Ni/ZnO吸附剂上溶剂油的超深度吸附脱硫

分别采用等体积浸渍法和共沉淀法制备了Ni质量分数为20%的Ni/ZnO吸附剂,采用N2吸附、X射线衍射和扫描电子显微镜研究了制备方法对Ni/ZnO吸附剂物化性质的影响,通过固定床吸附实验评价了Ni/ZnO吸附剂对溶剂油的吸附脱硫性能。实验结果表明,共沉淀法制备的Ni/ZnO吸附剂的比表面积和孔体积分别高达66.7m2/g和0.236cm3/g,吸附脱硫性能明显优于等体积浸渍法制备的Ni/ZnO吸附剂。在溶剂油中硫含量为145.0g/mL、吸附温度300℃、压力1.0MPa、进料液态空速6h-1、氢气与溶剂油体积比300(氢气体积为标准状况下的体积)的条件下,连续运转200h,共沉淀法制备的Ni/ZnO吸附剂对有机硫化物的脱除率始终大于90%,硫容量约为150mg/g。该吸附剂对原料有很好的适应性,可再生,多次循环使用后脱硫性能仅略有降低,具有潜在的工业应用价值。     

Ti掺杂对Ni/ZnO-TiO2吸附剂用于FCC轻汽油脱硫性能的影响

采用混捏法制备了不同Ti含量的ZnO-TiO₂载体,采用等体积浸渍法制备了NiO/ZnO-TiO₂汽油脱硫吸附剂前驱体,并采用X射线衍射(XRD)、压汞、NH₃程序升温脱附(NH₃-TPD)、H₂程序升温还原(H₂-TPR)和H₂程序升温脱附(H₂-TPD)等手段对其进行了表征。以催化裂化轻汽油为原料,于氢气氛围下对NiO/ZnO-TiO₂前驱体还原得到Ni/ZnO-TiO₂吸附剂,在固定床上考察了Ti掺杂对该吸附剂脱硫性能的影响。结果表明：Ti的掺杂提高了Ni/ZnO吸附剂中活性组分Ni的分散度,增加了Ni活性位点,增强了吸附剂中强酸酸性及酸强度,Ti掺杂的吸附剂脱硫性能显著提高;Ti的掺杂能够减少游离Ni,有效抑制烯烃饱和;吸附剂脱硫性能随着Ti掺杂量的增加呈现先增强后减弱的趋势,当Ti掺杂质量分数为5%时,吸附剂具有最优脱硫性能,能够将FCC轻汽油中硫质量分数由300 μg/g降低至5 μg/g以下,穿透硫容为6.711%(每克吸附剂吸附硫67.11 mg),烯烃质量分数增加0.6百分点,降低了汽油辛烷值损失。     

Ni/ZnO-SiO2-Al2O3吸附剂上加氢汽油的深度临氢吸附脱硫

采用等体积浸渍法和湿混法制备NiO/ZnO-SiO2-Al2O3吸附剂前体,经还原得到Ni/ZnO-SiO2-Al2O3吸附剂。利用XRD和压汞法对其晶体结构进行表征,采用固定床吸附实验评价吸附剂对加氢汽油的吸附脱硫性能。结果表明,与等体积浸渍法制备的吸附剂前体相比,湿混法制备的吸附剂前体的比表面积大,孔体积相当,还原后所得吸附剂的脱硫活性好。以山东恒源石化公司的加氢汽油为原料,在吸附温度350 ℃、压力2.0 MPa、进料液态空速7 h-1、氢气与溶剂油体积比60的条件下,可以将加氢汽油中的硫质量分数从69 μg/g降至10 μg/g以下,而汽油RON仅降低0.6个单位,硫容量（w）约为9.98 %。该吸附剂对原料有很好的适应性,可再生,多次循环使用后脱硫性能基本不变。     

