Cu~+-13X上噻吩与苯并噻吩的竞争吸附

以噻吩(TP)、苯并噻吩(BT)和正己烷配制模拟汽油,就如何提高Cu+-13X分子筛对噻吩的选择性进行了一系列的静态吸附及动力学吸附研究。结果表明:增加模拟汽油中噻吩的初始质量分数,可以增大Cu+-13X对噻吩的吸附量,提高噻吩对苯并噻吩的竞争吸附性能。当模拟汽油中苯并噻吩、噻吩的初始质量分数分别为500,700μg/g时,Cu+-13X对噻吩的吸附量就大于苯并噻吩;当模拟汽油中苯并噻吩、噻吩的初始质量分数分别为350,850μg/g时,Cu+-13X对噻吩的选择性大于苯并噻吩,噻吩在竞争吸附中占优势。     

Cu（Ⅰ）-13X吸附噻吩/苯并噻吩的动态性能

采用液相离子交换法制备Cu（Ⅰ）-13X分子筛,进行噻吩（T）、苯并噻吩（BT）双组分的固定床动态吸附研究,考察模拟汽油原料中噻吩与苯并噻吩初始质量分数、床层停留时间、床层高度等条件对床层净化效果的影响.结果表明：随着模拟汽油原料中噻吩初始质量分数的增大,吸附剂饱和吸附容量增大,原料中噻吩初始质量分数为1 000μg/g时的吸附剂吸附容量比噻吩初始质量分数800μg/g时提高7.2%,增大原料中噻吩的初始质量分数,有利于苯并噻吩的脱除;床层停留时间较长有利于固定床吸附,停留时间由24 min增加至30 min时,吸附总容量增加19.2%,噻吩、苯并噻吩的饱和吸附量分别增加26.5%和25.5%;床层高度由16 cm增加至20 cm时,吸附剂饱和吸附容量增加8.9%,噻吩、苯并噻吩的饱和吸附量分别增加15.3%和6.6%.     

过渡金属离子改性Na-13X分子筛对噻吩类硫化物的吸附性能与机理

采用液相离子交换法制备Cu+-13X、Ni2+-13X和Co2+-13X吸附剂,利用XRD、FT-IR和Laser-raman等对其进行表征。在常温常压条件下,以含有噻吩、2-乙基噻吩和苯并噻吩的正己烷溶液为模拟汽油,通过静态吸附实验与动力学吸附实验研究了3种吸附剂对噻吩、2-乙基噻吩和苯并噻吩的吸附性能与机理,并采用Langmuir模型对静态吸附平衡数据进行拟合和Crank单孔扩散模型对动力学吸附数据进行拟合。实验结果表明过渡金属离子改性的分子筛对噻吩类硫化物有较高的吸附含量;改性后分子筛的选择吸附性能取决于吸附质与吸附剂之间的π络合作用和吸附剂的表面酸性,而受硫化物的空间位阻影响作用很小。     

碱土金属元素Mg对Cu~+-13X分子筛吸附脱硫性能的影响

以13X分子筛为载体,采用液相离子交换法制备了Cu+-13X吸附剂和负载碱土金属元素Mg的Mg2+/Cu+-13X吸附剂,并利用XRD,XRF,ESEM和激光拉曼光谱仪(HR-800)等手段对所制备的吸附剂进行了表征。以含有噻吩和2-乙基噻吩的正己烷溶液为模拟燃料油,分别从静态吸附、吸附动力学两方面研究了两种吸附剂的脱硫性能,采用Langmuir模型和竞争吸附的Langmuir模型对单、双组分硫化物的静态吸附平衡数据进行拟合;采用Crank单孔扩散模型对吸附动力学数据进行拟合。结果表明,当Mg2+/Cu+-13X吸附剂中Mg的质量分数为3.35%时,吸附性能最佳;实验数据与模型吻合均很好,计算得到了Mg2+/Cu+-13X吸附剂对噻吩和2-乙基噻吩单组分的最大吸附量分别为140.7mg?g?1和183.8 mg?g?1,较Cu+-13X吸附剂对噻吩和2-乙基噻吩单组分的最大吸附量(130.2 mg?g?1和173.6 mg?g?1)分别提高了8.1%和5.9%,Mg2+/Cu+-13X双金属吸附剂的脱硫效果明显好于Cu+-13X吸附剂;负载的Mg2+作为一种助剂,使分子筛形貌分布更加均匀规整,并且增加了吸附剂的Lewis酸含量,使其还原性增强,吸附性能提高。     

