Rhodiumkatalysierte Polyhydroformylierung mehrfach ungesättigter Fettstoffe - Verlustfreie Katalysatorrezirkulation durch ein neuartiges homogen-heterogen-Verfahren

Eine verlustfreie Katalysatorrezirkulation gelingt bei der Polyhydroformylierung von mehrfach ungesättigten Fettstoffen durch Verwenduing eines in Methanol und Wasser gleich gut löslichen, im Reaktionsprodukt aber völlig unlöslichen Rhodiumcarbonyl-Komplexkatalysatorsystems: Die Hydroformylierung von beispielsweise Linolensäuremethylester kann dann homogen katalysiert in methanolischer Lösung mit hohen Ausbeuten an der gewünschten Triformylverbindung ausgeführt werden. Nach der Reaktion wird das Methanol abdestilliert, der ausfallende Katalysatorkomplex in Wasser aufgenommen und vom Reaktionsprodukt abgetrennt. Eine Abtrennung des Katalysators durch Filtration ist ebenfalls möglich. Nach dem Abdampfen des Wassers wird das Katalysatorsystem wieder in Methanol aufgenommen und ohne Aktivitätsverlust in den Prozeß zurückgeführt. Vor allem das Lithiumsalz der Triphenylphosphanmonosulfonsäre bildet als Komplexligand für das Rhodiumcarbonyl ein Katalysatorsystem mit dem gewünschten Löslichkeitsverhalten für die homogen-heterogen-Technologie der Hydroformylierung höhermolekularer Olefine, wie beispielsweise der mehrfach ungesättigten Fettstoffe. Rhodium-catalyzed polyhydroformylation of multiple unsaturated fatty substances - catalyst recycling without waste by a novel homogeneous-heterogeneous procedure. A catalyst recycling in the polyhydroformylation of multiple unsaturated fatty compounds without waste is enabled by the use of rhodiumcarbonyl complex catalyst systems which are easily soluble in methanol and water but completely insoluble in the reaction product: The hydroformylation of, e.g. linolenic acid methylester, is performed homogeneously catalyzed in a methanolic solution with high yields. After the reaction, methanol is distilled off, the precipitated catalyst system is dissolved in water and separated from the hydroformylation products. It is also possible to separate the precipitated catalyst system by a filtration procedure. After evaporation of the water the catalyst system is redissolved in methanol and returned into the process without any loss of catalyst activity. Especially rhodiumcarbonyl complex catalyst systems with the lithium salt of triphenylphosphine-monosulfonic acid as complex ligand have a suitable solution behaviour for the novel homogeneous-heterogeneous technology in the hydroformylation of higher molecular olefins, e.g. multiple unsaturated fatty substances.     

Hydroformylierung mit wasser- und methanollöslichen Rhodiumcarbonyl/Phenyl-sulfonatoalkylphosphan-Katalysatorsystemen – Ein neues Konzept für die Hydroformylierung höhermolekularer Olefine

Hydroformylation with Water- and Methanol-soluble Rhodium Carbonyl/phenyl-sulfonatoalkyl-phosphine Catalyst Systems – A New Concept for the Hydroformylation of Higher Molecular Olefins The heterogenization of the homogeneous hydroformylating catalyst system enables the recovery of the catalyst from the reaction products by a simple phase separation but it is unfavourable that many advantages of the homogeneous catalysis are given up by this procedure. To avoid this drawback we used rhodium carbonyl/tert. phosphine catalyst systems soluble as good in methanol as in water for the homogeneously catalyzed hydroformylation of the olefin in methanolic solution. Only after reaction the product mixture is heterogenized by adding water forming an aqueous phase containing the catalyst system. It was shown by the hydroformylation of n-tetradecene-1 with rhodium carbonyl/phenyl-sulfonatoalkyl-phosphine catalyst systems that this new conception is very useful for the oxo reaction of high-molecular olefins.     

