Heterogeneous catalytic hydrogenation of canola oil using palladium

The hydrogenation of canola oil was studied using palladium black as a potential catalyst for producing partially hydrogenated fats with lowtrans-isomer content. Pressure (150\s-750 psig) appeared to have the largest effect ontrans-isomer formation. At 750 psig, 90 C and 560 ppm metal concentration, a maximum of 18.7%trans isomers was obtained at IV 53. A nickel catalyst produces about 50%rans isomers at the same IV. For palladium black, the linolenate and linoleate selectivities were 1.2 and 2.7, respectively. The maximum level oftrans isomers observed ranged from 18.7% to 42.8% (150 psig). Temperature (30\s-90 C) and catalyst concentration (80\s-560 ppm) affected the reaction rate with little effect ontrans-isomer formation and selectivities. At 250 psig and 50 C, supported palladium (5% Pd/C) appeared to be twice as active as palladium black. At 560 ppm Pd, 5% Pd/C produced 30.2%trans (IV 67.5), versus 19.0%trans for palladium black (IV 68.9). Respective linoleate selectivities were 15 and 6.6, while linolenate selectivities were approximately unity. Analysis of the oil samples by neutron activation showedapproximately a 1 ppm, Pdresidue after filtration.     

The hydrogenation of fatty oils with palladium catalysts. VI. Hydrogenation for margarine

Satisfactory margarine stocks have been made with a palladium on carbon catalyst in laboratory, pilot plant, and plant processing. The catalyst was shown to make a satisfactory product even when, on continued re-use, the ratio of oil to metal used reached 400,000 to 1.     

重整重芳烃油烯烃选择性加氢催化剂的研究

研究了负载在Al₂O₃载体上的贵金属钯基催化剂对重整重芳烃油选择性加氢脱烯烃反应的性能。以重整残余重芳烃油为原料,分别对催化剂载体、贵金属负载量和助剂添加量进行考察。结果表明,700 ℃焙烧混有2%Ni的γ-Al₂O₃和负载0.2%的贵金属Pd综合效果最理想。催化剂稳定性结果表明,催化剂在500 h能保证产品溴指数在200 mg-Br·（100g^）-1以下,原料中萘环的损失在2%以下。     

LHO-1降烯烃催化剂的工业应用

榆林炼油厂12万t/a催化裂化装置加工的原料为长庆石蜡基原油,混合原料性质较好,表现为重金属含量一般,残碳低,密度不高,易裂化及轻质油收率高等。为提高装置总液收率和进一步降低汽油组分中的烯烃含量,催化裂化装置开始试用LHO-1催化剂。工业实验表明,LHO-1的综合性能优于LBO-16催化剂。使用LHO-1降烯烃催化剂以来,H/C降低了22.9%,抗重金属污染性能较好,水热稳定性较好,流动性能较好,催化剂单耗由0.85 kg/t油降到0.82 kg/t油,油浆产率降低了1.2%,产品收率提高了1.1%,催化汽油烯烃含量较使用LBO-16催化剂降低约5%,变化不明显。     

Reactions of methoxy hydroperoxides derived from methyl oleate. Catalytic hydrogenation

Yield improvements in carbonyl compounds obtained by catalytic hydrogenation of methyl oleate ozonolysis products have been achieved by use of catalyst poisons and by the proper choice of catalyst support. Byproduct dimethyl azelate formation with palladium on charcoal was about 20% in the absence of a poison; 10%, with sodium acetate present in the support; 8%, with triethyl amine in solution. Palladium on calcium carbonate-lead acetate gave about 7%, palladium on zine oxide with pyridine or lead acetate present gave 9%. The literature is reviewed on the catalytic hydrogenation of methoxy hydroperoxides derived from ozonolyses in methanol. Presented in part at the Ozone Symposium, Southwest Regional Meeting of the American Chemical Society, Houston, Texas, December, 1963. A laboratory of the No. Utiliz. Res. and Dev. Div. ARS. USDA.     

Behavior of hydrogenation catalysts. I. Hydrogenation of soybean oil with palladium

A statistical method for evaluation of catalysts was used to determine the behavior of palladium catalyst for soybean oil hydrogenation. Empirical models were developed that predict the rate,trans-isomer formation, and selectivity over a range of practical reaction conditions. Two target iodine value (IV) ranges were studied: one range for a liquid salad oil and the other for a margarine basestock. Although palladium has very high activity, it offered no special advantage intrans-isomer formation or selectivity. Palladium can substitute for nickel catalyst, at greatly reduced temperature and catalyst concentrations, for production of salad oil or margarine basestock from soybean oil. Presented at the AOCS meeting, Chicago, May 1983.     

