负载AlCl_3催化剂合成挂式-三环[5.2.1.0~(2,6)]癸烷

采用液固反应法合成了负载AlCl3催化剂,用于催化桥式四氢双环戊二烯异构化合成挂式四氢双环戊二烯的反应。通过考察载体、负载量对催化剂活性的影响,选定SiO2作载体、负载量为60%的催化剂用于该反应;研究了负载催化剂用量、溶剂种类及反应时间对异构化反应的影响,得到了最佳反应条件:以挂式四氢双环戊二烯作溶剂,催化剂质量分数14%,反应时间2 h。在此条件下桥式四氢双环戊二烯的转化率为99%,挂式四氢双环戊二烯的选择性为97.9%。该过程反应后处理简单,环境友好。     

一步法合成挂式四氢双环戊二烯

制备了Ni/沸石双功能催化剂,筛选了催化剂载体,并以Ni/HY为催化剂、双环戊二烯为原料,考察异构化温度和催化剂用量对一步反应合成挂式四氢双环戊二烯转化率和选择性的影响,结果表明,双环戊二烯转化率大于96％,挂式四氢双环戊二烯收率达到21.4％,并关联了催化剂酸性与活性。     

催化异构化合成挂式四氢双环戊二烯

对催化异构化桥式四氢双环戊二烯合成挂式四氢双环戊二烯的反应进行了研究。考察了无水AlCl₃催化下，溶剂、溶剂用量、催化剂用量和反应时间对转化率以及选择性的影响。结果表明，以CH₂Cl₂为溶剂，CH₂Cl₂和桥式四氢双环戊二烯的用量比为0.8，催化剂用量为20％，反应时间为3 h，桥式四氢双环戊二烯的转化率为97.12％，挂式四氢双环戊二烯的选择性为99.28％。     

挂式四氢双环戊二烯合成工艺研究进展

以双环戊二烯为原料,通过加氢、异构化两个过程得到一种高能量密度燃料——挂式四氢双环戊二烯(exo-THDCPD)。综述了exo-THDCPD制备过程涉及的技术现状,包括反应原理、工艺路线、主要技术参数等内容。重点介绍了加氢与异构化催化剂种类及制备方法、加氢与异构化工艺流程的研究进展。总结出非贵金属合金催化剂为加氢催化剂的研究重点;延长固载化Al Cl3催化剂的使用寿命、提高分子筛催化剂的抗积碳能力、降低离子液体催化剂的生产成本是异构化催化剂的3个研究方向;提高双功能催化剂的选择性对"一锅法"制备exo-THDCPD意义重大;液相串联工艺有望实现exo-THDCPD的连续化工业生产。     

镍基催化剂催化双环戊二烯加氢反应的研究

采用固载化骨架镍催化剂对双环戊二烯(DCPD)固定床连续催化加氢合成四氢双环戊二烯进行了研究。考察了温度、压力、氢油比和空速对DCPD加氢反应的影响,结果表明:固载化骨架镍催化剂对DCPD液相加氢合成桥式四氢双环戊二烯(endo-THDCPD)具有良好的催化作用。DCPD液相加氢反应过程与反应温度、压力、氢油体积比及空速有关,在反应温度为40℃,压力为2.5 MPa,氢油体积比为200,空速为2 h-1条件下,对催化剂进行了500 h长周期运转,DCPD的转化率达到95%以上;然后对催化剂进行了再生实验研究和XRD、SEM及BET表征,结果表明:催化剂活性、稳定性和再生性能良好。     

