HBF4溶液中全铅液流电池

报道了一种HBF₄水溶液中的全铅液流电池,正、负电极电解液均采用Pb（BF₄）₂的HBF₄水溶液.在酸性的四氟硼酸铅电解液中考察了石墨电极和玻碳电极作为工作电极的循环伏安性能,石墨电极较适于用作全铅液流电池的正、负电极.采用石墨电极作为电池的正、负电极并在四氟硼酸铅酸性电解液中进行充放电实验,其中Pb（BF₄）₂浓度分别为0.5、1.0和1.5 mol·L^-1,且保持游离的HBF₄浓度为1.0 mol·L^-1.该电池为单液流电池,不需要隔膜分隔正、负极的电解液,电流密度为10、20和40 mA.cm^-2,当限定充电容量为7.0 mAh.cm^-2,放电电压截止到1.0 V时,平均库仑效率大于87%,平均能量效率大于68%;当电解液采用1.0或1.5 mol·L^-1 Pb（BF₄）₂+1.0 mol·L^-1HBF₄水溶液时,在10及20 mA.cm^-2电流下的能量效率最高可超过74%.     

H2WO4/GO的制备及其超声-氧化脱除模拟油中的硫化物

以钨酸和氧化石墨烯为原料,利用浸渍法将钨酸负载到氧化石墨烯上制得H₂WO₄/GO。采用XRD、FT-IR、SEM、BET表征确定H₂WO₄/GO的形态及其结构。以H₂WO₄/GO作为催化剂,H₂O₂作为氧化剂,乙腈作为萃取剂超声氧化脱除模拟油中的二苯并噻吩（DBT）。实验表明,在模拟油为5 mL,钨酸的负载量为30%（质量分数）,催化剂为0.02 g,乙腈为1 mL,H₂O₂/S（mol ratio）为8,反应温度为50℃,超声功率为150 W的最佳反应条件下,二苯并噻吩（DBT）、4,6-二甲基二苯并噻吩（4,6-DMDBT）、苯并噻吩（BT）的脱除率分别达到96.6%、81.2%、72.8%。同时,考察了催化剂的循环使用性能,并对超声氧化脱硫机理进行了研究。     

汽油活性炭基脱硫吸附剂的制备与评价

以250℃温度下浓硫酸改性后的活性炭为载体,采用浸渍法制备了以MnO₂为活性组分的活性炭基的汽油脱硫吸附剂MnO₂/AC,考察了吸附剂的制备条件及脱硫条件对脱硫效果的影响。研究结果表明,适宜的吸附剂制备条件为,以Mn(NO₃)₂为活性组分前驱物,Mn(NO)₂浸渍液浓度0.15mol/L、常温下浸渍24h、焙烧温度350℃、焙烧时间2h。该吸附剂在静态吸附温度120℃、吸附时间2h、剂油质量比0.10的条件下可使原料油硫的质量分数从628.6×10^-6降至221.5×10^-6,脱硫率达到64.8%;在动态吸附温度60℃、空速1.76h^-1的条件下,初始流出汽油硫的质量分数降至21.8×10^-6,初始脱硫率达到96.5%。     

Fe/Zr-SBA-15的制备及其催化氧化脱硫性能

为进一步提高氧化脱硫效果,采用直接水热法合成了不同Fe/Zr物质的量比改性的SBA-15分子筛(Fe/Zr-SBA-15),采用XRD、N₂吸附-脱附、TEM和UV-vis等对其进行了表征。Fe/Zr-SBA-15中Zr取代Si进入了分子筛骨架,大部分Fe物种分散良好,存在少量的聚集态铁的氧化物。以Fe/Zr-SBA-15-1.0为催化剂、H₂O₂为氧化剂、乙腈为萃取剂,分别考察了反应温度、O/S物质的量比和催化剂用量对模拟油中二苯并噻吩(DBT)的氧化效果。在反应温度50℃,O/S物质的量比为4,催化剂用量6 g/L的条件下,DBT的脱除率达到97.1%,这是由于催化剂中的Fe³⁺提供氧化活性中心和Zr⁴⁺提供的吸附中心的双重作用,且催化剂回收利用四次后,DBT的脱除率仍可达到91.3%。     