Hydroformylation with recycled rhodium catalyst and one-step esterification-acetalation: A process for methyl 9(10)-methoxymethylenestearate from oleic acid

Previous studies on hydroformylation of methyl oleate with rhodium and triphenylphosphine or triphenylphosphite have led to a laboratory process for recycling the precious metal catalyst. Another catalyst recycling process has now been studied as the basis for converting commercially available oleic acid into the enol ether of methyl formylstearate. The process involves one-step esterification-acetalation of formylstearic acid made by hydroformylating oleic acid with rhodium and triphenylphosphine. Esterification-acetalation is done in a recycling system with methanol, an acid-exchange resin for catalysis, and molecular sieves to remove water from the reaction mixture. The dimethyl acetal methyl ester formed from formylstearic acid is thermally cracked and distilled in one pot to produce the enol ether, methyl methoxymethylenestearate. The soluble rhodium catalyst in the distillation residue is combined with the insoluble catalyst from filtration and recycled for hydroformylation. The product methoxymethylenestearate is a versatile and stable derivative for various potential industrial applications. Presented at the AOCS meeting, Cincinnati, September 1975.     

Mizellare Zweiphasen-Hydroformylierung von ungesättigten Fettstoffen mit wasserlöslichen Rhodiumcarbonyl/tert. Phosphan-Komplexkatalysatorsystemen

Micellar Two Phase-Hydroformylation of Multiple Unsaturated Fatty Substances with Water Soluble Rhodiumdicarbonyl/tert. Phosphine Catalyst Systems Low- and medium-molecular ω-unsaturated carboxylic acid methyl esters inclusive of the ω-decenoic acid ester can be hydrofomylated successfully according to the two phase method in an aqueous-organic medium using the water soluble rhodium carbonyl/tris(sodium-m-sulfonatophenyl)phosphine complex as catalyst system. Highermolecular unsaturated fatty acid esters, e.g. the triple unsaturated linolenic acid methyl ester or fatty oils like linseed oil can be hydroformylated only according to the micellar two phase technique in course of which surfactant micelles cause a solubilisation of the water insoluble unsaturated fatty substances in the aqueous catalyst phase. The different efficiences of the various types of surfactants for the micellar two phase hydroformylation was investigated and interpreted. Best suitable for the micellar two-phase hydroformylation are cationic surfactants. By means of these surfactants linolenic acid methyl ester could be hydroformylated to the triformyl derivative with a selectivity of 55%. The recovery of the catalyst solution free from losses of rhodium succeeded by simple phase separation in a technically satisfying manner.     

双环戊二烯在水溶性铑膦络合催化体系中的氢甲酰化反应

研究了采用水溶性铑膦络合催化体系对双环戊二烯的氢甲酰化反应，考查了反应温度、相转移剂ＣＴＡＢ、铑催化剂浓度等对反应的影响。氢甲酰化反应的产物经ＧＣ／ＭＳ鉴定是不饱和的三环癸单醛     

水溶性铑-膦络合物催化烯烃氢甲酰化反应--阳离子表面活性剂的加速作用

介绍了以水溶性铑-膦络合物RhCl(CO)(TPPTS)₂作为催化剂前体在水/有机两相体系中催化烯烃氢甲酰化反应研究的进展,阐述了阳离子表面活性剂的加速作用和介稳态胶束-离子对协同作用机理关系.通过两相体系中界面分子组装和选择与烯烃分子链长相匹配的表面活性剂, 设计制备了高区域选择性复合催化剂体系.当采用双长链表面活性剂与铑-膦络合物组成的复合催化体系时,在不搅拌的情况下就显示出极高的催化活性.     

Zweiphasen-Hydroformylierung höhermolekularer Olefine mit ethoxyliertem Tris-(p-hydroxyphenyl)phosphan als Komplexligand für den Rhodiumcarbonyl-Katalysator

Two-phase Hydroformylation of Higher Molecular Olefins by Ethoxylated Tris(p-hydroxyphenyl)-phosphine as Complex Ligand for the Rhodiumcarbonyl Catalyst Water-soluble rhodiumcarbonyl complexes with new nonionic complex ligands prepared by ethoxylation of tris(p-hydroxyphenyl)phosphine were successfully used in the two-phase hydroformylation of higher-molecular olefins. Their efficiency depends likely on a temperature controlled circulation of the catalyst complex between the organic and the water phase: At the temperature of the hydroformylation (100–130 °C) the ethoxylated tri-(p-hydroxyphenyl)phosphine becomes water-insoluble (appearance of a miscibility gap) and is now available for the catalysis in the organic phase. After cooling to room temperature the catalyst system is dissolved again in the water phase and can be recovered by a simple phase separation.     