F/HY催化剂用于挂式四氢双环戊二烯的制备

采用室温过量浸渍法,制备不同F用量改性的HY分子筛催化剂。采用氨程序升温脱附法(NH3-TPD)、X线衍射仪(XRD)、傅里叶变换红外光谱仪(FT-IR)对催化剂的结构及酸性质进行表征,并在桥式四氢双环戊二烯(endo-TCD)制备挂式四氢双环戊二烯(exo-TCD)的反应中考察催化剂的催化性能。结果表明:最适宜的反应条件为以1.0%F/HY为催化剂,活化温度300℃,反应温度240℃,催化剂与原料质量比0.25∶1,溶剂环己烷与endo-TCD的摩尔比10∶1,初始压力1.0 MPa,反应时间1.5 h。最优条件下桥式四氢双环戊二烯的转化率达到92.6%,挂式四氢双环戊二烯的收率达到了59.4%。失活的催化剂可以通过550℃高温焙烧再生,其活性变化不大。     

SRNA-4非晶态合金催化双环戊二烯液相加氢反应研究

采用SRNA-4非晶态合金催化剂对双环戊二烯(DCPD)进行了加氢反应考察,研究了搅拌速度、温度、压力和催化剂浓度各条件对双环戊二烯加氢反应的影响.结果表明DCPD加氢反应为连串反应,中间产物主要为9,10-二氢双环戊二烯(9,10-DHDCPD)和少量1,2-二氢双环戊二烯(1,2-DHDCPD);DCPD易于加氢生成中间产物9,10-DHDCPD,其继续加氢为四氢双环戊二烯(endo-THDCPD)需要较为剧烈的条件.DCPD加氢过程选用两段法,第一段为温度110℃,第二段为130℃,压力均为1.5MPa,催化剂浓度1.18%.非晶态合金(催化剂)对DCPD的加氢反应活性明显高于Raney Ni,可进行1、2位加氢反应生成1,2-DHDCPD,并且催化剂用量少,反应温度和反应压力低,反应时间短,生成副产物少.     

茂金属催化剂——双环戊二烯二氯化钛的研究及应用

介绍了茂金属催化剂中双环戊二烯二氯化钛的几种合成方法。并对这些合成方法中的金属钠法、蒽镁法、二乙胺法进行了对比说明。描述了在催化加氢反应过程中的反应机理,介绍了国际国内的市场情况。对双环戊二烯二氯化钛合成技术及催化加氢工艺路线存在的不足和需要完善的地方进行了阐述。     

双环戊二烯连续加氢用镍基催化剂研究

制备了用于双环戊二烯(DCPD)固定床连续式加氢合成桥式四氢双环戊二烯的负载型Ni基催化剂。利用低温氮气吸附(BET)、X射线晶体衍射(XRD)以及程序升温还原(H2–TPR)等手段对催化剂进行表征。结果表明,Ni–Cu/γ–Al2O3催化剂具有更好的加氢活性和稳定性,Cu的加入可降低Ni O的还原温度,促进Ni O在载体表面的分散,有利于加氢活性的提高。此工作为筛选更适合DCPD固定床连续加氢催化剂提供理论和实验依据。     

四氢双环戊二烯异构化过程的溶剂效应

采用无水AlCl3为催化剂,考察了使用不同溶剂对桥式四氢双环戊二烯(endo-THDCPD)异构化为挂式四氢双环戊二烯(exo-THDCPD)过程中反应速率、反应转化率、收率、选择性及杂质生成量的影响。采用气相色谱对反应原料、产物及杂质进行定量分析。结果表明溶剂的使用对于异构化反应有显著的影响：甲苯作溶剂时对反应有很大的抑制作用,而1,2-二氯乙烷作溶剂时,则有明显改善,在催化剂浓度3％(wt)、最佳反应温度60℃条件下,反应结果：转化率97．73%、收率97.66％、选择性99．93％。同无溶剂反应时相比,最佳反应温度降低、产物中金刚烷生成量减少同时无焦油产生。实验中以原料endo-THDCPD为对象考察1,2-二氯乙烷作溶剂时的反应动力学,得到了动力学方程。     

Quantitative measure of geometrical isomerization during the partial hydrogenation of triglyceride oils

A mathematical model has been developed using a digital computer for the calculation of the isomerization index for partially hydrogenated oils such as cottonseed, soybean, peanut or corn oil. The isomerization index is defined as the ratio of the rate of geometrical isomerization of an unsaturated group to the rate of hydrogenation. Isomerization indices from about 0.3 to 11 were found to occur for hydrogenations using commercial nickel catalysts. Calculation of both an isomerization index and a selectivity ratio will be useful methods of quantitatively characterizing the partial hydrogenation of triglyceride oils or the type of hydrogenation which can be obtained by various catalysts.     