磷钨酸功能化氮化碳的制备及其氧化脱硫研究

以磷钨酸和氮化碳为原料,合成磷钨酸功能化的氮化碳(g-C₃N₄/HPW),并采用XRD、SEM、FT-IR对其结构进行表征。以g-C₃N₄/HPW为催化剂,过氧化氢作为氧化剂,咪唑氟硼酸盐为萃取剂氧化萃取一体法脱除模拟油中的二苯并噻吩(DBT)。考察了反应温度、催化剂加入量、双氧水加入量、萃取剂加入量、硫化物类型等因素对脱硫效果的影响。结果表明,在模拟油为5 mL,g-C₃N₄/HPW为0.02 g,H₂O₂加入量为1.0 mL,BF₄ 为1.5 mL,反应温度70 ℃,反应120 min的条件下,DBT的转化率可达到93%。反应体系循环使用4次催化剂的活性没有明显的降低。     

活性炭纤维吸附脱除NO过程中NO氧化路径分析

在小型固定床吸附实验台上开展了黏胶基活性炭纤维吸附脱除NO的实验研究。采用H₂O₂溶液浸渍以及热处理方法对活性炭纤维表面进行修饰,以获得表面孔隙结构接近而含氧官能团含量不同的样品;考察样品在惰性氮气气氛、含氧气氛下吸附脱除NO的效果,以及表面含氧含氮官能团的变化规律。探讨了含氧官能团在NO催化氧化过程中的作用及含氧气氛下O₂对于NO转化为NO₂的影响,分析了活性炭纤维表面吸附的NO向NO₂的主要转化途径。结果表明,在氮气气氛下活性炭纤维表面C-O官能团对吸附态的NO起到氧化作用,吸附态NO被C-O官能团氧化生成-NO₂官能团;在含氧气氛下活性炭纤维吸附NO后表面出现-NO₂、-NO₃官能团,通过长时间实验测定三种样品在含氧气氛下对NO吸附的效果,发现三种样品稳定时催化氧化效果一致,表明含氧官能团对初始NO的物理吸附影响较大,而对整个吸附过程影响较小。吸附在活性炭纤维表面上的NO与环境气氛中的游离态O₂发生氧化反应是NO转变为NO₂的主要途径。     

过氧磷钨酸催化氧化脱除模拟油中的含硫化合物

考察了以H₂O₂为氧化剂, 过氧磷钨酸为催化剂催化氧化脱除模拟油中的含硫化合物苯并噻吩(BT)和二苯并噻吩(DBT). 讨论了催化剂用量、反应温度、反应时间和剂油体积比等因素对反应的影响. 实验结果表明, 当催化剂用量为0.48%(质量分数), V(H₂O₂)∶V(Oil)=1∶50, 反应时间为60 min, 反应温度为60 ℃时, BT的脱除率达到96.48%, DBT的脱除率达到99.42%. 动力学研究结果表明, 过氧磷钨酸为催化剂的氧化脱除模拟油中的含硫化合物的反应为表观一级反应.     

CuWO4/C复合物的制备和其在模拟油氧化脱硫中的应用

用混合煅烧法制备了CuWO₄/C复合物,并采用XRD、SEM、和BET等技术对其结构进行表征。以CuWO₄/C复合物为催化剂、过氧化氢为氧化剂、1-乙基-3-甲基咪唑硫酸乙酯盐离子液体为萃取剂氧化脱除模拟油中的二苯并噻吩(DBT)。考察了反应温度、双氧水加入量、萃取剂加入量等因素对脱硫效果的影响。结果表明,在相同的实验条件下,相比于CuWO₄,CuWO₄/C复合物具有更高的脱硫率。在模拟油为5.0 mL、催化剂加入量为0.02 g、H₂O₂加入量0.2 mL、萃取剂加入量1.0 mL、反应温度70℃、反应时间180 min的最佳实验条件下,DBT转化率可达到98.2%,催化剂循环使用四次活性没有明显降低。     

模拟油品氧化脱硫及反应动力学研究

在H₂O₂/WO₃/ZrO₂氧化体系中对以甲苯为溶剂、二苯并噻吩(DBT)为模型含硫化合物的模拟油品(硫的质量分数为1540×10^-6)进行了氧化脱硫研究,考察了反应温度、反应时间、氧化剂加入量、催化剂用量对DBT转化率的影响。实验结果表明,在反应温度50℃,反应时间90min,氧化剂加入量油/H₂O₂的体积比为20∶1和催化剂用量0.02g/mL的适宜氧化脱硫条件下,96%以上的DBT氧化为容易分离脱除的二苯并噻吩砜(DBTOs);同时研究了DBT氧化反应动力学,得知DBT氧化反应为一级反应,表观活化能E_a为55.37kJ/mol,指前因子A为3.35×10⁷min^-1。     