Catalytic behavior of silica-supported polyalumazane-Co-Ru bimetallic complex for the hydroformylation of cyclohexene

Summary The cobalt and ruthenium bimetallic complex of an inorganic polymer, polyalumazane (abbr. as Al-N-Co-Ru), was prepared. The catalytic behavior of this complex for the hydroformylation of cyclohexene was studied. The conversion percents were more than 90% in a certain reaction temperature and pressure. Both of the conversion and product composition was also affected by the Ru/Co ratio in catalyst and the CO/H₂ ratio in reactant gas. Aldehyde was firstly formed in the hydroformylation, and then it was further hydrogenated to form the corresponding alcohol. There was no any other by-product formed in the reaction. Compared with the corresponding homogeneous catalyst system, the Al-N-Co-Ru catalyst has higher catalytic activity and stability with lower Ru/Co ratio (1.86). After reused for several times, the catalyst did not lose its activity. The total turnover number was more than 2500 (based on the amount of cobalt used).     

水溶性铑络合物催化1-十二碳烯氢甲酰化反应器构型的初步探索

Hydroformylation of 1-dodecene was studied in a biphasic system using water-soluble rhodium complex [RhCl(CO)(TPPTS)2] as catalyst in the presence of cetyl trimethyl ammonium bromide as surfactant to enhance the reaction rate. Efforts were devoted to improve the performance of hydroformylation by exploring reactor the reaction configuration which enhanced the mixing, dispersion and interphase mass transfer. Experiments were carried out in a 0.5L autoclave at the total pressure of 1.1MPa and temperature from 363K to 373K. Several surface aeration configurations were tested, and higher hydroformylation rate with higher normal/branched aldehyde ratio produced were achieved. The experience suggest that improved reactor configuration by taking reaction engineering, measures is beneficial to better process economy in alkene hydroformylation.     

Lineare Tensidalkohole aus Olefinen mit innenständiger Doppelbindung

Linear Tenside Alcohols from Olefines with Inner Double Bond The reaction of olefines with carbon monoxide and methanol in presence of the catalyst system cobalt/pyridine, called hydrocarboxymethylation, leads to carboxylic acid methylesters with a fatty acid rest which is 1 C-atom longer in comparison to the initial olefine. The influence of various reaction parameters on space-time yield and selectivity and linearity or distribution of the products is demonstrated in the example of linear and branched olefines with terminal and internal double bond. The hydrocarboxymethylation procedure which easily gives access to alcohols, carboxylic acids and amines of the tenside range (C₁₂-C₁₈) by the carboxylic acid methyl esters, is compared with other methods for production of tenside raw materials (Ziegler-Alfol process, conventional and modified hydroformylation, process on native basis).     

Hydroformylierung einfach und mehrfach ungesättigter Fettstoffe mit heterogenisierten Cobaltcarbonyl- und R

Hydroformylation of mono and multiple unsaturated fatty substances with heterogenized cobaltcarbonyl and rhodiumcarbonyl catalysts. Heterogenized cobalt and rhodiumcarbonyl catalyst systems can be used for the hydroformylation of mono and polyunsatured fatty substances in a technically simple and satisfying manner to useful chemical intermediates. The used solid tert. phosphane complex ligands have a silicate matrix and therefore they are also suitable for the cobalt catalyzed hydroformylation which is best performed at temperatures of 160–180^oC. The cobalt catalyzed reaction gives with polyunsaturated fatty substances almost only products with monofunctionalized fatty acid chains. Whereas, the rhodium catalyzed reaction gives with linolic acid compounds inhomogeneous mixtures of mono- and diformyl derivatives of these fatty substances. The heterogenized rhodium carbonyl catalyst systems therefore seem to be more suitable for the hydroformylation of monounsaturated compounds. This is also true for rhodiumcarbonylsupported aqueous phase-catalysts which give likewise mixtures of mono and diformyl derivatives in the hydroformylation of polyunsaturated fatty substances. In batch process after the complete conversion of the olefin and reduction of the CO/H₂-pressure the loss of catalyst metal from the support is negligible and in most cases below the detection limit (<1 ppm).     

