Ni/Al_2O_3-M_xO_y催化剂催化松香加氢的催化性能及产物组成

研究了Ni/Al2O3-MxOy,催化剂催化松香氢化反应的催化性能,结果表明Ni/Al2O3-MxOy催化剂催化松香氢化具有较好的催化性能,枞酸转化率可达98%以上,氢化产物达到国家普通氢化松香(特级)标准.产物主要组分与Pd/C催化剂催化所得的氢化产物基本相同.     

松香低压催化加氢反应的研究

采用 FYX-2 G型高压搅拌釜 ,在温度 1 60°C、压力 1 .0 MPa条件下 ,测定了松香催化加氢转化率与 Pd/ C催化剂含水量的关系 ,可见加氢反应速度随催化剂含水量的减少而增加。考察了搅拌器类型、搅拌转速对高压釜持气量及枞酸转化率的影响 ,认识到松香催化加氢是外扩散控制的反应 ,当搅拌转速达 60 0 r/ min时 ,基本上能消除外扩散的影响。比较了 Raney-镍与 Pd/ C催化剂对松香催化加氢的活性 ,实验表明在低氢压 1 .0 MPa下 ,只有 Pd/ C催化剂才能制备出合格的氢化松香产品     

Pd/C上松香催化歧化反应集总动力学

以松香为原料、改性Pd/C为催化剂、200#油为溶剂及N2为保护气,进行松香催化歧化反应集总动力学的研究。在消除内外扩散影响的条件下,在线跟踪48315～53315 K的反应产物并用毛细管柱气相色谱法测定反应体系组成随时间的变化关系。根据松香歧化反应机理和特点,借鉴集总思想和方法,按结构族组成和动力学相近原则划分该复杂反应体系的集总组分,构建了Pd/C上松香歧化集总反应网络,建立了枞酸型树脂酸、海松酸型树脂酸、氢化枞酸型树脂酸、氢化海松酸型树脂酸和脱氢枞酸五集总动力学模型;采用Levenberg-Marquart法,以Matlab编程和SPSS数理统计软件估算了模型参数,得到枞酸型树脂酸脱氢、加氢,海松酸型树脂酸加氢反应过程的活化能分别为11139 kJ·mol-1、10876 kJ·mol-1、9735 kJ·mol-1,结果表明,所建动力学模型与实验数据吻合良好,并能预测反应在54315 K的集总组分浓度分布。     

Raney镍上松香催化加氢反应动力学研究

以松香为原料、Raney镍为催化剂和200#油为溶剂进行松香催化加氢反应研究。在消除松香加氢过程内外扩散影响的条件下,利用毛细管气相色谱法在线跟踪分析压力为5.0 MPa、温度为423~453 K下反应物浓度随时间的变化关系,对反应过程进行拟均相动力学研究,结果表明,松香催化加氢的反应速率与枞酸浓度呈0.5级反应,其动力学方程为r=5.68×105e-7.T5997c0A.5,表观活化能为63.18 kJ/mol。     

溶剂法氢化松香生产过程中溶剂变化的原因分析

溶剂法氢化松香生产过程中,循环使用的溶剂总量变化不大,但其轻组分因更容易挥发而在生产过程的各个环节流失,含量会逐渐降低;而在加氢反应的温度和氢化松香的蒸馏条件下,松香中的部分重油和少量松香脱羧产物被分离出来进入溶剂,造成重组分含量逐渐增加。溶剂的变化是影响氢化松香质量的一个因素。     

Influence of temperature on the hydrogenation of Australian Loy-Yang brown coal. 1. Oxygen removal from coal and product distribution