CeO2对CuCl/活性炭吸附剂C2H4/C2H6吸附分离性能促进作用

通过等体积浸渍方法制备了添加CeO₂助剂的用于C₂H₄/C₂H₆吸附分离的CuCl/活性炭(AC)吸附剂,使用氮气吸附-脱附曲线、X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、能量分散X射线光谱(EDX)等分析方法对吸附剂进行了表征.结果表明,吸附剂表面Cu(II)在氮气气氛焙烧过程中被部分还原成Cu(I).重点研究了Ce元素的添加对于吸附剂的C₂H₄/C₂H₆吸附分离性能的影响,等温吸附曲线结果表明添加了CeO₂的吸附剂通过降低乙烷的吸附容量从而显著提高了吸附分离性能. XRD及XPS结果表明,和未添加助剂样品相比,其表面晶体团簇较小,分散性更好, Cu(II)还原程度更高.添加CeO₂的吸附剂样品5Ce50Cu(CeO₂和CuCl2的质量分数(w)分别为5%和50%)获得了最好的吸附分离效果,相对于未添加CeO₂的样品50Cu,其在660 kPa下的吸附选择性由4.2提升到8.7.     

Evaluation of adsorption and kinetics of neem leaf powder (Azadirachta indica) as a bio-sorbent for desulfurization of dibenzothiophene (DBT) from synthetic diesel

The need for a sustainable environment has necessitated the development of a green adsorbent that is efficient, cheap, and readily available to serve as an alternative adsorbent for the removal of the refractory sulfur-containing compound from diesel. In this current study, neem-leaf powder (NLP) was activated using H₂SO₄ and tested in desulfurization adsorption experiments of synthetic diesel containing Dibenzothiopene (DBT) during a batch operation. The synthetic diesel contained 0.1 g of DBT in 100 mL of hexane. Before testing, physio-chemical characteristics of the adsorbent were checked via Fourier transmission infrared (FTIR) spectroscopy for surface chemistry; via N₂ physisorption at 77 K for textural properties; SEM quipped with EDX for morphology and elemental composition; and XRD for purity and crystallinity. The results showed that the physico-chemical nature of the adsorbent played a significant role in enhancing the adsorption capacity of the material for DBT. Activated NLP displayed DBT removal of 65.78% at 30 °C using 0.8 g of the adsorbent. Furthermore, the behaviour of the adsorbent during the adsorption could be adequately described using the Freundlich isotherm model. Pseudo-first-order and pseudo-second-order kinetics model describe well the adsorption kinetics of DBT onto the activated NLP.     

低温一步法活性炭基脱硫剂的制备与评价

以木屑为原料,在低温条件下一步法制得活性炭基吸附剂,考察了吸附剂制备条件和液-固、气-固吸附条件对吸附剂脱硫性能的影响。结果表明,吸附剂的最佳制备条件为,浸渍液与木屑质量比为1：1,浸渍液中硝酸质量分率为30%、吸附剂表面NiO负载量为5%,常温下浸渍24 h,400℃焙烧3 h。该吸附剂在0.2 g吸附剂/10 mL模拟油、温度为40℃及时间为5 h的液-固吸附脱硫的条件下,脱硫率为28.36%,吸附四次后饱和吸附硫容量可达2.34 mgS/g;在气-固吸附温度为250℃、空速为6.3 h^-1的条件下,饱和吸附硫容量为2.37 mgS/g;高温气-固吸附脱硫对吸附剂的影响表明,与脱硫前相比,吸附剂在比表面积、总孔体积、微孔体积均有明显提高,这说明气-固吸附脱硫过程同时实现了活性炭的扩孔活化。甲苯溶剂再生实验表明,经五次再生后吸附剂的再生性能均可达90%以上。     

Synthesis and characterization of MFe2O4 sulfur nanoadsorbents

Nanoparticles of ferrites (Fe₃O₄, NiFe₂O₄, CuFe₂O₄, and MnFe₂O₄) were prepared by a reverse (water/oil) microemulsion method. The microemulsion system consisted of cetyltrimethylammonium bromide, 1-butanol, cyclohexane, and a metal salt solution. The procedure was carried out using aqueous ammonia as the coprecipitating agent. Nanosized particles were characterized by thermal analysis, X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and pyridine adsorption. The NiFe₂O₄ sample exhibited narrow mesoporous pore size distribution and high surface area ≈233 m²/g. It achieved good adsorption activity towards the dibenzothiophene (DBT) compound (166.3 μmol/g of DBT adsorbent). The structural properties obtained were very interesting for potential applications in the desulfurization process in petroleum refining.     

