Carbonylation Of Methyl Acetate Research Articles

Process optimization study on the carbonylation of methyl acetate

Acetic anhydride is the important organic chemical raw material, and is used widely in chemical industry, pharmaceutical industry, dyes, spices and other fields. In this paper, the process of carbonylation of methyl acetate in rhodium iodine catalyst system was studied, and the suitable reaction conditions were determined. At the same time, the kinetic model was established. The optimum reaction conditions were as follows: the reaction pressure was 5 MPa, the hydrogen content was 8%, the amount of iodomethane was 15%, the amount of lithium iodide was 3%, the reaction temperature was 150 °C and the reaction time is 3 h. Under the above reaction conditions, the selectivity of the reaction is close to 100% and the conversion is as high as 92%. The macroscopic kinetic model of the reaction was established in the temperature range of 120 °C–150 °C. The reaction is an irreversible reaction without the formation of by-products and the dynamic equation is also given in the Conclusions section.

ChemInform Abstract: 2015 Paul N. Rylander Award Address: Selected Advances in Catalysis and Reactor Systems for the Generation of Acetates and Propionates Using Carbonylation

AbstractReview: [28 refs.

2015 Paul N. Rylander Award Address: Selected Advances in Catalysis and Reactor Systems for the Generation of Acetates and Propionates Using Carbonylation

The introduction of carbonyl functionality using carbonylation in its various forms represents some of the largest volume and most successful applications of homogeneous catalysis in the chemical industry. These reactions have a diversity of mechanisms which, once understood, allow the manipulation of the catalytic processes in unique ways and offers options for interesting reactor designs. This review will focus on the generation of acetates and propionates, two of the simplest entities that can be generated by carbonylation, and discuss how mechanistic knowledge can be used to develop new catalysts and new reactor configurations in carbonylation processes when desired. Examples will include the development of (i) a Rh–MeI–Li catalyzed carbonylation of methyl acetate to acetic anhydride, (ii) a Mo catalyzed carbonylation of ethylene to propionic acid and propionic anhydride, (iii) a molecular Ir–La catalyst supported on carbon for heterogeneous carbonylation of methanol, (iv) alternative reactor designs including a fluidized bed reactor for heterogeneous carbonylations, and (v) a vapor takeoff reactor using ionic liquids for the generation of acetates and propionates which ultimately led to a process for the generation of acetic acid that uses N-methylpyridinium iodide salts to replace methyl iodide as a cocatalyst in Rh catalyzed methanol carbonylation.

Lewis Acids and Lewis Acid-Functionalized Ligands in Rhodium-Catalyzed Methyl Acetate Carbonylation

The application of Lewis acids and Lewis acid-functionalized ligands as activators for methyl acetate in the rhodium-catalyzed carbonylation of methyl acetate to acetic anhydride has been investigated. The reaction of methyl acetate with B(C6F5)3 results in the formation of the adduct [MeOAc·B(C6F5)3]. The combination of this adduct with [Rh(OAc)(CO)2]2 results in a transfer of the Lewis acid to the rhodium complex, rather than an anticipated oxidative addition reaction. In a second approach, novel Lewis acid-functionalized rhodium(I) complexes [Rh(CO)Cl(BPP)], [Rh(CO)2(BPP)]SbF6, and [Rh(MeCN)2(BPP)]SbF6 (BPP = PhB(C6H4PPh2)2) have been prepared. The lack of reactivity of [Rh(CO)2(BPP)]SbF6 toward MeOAc has shown that the rhodium–boron interaction is too strong for activation of methyl acetate, and no carbonylation activity was observed under the conditions used.

Dicarbonylrhodium(I) Complexes of Bipyridine Ligands with Proximate H‐Bonding Substituents and Their Application in Methyl Acetate Carbonylation

AbstractA series of cationic cis‐dicarbonylrhodium(I) complexes [Rh(L)(CO)2]SbF6 has been prepared containing 2,2′‐bipyridine ligands with proximate H‐bonding substituents R in the 6‐ and 6′‐position (R = OH, NH2, COOEt and PO(OEt)2). The solid‐state structures have been determined by X‐ray crystallography for the complexes where R = OH, NH2 and COOEt. The molecular structures have revealed metal–metal and π–π interactions between the square‐planar complexes resulting in the formation of molecular chains in the solid state. IR studies on the reaction of [Rh(bipy)(CO)2]SbF6 with MeI have shown the formation of a neutral complex [RhI(CO)(bipy)], which undergoes oxidative addition of MeI much faster than the cationic complex [Rh(bipy)(CO)2]+. Although all complexes show good activities for the carbonylation of methyl acetate, this is believed to be due to their instability and the formation of [RhI2(CO)2]– under the reaction conditions.

