高纯四氢芳樟醇的研究

在一定条件下,芳樟醇可高选择性地氢化成四氢芳樟醇,氢化选择性与催化剂的特性、氢化温度及芳樟醇来源有关。在适宜的氢压及搅拌条件下,改变催化剂的特性、反应温度及使用不同来源的芳樟醇能提高加氢产物中四氢芳樟醇的含量。以日本进口的合成芳樟醇（含量98.7%）为原料,采用W-6型雷尼镍为催化剂,在（60±10）℃、1～3 MPa氢压的条件下进行氢化,所得四氢芳樟醇含量为98.7%,选择性为100%。     

Liquid‐Phase Hydrogenation of m‐phenoxybenzaldehyde to m‐phenoxybenzylalcohol Using Raney Nickel Catalyst: Reaction Kinetics

Kinetics of the liquid‐phase catalytic hydrogenation of m‐phenoxybenzaldehyde to m‐phenoxybenzyl alcohol have been investigated over the Raney nickel catalyst. Effects of hydrogen partial pressure (500‐2000 kPa), catalyst loading (1.6‐6.4 g.L^?1), m‐phenoxybenzaldehyde concentration (0.2‐0.8 mol.L^?1) and temperature (333‐363 K) on the progress of the reaction were studied. The speed of stirring > 15 rps has no effect on the initial rate of reaction. Effects of various catalysts and solvents on the hydrogenation of m‐phenoxybenzaldehyde have been investigated. The reaction was found to be first order with respect to the hydrogen partial pressure, catalyst loading and m‐phenoxybenzaldehyde concentration. Several Langmuir‐Hinshelwood type models were considered and the experimental data fitted to the model involving surface reaction, between dissociatively adsorbed hydrogen and molecularly adsorbed m‐phenoxybenzaldehyde.     

癸二睛加氢制癸二胺骨架镍催化剂的研究

本文介绍了癸二脯加氢制癸二胺用骨架镍催化剂的制备方法、活化条件,以及反应温度、压力、接触时间等因素对转化率的影响,揭示了骨架镍催化剂的反应特性和用于癸二脑加氮的最佳操作条件。     

均匀设计研究溶剂法腰果酚催化加氢工艺

以正丁醇为溶剂,采用均匀设计实验,考察了反应温度、氢气压力、反应时间以及催化剂用量对腰果酚催化加氢工艺的影响.在高压釜中填料100 mL的腰果酚以及200 mL的正丁醇,加入雷尼镍催化剂4.0 g,反应温度设定为80℃,氢气压力为3.6 MPa,反应5 h,重复进行3次实验,转化率均可达100%.将催化剂重复利用5次,其催化活性并没有降低.     

纳米镍粉的固相合成及其催化活性研究

介绍了以NiSO₄·6H₂O和NaOH为原料，固相法合成镍纳米粉。通过XRD、TEM、SEM和XPS等测试手段对产物表面结构进行表征。结果表明，产物为球形分布均匀的纳米镍粉，平均粒径为(30±5) nm。同时考察了不同还原温度和时间下得到的产物的催化活性以及反应中温度、压力和含量等对硝基苯加氢还原催化活性的影响，并在相同的条件下，和Raney Ni进行比较。还原实验表明，400 ℃还原4 h的产物质量分数为4.13%时,硝基苯转化率高达26.26%,催化加氢活性高于Raney Ni,是相同条件下Raney Ni的9倍左右。压力为0.8 kPa时，硝基苯转化率高达76.42％。     

新型固定床Raney镍(Ⅱ)成型合金的浸取过程

以20%的拟薄水铝石为黏结剂制备新型固定床Raney镍催化剂,采用苯加氢为模型反应,研究了前驱物成型合金浸取条件对催化剂加氢活性的影响.实验结果表明,对于860℃焙烧2 h后的成型合金,以10%～20%的NaOH溶液在80～90℃浸取3～4 h可得到具有较高加氢活性的固定床Raney镍催化剂.浸取反应可在1～4 h内基本完成,浸取后催化剂表面出现微孔结构,具有较好的苯加氢活性和活性稳定性,可在120℃、0.5 MPa、空速2 h^-1的缓和条件下实现苯的完全转化.     

