Preparation of Ag/TiO2-zeolite adsorbents,their desulfurization performance,and benzothiophene adsorption isotherms

Russian Journal of Physical Chemistry A - A series of Ag/TiO2-NaY (TY) composite adsorbents were successfully prepared and characterized by X-ray diffraction (XRD), Fourier transform infrared...     

Adsorption of carbon dioxide on microporous carbon adsorbents

Adsorption isotherms of carbon dioxide on microporous carbon adsorbents prepared by activation with potassium sulfide in water vapor were measured. The measurements were carried out in the pressure interval from 1 Pa to 0.1 MPa at temperatures from 216.2 to 293.15 K. Based on the theory of volumetric filling of micropores, the main structural and energetic parameters of the microporous carbon adsorbents were calculated. The adsorption isosters of carbon dioxide were calculated from the adsorption isotherms in the same pressure and temperature ranges and approximated by linear dependences. The plots of the differential mole isosteric heats of adsorption vs amount adsorbed were constructed by using the adsorption isosters.     

半焦吸附剂烟气脱硫脱硝性能

采用廉价半焦为原料,经硝酸氧化和高温热处理改性后,负载金属氧化物制备半焦吸附剂,考察吸附剂的脱硫脱硝性能和再生性能,并利用BET、TEM和TPD等手段研究影响半焦吸附剂性能的内在因素.结果表明,当烟气组成为NO-O2-N2时,吸附剂具有良好的脱硝性能,失活吸附剂经水洗再生后,脱硝活性恢复较好;当烟气组成为SO2-O2-...     

Preparation and performance evaluation of resin-derived carbon spheres for desulfurization of fuels

A polystyrene-based ion-exchange resin was employed as the precursor for preparation of resin-derived carbon spheres(RCSs) through KOH activation with various impregnation ratios.Pore structure,yield and hardness,surface functional groups of the samples and their adsorption performance towards dibenzothiophene(DBT) were investigated.The RCSs with large surface areas(up to 2696m2/g) and total pore volumes(up to 1.46 cm3/g) exhibited larger adsorption capacities than a commercial activated carbon,F400.Polanyi-Dubinin-Mane(PDM) model was applied to fit the adsorption data,which proved that micropore filling was involved during the adsorption process.Moreover,a good linear relationship was observed between the extra-micropore volume and adsorption capacity.Intra-particle diffusion(IPD) model was used to describe the kinetic data of DBT onto the adsorbents.The adsorption processes were divided into three stages according to the different diffusion parameter.The selective adsorption towards DBT in the presence of competing compounds was also investigated and the high selectivity of the RSCs towards DBT may be attributed to the large quantity of acidic oxygen-containing groups.     

载铜球形活性炭的制备及其吸附脱硫性能的研究

以122型弱酸性酚醛系阳离子交换树脂为炭前驱体,经过Cu²⁺交换、炭化和CO₂活化等过程制备得到负载金属铜的球形活性炭,对其进行了SEM、XRD、AAS和BET表征,采用动态吸附实验研究了其对模拟汽油中噻吩类硫化物的吸附性能,并且考察了甲苯和环己烯对其吸附性能的影响,对吸附脱硫机理进行了初步研究。结果表明,载铜球形活性炭上Cu以单质形态存在,并主要与硫原子产生配位作用,提高了对噻吩类硫化物的吸附性能,对噻吩(T)、3-甲基噻吩(MT)、2,5-二甲基噻吩(DMT)和苯并噻吩(BT)的饱和硫容依次为0.938、1.230、1.581和3.744 mg/g,吸附选择性依次为T < MT < DMT < BT。模拟汽油中加入甲苯和环己烯后,饱和硫容分别下降了77%和56%,这是甲苯和环己烯通过π电子与Cu发生作用,从而与硫化物产生竞争吸附导致的。     

制备方法对AgCeY吸附剂脱硫性能的影响

以硅铝比为5.3的NaY分子筛为母体,分别采用微波辅助离子交换法(AgCeY-1)、水热离子交换法(AgCeY-2)和液相离子交换法(AgCeY-3)制备了AgCeY-n吸附剂,并利用XRD、BET、XPS和Py-FTIR对吸附剂进行了表征。以噻吩和苯并噻吩为模型硫化物,甲苯和环己烯为竞争吸附组分,考察了制备方法对制备得到的吸附剂脱硫性能的影响。结果表明,AgCeY-n吸附剂上Ag、Ce元素分别以Ag~+、Ce~(4+)形式存在。经微波辅助离子交换法制备得到的AgCeY-1吸附剂表面Ag~+、Ce~(4+)含量均最高,且具有最高的L酸和B酸量。AgCeY-n吸附剂对硫化物的吸附选择大小顺序为:BTTP,竞争吸附组分对AgCeY-n吸附脱硫性能的影响顺序为:环己烯甲苯。在所研究的制备方法中,微波辅助离子交换法所需时间最短(20 min),合成的AgCeY-1对所研究的模拟油的吸附效果均最好,且具有较好的重复使用性能。各吸附剂对TP和BT的脱除能力大小顺序为:AgCeY-1AgCeY-2AgCeY-3。     