First metal complexes of 6,6′-dihydroxy-2,2′-bipyridine: from molecular wires to applications in carbonylation catalysis

The first square planar rhodium(I) complexes containing the 6,6'-dihydroxy-2,2'-bipyridine ligand have been prepared. The complexes form molecular wires in the solid state and are active catalysts for the carbonylation of methyl acetate.

Tin–Chromium-modified Nickel/Activated Carbon Catalyst for Vapor-phase Carbonylation of Methyl Acetate to Acetic Anhydride

Abstract In the present work, a series of Ni/AC, Ni–Sn/AC, and Ni–Sn–Cr/AC catalysts were prepared by incipient wetness impregnation. Activity tests were performed in a continuous flow fixed-bed reactor. The conversion of methyl acetate and selectivity of acetic anhydride reached 81.1 and 38.8% respectively over the screened Ni–Sn–Cr/AC catalyst under optimal reaction conditions. Catalysts were characterized by means of BET and XRD.

ロジウム錯体の高分子樹脂担体への固定化と触媒反応

The concept to immobilize homogeneous catalyst such as rhodium complex to solid support has received considerable attention, as it simplifies the separation of catalyst from product and also it solves the loss of expensive metal complex in separation area. Since rhodium carbonyl iodide complex, as a typical homogeneous catalyst, is an anion, ionic bond immobilization of the rhodium complex anion to pyridinium cation polymer resin support was studied. The catalytic behavior for methanol carbonylation is mainly studied with comparison to that for methyl acetate carbonylation and methyl formate isomerization. A batch autoclave was used as the reactor. The reaction rate was measured from the rate of carbon monoxide consumption or analysis of liquid compositions. As the ion exchange equilibrium extremely favors the cation polymer resin, virtually all rhodium was immobilized, however, the immobilization characteristic was affected by the liquid compositions. The heterogeneous catalyst exhibited equivalent or higher activity compared to the homogeneous catalyst without further additives like water or lithium iodide.

Carbonylation of methyl acetate in the presence of polymeric rhodium-containing catalysts

New catalytic systems based on RhCl3 and polymeric nitrogen- and oxygen-containing supports were proposed for the carbonylation of methyl acetate to acetic anhydride. The catalytic systems possess a high activity typical of homogeneous catalysts. The high activity is retained upon the repeated use of the catalyst separated from the reaction products. The nitrogen-containing polymers of the chitosan type serve as cocatalysts. In their presence, the induction period disappears, and the catalytically active species are stabilized, thus enabling the replacement of expensive LiI for cheaper salts of this metal.

Homogeneous catalysis: mechanisms and industrial applications

1. Chemical Industry and Homogeneous Catalysis 1.1 Feed Stocks, Fuels and Catalysts 1.2 Crude Oil to Gasoline and Basic Building Blocks by Heterogeneous catalysts 1.3 Basic Building Blocks to Downstream Products by Homogeneous Catalysis 1.4 Comparison among Different Types of Catalysis 1.5 Catalyst Recovery 1.6 Environmental Issues Problems Bibliography 2. Basic Chemical Concepts 2.1 Ligands 2.2 Metals 2.3 Important Reaction Types Problems Bibliography 3. Methods of Investigation 3.1 Catalytic cycle and intermediates 3.2 Spectroscopic Studies 3.3 Kinetic Studies 3.4 Model Compounds 3.5 Computational Techniques (Theoretical Calculation) 3.6 Asymmetric Catalysis Problems Bibliography 4. Carbonylation and Related Reactions 4.1 Introduction 4.2 Carbonylation and Manufacture of Acetic Acid 4.3 Carbonylation of Other Alcohols 4.4 Carbonylation of Methyl Acetate 4.5 Carbonylation of Alkynes 4.6 Other carbonylation and hydrocarboxylation reactions 4.7 C 1-Chemistry 4.8 Engineering Aspects Problems Bibliography 5. Hydrogenation and Other Hydrogen Based Catalytic Reactions 5.1 Hydrogenation 5.2 Hydroformylation 5.3 Other Hydroformylation reactions 5.4 Asymmetric Hydroformylation 5.5 Hydrosilylation 5.6 Hydrocyanation 5.7 Hydroamination Problems Bibliography 6. Polymerization and Selective Oligomerization of Alkenes 6.1 Introduction 6.2 Early Catalysts for Polyethylene and Polypropylene 6.3 Modern Ziegler-Natta Catalyst 6.4 Mechanistic Studies 6.5 Single Site Catalysts 6.6 Ethylene Polymerization with Polar comonomers 6.7 Polymers of Other Alkenes 6.8 Oligomerization of Ethylene 6.9 Engineering Aspects Problems Bibliography 7. Selective C-C Bond Forming Reactions With Alkenes 7.1 Introduction 7.2 Di-, Tri-, Tetramerization and Codimerization reactions 7.3 Metathesis Reactions 7.4 Pd-Catalyzed Cross Coupling Reactions 7.5 Metal catalyzed Cyclopropanation and Cycloaddition Problems Bibliography 8. Oxidation 8.1 Introduction 8.2 Wacker Oxidation 8.3 Metal-Catalyzed Liquid-Phase Autoxidation 8.4 Polymers from Autoxidation Products 8.5 Selective Oxidations 8.6 Engineering and Safety Considerations Problems Bibliography