复合分子筛深度脱硫性能研究

实验制备了复合分子筛MCM-41/Y,并进行Ag+优化。常温常压下在固定床吸附器中对其吸附脱硫性能分别在噻吩和二苯并噻吩模拟汽油体系下进行研究。实验结果显示Ag+优化后,Ag+/MCM-41/Y的脱硫性能大大增强。在实验室色谱检测条件下,对噻吩体系,吸附性能较好的Ag+/MCM-41/Y吸附剂每克可以得到约7毫升的无硫模拟汽油;对于二苯并噻吩体系,每克Ag+/MCM-41/Y吸附剂则可以得到约25毫升的无硫模拟汽油,并且吸附剂在350℃经煅烧再生多次后吸附效果保持不变。     

高硫柴油吸附脱硫剂的研究

研究了不同的Cu2+分子筛在常温常压下吸附高硫柴油中的硫化合物。采用水热合成法和离子交换法制备含Cu2+分子筛(CuMCM41和CuZSM5),用于固定床吸附脱硫。其中每克CuMCM41处理5 mL高硫柴油后达到饱和,并且能把含硫量降到300×10-6(质量分数)。吸附剂对硫化物具有很强的选择性,用CuMCM41来吸附模拟柴油,吸附结果表明它对噻吩和苯并噻吩的吸附性比对萘要强。     

改性沸石对废水中Cu2+、Cr3+的去除作用研究

用Na OH碱熔-水热法处理得到的改性斜发沸石作为吸附交换剂,对模拟废水中以Cu2+、Cr3+为代表的重金属离子进行吸附处理。研究了不同吸附时间、投加量以及初始浓度条件下,改性斜发沸石对Cu2+、Cr3+的去除效果。实验结果表明:改性沸石与水样中Cu2+、Cr3+的质量比分别为18.75∶1、13.33∶1时,对Cu2+、Cr3+的去除率分别达88.0%、87.4%,且为快速吸附平衡过程。此外,用Na Cl溶液和Na Cl溶液加氨水对吸附Cu2+饱和的改性沸石进行再生实验,再生率较高,改性斜发沸石可以多次重复利用。     

Al-MCM-41介孔分子筛深度吸附脱硫的研究

以十六烷基三甲基溴化铵为模板剂、铝酸钠为铝源、硅酸钠为硅源、用水热合成法制备了不同硅铝比的Al-MCM-41分子筛,负载不同金属离子对其改性,并用X射线衍射仪(XRD)、N2气吸附等方法对其进行了表征。同时,考察了Al-MCM-41(80)负载不同金属离子作为吸附剂对模拟汽油的脱硫性能。结果表明,Al-MCM-41(80)在353 K时的脱硫效果最好;负载金属离子Fe3+、Ni2+、Zn2+、Cu2+、Co2+、Ce3+的脱硫效果顺序为:Ni2+>Co2+>Zn2+>Fe3+>Ce3+>Cu2+;芳烃的加入降低了分子筛对噻吩的选择性。     

Y型分子筛催化γ-丁内酯气相胺解反应的催化性能

研究了经金属硝酸盐浸渍改性的Y型分子筛对γ-丁内酯与乙醇胺气相反应合成N-羟乙基吡咯烷酮(NHP)反应的催化性能,结果表明,分子筛的催化性能主要随改性阳离子的变化而不同。其中,CuY具有最高的初始活性,γ-丁内酯转化率达到50%以上,而经Cu离子改性的含稀土Y型分子筛具有较高的催化活性与稳定性。进一步考察了焙烧温度、反应温度、催化剂粒径等对催化剂性能的影响。再生实验表明,反应过程中分子筛的失活是不可再生的,说明是由于反应过程中生成的水蒸汽使分子筛的结构遭到破坏,而含稀土的分子筛由于含有稀土而使其具有较高的水热稳定性。     