Reaction of cyclopropene esters with hydrogenation catalysts

Methyl esters of stereulic and malvalic acids were heated under nitrogen in the presence of various hydrogenation catalysts, and the effect on the cyclopropene moiety was established. Similar tests were conducted with cottonseed oil, which contains glycerides of sterculic and malvalic acids. Palladium catalysts, and some palladium compounds which were tested, readily gave cyclopropene-free products, while nickel and platinum catalysts did not. Palladium catalysts freshly activated with hydrogen were not as active as those freed of adsorbed hydrogen. The catalysts could be reused. Heating cottonseed oil (0.73% cyclopropenes, calculated as trimalvalin) with 0.02% palladium, as a 10% palladium-on-carbon catalyst, gave a cyclopropene-free oil after 2 hr at 150 C. The treated oil was unaltered in appearance, and the noncyclopropene components were unaffected. Heating methyl sterculate with palladium catalyst produced a mixture of unsaturated condensation products and a number of unsaturated monoesters of practically unchanged molecular weight. The palladium treatment was shown to cleave the cyclopropene ring and produce methyl and methylene substituted fatty acid groups. Presented at the AOCS-AACC Joint Meeting, Washington, D.C., April 1968.     

废旧聚丙烯/活性炭微波共裂解制取可燃裂解气与轻质裂解油

为实现对废旧塑料的资源化利用,本文采用微波裂解法,以废弃聚丙烯（PP）为裂解原料、颗粒状活性炭为吸波材料通过微波共裂解制取可燃裂解气与轻质裂解油。实验研究了不添加催化剂时微波功率对裂解所得裂解气、裂解油和固体碳的影响,以及添加不同种类金属氧化物作为辅助催化剂时对裂解产物的影响,并详细研究了MgO、ZnO的添加量和功率对产物的影响。研究发现,不添加催化剂时裂解气的产率可达40%,其中H₂、CH₄约占气体总体积的40%,裂解油的产率为40%左右,固体碳的产率为15%左右。裂解油中烷烃、烯烃和单环芳烃三者的总含量可达90%以上,裂解油的相对密度介于0.7~0.8之间,属于轻质裂解油;添加不同金属氧化物后部分金属氧化物可加深PP的裂化程度,其中MgO可显著提高CH₄的含量,ZnO可显著提高H₂的含量,且金属氧化物可进一步提高裂解油中单环芳烃的含量;结合响应面分析PP的最佳裂解条件为：加入MgO后功率范围在660~720W,催化剂量在0.6~1g;加入ZnO后功率范围在680~740W,催化剂量在0.4~1g。     

Catalytic behavior of palladium in the hydrogenation of edible oils

Palladium supported on alumina was used to hydrogenate soybean and canola oil. Previous literature reports indicated that palladium forms moretrans isomers than nickel. At 750 psig, 50 ppm palladium, and at 70 C, only 9.4%trans were formed when canola oil was hydrogenated to IV 74. In general, high pressure and low temperature favored lowtrans formation with no appreciable loss in catalyst activity. The effect of pressure, temperature and catalyst concentration on reaction rate,trans formation and selectivity is presented. A survey of various catalyst supports is discussed. Apparent activation energies of 6.3 to 8.9 kcal/mol were obtained; they are in good agreement with values reported in the literature.     

SiO_2为载体负载Pd催化加氢合成2,4-二氟苯胺的研究

用浸渍法制得0.2%铁元素改性的SiO2为载体的负载5%Pd催化剂对2,4-二氟硝基苯常压催化加氢,用沸点、元素分析I、R和1H NMR对它的结构进行了表征,证明为目标产物2,4-二氟苯胺;确定优化工艺条件为:反应物0.1 mol,催化剂0.26 g,80 mL无水乙醇作溶剂,反应温度为50℃,0.1 MPa下氢化反应2 h,产率为97.9%,产物的纯度达98.4%。     