Development of a continuous process for the hydroformylation of long-chain olefins in aqueous multiphase systems

The challenging task of homogeneous catalysis is the efficient combination of reaction and catalyst recycling. In the hydroformylation of long-chain olefins generally cobalt-based catalysts are used, but in our investigation we used rhodium-based catalysts, because of their higher activity in comparison to cobalt catalysts. In hydroformylation reactions, the recycling of the expensive rhodium catalyst as well as the selectivity to linear aldehydes are very challenging. Multiphase systems offer the possibility to increase the interfacial area during reaction on the one hand and to separate the metal–ligand complexes easily from the organic product phase after reaction, to recycle the expensive catalyst for further reactions, on the other hand. Solubilisers such as surfactants or polar solvents can be used to formulate such a tuneable solvent system. Upon cooling of the reaction mixture, phase separation is achieved. Based on that combination of reaction and phase separation for catalyst recycling, a novel process concept was developed for the hydroformylation of long-chain olefins. In order to show the applicability of that concept in a continuous process a fully automated miniplant was designed.     

Hydroformylation of 1-hexene in supercritical carbon dioxide using a heterogeneous rhodium catalyst. 1. Effect of process parameters

The hydroformylation of 1-hexene in supercritical carbon dioxide is catalyzed with a heterogeneous rhodium catalyst that is active, selective, and stable for the formation of heptanal. The aldehyde yield and regioselectivity can be affected through changes in catalyst support structure, CO₂ solvent pressure, and reaction temperature. A complex reaction pathway model is described that allows determination of rate constants, which are in turn, evaluated as a function of temperature and pressure. Analysis reveals an activation volume of −474 cm³/mol and activation energy of 31.9 kJ/mol for the hydroformylation pathways.     

甲基萘烷基化催化剂上积炭的表征

研究了HZSM—5沸石催化甲基萘与甲醇的烷基化反应。采用热重分析、红外光谱分析、元素分析和色—质联机分析等手段，对甲基萘与甲醇烷基化失活催化剂上积炭的二氯甲烷溶解炭(焦炭前身物)和不溶解炭物进行了表征。实验结果表明：焦炭前身物主要由三环取代芳香化合物组成，并有芳醚类化合物存在。HZSM—5沸石催化剂失活的原因可能是由甲醇自身反应生成的烃类化合物进一步与萘环反应形成多环芳香化合物引起的。     

Supercritical carbon dioxide as an alternative reaction medium for hydroformylation with integrated catalyst recycling

The cobalt-catalyzed hydroformylation of 1-octene using the complex bis{tri(3-fluorophenyl)phosphine}hexacarbonyldicobalt (1) and Co₂(CO)₈ as pre-catalysts in supercritical carbon dioxide (scCO₂) as a reaction medium was investigated. The catalytic performance in scCO₂ was compared to the one in toluene as a conventional solvent. Similar activities and selectivities were obtained in both reaction media. In scCO₂, a substantial improvement of the selectivity for aldehydes was found by using (1) (P:Co = 1:1) in comparison to the unmodified catalyst Co₂(CO)₈ (P:Co = 0:1). Surprisingly, further addition of (m-FC₆H₄)₃P (P:Co = 6:1 and 11:1, respectively) resulted in a little enhancement of the aldehydes selectivity only, whereas the conversion and, hence, the aldehydes yield were reduced. A concept for catalyst recycling by using scCO₂ was introduced. It was found that (1) was insoluble in the cold reaction mixture and was completely soluble in the supercritical reaction medium. By cooling the reactor content after the olefin conversion, the catalyst was regenerated as a solid, separated by filtration and could be recycled several times.     