A study is made of the composition of the solid, liquid and gaseous fractions produced by hydrogenation of Australian Loy-Yang brown coal at temperatures ranging from 300 to 500 °C. The high oxygen content of the coal (25.5 wt%) is not found to result in a proportionally higher hydrogen consumption when compared to previously published results for a coal with approximately half the oxygen content. Oxygen is found to be removed from the coal mainly as carbon dioxide and water, most probably by decarboxylation and dehydration reactions. At temperatures up to ≈400 °C hydrogen is consumed almost solely by transference from the solvent tetralin to the coal. By this temperature both the maximum degree of conversion and the maximum oil yield are reached. The heavy oil fraction at 400 °C is composed mainly of asphaltenes and preasphaltenes. Above 400 °C hydrogen is consumed from both solvent and gas. A major part of this appears to be involved in the stabilization of decomposition products from the tetralin. The yield of pentane-soluble material is relatively constant up to 450 °C, however, at higher temperatures conversion of asphaltenes and preasphaltenes to pentane-solubles occurs in conjunction with gasification to C₁–C₃ hydrocarbons. Despite the fact hydrogen consumption and oxygen removal both increase with rising hydrogenation temperature, the H/C atomic ratio for the three heavy oil fractions decreases over the same range.     

Spectrophotometric analysis of tall oil rosin acids

Summary About half of the rosin acids in whole and distilled tall oil consist of abietic and neoabietic acids, as distinguished from hydroabietic acids, dehydroabietic acid, and the pimaric acids. In this respect the tall oil rosin acids are similar to those from gum or wood rosin. This was established by spectrophotometric analysis of the rosin acids from whole tall oil, double distilled tall oil, rosin acids crystallized from tall oil, and rosin acids separated from tall oil by fractional distillation. The rosin acids crystallized from tall oil contained the highest percentage of abietic acid, but the sum of abietic and neoabietic acids was only slightly higher. The rosin acids from acid refined tall oil contained appreciably less abietic and neoabietic acid than the others. Before spectrophotometric analysis the rosin acids were isolated from the tall oils in about 95% yield by cyclohexylamine precipitation.     

Reaction mechanism of coal hydrogenation: 2. Three rings solvent system

Taiheiyo coal was hydrogenated in phenanthrene, 9,10-dihydrophenanthrene, 1,2,3,4,5,6,7,8-octahydrophenanthrene and perhydrophenanthrene under 10 MPa (initial pressure) of hydrogen or nitrogen with or without stabilized nickel as catalyst at 400 °C for 15 min. Preasphaltene, asphaltene and oil conversions and the conversion of solvents were measured, and the amounts of hydrogen absorbed by coal from molecular hydrogen and from donor solvent were calculated. The main route of reaction appears to be the direct hydrogenation of coal by molecular hydrogen and the contribution of hydrogenation via the solvent was greater than in the case of the two rings solvent system.     

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 .     

松脂直接催化歧化反应过程分析

采用GC和GC-MS-DS联用技术在线跟踪分析了Pd/C催化剂上松脂直接催化歧化反应过程主要化学组成随时间的变化关系,并探讨了松脂催化歧化反应机理. 考察了不同反应条件对歧化反应产物的影响,结果表明,松脂可直接催化歧化反应同时获得歧化松香和对伞花烃,在250℃、催化剂用量0.05%(占松脂的质量)的反应条件下,反应90 min时脱氢枞酸与枞酸含量分别占酸性物含量的79.15%和0,对伞花烃含量占中性油含量的62.52%;松脂中酸性物的反应速度大于中性油,在二者同时进行的氢转移反应中,树脂酸脱氢与萜烯脱氢反应均是主反应;以松脂为原料的歧化反应速度大于松香为原料的歧化反应速度,直接以松脂为原料进行一步催化歧化反应,萜烯不仅作为溶剂降低了反应体系的粘度,促进了液固传质并促进了枞酸芳构化反应的进行,同时树脂酸提供了有机酸的质子源,使松节油中的双环单萜异构并芳构化形成对伞花烃. 本研究为该反应动力学研究和反应条件优化提供了理论依据.     

