Aluminum impregnated silica catalyst for Friedel-Crafts reaction:Influence of ordering mesostructure

Friedel-Crafts alkylation of benzene with linear chain olefin (C10-C14),which is an important reaction of synthetic detergent,was studied via different catalysts of aluminum impregnated silica molecular sieves.AlCl3 was immobilized on silica molecular sieves with different channel structures,hexagonal packing channels network (SBA-15,MCM-41),and disordered channel network (SiO2,SiO2-Gel) by impregnation.XRD and N2 adsorption-desorption isotherms confirmed that the specific mesoporous structures were maintained for order channel network catalyst after impregnation.Catalytic activities were investigated under different conditions.The influences of channel structure were discussed.The results showed that catalyst based on mesoporous like SBA-15 had the highest catalytic activities and 2-LAB selectivity compared with other catalysts in this work.The highest 2-LAB selectivity was nearly 50％ when 1-dodecene conversion was nearly 100％.At low 1-dodecene conversion or higher benzene/1-dodecene molar ratio,2-LAB selectivity was nearly 60％.     

Alkylation of benzene with 1- dodecene over usy zeolite catalyst: Effect of pretreatment and reaction conditions

Catalytic activity, stability and selectivity of USY zeolite catalyst for alkylation of benzene with 1-dodecene were investigated using a continuous fixed bed high pressure microreactor. It is found that the catalytic activity and stability depend closely on the pretreatment temperature of catalyst and reaction conditions. The best result was obtained at 120 °C and 3.0MPa with 8 molar ratio of benzene to 1-dodecene, and 4 h-1 weight hourly space velocity of reactant over the catalyst with the pretreatment temperature of 500 °C. Under this condition, the reaction conversion was nearly 100% and no deactivation was observed within the employed 50 h of time on stream with the selectivity of 2-phenyldodecene being 22%. This paper is dedicated to Professor Wha Young Lee on the occasion of his retirement from Seoul National University. On a research leave from Department of Chemical Engineering, Nanjing University of Technology, Nanjing 210009, China.     

碳基对甲苯磺酸催化剂在烷基化反应中的研究

利用可溶性淀粉和对甲苯磺酸混合物的部分炭化制备了碳基对甲苯磺酸催化剂,研究了该催化剂在苯与1-十二烯烷基化反应中的催化性能,考察了催化剂的处理温度、苯烯摩尔比、反应时间、催化剂的质量分数等因素对烷基化反应的影响以及催化剂的再生性能。结果表明：该催化剂在苯与1-十二烯烷基化反应中具有较好的催化活性和可再生性。在催化剂的处理温度为200℃、苯与1-十二烯的摩尔比为8,催化剂的质量分数5％和回流反应2．0h的条件下,1-十二烯的转化率为94．3％,LAB的选择性为95．0％,2-LAB的选择性为75．0％。     

Continuous reaction performances of benzene alkylation with long chain olefins catalyzed by ionic liquid

Based on a compulsive mixing-reacting-separating-recycling small experimental setup,the continuous reaction performances of benzene alkylation with long chain olefins catalyzed by [BMIM]Cl-AlCl₃ ionic liquid were investigated. Three different situations including normal continuous operation mode (reagent materials), sidetrack feeding from different axial positions along the static mixing reactor (reagent materials) and normal continuous alkylation using industrial paraffin and olefins materials were examined. Even under the relatively hypecritical reaction conditions, the single pass conversion of pure 1-dodecene could reach to nearly 100.0%, and the selectivity of 2-phenyl isomer was higher than 37.7%. Although the positions along the reactor for sidetrack feeding were different, the 100.0% single pass conversion of 1-dodecene was also attained before the outlet of the reactor. The refined industrial olefins as raw material could meet with the requirements of continuous alkylation. The influences of impurities such as di-olefins and non-benzene aromatics on the catalytic activity and stability should be studied further.     