用H2O2再生被H2S污染的天然气吸附剂

考察了吸附剂K-1对H₂S的吸附特性和H₂S滞留比对CH₄吸附能力的影响，研究了H₂O₂溶液浓度对吸附剂性能的影响，以及H₂O₂溶液氧化法在不同H₂S滞留比时吸附剂的再生效率。实验结果显示，吸附剂对H₂S具有很强的吸附能力和吸附不可逆性，滞留H₂S可导致吸附剂对CH₄吸附能力大幅下降；H₂O₂溶液浓度应控制在12% (重量分数)以下，高浓度的H₂O₂溶液会破坏吸附剂本身的孔结构，H₂O₂溶液氧化法对H₂S污染型，尤其是低污染型吸附剂具有很好的再生效果。通过对重复再生吸附剂的结构参数和再生产物的分析，讨论了H₂O₂溶液氧化法的再生机理。     

Ni/ZnO吸附剂脱除催化裂化汽油中的硫

 采用等体积浸渍法制备了Ni质量分数为4%的Ni/ZnO吸附剂，以FCC汽油为原料，通过固定床吸附实验评价了Ni/ZnO吸附剂对催化裂化汽油的吸附脱硫性能以及吸附剂的再生性能。结果表明，较高的反应温度、压力和较低的体积空速有利于提高Ni/ZnO对FCC汽油的吸附脱硫效果，并且汽油辛烷值损失小。Ni/ZnO吸附剂脱硫的适宜操作条件为: 温度370～380℃，吸附压力2.0MPa，氢/油摩尔比1.5，体积空速4.0h^-1，此时吸附剂的穿透硫容 (硫质量分数达到30μg/g时，认为吸附剂穿透，测定吸附剂中的硫质量分数，即为吸附剂的穿透硫容。)为2.54%，汽油辛烷值损失1.1个单位。该吸附剂可以再生，多次循环使用后其脱硫性能基本保持不变。     

Ni/SFCC催化黑柴油加氢-裂解-脱硫同时制备汽油和柴油的性能

为了解决地炼厂黑柴油含硫高、十六烷值低和安定性差等问题，采用高压搅拌反应釜进行黑柴油加氢-裂解-脱硫同时制备汽油和柴油研究。以废催化裂化触媒为载体、镍为活性组分，采用等体积浸渍法制备了废催化裂化触媒负载镍催化剂(Ni/SFCC),使用低温物理吸附、XRD、TG-DTA和H₂-TPR等分析测试方法表征了催化剂形貌。结果表明：Ni(NO₃)₂/SFCC在480～562 K为硝酸镍热分解，在820 K和881 K时达到恒重；催化剂前驱体还原温度为573～813 K;在513 K、3.0 MPa、80 min、搅拌转速600 r/min、催化剂质量分数5%反应条件下，产品柴/汽比为67/33,硫含量≤10 mg/kg。     

分子筛基液化石油气精脱硫吸附剂的制备与评价

考察了5A,ZSM-5,13X,NaY等不同类型分子筛的脱硫性能,并以NaY分子筛为载体,采用等体积浸渍法制备了以Cu2+,Zn2+,Ag+为活性组分的分子筛基液化石油气(LPG)精脱硫吸附剂,考察了吸附剂的制备条件,并采用固定床反应器考察了吸附条件对吸附剂脱硫效果的影响。实验结果表明,CuY吸附剂的脱硫性能最好,其适宜的制备条件为:以Cu(NO3)2为活性组分前体,吸附剂中Cu的负载量为9%(w)、浸渍温度60℃、焙烧温度400℃、焙烧时间2 h。在吸附温度为常温、0.6MPa、液态空速1 h-1的条件下,CuY吸附剂可使LPG中的硫含量从198 mg/m3降至5 mg/m3以下。当LPG中的硫含量降至5 mg/m3时,CuY吸附剂的计算穿透硫容为1.23%(w)。     