Continuous mode linoleic acid hydrogenation on Pd/sibunit catalyst

Catalytic hydrogenation of linoleic acid and oleic acid to stearic acid over palladium on mesoporous carbon sibunit (Pd/sibunit) catalyst was studied in a continuous trickle-bed reactor with the weight hourly space velocity 5.4 h⁻¹ at 120°C and 30 bar using tall oil fatty acid (TOFA) as reactor feed. Stearic acid preparation using TOFA as a raw material is of industrial importance. Pd/sibunit catalysts with spherical particle shape of the size 1.62 mm were synthesized with the palladium loadings 0.5, 1, and 2 wt %. The metal dispersion (%), metal particle size (nm), as well as metallic surface area (m²/g metal) of the three synthesized Pd/Sibunit samples were measured by CO chemisorption. The Pd/C catalysts were tested in linoleic acid hydrogenation, showing promising behavior in terms of activity, selectivity and stability to be used in fixed bed applications. The product stream from the fixed bed reactor was saved and analyzed by X-ray fluorescence (XRF) and direct current plasma (DCP) spectroscopy. The catalyst activity increased with the Pd loading. The lowest metal loading of 0.5 wt % gave the least prone to initial deactivation and thus the most stable catalyst. This catalyst can be recommended for farther pilot testing.     

Selective hydrogenation of soybean oil in the presence of copper catalysts

Many investigators associate the poor keeping properties of soybean oil with its linolenic acid content. On the other hand the high linoleic acid content is a desired property from a nutritional point of view. We have therefore developed a process for the preferential reduction of the linolenic acid content by selective hydrogenation. Conventional catalysts for the hydrogenation of fats have a rather low selectivity in this respect. When linolenic acid in soybean oil is hardened (e.g., with a nickel catalyst), most of the linoleic acid is converted into less unsaturated acids. It was found that linolenic acid is hydrogenated much more preferentially in the presence of copper catalysts than in that of nickel and other hydrogenation catalysts. At a linolenic acid content of 2%, soybean oil hardened with nickel catalyst contained about 28% linoleic acid, whereas with copper catalyst the hardened soybean oil contained 49% linoleic acid. By means of our process it is possible to manufacture a good keepable oil of, e.g., I.V. 115 and containing 1% linolenic acid and 46% linoleic acid. The storage stability of this product is comparable with that of sunflower-seed oil. A liquid phase yield of 86% is obtained after winterization at 5C for 18 hr. The high selectivity for linolenate reduction of copper catalysts must be ascribed to the copper part of the catalyst. Investigations into the structure of the catalyst indicate that the active center consists of copper metal crystallites; whether these centers are promoted by the carrier or traces of other substances is under investigation.     

粗菜籽油制备生物柴油及放大实验研究

为了考察项目组自行开发的新型催化剂(SXL)的催化效率,以粗菜籽油为原料,SXL为催化剂,酯交换反应为基础,研究产物生物柴油的转化率和产率。结果表明:小试优化反应条件以100 g粗菜籽油为原料油、醇油比(摩尔比)7∶1、催化剂用量(质量分数)为2.5%、反应温度为60℃、反应时间为2 h下,生物柴油转化率和产率均达到98%以上。放大实验结果:在20 L反应釜中,投入6.50 kg粗菜籽油,以小试条件为基础,原料油转化率、生物柴油产率和甘油产率可达95%以上。表明SXL具有良好的发展前景。     

Supported gold catalysis in the hydrogenation of canola oil

The catalytic activity of gold supported on silica orγ-alumina has been studied in the hydrogenation of canola oil. In the hydrogenation of butadiene and pentene using these catalysts, high stability, low yield oftrans-isomers and high monoene selectivity have been reported in the literature. Catalysts containing 1% and 5% Au w/w on porous silica andγ-alumina were active in hydrogenating canola oil in the range of 150 to 250 C and 3550 to 5620 kPa. The activity level of these catalysts was about 30 times lower than that shown by the standard AOCS Ni catalyst based on the concentration of metal (g Au/L oil). Up to 91% monoene content was obtained using these catalysts in comparison with a maximum of 73% for the AOCS standard Ni catalysts. Gold catalysts can be recovered easily by filtration and reused several times without a decrease in activity. The hydrogenated oil was nearly colorless. No gold was detectable in the oil. Contrary to claims in the patent literature, the gold catalyst produces higher concentrations oftrans-isomers than does nickel. However, using gold catalysts the complete reduction of linolenic acid in canola oil can be achieved at a lowertrans-isomer content in the products than that obtained by using the AOCS standard nickel catalyst.     