The carbonylation of methylacetate to acetic anhydride catalysed by [Cp [formula omitted]Rh(CO) 2] in the absence of hydrogen

[Cp ∗ Rh(CO) 2] catalyses the carbonylation of methylacetate to acetic anhydride at 6.9 mol dm 3 h −1 in the absence of hydrogen; [Cp ∗ RhI 2(CO)] which forms from it is also catalytically active giving rates of 1.2 mol dm 3 h −1 under the same conditions. ▪

Nickel-catalyzed carbonylation of methyl acetate to acetic anhydride

Liquid phase carbonylation of methyl acetate to acetic anhydride using nickel catalyst with methyl iodide promoter is reported. Effect of different catalyst precursors, total reaction pressure, hydrogen partial pressure, temperature, catalyst, lithium acetate and methyl iodide concentration, a variety of ligands on the activity and selectivity of nickel catalyst has been investigated. Additionally, FT-IR spectra of the reaction solution were studied and possible side reactions in the carbonylation were examined. Based on these observations, a proposed mechanism for the homogeneous nickel-catalyzed carbonylation of methyl acetate was discussed.

Carbonylation of methyl acetate in the presence of rhodium catalysts based on pyrrolidinopyridine polymers

Carbonylation of methyl acetate in the presence of rhodium catalysts based on pyrrolidinopyridine polymers

Kinetic study on the carbonylation of methyl acetate to acetic anhydride catalyzed by partially quaternized poly(4-vinylpyridine) bound rhodium complexes

Kinetic study on the carbonylation of methyl acetate to acetic anhydride catalyzed by partially quaternized poly(4-vinylpyridine) bound rhodium complexes

Kinetic study on the carbonylation of methyl acetate to acetic anhydride catalyzed by partially quaternized poly(4-vinylpyridine) bound rhodium complexes

The carbonylation of methyl acetate to acetic anhydride catalyzed by a partially quaternized poly(4-vinylpyridine) bound rhodium complex with methyl iodide as the promotor has been investigated. The reaction was verified to be first order with respect to both rhodium and methyl iodide in the presence of lithium acetate and provided that the partial pressure of carbon monoxide was above 1.5 MPa. The oxidative addition of methyl iodide to the active rhodium species and the subsequent reaction of acetyl iodide with methyl acetate to produce acetic anhydride were discovered to be the two rate-determining steps, of which the latter depended on the concentration of lithium acetate. A possible reaction mechanism was suggested. The activation parameters were determined and revealed that a higher catalytic activity of the partially quaternized poly(4-vinylpyridine) bound rhodium complex for the carbonylation of methyl acetate to acetic anhydride was essentially due to the reduction of activation energy. © 1997 John Wiley & Sons, Ltd.

C 1 to acetyls: catalysis and process

Carbonylation of methanol and methyl acetate to acetic acid and acetic anhydride are the only current examples of C 1 processes displacing petrochemical routes for the manufacture of commodity chemicals. Modem carbonylation processes are based upon an iodide promoted, homogeneous rhodium catalyst operating under mild reaction conditions (150°C–200°C, 25–45 bar). This highly selective catalytic cycle is described, and contrasted with other catalytic metals. The embodiment of Rh/I catalysis in commercial BP Chemicals methanol and methyl acetate carbonylation processes is also described, illustrating the process simplicity arising from high selectivity. The now extensive literature on attempts to support the rhodium catalyst in iodide promoted systems is reviewed. In the liquid phase, catalytic behaviour similar to that for the homogeneous system is claimed, although proper comparative data and conclusive evidence for catalyst immobilisation is generally lacking. A number of supported rhodium systems are reported to be active under vapour phase conditions, and activated carbon is also found to promote carbonylation activity of certain base metals, notably nickel. Issues affecting commercial viability include catalyst lifetime, gaseous by-product formation and efficiency of utilisation of precious metal components. Literature on carbonylation in the absence of iodide promoter, and on direct routes to acetyls from synthesis gas or methanol only is also reviewed. All require step changes in catalytic performance in order to approach commercial viability.

