Ind. Eng. Chem. Res. 2000, 39, 3958-3997
REVIEWS Engineering Aspects of Industrial Liquid-Phase Air Oxidation of Hydrocarbons
Akkihebbal Krishnamurthy Suresh
Department of Chemical Engineering, IIT Bombay, Powai, Mumbai 400 076, India
Man Mohan Sharma† and Tamarapu Sridhar*
Department of Chemical Engineering, Monash University, Clayton, Victoria 3168, Australia
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Liquid-phase air oxidation of hydrocarbons, notably p-xylene, cumene, ethylbenzene/isobutane, cyclohexane, and n-butane, is of great scientific, technological, and commercial importance. This state-of-the-art paper covers the chemistry and engineering science aspects of these reactions. The role of uncatalyzed reactions and metal ion and mixed metal ion catalysts with bromide activation is discussed. An analysis is presented for the role of mass transfer in influencing the rate of reaction and selectivity for the desired product. Different types of reactors that are used, notably bubble-column reactors and mechanically agitated reactors, are analyzed, and a simple basis is provided for selection of reactors. Some emerging oxidation systems, notably oxidation of cycloalkenes (cyclohexene/cyclooctene/cyclododecene) and oxidation of isobutane under supercritical conditions, are presented. New strategies for conducting air oxidations, such as in biphasic systems (including fluorous biphasic systems), biocatalysis, photocatalysis, etc., are emerging and illustrate the considerable tailoring of the reaction microenvironment that is becoming possible. In some cases, it may be possible to manipulate chemo-, regio-, and enantioselectivity in these reactions. Contents
1. 2. 3. 4. Introduction Scope and Structure of the Review Historical Development A Survey of Industrial Hydrocarbon Oxidations 4.1. p-Xylene and Other MC Oxidations 4.2. Oxidation of Cyclohexane, Other Saturated Hydrocarbons, and Terpenes 4.3. LPO-Based Routes to Phenol and Benzylic Alcohols 4.4. The Oxirane Process: Oxidation of iso-Butane and Ethylbenzene 4.5. Acetic Acid from Paraffin Oxidation 5. Mechanism of Hydrocarbon Oxidation 5.1. Initiation 5.2. Propagation 5.3. Termination 5.4. Degenerate Chain Branching 5.5. Overall Kinetic Features Based on the Mechanism 5.6. Catalysis of Organic Oxidations 5.7. Co-oxidations 6. Chemistry of Selected Oxidations 3959 3959 3960 3963 3964 3965 6.1. p-Xylene and Other MC Oxidations 6.2. Oxidation of Cyclohexane 6.3. Oxidation of Cumene 6.4. Oxidation of Isobutane 6.5. Oxidation of Cycloalkenes 6.6. Oxidation of Vinyl Cyclohexene and Vinyl Cyclohexane 6.7. Miscellaneous Oxidations 7. Kinetics of Hydrocarbon Oxidation 7.1. Laboratory Reactors 7.2. Kinetic Models from Laboratory Studies 8. Processing Options 8.1. The Case for Liquid-Phase Air Oxidation 8.2. Reactor Configurations and Materials 9. Role of Mass Transfer in Liquid-Phase Oxidations 9.1. Mass-Transfer Rates at Elevated Temperatures and Pressures and under Actual Oxidation Conditions 9.2. Influence of Mass Transfer on Liquid-Phase Oxidations 10. Rate Oscillations and Other Nonlinear Phenomena 3973 3974 3974 3975 3977 3979 3979 3979 3980 3981 3982 3982 3983 3984 3984
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11. Safety Issues in Organic Oxidations 12. New Developments in Organic Oxidations 12.1. Biphasic Mode of Operation 12.2. The Role of Ultrasound in Oxidation Reactions 12.3. Oxidation in Supercritical Media 12.4. Photochemical Activation of Oxidation Reactions 12.5. Enzyme-Catalyzed Reactions 12.6. Use of O2 + H2 and O2 + CO as Oxidants 12.7. Catalyst Developments 12.8. Stereospecificity in Organic Oxidations 13. Conclusions References 1. Introduction
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is, therefore, to review these developments and analyze their implications for future industrial practice in this area. 2. Scope and Structure of the Review The review addresses hydrocarbon “autoxidations”, that is, oxidations in which molecular oxygen is activated via a free-radical chain process. These are also classified as “homolytic” processes,4 insofar as they originate from the homolytic breakage of a C-H bond. Thus, those processes (“heterolytic”) in which oxygen activation occurs by direct reaction with a reducing metal ion (the Wacker process is an example) are largely excluded from the scope of this review. As already stated, the emphasis is on the engineering aspects, and discussion of the mechanistic aspects is kept brief. Although the attempt is to study hydrocarbon oxidations in a unified manner, individual peculiarities are often important to industrial practice, and these are highlighted where relevant. Examples from various hydrocarbon