吸附脱硫技术生产清洁油品

与传统的加氢脱硫技术相比,吸附脱硫技术具有投资成本低、操作条件温和、脱硫率高等特点,近年来得到迅速发展.本文综述了吸附脱硫领域的最新研究成果,着重介绍了相关的吸附机理以及典型的工艺,并对吸附脱硫技术存在的问题及发展前景进行了评述与展望.较低的硫容、硫化物选择性以及再生性能是目前吸附脱硫存在的主要问题,吸附工艺的设计优化和吸附机理的研究将是今后研究的主要方向.     

磺酸型树脂酰胺化修饰及修饰产物的吸附脱硫研究

吸附技术以其低成本、低损耗和非破坏性等特征,在化工的清洁化方面受到广泛关注,对于汽油、柴油等烃类燃料的深度脱硫而言,吸附工艺正逐步显示出良好的应用前景[1～3].吸附剂是吸附技术的核心,已经使用或正在研制的烃类脱硫用吸附剂主要是一些无机材料,如经过不同修饰的分子筛和金属氧化物等[4～6].有机高分子吸附剂的开发研究还处于起步阶段,但已经发现有些聚合物材料可以通过化学修饰或负载,起到对烃体系中硫化物的吸附脱除作用[7～9].     

吸附脱硫技术生产清洁油品的研究进展

与传统的加氢脱硫技术相比,吸附脱硫技术具有投资成本低、操作条件温和、脱硫率高等特点,近年来得到迅速发展。本文综述了吸附脱硫领域的最新研究成果,着重介绍了相关的吸附机理以及典型的工艺,并对吸附脱硫技术存在的问题及发展前景进行了评述与展望。较低的硫容、硫化物选择性以及再生性能是目前吸附脱硫存在的主要问题,吸附工艺的设计优化和吸附机理的研究将是今后研究的主要方向。     

大孔吸附树脂负载氢氧化锰作催化剂空气氧化水中硫化物的研究

采用ＮＫＡ２型大孔吸附树脂负载氢氧化锰作催化剂，研究模拟水样中硫化物的空气氧化过程和影响因素，并对煤气和焦化工业含硫废水进行氧化试验．结果表明，在ｐＨ９～１１和不低于３０℃的条件下，浓度６３０～３８００ｍｇ／ｌ的Ｓ２－可在１～３小时内达到９９％的氧化率，树脂负载催化剂可重复使用．     

铕在D751树脂上吸附性能的研究

用D751树脂对Eu~(3+)进行吸附性能研究。测定了树脂对Eu~(3+)的吸附容量409.7mgEu~(3+)·g~(-1)树脂,温度对吸附分配系数的影响,焓△H=25.85×10~3J·mol~(-1)。表观吸附速率常数及表观活化能E_a=26.45×10~3J·mol~(-1)。并用化学法及红外光谱等探讨了吸附机理。     

D315树脂吸附脱除SO^2—4研究

本文研究了用Ｄ３１５树脂吸附脱除蚕蛹复合氨基酸水解液中ＳＯ＾２－４的方法。试验结果表明：Ｄ３１５树脂对ＳＯ＾２－４的静态交换容量为１０ｍｇ／ｍｌ树脂，吸附平衡时间４０分钟，ｐＨ４．５０。被吸附的ＳＯ６２－４可用６．６ＢＶ，１ｍｏｌ／ｌ的氨水以１．５ＢＶ／ｈｒ的流速完全洗脱。     

汽油吸附脱硫研究进展

吸附脱硫方法以其操作简单、投资少、适合于深度脱硫、无污染等优点得到了较快的发展。本文较详细地介绍了活性炭、分子筛、金属氧化物和黏土材料等汽油脱硫吸附剂的研究进展。     

D301树脂吸附铼(Ⅶ)的研究

本文研究了D301树脂对铼(Ⅶ)的吸附性能,结果表明在T=298 K,pH=2.7的HAc-NaAc缓冲溶液中静态饱和吸附容量为715 mg·g^-1;0.5~5.0 mol·L^-1 HCl溶液可以不同程度地解吸树脂上的铼,其中4.0 mol·L^-1 HCl作为解吸剂时,一次解吸率可达100%。反应开始阶段的表观吸附速率常数k_{298 K}=7.2×10^-5 s^-1;等温吸附服从Freundlich经验式;吸附反应的ΔH=-4.4 kJ·mol^-1;吸附物中树脂功能基与Re(Ⅶ)的物质的量比约为1∶1。并用化学法和红外光谱探讨了吸附机理。     

酚醛型吸附树脂吸附咖啡因的热力学研究

利用酚醛型吸附树脂JDW－2（自制）和DuoliteS-761对咖啡因的吸附进行了研究，在303－323K和研究的浓度范围内，JDW－2和DuoliteS-761对咖啡因吸附平衡数据符合Freundlich吸附等温方程。Freundlich吸附等温线和等量吸附焓表明：JDW－2和DuoliteS-761对咖啡因吸附是放热过程，我们对咖啡因在JDW－2和DuoliteS-761上的吸附焓，自由能，吸附熵也作了测试，并对吸附行为作了合理解释。     