纳米镍粉上硝基苯加氢制苯胺反应性能研究

以NiSO4.6H2O、NaOH和H2为原料,采用低温固相法制备了分布均匀、平均粒径为20～35 nm的纳米镍粉,并采用X射线衍射(XRD)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)和X射线光电子能谱分析(XPS)等微观分析手段对产物表面结构和价态进行了表征。研究了纳米镍粉加氢还原硝基苯制备苯胺体系中温度、氢压力、催化剂用量等因素对转化率的影响,并与Raney Ni的活性做了比较。结果表明,纳米镍粉催化加氢活性高于RaneyNi,是同条件下Raney Ni的9倍左右;催化剂用量4wt%～6wt%(质量含量,下同),温度为120℃为还原的最佳条件;同时发现氢压力对转化率也有着较大影响,当压力达到0.8 MPa,硝基苯转化为苯胺的转化率高达76.42%。     

采用骨架钴和骨架镍催化剂加氢还原制备糠醇的研究

从钼、铬、铜和铁中筛选金属铬和铁作为助催化剂加入骨架钴或骨架镍催化剂，铬和铁的量分别为催化剂质量的３％和１％。在１００～１２０℃、１０～１２ＭＰａ条件下，用上述骨架钴或骨架镍催化剂在乙醇溶剂中，氢化还原糠醛制备糠醇。用骨架镍催化剂，反应产物含有７８５％的糠醇和１９６％的四氢糠醇；用骨架钴催化剂，反应产物含有９８８％的糠醇和０８％的四氢糠醇，收率９４％。在无乙醇溶剂条件下，反应产物含有９０５％的糠醇、０３％的四氢糠醇和９２％的糠醛。在１８０℃条件下，反应产物含有９０８％的糠醇和８９％的四氢糠醇。     

Epoxidation of allyl alcohol with hydrogen peroxide over titanium silicalite TS‐2 catalyst

The influence of the technological parameters on the course of the epoxidation of allyl alcohol with 30% H₂O₂ in the presence of titanium silicalite TS‐2 catalyst and methanol as a solvent was studied. The process was performed in an autoclave at the autogenic pressure. The influence of temperature in the range 20–120 °C, molar ratio of allyl alcohol/H₂O₂ (1:1–10:1), methanol concentration in the reaction mixture (10–80% w/w), catalyst TS‐2 concentration (0.1–2.0% w/w) and reaction time (1–8 h) were investigated. The functions describing the process were: selectivity of transformation to glycidocidol in relation to allyl alcohol consumed, selectivity of transformation to organic compounds in relation to hydrogen peroxide consumed, conversions of allyl alcohol and hydrogen peroxide. Copyright © 2007 Society of Chemical Industry     

Reductive amination of 12-ketostearic acid

In the preparation of 12-aminostearic acid by reductive amination of 12-ketostearic acid, the keto acid is first contacted with ammonia under pressure to produce an intermediate, not isolated, which is then hydrogenated to give the product. Variables such as time and temperature of reaction, hydrogen pressure, and amount and type of catalyst were examined to find optimum conditions for high yield and purity of 12-amino-stearic acid. With a hydrogenation pressure of 500 psi and 10% Raney nickel catalyst an essentially quantitative yield of product was obtained having a purity of 94%. With 34% catalyst and 260 psi hydrogen, a 98% yield of 98% pure product was obtained. Presented at the AOCS Meeting, San Francisco, April 1969.     