Acetale als neuartige Kraftstoffadditive aus Glycerin und Olefinen

Long chain olefins are converted into aldehydes by hydroformylation using synthesis gas CO/H₂ and further converted in an acid‐catalyzed conversion with glycerol in a one‐pot procedure. Yields are up to 95 %. The obtained mixtures of 5‐ and 6‐membered rings are potential fuel additives offering alternative use of glycerol from renewable resources. By optimization of reaction conditions such as catalyst precursor, ligand, pressure, temperature, solvent or catalyst/substrate ratio a highly selective hydroformylation towards linear acetals was achieved. For synthesis of larger amounts, glycerol was converted with alkenes on a 2‐L‐scale and with aldehydes on a 60‐L‐scale.     

液相合成甲醇催化剂活性的研究

The effects of reduction procedure, reaction temperature and composition of feed gas on the activity of a CuO-ZnO-Al2O3 catalyst for liquid phase methanol synthesis were studied. An optimized procedure different from conventional ones was developed to obtain higher activity and better stability of the catalyst. Both CO and CO2 in the feed gas were found to be necessary to maintain the activity of catalyst in the synthesis process. Reaction temperature was limited up to 523K, otherwise the catalyst will be deactivated rapidly. Experimental results show that the catalyst deactivation is caused by sintering and fouling, and the effects of CO and CO2 on the catalyst activity are also investigated. The experimental results indicate that the formation of water in the methanol synthesis is negligible when the feed gas contains both CO and CO2. The mechanism for liquid-phase methanol synthesis was discussed and it differed slightly from that for gas-phase synthesis.     

Kinetics and mass transfer in hydroformylation—bulk or film reaction?

The kinetics of a gas–liquid reaction, alkene hydroformylation was studied in the presence of a homogeneous catalyst in a pressurised laboratory‐scale semibatch reactor. Hydroformylation of propene to isobutyraldehyde and n‐butyraldehyde was carried out at 70–115°C and 1–15 bar pressure in 2,2,4‐trimethyl‐1,3‐pentanediol monoisobutyrate solvent with rhodium catalyst using the ligands cyclohexyl diphenylphosphine. In order to evaluate the influence of mass transfer, experiments were made using varied stirring rate from 100 to 1000 rpm at 100°C and 10 MPa syngas pressure. Only at higher stirrings rates, the reaction took place in the kinetic regime. A reactor model was developed comprising both complex kinetics and liquid‐phase mass transfer. The model was based on the theory of reactive films. The model is able to predict under which circumstances the hydroformylation process is affected by liquid‐phase diffusion of the reactants. Experimental data and model simulations are presented for the hydroformylation of propene in the presence of a homogeneous rhodium catalyst.     

硫酸高铈改性离子交换树脂催化合成丁酸异丁酯的研究

采用硫酸高铈与阳离子交换树脂反应制备的改性离子交换树脂催化合成丁酸异丁酯。考察了催化剂用量、醇酸物质的量比、反应时间、带水剂种类及催化剂重复使用性等因素对收率的影响。结果表明该催化剂与反应体系形成非均相物系,具有易分离回收,催化活性高,反应时间短,出水速率快,合成工艺流程简单,操作方便,不易腐蚀设备,废液排放量少,不需加带水剂即可获得较为理想的收率等优势,基本革除了浓硫酸为酯化催化剂存在的设备腐蚀严重、后处理工艺复杂、废液排放量多等弊端。硫酸高铈改性离子交换树脂是合成丁酸异丁酯的高效、经济且环境友好的酯化催化剂,具有一定的工业化应用前景。适宜反应条件为:正丁酸0.15mol,醇酸物质的量比1.3,催化剂2.0g,反应时间40min,收率85.7%。     

正戊醛的合成工艺研究

以1-丁烯和合成气为原料,对氢甲酰化制备戊醛的工艺进行了研究。在热力学计算的基础上,主要考察了均相催化体系下膦铑比（摩尔比）、催化剂浓度、丁烯用量、反应温度、时间、压力、搅拌速度等条件对1-丁烯氢甲酰化反应的影响。在保持1-丁烯较高转化率和戊醛较高选择性的条件下,给出了适宜的工艺条件：反应温度为100℃左右,反应压力2．2MPa,搅拌速率250rpm,反应时间30min,催化剂浓度300—350ppm,膦铑比为400～500。