FCC轻汽油中C5烯烃临氢反应宏观动力学研究

在压力0.5~2.0 MPa、反应温度313~413 K、液体空速2.5~30 h?1的范围内,在管式滴流床反应器中,对C5烯烃在Ni/Al2 O3催化剂上的临氢反应进行了宏观动力学研究.结果表明,C5直链烯烃加氢反应对烯烃的反应级数为1,对氢压的级数为2.16,加氢活化能为21.11 kJ?mol?1;戊烯-1、3-甲基-1-丁烯、2-甲基-1-丁烯双键异构反应对烯烃的反应级数都为1,异构活化能依次为27.6、42.24、79.62 kJ?mol?1.表明了在相同条件下,烯烃加氢反应速率大于异构化反应速率,C5支链烯烃比直链烯烃更难异构.通过对实验数据的拟合得到反应动力学参数和动力学方程,对方程的检验表明,计算值与实验值吻合较好,误差基本在10%以内,表明在实验条件范围内,模型具有较高的可信度,可用于反应过程模拟和反应器的设计.     

Aspekte bei der Hydrierung von Fetten und Fettsäuren

Aspects of Hydrogenation of Fats and Fatty Acids Hydrogenation of fat products is of great significance, both for human and animal nutrition as well as for technical purposes. In the area of nutrition, adequate food for the increasing world population is unthinkable without utilization of all fat resources, that can be made available as food fats only after catalytic hydrogenation. In the area of technical use, a similar development is observed owing to shortage of mineral oils. Thus, fatty alcohols derived from vegetable oils and waxes can already compete in price with fully synthetic fatty alcohols derived from mineral oils. In the past 70 years of hydrogenation of fats till the present time, catalysts based on nickel have been most commonly used. In addition, small proportions of catalysts based on copper and noble metals have also been used. Homogenous catalysts have been used very recently. The present communication deals primarily with the hydrogenation of neutral fats and fatty acids using nickel catalysts. The aspects of selectivity and isomerization in the partial hydrogenation of neutral fats are discussed. In the hydrogenation of fatty acids and their derivatives, emphasis is laid on other factors, such as activity, poisoning and acid resistance of the catalyst. These factors are discussed.     

载体酸性对Pt/USY菲加氢制烷基金刚烷的影响

以Pt为活性组分、经不同浓度草酸铝处理的USY分子筛为载体,制备了Pt/USY催化剂,并用于菲一步加氢饱和反应和加氢异构反应体系。由于金属活性位点Pt上易发生加氢反应,USY载体酸性位点上易发生异构反应和裂解反应,实验分别考察了Pt颗粒、载体的酸强度和酸量对菲转化率和产物分布的影响。结果表明,活性金属Pt颗粒尺寸及分散度直接影响菲加氢饱和产物分布;草酸处理后制备的催化剂Pt/0.05-USY、Pt/0.1-USY较未经酸处理的Pt/USY更利于菲加氢反应。全氢蒽是菲向目标产物烷基金刚烷转化的关键中间产物,异构产物烷基金刚烷生成需在USY分子筛Br?nsted酸位点完成;随着催化剂载体酸量和酸强度的降低,裂解反应程度迅速减弱;菲加氢反应最终产物以加氢饱和反应产物为主;使用Pt/0.1-USY催化剂异构反应产物烷基金刚烷收率为2.3%。     

Influence of metal particle size in the hydrogenation of citral over Ru/C

Selective hydrogenation of citral has been studied under mild conditions over Ru catalysts supported on activated carbon. Geraniol, nerol, citronellal and isopulegol were the main reaction products. Isopulegol is obtained by isomerization of citronellal. Small amounts of citronellol are formed through the hydrogenation of citronellal. The specific catalytic activity per Ru surface atom as well as the products distribution remains constant with changing metal particle size. A comparison with results obtained on the hydrogenation of cinnamaldehyde on the same Ru/C catalysts is reported.     