Pd/Fe对-二氯苯的催化脱氯及其动力学

o-Dichlorobenzene (o-DCB) was dechlorinated by Pd/Fe powder in water through catalytic reduction. The dechlorination reaction is believed to take place on the surface site of the catalyst via a pseudo-first-order reaction. The final reduction product of o-DCB is benzene. The dechlorination rate increases with the increase of bulk loading of palladium due to the increase of both the surface loading of palladium and the total surface area. Dechlorination efficiency accounts for 90% at Pd/Fe mass ratio 0.02% and metal to solution ratio about 53.3g-L-1 in 120 minutes. Dechlorination is affected by the reaction temperature, pH, Pd/Fe ratio and the addition of Pd/Fe. Ea is found to be 102.5kJ.mol-1 in the temperature ra,nge of 287-313K.     

Biodiesel production from waste animal fats using pyrolysis method

It is necessary to utilize waste cooking oil as a raw material of biodiesel because the land area available for cultivation in Japan is limited. Waste cooking oil also includes long-chain saturated compounds and free fatty acids derived from animal fats. The former has a high freezing point and the latter forms a soap with the alkali catalyst typically used in biodiesel production, reducing the yield. To make waste cooking oil available for biodiesel production, pyrolysis of the waste oil was attempted. The resulting triacylglycerols were found to decompose at 360 to 390 °C, fatty acids were generated by cleavage of the ester bond, and short-chain hydrocarbons and short-chain fatty acids were generated by cleavage of the unsaturated bonds in the hydrocarbon chain. When the retention time was extended with a reaction temperature of 420 °C, light-oil hydrocarbons were generated by decarboxylation of the fatty acids. By adding palladium supported by activated carbon (Pd/C) as a catalyst, decarboxylation was promoted, and hydrocarbons comparable to light oil were selectively obtained in high yield at 85 wt.%. Compared to the biodiesel obtained by transesterification, the biodiesel obtained by pyrolysis showed improvement of about − 5 °C in the pseudo-cold filter plugging point.     

从废钯碳催化剂中回收钯的研究

介绍了从催化氧化法生产葡萄糖酸钠的废钯碳催化剂中回收钯的方法,着重对焚烧法回收钯的方法作了研究。用此法回收的海绵钯质量分数达到99.95%,批量回收的回收率达到98%,在一定程度上降低了葡萄糖酸钠的生产成本。     

The hydrogenation of fatty oils with palladium catalyst. I. Hydrogenation of castor oil

Summary A good quality of castor wax was prepared in the laboratory at 100°C. and 45 p.s.i.g., using a modified palladium catalyst. The product obtained had an iodine value of 4, a hydroxy value of 145, and acid value of 1.8, and a capillary melting point of 86°.     

High Oleic and Low <Emphasis Type="Italic">Trans</Emphasis> Fatty Acid Formation by an Electrochemical Process

Electrochemical hydrogenation employing a mediator of formate/formic acid resulted in partial hydrogenation of vegetable and soybean oil at 20–40 °C and ambient pressure when palladium supported on alumina was employed as a catalyst. An oleic acid content of 48% with a corresponding iodine value of 81 for the vegetable oil hydrogenated at 20 °C was obtained. The total trans fatty acid content and especially the 18:1 trans fatty acid were found to increase with the reaction temperature and time. Nonetheless, relatively low total trans and 18:1 trans fatty acid (7 and 3.8%, respectively) contents were found when the vegetable oil was partially hydrogenated to achieve an iodine value of 112.     

Castor oil hydrogenation by a catalytic hydrogen transfer system using limonene as hydrogen donor

The hydrogenation of castor oil was investigated using a catalytic transfer hydrogenation system in which palladium on carbon was the catalyst and limonene was the solvent and hydrogen donor. The highest percentage of castor oil modification occurred at 178°C using 1% Pd/C and an oil/limonene ratio of 1∶3. The optimized system presented very good reproducibility and 100% conversion of the ricinoleate. GC using a mass spectrometer as detector and ¹H NMR spectra of the products indicated that hydrogenation was accompanied by dehydrogenation leading to a mixture of 12-hydroxy and 12-keto stearic derivatives.