol compounds to the corresponding disulphides. A photometric procedure for the estimation of vanadium(V) in the presence of vanadium (IV) and diverse ions is described. A reinvestigation of the reaction of se(IV) in 4-8M hydrochloric acid with thiosalicylic acid confirms that the Se(IV) acts purely as an oxidant to yield only the corresponding disulphide (RSSR) and not an equimolar mixture of RSSeSR and RSSR.     

用Dawson型聚氧钨酸乳液催化氧化燃油超深度脱硫

合成了Dawson型聚氧钨酸乳液催化剂Q18P2W18,Q18P2W17,和Q18P2W12.采用红外光谱和固体核磁技术对其进行了表征,并用于温和条件下H2O2氧化4,6-二甲基二苯并噻吩(4,6-DMDBT)、二苯并噻吩(DBT)、苯并噻吩(BT)和2,5-二甲基噻吩(2,5-DMT)等含硫化合物的反应中.结果表明,...     

A Highly Stable and Magnetically Recyclable Nanocatalyst System: Mesoporous Silica Spheres Embedded with FeCo/Graphitic Shell Magnetic Nanoparticles and Pt Nanocatalysts

We have developed a highly stable and magnetically recyclable nanocatalyst system for alkene hydrogenation. The materials are composed of mesoporous silica spheres (MSS) embedded with FeCo/graphitic shell (FeCo/GC) magnetic nanoparticles and Pt nanocatalysts (Pt‐FeCo/GC@MSS). The Pt‐FeCo/GC@MSS have superparamagnetism at room temperature and show type IV isotherm typical for mesoporous silica, thereby ensuring a large enough inner space (surface area of 235.3 m² g^?1, pore volume of 0.165 cm³ g^?1, and pore diameter of 2.8 nm) to undergo catalytic reactions. We have shown that the Pt‐FeCo/GC@MSS system readily converts cyclohexene into cyclohexane, which is the only product isolated and Pt‐FeCo/GC@MSS can be seperated very quickly by an external magnetic field after the catalytic reaction is finished. We have demonstrated that the recycled Pt‐FeCo/GC@MSS can be reused further for the same hydrogenation reaction at least four times without loss in the initial catalytic activity.     

Determination of Vanadium(V) and Vanadium(IV) in Bismuth- and Copper-Containing Compounds by Controlled-Potential Coulometry

It was shown that vanadium(V) and vanadium(IV) can be determined at a large Pt electrode in H₂SO₄ solutions in the presence of copper and bismuth by controlled-potential coulometry with RSD no worse than 0.2%. Compounds of the composition Bi₄V_1.8Cu_0.2O_{10.7 – x} were analyzed.     

Determination of Vanadium(IV) and Vanadium(V) in Benfield Samples by IEC with Conductivity Detection

In this study, the determination of vanadium valence state, V(IV) and V(V) has been achieved using ion-exchange chromatography with conductivity detector. In this method, V(IV) was determined as V(IV)-EDTA complex and V(V) as vanadate ion. Determination of V(IV) was successfully done using 3 mM carbonate/bicarbonate/EDTA at pH 8.6 as the eluent. The additive, EDTA in the mobile phase did not seem to interfere with the V(IV) analysis. The detection of V(V) was achieved with 5 mM disodium hydrogen phosphate buffer at pH 10.4. A linear calibration graph over VO₃ ^? and V(IV) with concentration ranges 5–15 mg L^?1 gave the detection limit at 0.09 and 0.1 mg L^?1, respectively. Both V(IV) and V(V) were successfully determined in Benfield sample, with concentrations of V(IV) and V(V) at 4 and 11,000 mg L^?1, respectively.     

Spectrophotometric Investigation of Vanadium (V)-N-Pyridylaminothioformyl-N'-phenylhydroxylamine

The pink complexes of vanadium (V) and N-pyridylaminothioformyl-N′-phenylhydroxylamine are extractable into chloroform. Spectrophotometric studies show that the 1:2 complex predominates in the acidity range of 2.5-6 N HCl. The values of the stability constants, stepwise and overall, have been calculated following extended Yatsimirskii, Leden and Harvey-Manning methods.     

多重响应性复合介孔二氧化硅纳米微球的制备及其在抗腐蚀涂层上的应用

以正硅酸乙酯(TEOS)为硅源,制备介孔二氧化硅纳米微球(MSNs),利用原子转移自由基聚合(ATRP)技术在MSNs表面接枝聚甲基丙烯酸二甲胺乙酯(PDMAEMA)作为缓释开关,成为智能纳米容器(PDMAEMA-MSNs),装载防腐蚀剂-苯并三唑(BTA)验证其双重刺激响应性释放性能。采用透射电子显微镜(TEM)、热重分析(TGA) 、X-射线光电子能谱(XPS)以及傅里叶红外光谱(FT-IR)分析手段表征了MSNs的结构、形貌及表面功能化过程,并使用荧光光谱仪实时监测BTA在不同PH、温度下的释放过程。实验结果表明,智能纳米容器掺杂于SiOx/ZrOy中实现了BTA的双重响应性释放,形成Cu-BTA复合膜,起到铜金属防腐蚀的作用。     

Polyfunctional Anion Exchanger as Sorbent of Copper(II) and Vanadium(V) Ions

Sorption of copper and vanadium ions from aqueous solutions by cross-linked anion exchanger based on a copolymer of glycidyl methacrylate with styrene and polyethylenimine was studied. The effect of the solution pH on the completeness of sorption is considered.     