苯与1-十二烯烷基化反应的研究进展

介绍了苯与1-十二烯烷基化反应制备直链烷基苯(LAB)的国内生产近况，讨论了固体酸催化剂催化苯与1-十二烯烷基化反应的研究情况，分析了离子液体催化苯与1-十二烯烷基化反应的研究进展，同时，对苯与1-十二烯烷基化反应的研发趋势提出了展望。     

Benzene Alkylation with 1-Dodecene over H-Mordenite Zeolite

The alkylation of benzene with 1-dodecene was studied over solid-acid zeolites, such as H-mordenite, H-USY, HY, and H-ZSM-5, in a batch reactor at 140°C and 10 atm. H-mordenite showed the highest selectivity of 78.2% for 2-phenyldodecane with 100% conversion. Depending on the catalyst amount (from 0.5 to 1.0 g) and the molar ratio of benzene to 1-dodecene (from 7 to 10), the conversion of 1-dodecene varied in the range from 63.8 to 100%. Furthermore, modification of H-mordenite by dealumination using nitric acid and by solid ion exchange with Mg²⁺ and Fe³⁺ ions led to the improvement of the selectivity for 2-phenyldodecane, and simultaneously reduction of the conversion of 1-dodecene is observed. In addition, it was found by pyridine adsorption FT-IR study that both strong Brønsted and Lewis acid sites are closely related to the conversion.     

高活性、高选择性骨架镍在糠醇加氢中的应用研究

研究了以骨架镍为加氢催化剂,以糠醇为原料制备四氢糠醇。在中温和高温下制备了两种骨架镍催化剂A和B,研究了不同的反应条件对两种骨架镍催化剂的影响,确定了最佳反应条件。骨架镍催化剂A在60℃,7MPa,用量为4g/100mL糠醇时,四氢糠醇选择性99 56%,收率可达99 41%。骨架镍催化剂B在60℃,5MPa,用量为4g/100mL糠醇时,四氢糠醇的选择性、收率可接近100 00%。     

[Bmim]Cl-xAlCl_3催化合成十二烷基苯

采用AlCl3和[Bmim]Cl不同摩尔比的[Bmim]C1-xA1C13离子液体为催化剂,研究了不同条件下1-十二烯与苯的烷基化反应。实验结果表明,以A1Cl3和[Bmim]Cl的摩尔比为2.0([Bmim]Cl-2A1C13)的离子液体为催化剂,在反应温度25℃、反应时间30 min,苯、烯及离子液体的摩尔比为5︰1︰0.03的条件下,正十二烯的转化率可达98.32%,2-LAB的选择性可达36.76%。离子液体和产物可形成易于分离的双液相,简化了催化剂与产物的分离操作。     

Effective control of carbon number distribution during Fischer–Tropsch synthesis over supported cobalt catalyst

Effective control of carbon number distribution in FTS has been demonstrated with co-fed 1-olefins in a trickle bed reactor. Addition of 1-octene or 1-dodecene in the n-paraffin solvent could greatly enhance the selectivity of heavy wax and increase the middle distillate to a certain extent directly from syngas, with a marked increase in CO conversion while suppressing the formation of lighter hydrocarbon products compared to the conventional FTS. In the case of co-fed 1-dodecene, the disproportionate reaction was obviously observable, which resulted in a symmetrical product distribution and gave a much higher selectivity in the middle distillate.     

Continuous reaction performances of benzene alkylation with long chain olefins catalyzed by ionic liquid

Based on a compulsive mixing-reacting-separating-recycling small experimental setup,the continuous reaction performances of benzene alkylation with long chain olefins catalyzed by [BMIM]Cl-AlCl₃ ionic liquid were investigated. Three different situations including normal continuous operation mode (reagent materials), sidetrack feeding from different axial positions along the static mixing reactor (reagent materials) and normal continuous alkylation using industrial paraffin and olefins materials were examined. Even under the relatively hypecritical reaction conditions, the single pass conversion of pure 1-dodecene could reach to nearly 100.0%, and the selectivity of 2-phenyl isomer was higher than 37.7%. Although the positions along the reactor for sidetrack feeding were different, the 100.0% single pass conversion of 1-dodecene was also attained before the outlet of the reactor. The refined industrial olefins as raw material could meet with the requirements of continuous alkylation. The influences of impurities such as di-olefins and non-benzene aromatics on the catalytic activity and stability should be studied further. __________ Translated from Chemical Reaction Engineering and Technology, 2006, 22(4): 289–293 [译自: 化学反应工程与工艺]     