oxidations are liberally used, but the commercially important oxidations form the center of attention. The commonality of mechanisms and industrial importance both make for an emphasis on processes involving the oxidation of secondary and tertiary carbon atoms. Within this perimeter, both catalyzed and uncatalyzed oxidations are discussed. Air has tended to be the preferred source of oxygen in the past for reasons of both safety and economics, and the focus here is naturally on air oxidations. However, some recent developments on the use of enriched air or even pure oxygen are included as they could be of interest to future designs. Even though gas- and liquid-phase homolytic oxidations share common mechanisms, the reaction rate and selectivity are usually better in the case of liquid-phase oxidations. The reasons, at least partly, have to do with the higher density of the liquid phase. Hence, except in the case of lighter hydrocarbons for which very high pressures become necessary to maintain a liquid phase at reaction temperatures, oxidation in the liquid phase turns out to be the natural choice. Isobutane presents an interesting case for which a minor shift in reaction conditions can make the reaction occur under gas or liquid or supercritical conditions. This case is considered in some detail, but for the rest, it is the liquid-phase oxidations that form the focus here. Finally, emphasis has been placed on the developments of the last two decades or so, and references are made to earlier literature wherever relevant. Historically, a fundamental understanding of the nature and mechanisms of oxidation reactions has proceeded in parallel with industrial practice, as has been the case with so many other areas of human endeavor. We begin our discussion of hydrocarbon oxidations, with a brief historical account in section 3. This is followed, in section 4, by a broad survey of the field of industrial oxidations, which provides the backdrop for further discussion. Because oxidation of hydrocarbons ultimately gives carbon dioxide and water, it is clear that it is partial oxidations that are of greatest interest to the industry, and the success of an industrial oxidation process depends on proper control of the reaction to yield the desired intermediates with reasonable selectivities. The complex chemistry of hydrocarbon oxidations leads to a multiplicity of products even at fairly early stages in the conversion. An understanding of the chemistry is,
Processes involving the oxidation of hydrocarbons in the liquid phase, using air or oxygen, are of great importance to industrialized economies because of their role in converting petroleum hydrocarbon feedstocks such as alkanes, olefins, and aromatics into industrial organic chemicals important in the polymer and petrochemical industries. Some notable examples are the oxidations of p-xylene to terephthalic acid and dimethyl terephthalate, of cyclohexane to cyclohexyl hydroperoxide and cyclohexanol/cyclohexanone, of cumene to cumene hydroperoxide, and of iso-butane to tert-butyl hydroperoxide and tert-butyl alcohol. Some of the major inefficiencies in the production of such chemicals can often be traced to the operation of the reactor. Oxidative transformations of functional groups are also basic to organic chemistry and are used extensively in the laboratory and industrial synthesis of a variety of fine organic chemicals. It is therefore not surprising that this class of reactions has spawned much study and research. In recent times, increasing environmental concerns have also acted as a significant driving force of research. The mechanisms that operate in organic oxidations and the theoretical underpinnings of such mechanisms have thus been studied in detail, and extensive treatises on the chemistry of oxidation processes are available.1-3 What is perhaps surprising is that, barring a few exceptions,4,5 an exhaustive review of the engineering aspects of such reactions is lacking. Information about these aspects is still largely to be found scattered in various places, amidst discussions of specific processes. The main objective of the present paper is therefore to bring together and discuss, in a unified manner, the literature on hydrocarbon oxidations, with a strong emphasis on the engineering aspects of relevance to industrial practice. The last few decades have seen several advances in this area, much of it only available in patents. A second objective of this paper
* Author to whom correspondence should be addressed. Tel: 613 9905 3427. Fax: 613 9905 9649. E-mail: tam.sridhar@ eng.monash.edu.au. † Permanent address: 502, “Saurabh”, Plot 39, Swastik Park, Chembur, Munibai 400 071, India.