Physicochemical properties and desulfurization activities of metal oxide/biomass-based activated carbons prepared by blending method

Column activated carbons were prepared from walnut shell chars and transition metal oxide powders (i.e. Co₂O₃, Ni₂O₃, CuO and V₂O₅) with blending method. Samples were characterized by N₂ adsorption–desorption, X-ray diffraction, X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy. The texture properties of all modified activated carbons with metal oxides dosage of <5 wt% did not change evidently. The basic functionalities of these activated carbons increased relative to blank carbon. Moreover, metal species with different oxidation states coexisted on the modified activated carbons. The optimal dosage of all metal oxides was 2 wt%. The sulfur capacities of these modified activated carbons were 7.7–46.0 % higher than that of blank activated carbon and the highest occurred for V₂O₅ modified activated carbon. The improved desulfurization performance was mainly attributed to the higher catalytic activity of the active metal oxides formed in the presence of O₂ during the desulfurization process.     

Adsorption of carbonyl sulfide on modified activated carbon under low-oxygen content conditions

Activated carbon sorbents impregnated with KOH, Fe(NO₃)₃, Cu(NO₃)₂, Zn(NO₃)₂ or Co(NO₃)₂ and their applications in catalytic oxidation reaction of COS were investigated. The results showed that the activated carbon modified with 10 % (mass percentage) KOH enhanced the adsorption ability significantly. And it was also found that the oxygen content and temperature were the two most important factors in the COS adsorption. Further investigation on the pore structures of the samples with X-ray photoelectron spectroscopy indicated that an adsorption/oxidation process happened in the KOH modified activated carbon in which the major existing forms of sulfur were SO₄ ^2? and S species. The oxidation of COS suggested that KOH in the micropores may play a catalytic role during the adsorption. On the other hand, we found that the desorption activation energy from KOHW was higher than that from AC by the CO₂-TPD spectra, which indicated the adsorption of CO₂ on KOH impregnated activated carbon was stronger. The strong adsorption could be attributed to the basic groups on the activated carbon surface. In conclusion, the activated carbon impregnated with KOH promises a good candidate for COS adsorbent.     

Synthesis and characterisation of magnetic activated carbon/diopside nanocomposite for removal of reactive dyes from aqueous solutions: experimental design and optimisation

In this work, a series of magnetic activated carbon/nanodiopside (Fe₃O₄/AC/Diop) nanocomposites were synthesised and used for the removal of reactive green KE-4BD dye from the aqueous solution. After preparation of nanodiopside by sol-gel method and activated carbon from coconut husk, first, Fe₃O₄/AC composite was prepared by in situ synthesis of Fe₃O₄ nanoparticles between activated carbon pores, and then, different percentages of Fe₃O₄/AC/Diop nanocomposites were prepared by simple mixing of Fe₃O₄/AC composite and Diop in ethanol. Formation of Fe₃O₄/AC and Fe₃O₄/AC/Diop composites was characterised by FTIR, field emission scanning electron microscopy, BET, XRD and vibrating sample magnetometer analyses. Thermogravimetric analysis was used to show the adsorption capacity of the adsorbent more accurately. Effects of amount of adsorbent, initial pH, contact time and dye concentration on reactive green dye removal were also studied using central composite design. Optimal conditions for maximum reactive green KE-4BD dye adsorption (98.35%) process were as follows: pH= 4.90, adsorbent amount: 0.015 g, dye concentration: 37.17 mg/L and contact time: 10.12 min, respectively. In addition, the adsorption kinetics, thermodynamics and isotherms were examined. Adsorption isotherms (q_max: 344.827 mg/g), kinetics and thermodynamics were demonstrated that the sorption processes were better described by the pseudo-second-order equation and the Langmuir equation.     