库仑滴定法测定钒电池电解液中钒(Ⅲ)与钒(Ⅳ)的含量

钒电池是利用不同价态的钒离子在硫酸电解质溶液中发生氧化还原反应,实现化学能与电能之间的相互转换,从而具有大容量的快速充放电且功率和容量可调节等优点,被相关行业认为是最佳新能源储存介质[1-2]。该电池的容量和充放电效率,与电解液中不同价态的钒离子浓度有关,而该电解液中的钒离子的起始状态通常为钒(Ⅲ,V3+)和钒(Ⅵ,VO2+)混合态,当两种离子浓度的比值为1时,电池比容量达到最大[3-4],因此如何简便、快速且高效的测定V3+和VO2+的含量,对产品的质量控制意义重大。     

Silver Nitrate/Oligo(ethylene Oxide) Surfactant/Mesoporous Silica Nanocomposite Films and Monoliths

A lyotropic, liquid crystalline (LC) phase of a silver nitrate/oligo(ethylene oxide), water, and acid mixture was used for one-pot synthesis of mesoporous silica materials in which Ag(+) ions are uniformly distributed. We established that the AgNO(3)-to-surfactant mole ratio is very important in a 50 wt% surfactant/water system to preserve the hexagonal LC phase before and after the addition of the silica source. Below a 0.6 AgNO(3)-to-surfactant mole ratio, the mixture is liquid crystalline and serves as a template for silica polymerization. However, between 0.6 and 0.8 AgNO(3)-to-surfactant mole ratios, one must control the composition of the mixture during the polymerization processes. Above a 0.8 mole ratio, Ag(+) ions undergo phase separation from the reaction mixture by complexing with the surfactant molecules. The resulting silica materials obtained from AgNO(3)/surfactant ratios above 0.8 have anisotropy but without a hexagonal mesophase. Here, we establish a AgNO(3) concentration range in which the LC phase is preserved to template the synthesis of mesoporous silica, and we discuss the structural behavior of the mixtures at AgNO(3)/surfactant mole ratios of 0.00-2.00, using POM, PXRD, FTIR, and UV-Vis absorption spectroscopy. Copyright 2001 Academic Press.     

Intermediates of Asymmetric Oxidation Processes Catalyzed by Vanadium(V) Complexes

The [VO(acac)₂]/Schiff base [R-2-(N-3,5-di-tert-butylsalicylidene)amino-2-phenyl-1-ethanol, S-2-(N-3,5-di-tert-butylsalicylidene)amino-3,3-dimethyl-1-butanol, S-2-(N-3,5-di-tert-butylsalicylidene)amino-3-methyl-1-butanol, or R-2-(N-3,5-di-tert-butylsalicylidene)amino-3-phenyl-1-propanol]/H₂O₂ catalytic systems for the asymmetric oxidation of sulfides and the [VO(acac)₂]/(3bR,4aR)-2-(3,4,4-trimethyl-3b,4,4a,5-tetrahydrocyclopropa[3,4]cyclopenta[1,2-c]pyrazol-1-yl)ethanol/tert-butyl hydroperoxide/TBHP and VO(OAlkyl)₃/[2,2]paracyclophane-4-carboxylic acid N-(1,1-dimethylethyl)-N-hydroxamide/TBHP catalytic systems for the asymmetric epoxidation of allylic alcohols were studied using ¹³C, ⁵¹V, and ¹⁷O NMR spectroscopy. The key intermediates of these systems (peroxo and alkylperoxo complexes of vanadium(V)) were detected, their structures in solution were studied, and the reactivity was evaluated.     

介孔二氧化硅纳米球对水中Mo(VI)的吸附研究

本研究制备了介孔二氧化硅纳米球(MSN),并用之吸附脱除水中的Mo(VI)。应用扫描电镜、介孔分析仪、红外光谱等对MSN进行了表征。考察了pH、吸附时间、MSN投加量和温度对水中Mo(VI)脱除率的影响,并在单因素试验基础上通过正交试验法确定了Mo(VI)的最佳脱除条件：pH=3,MSN投加量为 8.5g/L,吸附时间为36h。在优化吸附试验条件下MSN对加标水中Mo(VI)的脱除率为93.6% ~ 97.3%。