负载型氨基酸离子液体的制备及其对二氧化碳的吸附性能

采用浸渍蒸发法将四甲基铵甘氨酸([N1111][Gly])和四甲基铵赖氨酸([N1111][Lys])两种离子液体分别负载到硅胶(SG)表面,利用EA、TGA、BET和FT-IR等技术对所得到的吸附剂进行表征,考察了离子液体种类、离子液体负载量和温度等条件对其CO_2吸附性能的影响。结果表明,离子液体成功负载到硅胶表面,所制得的负载型氨基酸离子液体对二氧化碳具有良好的吸附性能。在所考察的温度范围(303.15-323.15 K)内,温度越高,平衡吸附量越小;在负载量为10%-60%,随着负载量的增加,平衡吸附量先增加后减小。对于[N1111][Gly]/SG,当负载量为22.4%(质量分数)、吸附温度为30℃、压力为0.1 M Pa时,二氧化碳的平衡吸附量可达到41 mg/g(相对于1 mol AAILs吸附0.62 mol CO_2),而且,吸附20 min即可达到平衡吸附量的90%。吸附剂在循环使用六次之后,其结构与性能均保持良好。     

Preparation and characterization of polyaniline/manganese dioxide composites and their catalytic activity

This paper is devoted to the preparation of polyaniline/MnO2 (PANI/MnO2) composites via chemical oxidation of aniline in H2SO4 medium using beta-MnO2 as an oxidant. The parameters affecting the polymerization reaction are considered. These parameters are [aniline], amount of beta-MnO2, stirring time, and polymerization temperature. SEM, FT-IR, XRD, and TGA techniques are used to characterize the resulting composites. XRD measurements reveal the distortion of the crystal structure of beta-MnO2 after the polymerization reaction. Thus, the XRD pattern of PANI is predominating. The crystalline composites are obtained using higher molar ratio of [Ox]/[ANI] and at higher temperature. Increasing the amount of beta-MnO2 led to an increase in the acidic character of the obtained composites due to adsorption of excess H+ on the oxide surface. The thermal stability of the composites decreased with increasing both [aniline] and stirring time, while it increased with increasing amount of beta-MnO2. The applications of the composites in the oxidative degradation of Direct Red 81, Acid Blue 92, and Indigo Carmine dyes exhibited good catalytic activity in the presence of H2O2 as an oxidant. The reactions followed first-order kinetics and the rate constants were determined. The degradation reaction involved the catalytic action of the PANI counterpart of the composite toward H2O2 decomposition, which can lead to the generation of HO radicals as a highly efficient oxidant attacking the target dyes. The detailed kinetic studies and the mechanism of these catalytic reactions are under consideration in our group.     

Preparation of a kind of mesoporous carbon and its performance in adsorptive desulfurization

Carbon materials were prepared using mesoporous silica HMS with different pore sizes as the hard templates and water-soluble phenolic resin as the carbon source. The obtained materials were characterized by powder X-ray diffraction, transmission electron microscopy and N₂ physical adsorption, and were used in adsorptive desulfurization. It has been shown that the carbon material prepared using HMS with larger pore size (>3 nm) presented uniform wormlike mesopore of 2.3 nm and large BET surface area (1903 m²/g). The mesoporous carbon was an excellent adsorbent to remove the refractory sulfur compound in diesel, especially dibenzothiophene and 4, 6-dimethyldibenzothiophene.     

四氟硼酸改性活性炭的制备及其吸附脱除二苯并噻吩性能

采用浸渍法制备了四氟硼酸(HBF₄)改性活性炭,并研究了其对模拟油中二苯并噻吩(DBT)的吸附脱除性能。利用傅里叶红外光谱(FT-IR)、差示热分析仪(TG-DTA)、X射线光电子能谱(XPS)以及N₂吸附技术对吸附剂的表面态和孔结构进行了表征,考察了四氟硼酸浓度、热处理温度以及模拟油中DBT浓度对吸附脱硫效果的影响。结果表明,经质量分数0.5%的HBF₄溶液浸渍、140 ℃热处理后,在剂油比1:100条件下,活性炭的吸附容量为352 mg/g,较未改性活性炭提高了72.5%。     