分子筛选择性吸附脱除硫化氢的研究进展

氢燃料电池的兴起为氢气纯化领域带来新的挑战。氢气中痕量硫化氢(H₂S)对燃料电池中Pt/C催化剂的不可逆毒化作用,推动了H₂S深度脱除的研究工作。但目前能达到燃料电池级氢气要求的H₂S脱除研究的报道相对较少,通过对常规H₂S的吸附脱除研究现状进行系统梳理,重点概述沸石分子筛如斜发沸石、A型、X型、Y型和其他类型分子筛及其改性分子筛在H₂S吸附脱除领域的研究进展,简要介绍本课题组在H₂S深度脱除方面的研究进展,以期为燃料电池中氢的纯化提供技术思路。     

La含量对CuO/AC吸附剂结构及性能的影响

采用等体积浸渍法制备了不同La负载量的Cu O-La/AC(AC为活性炭)吸附剂。在吸附温度30℃、吸附压力0.3 MPa条件下，考察了吸附剂脱除氢气中羰基硫（COS）的性能，并利用XRD,BET,SEM、N2吸附-脱附等方法对吸附剂的结构进行表征，探讨了吸附剂微观结构与脱除COS性能之间的关系。实验结果表明，掺杂助活性组分La有助于CuO/AC吸附剂脱除COS的效果和穿透硫容的提高，且随La负载量的增加，吸附剂的比表面积、孔体积、吸附性能均呈现先增加后减小的趋势。La负载量为0.1%(w)的5CuO-La/AC吸附剂的CuO分散性最好，脱除COS性能最佳，穿透时间达到34 h，穿透硫容为29.67 mg/g。     

FCC汽油临氢吸附脱硫工艺研究

在固定床吸附装置上对催化裂化汽油进行吸附脱硫实验，对比了三种吸附剂的脱硫效果，考察了吸附温度、空速、氢气流量对催化裂化汽油吸附脱硫性能的影响。实验结果表明，适宜的吸附脱硫工艺条件为：吸附温度320 ℃，空速2.0 h-1，氢气流量60～140 mL/min。在此条件下，吸附剂的硫容量为4.02 mg/g。     

用芳构化增强的反应吸附剂对催化裂化汽油改质的实验研究

用固相混捏法制备了耦合芳构化功能的反应吸附脱硫催化剂,研究了该催化剂对FCC汽油的改质性能。采用XRD和Py-IR表征了吸附剂的晶体结构和酸性特征,在高压微反装置上对其进行了活性评价,研究了吸附剂组成与工艺条件对FCC汽油改质的影响,结果表明:制备的吸附剂的活性组分由结晶良好的ZnO和ZSM-5分子筛及Ni活性组分构成。随着吸附剂中HZSM-5含量的增加,吸附剂酸性增强,芳构化反应功能提高。工艺条件对FCC汽油改质影响的研究表明,升高温度有利于芳构化反应的进行,但会加速催化剂的结焦失活,影响吸附剂的脱硫效果;增加压力可以使反应中的氢分压升高,减缓吸附剂的失活,有利于反应吸附脱硫,但不利于芳构化反应;增加氢油比可以抑制生焦,保持吸附剂活性,有利于反应吸附脱硫和芳构化反应,但会造成氢耗增加和烯烃饱和;空速增加可提高处理量,但由于原料与吸附剂的接触时间减少,导致反应物分子不能充分与吸附剂上的活性位反应,不利于芳构化和反应吸附脱硫反应的进行。采用研制的芳构化增强的反应吸附脱硫工艺及其吸附剂处理胜华FCC汽油的结果表明,在反应温度为425℃,反应压力为1.0 MPa,氢油比为200∶1,反应空速为6 h-1条件下,达到产物硫质量分数10μg/g以下时,异构烷烃和芳烃含量明显提高,可以较好的保持汽油辛烷值。     