改性ZSM-5分子筛膜对二元噻吩类硫化物分离性能

采用二次水热合成法制得ZSM-5分子筛膜,并对其负载金属离子进行改性。XRD、SEM等表征结果表明,所合成的为ZSM-5分子筛膜。所制得的膜经过负载金属离子改性后用于模拟汽油中噻吩类二元硫化物的分离,研究了不同负载离子种类、负载离子浓度和活化温度对二元硫化物竞争吸附的影响,同时还考察了膜的再生效果。实验表明:当银离子浓度为0.2mol/L时硫化物的分离因子最高达到1.7;当活化温度为450℃时ZSM-5分子筛膜的分离性能最好;苯并噻吩对噻吩有较强的竞争吸附影响。从再生性能看,负银ZSM-5分子筛膜的分离性能具有较好的稳定性。     

负载稀土元素的Cu^＋-13X吸附噻吩的性能研究

研究了负载稀土元素的Cu^＋-13X对噻吩的吸附性能,实验分别从静态吸附、固定床动态吸附以及吸附剂再生后的吸附性能三方面进行研究。研究结果表明,负载稀土元素的Cu^＋-13X,其静态、动态以及再生吸附能力都比Cu^＋-13X有所提高。特别是负载稀土元素的Cu^＋-13X再生后对噻吩的固定床动态吸附,其吸附量可以达到新鲜吸附剂的90．3％,这相对与于Cu^＋-13X再生后对噻吩的吸附效果有很大的提高。     

Effects of oxygenates and moisture on adsorptive desulfurization of liquid fuels with Cu(I)Y zeolite

Oxygenates (i.e., ethanol and MTBE as required additives in gasoline) and moisture were found to have strong inhibiting effects on desulfurization by adsorption with zeolite. The effects of each individual molecule were studied quantitatively by using a model fuel (500 ppmw thiophene in 80% n-octane + 20% benzene). Cu(I)Y was used as the π-complexation sorbent. Ab initio molecular orbital calculations showed that the adsorption bond energies with Cu(I)Y were: 21.4 kcal/mol for thiophene; 31.0 kcal/mol for MTBE and 41.6 kcal/mol for ethanol. Separation or selectivity factors can be estimated from heats of adsorption, and the inhibiting effects were predicted to follow the order of the relative heats of adsorption: water > ethanol > MTBE > thiophene. The inhibiting effects were measured by the decreases in the desulfurization capacities of Cu(I)Y in the presence of each additive in the model fuel. The results were in agreement with the theoretical prediction. In addition, the desulfurization capacity was strongly dependent on the liquid hourly space velocity because of the diffusion limitation of thiophene in the zeolite crystals.     

Y型分子筛微波法改性及其选择性吸附脱硫性能

通过微波法进行液态离子交换对NaY分子筛进行改性，采用静态实验对不同吸附剂的脱硫性能进行了考察，筛选出Ce(Ⅳ)-Y吸附性能最好。采用固定床技术对Ce(Ⅳ)-Y的吸附脱硫能力进行了研究，同时运用程序升温脱附法（TPD）和频率响应方法（FR）对吸附脱硫机理进行了进一步探讨。采用微波法进行离子交换改性后的Ce(Ⅳ)-Y分子筛的离子交换度与传统水热法比较有明显提高，吸附容量较NaY有显著提高。     

超声法制备Ce^4＋/13X分子筛的吸附脱硫性能

采用在离子交换过程中引入超声的方法制备了Ce4 /13X分子筛,考察了超声法对分子筛的制备及脱硫性能的影响,并考察了静态吸附条件对Ce4 /13X在低硫模型汽油(硫含量为23 mg/kg)中的脱硫性能影响。结果表明,超声法可显著缩短分子筛离子交换平衡的时间,提高离子交换度,且能有效地提高活性组分Ce在分子筛表面的含量,脱硫实验结果也显示吸附容量有明显的提高。常温常压,吸附时间为2.5 h,剂油质量比为0.0072的条件下,Ce4 /13X对噻吩的脱硫效果最好,吸附量为0.07653mmol/g,脱硫率可达到76.5%。Freundlich等温式能很好地关联噻吩在Ce4 /13X上的吸附平衡数据。450℃空气气氛中焙烧4 h的方法,可较好地再生Ce4 /13X。     

Screening of Inorganic Adsorbents for Selective Adsorption of Thiophene from Model Gasoline