对氟苄胺的合成

以对氟苯甲醛、氨水和氢气为原料,乙醇为溶剂,雷尼镍为催化剂,在H2压力为1.5～2.0MPa的压力下反应合成对氟苄胺。考察了各因素对转化率和收率的影响。得出最佳工艺：n（对氟苯甲醛）：n（NH3）=1.0：2.5;w（对氟苯甲醛）：w（乙醇）=1.0：1.3;反应温度60～65℃;雷尼镍用量为对氟苯甲醛量的5%;反应时间为7～8h。在此工艺条件下,对氟苯甲醛转化为对氟苄胺的选择性可达95.3%,产品收率达85% 以上,精制后产品纯度w（对氟苄胺）＞99%。     

改性Raney Cu催化一乙醇胺脱氢合成甘氨酸

一乙醇胺在氢氧化钠的水溶液中〔w(NaOH)=12%～18%〕,用含有铬和锗等贵金属改性的RaneyCu催化剂脱氢合成甘氨酸。反应温度150～180℃,反应压力0 8～1 2MPa,反应时间2～4h。实验结果表明:改性RaneyCu催化剂比普通RaneyCu有更好的活性和使用寿命,使一乙醇胺的平均转化率从92%提高到97%,有效使用寿命(一乙醇胺的转化率≥90%)从5次延长到15次以上。     

Liquid‐Phase Catalytic Hydrogenation of p‐Chlorobenzophenone to p‐Chlorobenzhydrol over a 5 % Pd/C Catalyst

The kinetics of the liquid‐phase catalytic hydrogenation of p‐chlorobenzophenone have been investigated over a 5 % Pd/C catalyst. The effects of hydrogen partial pressure (800–2200 kPa), catalyst loading (0.4–1.6 gm dm^–3), p‐chlorobenzophenone concentration (0.37–1.5 mol dm^–3), and temperature (303–313 K) were studied. A stirring speed > 20 rps has no effect on the initial rate of reaction. Effects of various catalysts (Pd/C, Pd/BaSO₄, Pd/CaCO₃, Pt/C, Raney nickel) and solvents (2‐propanol, methanol, dimethylformamide, toluene, xylene, hexane) on the hydrogenation of p‐chlorobenzophenone were also investigated. The reaction was found to be first order with respect to hydrogen partial pressure and catalyst loading, and zero order with respect to p‐chlorobenzophenone concentration. Several Langmuir‐Hinshelwood type models were considered and the experimental data fitted to a model involving reaction between adsorbed p‐chlorobenzophenone and hydrogen in the liquid phase.     

Raney镍上松香催化加氢本征动力学

测定在不同类型搅拌器下高压釜的持气量和反应效果 ,认识到松香在Raney镍上催化加氢反应受到外扩散的严重影响 ,利用加入 2 0 0号溶剂油、改造搅拌器类型、提高搅拌速度的方法消除外扩散 ,使反应处于化学动力学控制区 ,然后采集动力学数据 ,经对 17种可能的反应机理模型进行筛选 ,推测的反应机理为 :松香中的主要成分枞酸分子不吸附 ,枞酸分子与催化剂表面上被吸附的氢原子进行反应 ,氢原子的吸附为控制步骤 ,据此导出其本征动力学方程 .     

磷钼酸改性骨架铜催化剂上巴豆醛选择加氢制巴豆醇的研究

采用磷钼酸（H₃PMo₁₂O₄₀）对骨架铜催化剂（Raney Cu）进行改性,并以巴豆醛选择加氢反应为探针反应,考察了（H₃PMo₁₂O₄₀）负载量和焙烧温度对Raney Cu催化剂性能的影响。研究表明,随着H₃PMo₁₂O₄₀负载量的增加,催化剂对巴豆醇的选择性上升,当负载H₃PMo₁₂O₄₀质量分数达到7.2%时,催化剂对巴豆醇的选择性达到最高,为35.8%,而未改性的Raney Cu催化剂对巴豆醇的选择性只有0.32%。还考察了磷钼酸改性的骨架铜催化剂上巴豆醛选择加氢反应的工艺条件,研究表明,反应温度、反应压力和催化剂用量对巴豆醛的转化率有较大的影响,但对巴豆醇的选择性影响较小。适宜的反应条件为：H₂分压0.6 MPa,温度333 K,催化剂用量0.30～0.35 g·（mL-CRAL）^－1,此时巴豆醇的收率约25%。     