Ag-Y/MIL-101吸附剂的制备及其吸附脱硫性能

通过银、钇双金属改性制备了Ag-Y/MIL-101吸附剂,并对Ag-Y/MIL-101进行了X射线衍射(XRD)、电镜(SEMEDS)、比表面积(BET)和热重(TG-DTG)表征。考察了Ag-Y/M IL-101金属负载顺序、金属负载浓度、金属溶液用量、负载时间对脱硫性能的影响,优化了吸附脱硫条件。结果表明,金属改性得到的Ag-Y/MIL-101保持了MIL-101的晶格结构。与M IL-101相比,Ag-Y/MIL-101的比表面积和孔容均有所下降。适宜Ag-Y/MIL-101的制备条件为:先负载银后负载钇,银离子和钇离子的负载浓度均为30 mmol/L,金属溶液用量均为1 mL,负载时间为8 h。适宜Ag-Y/MIL-101的吸附脱硫条件为:吸附剂用量0.05 g,模拟油为10 mL,吸附温度为60℃,吸附时间为8 h。在此条件下,Ag-Y/MIL-101对噻吩的吸附量达到21.7 mg/g。Ag能显著提高MIL-101的吸附硫容,Y能显著提高MIL-101的吸附选择性,因此,Ag-Y/MIL-101吸附剂中Ag和Y的协同作用使其拥有比MIL-101更高的硫容和噻吩脱硫选择性。     

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%。     

Bio-regeneration of p-complexation desulfurization adsorbents

More and more stringent regulations of gasoline and diesel oil were proposed with the awareness of environmental protection. Hydrodesulfurization (HDS) is a conventional method to remove sulfur compounds for industrial purpose. The main drawbacks of this …     

石油焦系活性炭的吸附脱硫

选取独山子石油焦为原料，以物理活化法制得比表面积达500m2/g～900m2/g的活性炭，进行吸附脱硫研究。采用酸氧化法对活性炭孔结构和微观孔径分布进行改性。酸氧化使活性炭表面酸性官能团含量明显增加，增加量约为原来的5倍。活性炭吸附脱硫性能随表面酸性官能团含量的增加而增大。理想的酸化条件是浓硝酸120℃氧化40min。通过静态吸附实验，活性炭吸附脱硫的最佳条件是，温度25℃，压力1.0MPa，静态吸附6h。最佳条件下吸附脱硫可使模型化合物硫的质量分数从137.9×10－6降至3.1×10－6。从活性炭孔径匹配考察可知，平均孔直径在0.8nm～2.1nm的活性炭对模型化合物硫的质量分数降低具有明显效果。     

高分散加氢脱硫催化剂制备及其对二苯并噻吩的催化性能

近年来,柴油发动机产生的废气污染已成为一个严重问题,环境法规对燃油中的硫含量限制越来越严格.因此,开发高效的深度加氢脱硫催化剂成为当今的热门课题之一.在柴油馏分中,由于存在空间位阻作用,二苯并噻吩(DBT)及其烷基取代的衍生物是最难脱除的.传统的加氢脱硫(HDS)催化剂通常是将活性金属担载在γ-Al2O3上.近年来,介孔材料如MCM-41,SBA-15,HMS,KIT-1和KIT-6等也被用作加氢脱硫催化剂载体,其大的比表面积有利于活性组分分散,大的规则孔径有利于反应物和产物扩散.其中,KIT-1介孔分子筛具有三维短蠕虫状介孔结构和大的比表面积,其酸性和水热稳定性都高于MCM-41.然而,由于无定形的孔壁使得介孔分子筛的酸性和水热稳定性较差,限制了其在石油化工领域的应用.而介微孔复合分子筛兼具了微孔分子筛酸性强、水热稳定性好和介孔分子筛的孔道优势,因此一经出现就引起了研究者广泛关注.有研究认为,增加载体酸性有利于加氢及促进C-S键氢解反应.载体中的微孔可高效吸附氢分子,降低HDS过程所需的温度和压力,实现温和条件下燃油超深度脱硫.目前,已有研究者将Y-MCM-41,介孔ZSM-5及Beta-KIT-6等多级孔分子筛用作催化剂载体,并进行了加氢脱硫性能研究,取得了良好效果.我们曾利用双模板剂一步晶化法水热合成了介微孔复合分子筛ZK-1.该分子筛既具有与KIT-1相似的短蠕虫状三维介孔孔道,又具有ZSM-5的微孔结构.其介孔孔径为2.7 nm,微孔孔径为0.6nm.该分子筛具有良好的水热稳定性和较高的酸性.本文在上述研究基础上,以不同硅铝比的ZK-1为载体通过过量浸渍法担载Co,Mo活性组分制备了CoMo/ZK-1 (Si/Al=30)和CoMo/ZK-1 (Si/Al=40)催化剂,并以相同方法制备了CoMo/γ-Al2O3,CoMo/AlKIT-1,CoMo/ZSM-5和CoMo/Mix(等量的ZSM-5和AlKIT-1混合物)催化剂作为对比.催化剂的N2吸附和NH3程序升温脱附表征结果表明,CoMo/ZK-1具有高于其他催化剂的比表面积(约700 m2/g)和介微孔结构,介孔孔径和微孔孔径分别为2.3 nm和0.6-1 nm.CoMo/ZK-1的酸量大于相同硅铝比的CoMo/AlKIT-1,这是由于ZK-1的介孔孔壁上含有沸石结构单元.通过H2程序升温还原表征可知,CoMo/ZK-1的高温氢耗峰面积较CoMo/γ-Al2O3和CoMo/ZSM-5相比明显减小,表明在CoMo/ZK-1上难还原的组分数量减少,载体与金属之间的相互作用减弱,这有利于金属组分的还原和硫化.紫外-可见漫反射光谱表征结果表明,在ZSM-5表面形成了大量的聚合态氧化钼物种,这是由于载体表面积小,金属组分分散不均匀.Co2AlO4或Co2SiO4相的出现是由于载体与金属间存在较强的相互作用.以ZK-1和AlKIT-1为载体的催化剂则避免了该情况的发生.从高分辨透射电镜照片可知,MoS2在ZK-1表面分散很均匀,其堆垛层数(2.5-2.7层)和片晶长度(3.9-4.0 nm)都达到较理想的数值,有利于形成更多的Co-Mo-S(Ⅱ)活性相.以二苯并噻吩为模型化合物,采用固定床反应器考察了上述6种催化剂的加氢脱硫活性.催化剂的脱硫率从高到低依次为:CoMo/ZK-1 (40)＞ CoMo/ZK-1 (30)＞ CoMo/γ-Al2O3＞ CoMo/ZSM-5＞ CoMo/Mix＞ CoMo/AlKIT-1.在较温和的反应条件(320℃,3MPa,WHSV=5h-1)下,CoMo/ZK-1对DBT的脱硫率达到93％以上.其原因主要是:(1)ZK-1的大比表面积使Co,Mo活性组分高度分散在载体表面;(2)载体与金属之间较适中的相互作用有利于活性组分的还原与硫化;(3)ZK-1含有的沸石结构单元使其比AlKIT-1具有更多的酸中心,有利于提高HDS反应活性.     