催化裂化（FCC）油浆作煤直接液化溶剂的研究进展

煤制油工艺等煤炭清洁高效转化技术是能源化工领域的研究热点,溶解性好、提供/传递氢能力强且热稳定性高,其溶剂选择、使用是影响煤制油工艺经济运行的关键。本文以煤液化溶剂作用为基础,通过对液化自身产物、废塑料及FCC油浆等煤直接液化溶剂的组成、性质及作用效果的综合评述,指出煤、溶剂、氢气间的混合并非理想混合,与煤H/C适宜、极性相近的溶剂在共处理过程表现出良好的协同作用,液化过程的转化率、轻质产物选择性明显提高。分析表明,协同作用的大小取决于煤、溶剂的组成、性质匹配。煤-重质烃共处理工艺利用富芳烃油浆溶解性好、提供/传递氢能力强的特点强化了煤热解加氢反应的进行,同时煤加氢液化产生的多孔残煤具有吸附性强的特点,有助于重质烃改质,使共处理转化率显著提高、轻质产物选择性增大。最后指出,煤-重质烃共处理的协同作用为改善煤、中质/重质芳烃的综合利用提供了可能。     

The determination of the unsaponifiable matter of tall oil distillates

Summary A comparison has been made of extraction efficiency of ethyl ether or petroleum ether in the removal of unsaponifiable matter of tall oil distillates, using the analytical procedures of A.S.T.M. or A.O.C.S. It has been shown that solvents can be used interchangeably. Results were within reasonable accuracy. Synthetic mixtures containing added abietic acid and rosin impurities, when heated at 300°C., increased in unsaponifiable content. Examination of the unsaponifiable extract from several tall oil, fatty acid fractions indicated that it was composed essentially of decarboxylated products of rosin and fatty acids.     

Reaction mechanism of coal hydrogenation: 1. Two-ring solvent system

Taiheiyo coal was hydrogenated in naphthalene, tetralin and decalin under 10 MPa (initial pressure) of hydrogen or nitrogen with stabilized nickel as catalyst at 400 °C for 15 min. Preasphaltene, asphaltene and oil conversions and the conversion of the solvents were measured. The hydrogen absorbed by coal from molecular hydrogen and from the donor solvent was calculated. The main reaction route appears to be the direct hydrogenation of coal by molecular hydrogen, with the side reaction via solvent by molecular hydrogen occurring only slightly, when an active catalyst such as stabilized nickel is present.     

Raney镍上松香加氢制备二氢和四氢枞酸的本征动力学

采用FYX-2G型高压搅拌釜,以Raney镍为催化剂,在温度423～453K、压力4.0～7.0MPa下进行松香催化加氢反应动力学的研究。利用改进搅拌器类型、提高搅拌速度、加入200#溶剂油和改变催化剂粒径的方法消除内外扩散,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,结果表明,Raney镍催化枞酸加氢生成二氢和四氢枞酸是并行反应,最可几反应机理为:松香中的主要成分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,生成二氢枞酸和四氢枞酸的活化能分别为47.18kJ.mol-1和106.35kJ.mol-1。     

乙烯C9加氢精制工艺研究

以上海金山石化乙烯裂解C9为原料,采用两段加氢工艺,在微反固定床反应器进行试验研究。试验表明,加氢后C9可作为溶剂油或高辛烷值汽油的调和组分,并通过产品溴价考察工艺条件对加氢效果的影响。结果表明,最适宜工艺条件为：一段温度70 ℃、压力3.0 MPa、空速2.0 h^-1、V(氢)∶V（油）为200∶1;二段分别为250 ℃、3.0 MPa、空速2.0 h^-1、V(氢)〖DK〗∶V（油）为200∶1。     

Phenyl modification of Mn‐containing mesoporous silica and catalytic oxidation of toluene

BACKGROUND: Catalytic oxidation of toluene with dioxygen is a fundamental industrial technology because the oxidized products are important intermediates for many fine chemicals. In this study, phenyl modification was utilized to alter catalyst surface characteristics in order to enhance activity. RESULTS: Phenyl groups were successfully immobilized on the surface of Mn‐containing hexagonal mesoporous silica (HMS) through a one‐step synthesis route, as demonstrated by detailed characterization. As a result, the surface of the catalyst Ph? Mn? HMS was more hydrophobic with a water droplet contact angle of 96°. In the oxidation of toluene to benzoic acid with dioxygen under solvent‐free conditions, this new catalyst showed higher activity and selectivity than non‐organomodified Mn? HMS, and the conversion and selectivity increased by a factor of 40% and 9%, respectively. CONCLUSION: Modification of the catalyst surface with phenyl groups was an effective strategy to increase activity in the oxidation of toluene. Both conversion and selectivity were improved and this is linked to the hydrophobic character of the surface. This organic modification strategy may also be extended for oxidation of other hydrocarbons. Copyright © 2009 Society of Chemical Industry     