MCM-22沸石催化剂的苯与长链烯烃烷基化性能

用NH3-TPD法研究了4种不同硅铝摩尔比的MCM-22沸石的酸性质,在常压间歇式反应器中考察了它们在苯与长链烯烃烷基化反应中的催化性能,并与HY和HZSM-5沸石催化剂进行了比较。实验结果发现MCM-22的催化活性与其强酸量有一致的关系,与其硅铝摩尔比无对应关系;MCM-22的活性比HY低,但对2-P的选择性远远高于HY,这说明了MCM-22对2-P具有形状选择作用。     

离子液体催化苯与长链烯烃烷基化的连续反应性能

在强制混合-反应-分离-循环实验装置上考察了酸性氯铝酸盐室温离子液体[BMIM][AlCl4]催化苯与长链烯烃烷基化反应的连续操作、沿反应管侧线分布式连续进料和工业烯烃原料进料的连续反应性能。实验结果表明,即使在相对苛刻的反应条件下,纯烯烃原料1-十二烯单程转化率也能在反应器内达到100.0%,2-苯基异构体选择性高于37.7%。虽然侧线连续进料的位置不同,但在反应器出口前1-十二烯可完全转化。精制过的工业烯烃原料可以满足连续烷基化反应的要求。     

High Active and Regioselective Hydroformylation of 1-Dodecene Catalyzed by Rh-BISBIS in a Two-Phase System

The hydroformylation of 1-dodecene under aqueous/organic two-phase reaction conditions with rhodium catalysts derived from BISBIS (sodium salt of sulfonated 2,2′-bis (diphenylphosphinomethyl)-1,1′-biphenyl) in the presence of cationic surfactants was studied; regioselectivities appear to be sensitive to pressure. In all cases, the activities and regioselectivities for linear aldehyde were higher.     

H2S分压对1-十二烯在NiMo/Al2O3催化剂上加氢反应的影响

在加氢裂化反应过程中，裂化产生的痕量烯烃会与H2S结合生成硫醇。为研究H2S对烯烃加氢及硫醇生成的影响，实验室采用微反以正-十二烯为模型化合物，考察了H2S存在下1-十二烯在NiMo/Al2O3催化剂上的加氢反应。结果表明，在一定范围内H2S分压的变化对1-十二烯的转化率没有明显影响，但对产品中异构烯烃的选择性有很大影响，并直接影响产物中十二碳硫醇的收率与分布。     

一种制备无氯苯甲醛的纳米催化剂的合成及性能

运用共沉淀法制备了系列锌锰复合纳米催化剂,并用于气相催化加氢苯甲酸合成无氯苯甲醛。经XRD,TEM,BET,IR等表征技术表明,其主要物相为ZnMnO3、ZnO和MnO2,粒径范围在80~200 nm.实验室及单管小试结果表明,该纳米催化剂不但具有很高的催化选择性,而且降低了反应温度。当反应温度为370±10℃、酸液时空速0.1 h-1、氢气时空速650±50 h-1时,苯甲酸的转化率高达99.0%,苯甲醛的选择性为94.5%。同样条件下,取140 kg的催化剂在厦门涌泉集团做了中试,得到苯甲酸的转化率为98%,苯甲醛的选择性为83.2%。     

金属／MgO上的乙醇水蒸气重整制氢

研究了氧化镁负载镍、铁、钴、锰、钼、铜和锡等金属催化剂在乙醇水蒸气重整反应的性能,结果表明在650℃,101．3kpa条件下,所有催化剂的活性都较高,乙醇接近完全转化,而对氢的选择性顺序为：Ni〉Co〉Sn〉Cu〉Fe〉Mo〉Mn。除镍的选择性是随温度上升之外,其他催化剂的选择性都随温度变化有个最佳值。镍催化剂的TPR和XRD表征表明,催化剂中存在3种形态的镍。     