几种吸附树脂对五氯酚钠吸附性能的研究

研究了几种树脂对五氯酚钠的吸附能力,其中戊二醛交联的壳聚糖树脂不仅有较好的吸附效果,动态吸附容量为187.5mg/g干树脂,而且易洗脱,洗脱率高达90%以上。     

改性Y型分子筛对FCC汽油脱硫性能的研究

采用液相离子交换法制备了Cu(I)Y、NiY、CeY分子筛,利用XRD、ICP/MS、N₂吸附脱附等技术对其物化性质进行了表征,使用固定床技术和色谱-硫化学发光检测(SCD)偶联技术系统考查了改性Y分子筛对FCC汽油的选择性吸附脱硫性能,着重探讨了FCC汽油选择性吸附脱硫过程中硫化物的脱除规律。结果表明,不同金属阳离子改性的Y分子筛对FCC汽油中不同硫化物选择性有所不同,对CeY分子筛:2-甲基-5-乙基噻吩<噻吩3硫醇< C₂噻吩<2或3-甲基噻吩<苯并噻吩<3,4-二甲基噻吩≈2,3,4-三甲基噻吩<四氢噻吩,而NiY与Cu(I)Y选择性相同:C₃硫醇<2-甲基-5-乙基噻吩2噻吩<2或3-甲基噻吩<噻吩<苯并噻吩<3,4-二甲基噻吩≈2,3,4-三甲基噻吩<四氢噻吩,改性Y分子筛对噻吩及小分子烷基取代噻吩类硫化物的选择性较差。     

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%。     

吡啶离子液体催化作用下的FCC汽油烷基化脱硫

合成一种Brønsted酸性离子液体[BPY]HSO₄,采用红外光谱和核磁共振对其进行表征。以[BPY]HSO₄为催化剂,对FCC汽油进行烷基化脱硫,考察反应温度、反应时间和剂油质量比对脱硫效果的影响及脱硫前后FCC汽油性质的变化,并对[BPY]HSO₄进行了再生。结果表明,在反应温度为65 ℃、反应时间为90 min和剂油质量比为0.09的条件下,FCC汽油的硫含量从580.0 μg/g降至6.4 μg/g,脱硫率为98.90%,满足中国国Ⅴ车用汽油硫含量标准(<10 μg/g);脱硫前后硫分布变化表明,在[BPY]HSO₄的催化作用下,前170 ℃馏分油中硫化物大部分转移到后170 ℃重馏分中,重馏分中硫化物可采用加氢方法进行脱除;PONA组成变化表明,烷基化脱硫过程对FCC汽油的烃类组成影响较小,且脱硫前后辛烷值变化不大;[BPY]HSO₄经萃取再生后可循环使用。     

Pervaporation performance of crosslinked polyethylene glycol membranes for deep desulfurization of FCC gasoline

An crosslinked polyethylene glycol (PEG) membrane was prepared for fluid catalytic cracking (FCC) gasoline desulfurization. Sulfur enrichment factor come to 4.75 and 3.51 for typical FCC gasoline feed with sulfur content of 238.28 and 1227.24 μg/g, respectively. Pervaporation performance of membranes kept stable within the long time run of 500 h, which indicated that crosslinked PEG membranes had the property of resisting pollution. Judging from chromatographic analysis, the membranes were more efficient for thiophene species. Effects of operation conditions including permeate pressure, feed temperature, feed flow rate and feed sulfur content level on the pervaporation performance were investigated. Permeation flux decreased with increasing permeate pressure while increased with the operating temperature increase. Sulfur enrichment factor increased firstly and decreased then when permeate pressure and temperature rose. The peak value occurred at 10.5 mm Hg and 358 K for model compounds feed (378 K for FCC gasoline feed). Arrhenius relationship existed between flux and operating temperature. Both sulfur enrichment factor and flux were shown to increase with increasing feed flow rate. Permeation flux increased while sulfur enrichment factor decreased as the feed sulfur content increased, but the influence of increasing sulfur content on pervaporation performance weakened when sulfur content come to 600 μg/g.     

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。     

Deep desulfurization of FCC gasoline by selective adsorption over nanosized zeolite-based adsorbents

Deep desulfurization of FCC gasoline by selective absorption was performed on various ion-exchanged nanosized Y zeolites. It was found that the metal ion as well as calcination conditions have significant influence on the absorption performance. The highest S absorption capacity was obtained on a HCuCeY sample calcined in N₂ atmosphere.     

Catalytic cracking of C5+ gasoline over hy zeolite

The catalytic conversion of a C5+ natural gasoline over the HY zeolite has been studied. The results show the formation of C2, C3 and C4 hydrocarbons with an apparent activation energy of ca. 39 kJ mol^-1. This revised version was published online in June 2006 with corrections to the Cover Date.     

Surface functionalization of silicon oxide at room temperature and atmospheric pressure

A novel method to derivatize silicon surfaces with 3-mercaptopropylsilane molecules has been developed and optimized. This method is based on an argon flow that increases the evaporation rate of the silane molecules by lowering the partial pressure of the silane molecules in gas phase above the liquid silane, at room temperature. X-ray photoelectron spectroscopy studies of the surfaces showed a dense monolayer coverage as well as hydrolysis of the silane methoxy groups. Atomic force microscopy was used to investigate the roughness of the surfaces after each step of the derivatization process. Since the final surface has a measured surface roughness of 0.19 nm, this method will be especially useful for further synthetic routes and advanced single molecule detection studies of interactions on surfaces as well as improvement of existing conventional techniques for surface derivatization and analysis.