Hydrogenation of fatty acid methyl esters to fatty alcohols at supercritical conditions

Extremely rapid hydrogenation of fatty acid methyl esters (FAME) to fatty alcohols (FOH) occurs when the reaction is conducted in a substantially homogeneous supercritical phase, using propane as a solvent, over a solid catalyst. At these conditions, the limitations of hydrogen transport are eliminated. At temperatures above 240°C, complete conversion of the starting material was reached at residence times of 2 to 3 s, which is several orders of magnitude shorter than reported in the literature. Furthermore, formation of by-products, i.e., hydrocarbons, could be prevented by choosing the right process settings. Hydrogen concentration turned out to be the key parameter for achieving the above two goals. As a result of the supercritical conditions, we could control the hydrogen concentration at the catalyst surface independently of the other process parameters. When methylated rapeseed oil was used as a substrate, the hydrogenation catalyst was deactivated rapidly. However, by using methylated sunflower oil, a catalyst life similar to that obtained in industrial processes was achieved. Our results showed that the hydrogenation of FAME to FOH at supercritical conditions is a much more efficient method than any other published process.     

枞酸单离与应用研究进展

枞酸是从天然可再生资源松香中分离得到的产品,由于松香是包含13种树脂酸的混合物,而且这些树脂酸多为同分异构体,导致其物理性质相近,使得枞酸单离非常困难,很多情况下是以混合物的形式应用于各种工业领域中,用途受到了一定的限制。本文介绍了枞酸的几种主要单离方法,分析了各种单离方法的优缺点,认为有机胺盐结晶法是枞酸工业生产最可行的方法。此外,本文还介绍了枞酸在合成生物活性物质方面的应用以及在医药、农药、精细化学品等领域的应用研究进展,最后,指出将松香所含的多种树脂酸逐一分离提纯,并以之作为原料,合成一系列具有生物活性的物质和药物,是未来枞酸综合开发利用的重点。     

松香催化加氢反应的研究进展

氢化松香是松香改性产品的主要品种之一,有广泛的工业用途。将松香催化加氢可去除枞酸型树脂酸的共轭不饱和性,克服其易于氧化变色的缺点。综述了40多年来国内外对松香催化加氢反应的研究进展。指出影响松香氢化反应的主要因素是催化剂种类及用量、反应温度和氢气压力。今后对松香催化加氢反应的研究主要是研制具有更高活性和选择性的新型催化剂,以进一步降低温度和压力。同时,诸如松香催化加氢的反应机理等理论问题也有待深入研究。     

The electrocatalytic hydrogenation of soybean oil

Soybean oil has been hydrogenated electrocatalytically at a moderate temperature, without an external supply of pressurized H₂ gas. In the electrocatalytic reaction scheme, atomic hydrogen is produced on an active Raney nickel powder cathode surface by the electrochemical reduction of water molecules from the electrolytic solution. Adsorbed hydrogen then reacts with an oil’s triglycerides to form a hydrogenated product. Experiments were carried out at 70°C with a flow-through electrochemical reactor operating in a batch recycle mode. The reaction medium was a two-phase mixture of soybean oil in a water/t-butanol solvent containing tetraethylammoniump-toluenesulfonate as the supporting electrolyte. In all experiments the reaction was allowed to continue for sufficient time to synthesize a brush hydrogenation product. The effects of oil content, applied current, solvent composition, and supporting electrolyte concentration on the efficiency of hydrogen addition to the oil and on the chemical properties of the hydrogenated oil product were determined. The electrohydrogenated oil is characterized by a high stearic acid content and a low percentage of totaltrans isomers, as compared to that produced in a traditional hydrogenation process.