Catalytic Hydrogenation of Aqueous Phase Nitrate Over Fe/C Catalysts

Catalytic hydrogenation of nitrate in water has been carried out over Fe/C catalysts at ambient temperature using batch and continuous reactors. In batch reaction nitrate reduction activity of 2.9 mmol g _metal ^?1  min^?1 with nearly 100% selectivity towards nitrogen was obtained. Column study shows nitrate reduction below 5 ppm for an initial concentration of 100 ppm. Break through capacity, to reach concentration of 45 mg L^?1, is more than 530 bed volumes. The catalysts were characterized using XRD, SEM–EDAX and XPS. With high selectivity and activity the catalytic system in present study could be a potential option for nitrate removal from water.     

纤维级1,3-丙二醇的制备

研制了一种细颗粒改性Ｒａｎｅｙ镍催化剂,考察了３－羟基丙醛(３－ＨＰＡ)加氢时,催化剂量、氢压、催化剂使用寿命及搅拌速度等影响因素。结果表明,在一定的条件下,加氢转化率可达１００%,１,３－丙二醇(１,３－ＰＤＯ)选择性大于９９%。但经加氢制得的１,３－ＦＤＯ中仍有较高醛含量,为此又制备了一种脱除１,３－ＰＤＯ中醛基的催化剂。在固定床反应器中,当反应温度为５０~９０℃、液时空速为１－５ｈ－１、待精制的粗１,３－ＰＤＯ中醛基含量小于２０００ｐｐｍ时,成品１,３－ＰＤＯ中的醛基含量可降至３０ｐｐｍ以下,符合生产高质量ＰＴＴ纤维的要求。     

Ni2P/SiO2催化剂制备及其乙酸加氢制乙醇催化性能评价

通过等体积浸渍和N₂气流中热处理过程制备了系列氧化硅负载过渡金属磷化物催化剂,经乙酸加氢制乙醇反应实验和动力学分析评价催化剂性能。研究结果表明,随着反应温度从280℃升高到340℃,乙酸转化率和乙醇选择性均逐渐提高。随着催化剂制备的P/Ni摩尔比从2：1增大到4：1,催化剂活性和乙醇选择性均先增大后减小,P/Ni摩尔比为3：1催化剂性能较佳。250℃热处理制备催化剂的催化性能优于200℃及300℃。Ni₂P/SiO₂催化剂活性和乙醇选择性均高于Co₂P/SiO₂催化剂。用次磷酸钠作为磷补充源制备催化剂的性能优于次磷酸钾。采用较佳条件下制备的Ni₂P/SiO₂催化剂,在温度340℃、压力2.0 MPa、氢酸进料量比10：1、质量空速0.4 h^-1条件下进行乙酸加氢反应,乙酸转化率为100%,乙醇选择性达到74.56%,并且适当升高反应温度会进一步提高乙醇选择性。     

LB-16有机硅杂化分子筛催化剂的制备及其在长链烷基苯合成中的应用

长链烷基苯(LAB)是制备合成洗涤剂烷基苯磺酸钠的主要原料,传统上LAB采用无机液体酸(HF)为催化剂将苯和长链烯烃烷基化而制得。在LAB的诸多异构体中,2-LAB因其更高的溶解性和可降解性而更受欢迎。使用低温成胶的策略,以水热合成法合成LB-16有机硅杂化分子筛催化剂,并考察其在LAB合成中的催化性能。结果表明,在反应温度190℃、空速0.2 h-1、苯烯物质的量比15∶1条件下,经过1 000 h催化试验,1-十二烯转化率大于99%,2-LAB选择性51%。LB-16有机硅杂化分子筛催化剂对苯与1-十二烯合成反应具有较好的催化活性和稳定性,同时对2-LAB具有较高的选择性,具有工业化应用前景。