Effect of the nature of sulfur compounds on their reactivity in the oxidative desulfurization of hydrocarbon fuels with oxygen over a modified CuZnAlO catalyst

The reactivity of thiophene, dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT), which are the representatives of the main classes of sulfur compounds that are the constituents of diesel fractions, was studied in the course of their oxidative desulfurization with oxygen on a CuO/ZnO/Al₂O₃ catalyst modified with boron and molybdenum additives. At T ≥ 375°C, the reactivity increased in the order thiophene < DBT < 4,6-DMDBT. The degree of sulfur removal in the form of SO₂ from hydrocarbon fuel, which was simulated by a solution of 4,6-DMDBT in toluene, was 80%. Under the assumption of a first order reaction with respect to sulfur compound and oxygen, the apparent activation energies of the test processes were calculated. An attempt was made to reveal the role of the adsorption of sulfur compounds in the overall process of oxidative desulfurization with the use of X-ray diffraction analysis, X-ray photoelectron spectroscopy, and differential thermal and thermogravimetric analysis with the massspectrometric monitoring of gas phase composition.     

Synergistic effect of nitrogen and molybdenum on activated carbon matrix for selective adsorptive Desulfurization: Insights into surface chemistry modification

This study reports the synthesis of mesoporous metal-modified nitrogen doped activated carbon (AC-N-Mo) from date seeds by ZnCl₂ activation and its applicability for selective adsorptive desulfurization of dibenzothiophene (DBT). The AC-N-Mo exhibits higher adsorption capacity for DBT at 100 mg-S/L with the maximum removal percentage of 99.7 % corresponding to 19.94 mg-S/g at room temperature than the unmodified carbon with 17.96 mg-S/g despite its highest surface area and pore volume of 1027 m²g^?1 and 0.55 cm³g^?1 respectively. The adsorption capacity breakthrough follows the order AC-N-Mo > AC-Mo > AC > AC-N. Also, AC-N-Mo displays excellent selectivity in the presence of aromatics (toluene, naphthalene, and 1-methylisoquinoline). The enhancement in the DBT uptake capacities of AC-N-Mo is attributed to the synergistic effect of nitrogen heteroatom that aids the dispersion of molybdenum nanoparticles on carbon surface thereby improving its surface chemistry and promising textural characteristics. The kinetic studies showed that the DBT adsorption proceeds via pseudo-second order kinetics while the isotherm revealed that Langmuir fit the data more accurately for the adsorbents. The physical properties (surface area, pore volume, particle size, etc.) and chemical properties (carbon content, etc.) of as-prepared adsorbents namely; AC, AC-N, AC-N-Mo, and AC-Mo were characterized by N₂– physisorption, X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Spectroscopy/Energy Dispersive Spectroscopy (SEM/EDS), Raman Spectroscopy (RS), Fourier Transform Infrared Spectroscopy (FTIR) and Ammonia-Temperature-Programmed Desorption (NH₃-TPD).     

Bio-regeneration of π-complexation desulfurization adsorbents

The coupling of adsorption desulfurization and biodesulfurization is a new approach to produce clean fuels. Sulfur compounds are firstly adsorbed on adsorbents, and then the adsorbents are regenerated by microbial conversion. п-Complexation adsorbent, Cu(l)-Γ, was obtained by ion exchanging Γ-type zeolite with Cu²⁺ and then by auto-reduction in helium at 450°C for 3 h. Dibenzothiophene (DBT) was used as a model compound. The effects of cell concentration, volume of oil phase, the ratio of aqueous phase to adsorbent on DBT desorption by a bacterium were studied. The amounts of DBT desorbed and 2-HBP produced can be apparently increased with addition of n-octane. BDS activity can be improved by increasing cell concentration and the ratio of water-to-adsorbent. 89% of DBT desorbed from the adsorbents can be converted to 2-HBP within 6 h and almost 100% within 24 h, when the volume ratio of oil-to-water was 1/5 mL/mL, the cell concentration was 60 g·L^-1, and the ratio of adsorbent-to-oil was 0.03 g- mL^-1. The amount of 2-HBP produced was strongly dependent on the volume ratio of oil-to-water, cell concentration and amount of adsorbent. Adsorption capacity of the regenerated adsorbent is 95% that of the fresh one after being desorbed with Pseudomonas delafieldii R-8, washed with n-octane, dried at 100°C for 24 h and auto-reduced in He.