混合氧化物载体对反应吸附剂Ni/ZnO的影响

The effect of mixed oxide support on the performance of the reactive adsorption desulfurization (RADS) for Ni/ZnO was invested by using thiophene in model gasoline in a fixed bed reactor. A series of oxide supports of Ni/ZnO was synthesized by co-precipitation method and characterized by XRD, N2-adsorption, TPR and NH3-TPD. It was found that the desulfurization capacity of Ni/ZnO is enhanced greatly when active components were supported on proper mixed oxide. Ni/ZnO supported on oxides exhibits much higher desulfurization efficiency and sulfur adsorption capacity than unsupported Ni/ZnO and the synthesized Ni/ZnO-SA adsorbent exhibits the highest efficiency for thiophene removal. The higher desulfurization activity and sulfur capacity of Ni/ZnO supported on SiO2-Al2O3 with small particle size, high specific surface area and large pore volume promotes the highly dispersion of active metal phase and the transfer of sulfur to ZnO with lower mass transfer resistance. γ-Al2O3 can weaken the interaction of active phases and SiO2 as well as increasing greatly the amount of weak acid. Therefore, these oxides have a great influence on the structure and chemical properties of the catalyst.     

Fabrication of hierarchical porous ZnO and its performance in Ni/ZnO reactive-adsorption desulfurization

To investigate the effect of texture structure on the desulfurization performance in the Ni/ZnO reactive adsorption desulfurization（RADS） system,two kinds of ZnO porous materials with rod-shaped morphology were synthesized and their structure was characterized by X-ray diffraction（XRD）,scanning electron microscopy（SEM）,transmission electron microscopy（TEM）,and N2 adsorption/desorption.The formation mechanisms of hierarchical porous ZnO（ZnO with meso and macro pores） were also studied.Their application performance was evaluated in the RADS process over Ni/ZnO absorbent.Due to the difference in structure between the two kinds of ZnO,the two ZnO based adsorbents showed different desulfurization activity.     

催化裂化汽油氧化吸附脱硫的研究

以氧气为氧化剂,硼酸为催化剂,活性白土为吸附剂,将催化氧化与吸附相结合,对催化裂化汽油进行了氧化吸附脱硫研究。结果表明,在氧气压力为2.0 MPa,氧化温度为80℃,氧化时间为60 min,催化剂用量占原料汽油的质量分数为3%,原料汽油与吸附剂质量比为20的优化条件下,汽油中的硫含量可从571.00μg/g降至68.52μg/g,脱硫率为88.00%,汽油的收率为83.4%。     

ZnO-活性炭脱硫吸附剂的制备及性能评价

采用混捏方法制备了以ZnO和活性炭为脱硫活性中心的脱硫吸附剂,采用XRD,BET,Py-IR等手段对吸附剂进行表征,并在10 mL固定床微型反应器上对吸附剂进行脱硫性能评价。实验结果表明,C3-B吸附剂（活性炭质量分数为30%）具有优异的脱硫性能,且性能稳定。以催化裂化加氢汽油为原料,在压力1 MPa、空速1.0 h-1、氢油体积比100:1、温度380 ℃的条件下,C3-B吸附剂的脱硫率为87.1%,产品的硫质量分数为10.0 μg/g,达到国Ⅴ排放标准要求。     