Hydrodesulfurization-treated (HDS-treated) gasoline with low sulfur content is an important source of primary fuel for fuel cells, although it contains sulfur compounds, thiophene (TP), benzothiophene (BTP), and thiophene alkylated derivatives, known as a poison for the reformer catalysts and the electrode catalysts of fuel cells. Adsorptive removal of TP from model organic liquid of HDS-treated gasoline was screened on different kinds of inorganic adsorbents: hydrous metal oxides, mixed metal oxides, aluminosilicates, acidic salts of multivalent metal, hetero polyacidic salt, and metal salts of iron hexacyanate. All the adsorbents showed very low TP uptake, less than 5% of the total TP amount when metal ions were not loaded on the adsorbent. On the other hand, some metal ion (Ag, Cu, and Ce) loaded adsorbents had good TP adsorptive properties. On simple metal oxides, Ag ion was better for the formation of adsorption center than Ce or Ni ions. In zeolite group, Ce-loaded Y-zeolite showed the largest TP uptake (99% of the total TP amount). Hydrous cerium oxide and the Ce-loaded adsorbents prepared from K₄[Fe(CN)₆], Silicagel, TiO₂, and ZrO₂ did not show TP selectivity. The effect of coexisting toluene on TP adsorption was studied from the TP solutions with and without toluene.     

模板剂对ZSM-5分子筛膜脱硫的影响

采用二次水热合成法,考察了模板剂的配比和种类对ZSM-5分子筛膜合成的影响,用X线衍射光谱仪（XRD）和扫描电子显微镜（SEM）进行表征,并用模拟汽油进行脱硫实验。结果表明：改变模板剂的配比时,随着四丙基氢氧化铵（TPAOH）的增加,膜颗粒形状逐渐变为规整,但过高的TPAOH配比会使膜颗粒变为不规整,TPAOH配比为30制得的ZSM-5分子筛膜结构最为规整且对噻吩（TP）的脱除效果最好;改变模板剂的种类时,“TPAOH+乙醇”的双模板剂制得的膜脱硫效果最好,进一步对双组分模拟汽油进行脱除时,可以得出双组分硫化物被脱除的效果好于单组分的模拟汽油。     

Deep desulfurization of gasoline using ion-exchange zeolites: Cu(I)- and Ag(I)-beta

Solid adsorbents Cu(I) and Ag(I) metal exchanged beta zeolites were prepared by solid-state ion-exchange (SSIE) method. Crystallographic structure of the prepared adsorbents has been characterized by XRD analysis. The texture of the prepared adsorbents was investigated using N₂ sorption. Pyridine IR measurements have been carried out to investigate the nature of the acid sites of the adsorbents. The deep-desulfurization performance of such adsorbents has been evaluated through fixed-bed adsorption technique with model gasoline containing thiophene and benzothiophene at ambient temperature and pressure. The obtained results revealed that the breakthrough capacities of Cu(I)- and Ag(I)-beta zeolite with the optimized Cu⁺ or Ag⁺ content are 0.239 mmol S/g and 0.237 mmol S/g, respectively. The remaining sulfur in the desulfurized gasoline is less than 1 ppmw. Their desulfurization capacity for actual FCC gasoline blend is reduced about 30% due to the competitive adsorption from olefins and aromatics. However, The capacity regeneration of Cu(I)- and Ag(I)-beta zeolite sorbents was carried out for 9 times. It is more than 95% recovery of desulfurization after the first regeneration, and it keeps little reduction after subsequent 8 times of regeneration. Such studies included the effect factors on desulfurization performance, such as metal exchange content, SiO₂/Al₂O₃ ratio, acidity, and other texture properties of the zeolite etc.     

载金属离子的13X分子筛对噻吩的吸附性能研究

采用Zn2+,Cu2+,N i2+,Ag+分别负载到13X分子筛制得吸附剂,考察了它们对噻吩的吸附能力,发现Ag+-13X吸附效果最好,与软硬酸碱理论解释的结果一致。测定了噻吩在Ag+-13X上的吸附动力学数据,并测定了其不同温度下的吸附平衡数据,采用Langmu ir模型进行拟合,与平衡数据吻合得很好,说明Langmu ir模型能够描述本体系的特征,从微观上探讨了其吸附机理,是分子尺寸和化学键的共同作用;考察了Ag+-13X对真实汽油的脱硫性能,结果表明对汽油中的噻吩类硫化物都有脱除效果,为其工业设计提供基础数据。