Dehydrogenation of methyl 12-hydroxystearate to methyl 12-ketostearate with Raney nickel

Suitable conditions have been found for the dehydrogenation of methyl 12-hydroxystearate to methyl 12-ketostearate with Raney nickel. Crude reaction mixtures contained 95% product when analyzed by gas-liquid chromatography (GLC). Isolated yields were 83%. Both catalyst concentration and type strongly influence the reaction. Laboratory-made methyl 12-hydroxystearate gave significantly better yields than commercial material, but satisfactory conversions were obtained from citrate-free commercial material. The extent of the dehydrogenation was determined by hydrogen evolution and GLC. Synthetic and analytical techniques used in studying this reaction are discussed. W. Utiliz. Res. Dev. Div., ARS, USDA.     

苯乙烯存在下苯乙炔选择性加氢过程的研究

用高压反应釜对一种骨架Ni催化剂和八种Pd/Al₂O₃催化剂在苯乙烯环境下,对连串反应苯乙炔的选择性加氢性能进行了实验评价。通过一系列实验考察了催化剂活性组分负载量、反应温度、反应压力、反应时间和搅拌速率对反应结果的影响。反应结果的评价指标为苯乙炔转化率、苯乙烯收率和二者的综合。研究结果表明,骨架Ni催化剂的活性和选择性均较差,不适宜用作苯乙烯环境下的苯乙炔加氢过程。对Pd/Al₂O₃型催化剂而言,较低的反应温度和微正压的反应条件对苯乙炔的选择性加氢有利;延长反应时间无助于苯乙炔转化率的提高,相反却会导致苯乙烯收率的迅速降低;提高搅拌速率可以消除相间扩散传质对反应过程的影响,因此对苯乙炔的选择性加氢是有利的。另外,在实验研究的反应条件范围内,苯乙炔的转化率似乎存在一个极限值,分析认为这可能是由于催化剂的比表面积和活性组分负载量太高引起的。     

DNS加氢还原制备DSD酸

在水相中,以磷酸氢二钠和磷酸二氢钾为缓冲剂和Raney Ni为催化剂,研究液相催化加氢还原4,4′-二硝基二苯乙烯-2,2′-二磺酸(DNS)制备4,4′-二氨基二苯乙烯-2,2′-二磺酸(DSD酸)。试验结果表明,适宜的工艺条件为:原料质量浓度150~175 g/L、催化剂为原料质量的4%、温度为45~50℃和压力为0.8 MPa。在此工艺条件下的产品纯度为98.4%。     

十二碳二腈加氢制十二碳二胺催化反应的研究

通过试验,优选了十二碳二腈加氢制十二碳二胺用骨架镍催化剂。介绍了催化剂的制备方法、活化条件以及反应温度、反应压力、接触时间、搅拌速率和催化剂用量等因素对转化率的影响,研究了骨架镍催化剂的反应特性和用于十二碳二腈加氢反应的最佳操作条件。     

载体对Ni基催化剂催化蒽醌加氢活性的影响

研究了载体对Ni基催化剂用于蒽醌法制备H₂O₂加氢活性的影响,同时对比了骨架镍的催化活性,考察Ni负载量对催化剂活性的影响。结果表明,负载在SiO₂上的催化剂比负载在γ-Al₂O₃上的催化活性高,对于Ni/SiO₂催化剂,Ni负载质量分数28.57%～50%时,加氢活性较高,按单位质量纯Ni上H₂O₂产量计算,Ni/SiO₂优于骨架镍催化剂,Ni负载量过高时,加氢活性降低。2-乙基蒽醌在Ni/SiO₂催化剂上的加氢为结构敏感型反应,当Ni在SiO₂的分散度达到约18%时,催化活性较佳。