Desulfurization by Oxidation/Adsorption Scheme over Ti3(PW12O40)4 Catalyst

Abstract

Due to the future specifications for sulfur content in gasoline, a lot of research work has been done to develop alternative methods for desulfurization. This work presents the results for the desulfurization by oxidation/adsorption scheme over Ti₃(PW₁₂ O₄₀)₄ catalyst. The desulfurization experiment was performed with hydrogen peroxide (H₂ O₂) as the oxidant in the presence of Ti₃(PW₁₂ O₄₀)₄/SiO₂-Al₂ O₃ catalyst and adsorbent prepared by the sol-gel method, by using dibenzothiphene (DBT) in petroleum ether as the model compound. The efficiency of Ti₃(PW₁₂ O₄₀)₄/SiO₂-Al₂ O₃ catalyst and adsorbent prepared by the sol-gel method towards DBT adsorption from model compound was studied. The effects of titanium content of the adsorbent and the reaction conditions, such as the reaction temperature, the amounts of adsorbent and hydrogen peroxide (H₂ O₂), and the reaction time, etc., on the desulfurization efficiency and regeneration performance of the catalyst were investigated. It was found that the Ti₃(PW₁₂ O₄₀)₄/SiO₂?Al₂ O₃ catalyst presented higher maximum desulfurization conversion than SiO₂-Al₂ O₃ solids. In addition, it showed higher desulfurization conversion after regeneration with N,N-dimethylamide. Optimal reaction conditions were determined as: a reaction temperature of 70°C, a Ti (titanium)/H(hydrogen) molar ratio of 3, an adsorbent amount of 5 wt%, a H₂ O₂/S molar ratio of 3, and a reaction time of 2 hr. As a result, the total sulfur content in the petroleum ether solution of DBT could be decreased after oxidation/adsorption scheme from an initial value of 200 μg/g to a value of 2 μg/g, and the desulfurization conversion reached 99%, which is a remarkable result. Further, the said adsorbent also had quite good regenerability.     

The Preparation of Ni/ZnO Adsorbent via a Low-Temperature Solid-State Method for Ultra-deep Desulfurization

Abstract

One novel synthetic approach has been proposed to prepare Ni/ZnO adsorbent via low-temperature solid-state reaction. Thermal analysis (thermogravimetry differential scanning calorimetry [TG-DSC]) revealed that the nickel–zinc oxalate precursor obtained is a single-phase composite oxalate. Transmission electron microscopy analysis (TEM) shows that the NiO/ZnO composite materials are composed of nanoparticles with good dispersivity, whereas the elements of Ni and Zn are well distributed. The activity evaluation indicates that the Ni/ZnO adsorbent has good ultra-deep desulfurization activity of removing organic sulfur compounds. The sulfur concentration in the treated gasoline is less than 1.0 μg/g, which meets the need of ultra-low-sulfur fuels for use in fuel cells.     

棒状Ni/CuO-ZnO的制备及其反应吸附脱硫性能研究

采用水热合成法制备了棒状CuO-ZnO复合氧化物,采用等体积浸渍法制备了Ni/CuO-ZnO吸附剂,采用TG、SEM,XRD,BET方法进行了表征。在固定床反应器中进行了吸附剂的反应吸附脱硫性能评价。结果表明：制备的CuO-ZnO复合氧化物呈棒状结构,复合氧化物适宜的焙烧温度为500 ℃;Cu的掺杂有效改进了反应吸附剂的脱硫性能,Cu的最佳掺杂量（w）为10%,掺杂Cu后脱硫率较Ni/ZnO平均脱硫率提高17.4百分点,且能延长有效脱硫时间,吸附剂在45 h左右仍能保持较高的脱硫活性。     

吸附剂吸附脱除催化裂化汽油中微量硫的研究

采用XFG-1吸附剂,于固定床反应器中研究了催化裂化(FCC)汽油中微量硫化物的吸附脱除技术。在吸附温度为350℃,吸附压力为2.0 MPa,进料体积空速为7 h-1,氢油体积比为60的最佳操作条件下,可将FCC汽油中硫的质量分数从85.97×10-6降低至9.50×10-6,脱硫率为88.95%,烯烃体积分数下降1.1个百分点。XFG-1吸附剂再生后可循环使用。与新鲜吸附剂相比,再生吸附剂的吸附活性虽略有下降,但脱硫性能稳定。采用XFG-1吸附剂脱硫,可获得质量达到国V清洁汽油标准(硫质量分数小于10×10-6)要求的FCC汽油。