苯加氢催化剂研究进展

介绍了苯加氢催化剂的分类,综述了均相催化剂、多相催化剂和离子液体催化剂的研究进展和生产工艺情况,其中多相催化剂可以对苯进行液相加氢和气相加氢。对苯加氢催化剂的评价和分析方法做了综述,讨论了苯加氢催化剂的加氢机理,对催化剂表面的吸附方式、反应速率的控制、苯和氢吸附的形式和分类问题做了说明。     

Fixed- Bed continuous hydrogenation of soybean oil with palladium- Polymer supported catalysts

To compare a continuous hydrogenation system with batch hydrogenation, soybean oil was treated with Pd and Ni catalysts in a fixed-bed system under conditions that gave trickle flow. The influence of processing variables such as space velocity, pressure, temperature and hydrogen flow on the selectivity, specific isomerization and the activity was investigated. Both the Pd and Ni catalysts gave significantly lower specific isomerization(trans isomer per drop in Iodine Value) when compared to reported values for batch hydrogenation with similar type catalysts. The linolenate and linoleate selectivities were also significantly lower. Heterogenized homogeneous Pd-on-polystyrene catalyst gave lower specific isomerization formation and higher selectivity than carbon-supported Pd catalyst at same conditions. This work indicates that Pd-on-styrene, Pd-on-carbon and extruded Ni catalysts, in fixed-bed continuous hydrogenation can produce soybean oil of desirable composition after further optimization.     

Hydroisomerization of model FCC naphtha over sulfided Co(Ni)–Mo(W)/MCM-41 catalysts

Deep hydrodesulfurization (HDS) of gasoline generally brings about the saturation of olefins and leads to the serious octane number losses. Conversion of linear olefins to branched ones followed by hydrogenation to isoalkanes would minimize such octane number losses. In this work, MCM-41-supported Co–Mo, Ni–Mo and Ni–W catalysts were prepared by the incipient wetness impregnation method, and compared with an industrial Co–Mo/γ-Al₂O₃ catalyst. The surface acidities were measured by the techniques of microcalorimetry and infrared spectroscopy for the adsorption of ammonia, and probed by the reaction of conversion of isopropanol. The isomerization and hydrogenation of 1-hexene as well as the HDS of thiophene were studied by using model FCC naphtha. It was found that the sulfidation enhanced significantly the surface Brønsted acidity that favored the skeletal isomerization of 1-hexene under the HDS conditions. Since the isomerization and hydrogenation of 1-hexene are the two competition reactions, the catalysts with relatively lower hydrogenation activity may have higher selectivity to the isomerization reactions. The Co–Mo/MCM-41 showed the high selectivity to the skeletal isomerization reactions due to its strong surface Brønsted acidity and the relatively low hydrogenation activity. On the other hand, the Ni–Mo/MCM-41 exhibited high hydrogenation activity and therefore low selectivity to the isomerization reactions although it possessed quite strong surface Brønsted acidity. The Ni–W/MCM-41 exhibited the low activity for the HDS of thiophene and isomerization of 1-hexene due to the poor dispersion of active metals.     

合成异丙胺工艺技术研究进展

异丙胺是应用广泛的低级脂肪醇胺,主要用于医药和农药等领域。随着一些下游产品的开发,对异丙胺的需求量也随之增长。合成异丙胺主要有异丙醇催化加氢胺化法和丙酮加氢催化胺化法。采用何种方法优势更大,主要取决于原料价格。镍基催化剂价格低廉,活性较高,是今后催化剂研究重点。丙酮法工艺成熟,但反应中副产物较多,生产成本较高;异丙醇反应副产物较少且易控制。