Preparation and properties of manganese dioxide studied by QCM

Electrodeposition and cycling of MnO₂ was tested by cyclic voltammetry and electrochemical quartz crystal microbalance (QCM). The electrodeposition from manganese sulfate and the material cycling are accompanied by strong and almost reversible water sorption close to the stoichiometric ratio 3:1. Similar reversible sorption of water was observed also on solid MnO₂ deposited as an “ink” (slurry) with PTFE as a binder on the QCM probe.     

Preparation and properties of manganese dioxide studied by QCM

Electrodeposition and cycling of MnO₂ was tested by cyclic voltammetry and electrochemical quartz crystal microbalance (QCM). The electrodeposition from manganese sulfate and the material cycling are accompanied by strong and almost reversible water sorption close to the stoichiometric ratio 3:1. Similar reversible sorption of water was observed also on solid MnO₂ deposited as an “ink” (slurry) with polytetrafluoroethylene as a binder on the QCM probe.     

Enhancement of the electrocapacitive performance of manganese dioxide by introducing a microporous carbon spheres network

An amorphous MnO(2)·nH(2)O/microporous carbon spheres (α-MnO(2)·nH(2)O/MCS) composite electrode material is prepared by a chemical co-precipitation method. It is observed that the amorphous MnO(2) particles are deposited on the surface of the MCS, which form a network with a uniquely developed three-dimensional open porous system containing macropores, mesopores and micropores. The electrochemical measurements reveal that the composite electrode material presents a much more stable and reversible capacitance behavior compared to the pure α-MnO(2)·nH(2)O in 1 M of Na(2)SO(4) electrolyte. The composite containing 25 wt% MCS exhibits optimal specific capacitance of 218.2 F g(-1) at 2 mV s(-1), and is still as high as 112.4 F g(-1) at 100 mV s(-1), while a drastic reduction from 197.0 F g(-1) at 2 mV s(-1) to only 40.7 F g(-1) at 100 mV s(-1) occurs for the pure α-MnO(2)·nH(2)O. The composite also shows a rather high electrode-specific capacitance of 3.13 F cm(-2) and a long cycle life. The remarkable enhancement in the electrochemical performance is mainly attributed to the microporous structure of the MCS contributing to the deposition of MnO(2) particles on the surface of the MCS, and the uniquely developed porous network of the composite facilitating the rapid transport of the electrolyte. These factors result in the high electrochemical utilization of MnO(2), a great reduction of the equivalent series resistance, and hence the relatively high and stable electrochemical behavior.