Carbonylation of methyl acetate to acetic anhydride using homogeneous nickel complex catalyst

Carbonylation of methyl acetate to acetic anhydride using nickel complex catalysts with iodide promoter and an organic N- or P-containing base as a ligand is reported. The effect of different types of ligands and reaction conditions on activity of the catalyst was investigated. The highest catalytic activity was observed with isoquinoline as a ligand. The activity of the catalyst was found to be enhanced significantly in the presence of hydrogen, while retaining its high selectivity to acetic anhydride. The activity decreased with increase in acetic anhydride concentration. The selectivity of acetic anhydride was found to be greater than 95–96% in the range of conditions studied.

Eastman chemical company acetic anhydride process

To the casual observer, the rhodium catalyzed carbonylation of methyl acetate would appear to be very similar to the well studied Rh catalyzed carbonylation of methanol. However, several significant differences manifest themselves upon switching from the well documented aqueous methanol carbonylation to the anhydrous methyl acetate carbonylation to acetic anhydride. These include fundamental operational changes imposed by the less favorable thermodynamics, significant changes in the by-products, and significant changes in the nature and operation of the catalyst system which, in addition to Rh and iodine, also requires the presence of both a salt and a reducing agent. The differences between the methanol carbonylation and the methyl acetate carbonylation can be explained via a mechanistic study which, based primarily upon high pressure kinetic and infrared data, leads to a unique mechanistic proposal. The key technical breakthroughs, how they led to a successful commercial process, and comparisons of the methyl acetate carbonylation to the methanol carbonylation will be discussed in detail. A brief historical development of the process is included.

The synthesis, properties, and crystal structure of nBu 4N[Rh(CO) 2(OAc) 2], and the exchange of acetate, chloride, and iodide in nBu 4N[Rh(CO) 2(X) 2

Reaction of nBu 4N[Rh)CO) 2Cl 2], 1, with silver acetate under CO gave the diacetate salt nBu 4N[Rh(CO) 2(OAc) 2, 2. The complex has been characterised spectroscopically [ν(CO term) 1986, 2066; ν(CO 2-monodentate) 1615 cm −1] and by a single-crystal X-ray determination. The anion is planar with monodentate acetates, Rh-O 2.074(6) and 2.053(7) Å. Complex 2 reacted immediately with MeI to give MeOAc and [Rh(CO) 2I 2] −, 3, which then oxidatively added more MeI normally. It also reacted with HCl to give HOAC and [Rh(CO) 2Cl 2] −. Evidence was obtained for the formation of a labile mixed anion [Rh(CO) 2I(OAC)] − on reaction of [Rh 2(CO) 4I 2] with nBu 4N + OAc −. It is unlikely that the promotional effect of acetate in methyl acetate carbonylation is due to the participation of acetato-rhodium complexes. Since the lithium acetate reacts readily with iodomethane to give lithium iodide, the observed promotion probably arises from the formation of LiI. MeI reacted with nBu 4N[Rh(CO) 2Cl 2], again via preliminary formation of nBu 4N[Rh(CO) 2I 2], which then added MeI normally. IR spectra showed that the equilibrium, 1 + 21 − ⇌ 3 + 2Cl −, favoured the chloride 1 in CH 2Cl 2, and the iodide 3 in methanol.

Reaktions‐ und verfahrenstechnische Aspekte der Heterogenisierung homogen‐katalysierter Synthesen

AbstractReaction and process engineering aspects of transforming homogenous catalytic syntheses into heterogeneous processes. In order to avoid the separation of the catalyst in homogeneous catalytic processes, the preparation of supported phase catalysts has attracted widespread attention in recent years. Most interest has focussed on the immobilization of transition‐metal complexes on solid supports for catalyzing carbon monoxide and olefin reactions. After a survey of the development of solid supported phase (SSP)‐ and supported liquid phase (SLP)‐catalysts two reactions in which SSP‐catalysts have been applied are considered in detail: The carbonylation of methyl acetate to acetic anhydride and the stereoselective hydrogenation of 2‐acylaminocinnamic acid to (S)‐phenylalanine, a derivative of L‐DOPA. In order to discuss the favourable characteristics and the disadvantages of SSP‐catalysts, they are compared to soluble catalysts. Furthermore, the design of both processes is discussed.