Ind. Eng. Chem. Res., Vol. 39, No. 11, 2000
therefore, essential if one is to appreciate the motivation behind much of the research and development in this area. Section 5 describes the salient aspects of the mechanisms that operate in hydrocarbon oxidations. Over the years, several catalysts have found application in such reactions for various reasons, and section 5 includes a discussion of the role of particular catalysts in modifying the reaction mechanism. Notwithstanding the unity of the mechanistic principles that underlie hydrocarbon oxidations, it is often the minor differences among them that are of interest from the point of view of industrial exploitation. Thus, whereas one expects from chemistry that the oxidation of an aldehyde (which occurs as an intermediate in oxidations leading to carboxylic acid) should be rapid, unoxidized aldehydic impurities are a major problem in terephthalic acid manufacture, because the product specifications for fiber-grade terephthalic acid are very stringent. Again, in the oxidation of cymene, the small extent of oxidation of the secondary C atom that occurs in parallel with the desired oxidation of the tertiary C atom has important implications for downstream processing. (The oxidation of ethylbenzene provides another similar example.) The section on general mechanisms is, therefore, followed by a section on the chemistry of commercially important oxidations. This section also treats some important emerging oxidation systems such as cycloalkenes and vinylcyclohexane/vinylcyclohexene. Given the complexity of the chemistry involved in hydrocarbon oxidation, and the fact that one often must estimate the kinetics from rate data in heterogeneous (gas-liquid) systems, the planning and execution of laboratory studies to establish true kinetics is usually a demanding task. Furthermore, the engineer must decide the level of detail at which he needs to establish the kinetics for the purpose at hand. Thus, the engineer is often forced to resort to an empirical approach to establish kinetics, with some basis from the known mechanisms. One therefore sees, in the literature, several lumped kinetic models for oxidation systems. These models and the issues involved in planning and executing kinetic investigations in this area are discussed in section 7. In many hydrocarbon oxidations, the desired intermediates have a tendency to undergo further reactions in the oxidizing medium. The limitations imposed by the chemistry on the selectivity to the desired intermediates that is achieved has often meant that conversions are kept low to minimize the formation of unwanted products. The need to achieve better selectivity at reasonable conversions has naturally been a major driving force for research. This, coupled with other issues such as safety and the need for control, presents a number of process options. Some of the issues involved and the processing options that emerge are considered in section 8. The high temperatures at which hydrocarbon oxidations are carried out and the need to maintain a liquid phase under these conditions results in high-pressure operation. Furthermore, the oxygen for the reaction must be supplied by a process of gas-liquid mass transfer. Thus, the oxidation reactors are usually highpressure gas-liquid contactors such as bubble columns and sparged, agitated reactors. Rational design of such equipment requires a knowledge, under conditions of pressure and temperature, of important mass-transferrelated quantities such as mass-tranfer coefficients, gas
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holdup, and interfacial area. Available information on these aspects is summarized in section 9. The kinetics of gas-liquid reactions such as hydrocarbon oxidations are, in general, subject to masstranfer limitations. Under appropriate conditions, the rate as well as the selectivity of such reactions can be influenced by mass transfer. Theories of mass transfer with chemical reaction have been fairly well developed, but there are only a few instances of their application to oxidation reactions. These studies are summarized in section 9.2. The complexity of chemical mechanisms in organic oxidations leads to highly nonlinear kinetics, which, in turn, often result in complex dynamic behavior. Many features of such behavior have been documented in experimental studies. The available information on such aspects is summarized in section 10. Safety is clearly a major consideration in hydrocarbonair contact, both in the design of industrial processes and in the planning of experimental research. Apart from hazardous possibilities of gas-phase oxidation such as autoignition, the dangers of ignition from an external source also deserve attention. Additional considerations assume importance in the design and operation of experimental rigs, which are usually designed so as to provide flexibility in operation and choice of operating parameters. The relevant aspects of this issue are elaborated in section 11. The usual motivating factors such as a search for better rates and selectivities, together with the recent emphasis on cleaner and safer processes, has meant that new processes and processing alternatives are always on the horizon. Section 12 discusses some major new developments in the area of organic oxidations, which hold promise for further development. Alternative catalysis and heterogeneous strategies (whether for catalysis or for simultaneous separation of reaction intermediates) are among the important themes. Much of this progress has appeared in the patent literature. Salient conclusions on the state of our understanding of industrial liquid-phase oxidations are summarizcd in section 13. 3. Historical Development History shows that the major developments in hydrocarbon oxidations have most often been motivated by the need for appropriate feedstocks for the evergrowing polymer industry. In the following section, we seek to examine the development of the more practical aspects of technology, on one hand, and the evolution of theoretical insights, on the other, in this field. Although this historical account does not claim to be exhaustive, it does show the complementary manner in which advances along the two fronts have been made, and it serves to highlight areas in which understanding still lags behind practice. From early days, the functionalization of naturally occurring petroleum components through reaction with air was naturally seen as the simplest way to derive useful chemicals. The research of Semenov (and later Bolland and others) in the first half of the twentieth century clarified the concepts of chain reactions and put the theory of free-radical autoxidations on a firm basis.1,3 Industrial practice also developed alongside. Whereas early processes for the oxidative transformation of petroleum feedstocks involved vapor-phase oxidations (ethylene to ethylene oxide, for example), liquid-
Ind. Eng. Chem. Res., Vol. 39, No. 11, 2000 3961
phase oxidation processes began from the 1950s. The Wacker process for the conversion of terminal olefins to carbonyl compounds and the Hock process for the production of phenol from cumene (via the hydroperoxide) were commercialized during this period. The cumene-phenol process was developed, by Distillers Co. in the U.K. and Hercules Powder Co. in the U.S., from a reaction discovered by Hock and Lang during the war. (A parallel development by A. Farkas in the Wilmington research labs of Union Oil Co., which went unpublished because of the company’s interest in naphthenic hydroperoxides, is described by Farkas6.) At that time, the free-radical chemistry of such reactions had just been established. Several major contributions to that field, such as the concept of activation of a tertiary H atom by a phenyl ring (which leads to the specificity of oxidation in this process) and an understanding of the role of impurities, came during the process-development effort.7 Several developments of an engineering nature also played a part in the final commercialization, such as the improvement in rate and selectivity through staging of reactors and the imposition of a temperature profile (with the temperature decreasing as the hydroperoxide concentration increases) on the reactor cascade. The cumene-phenol process accounts for most of the installed capacity for phenol in the world today and is expected to maintain its dominant position as long as the coproduct acetone has a market.8 Homogeneous catalysis of liquid-phase oxidations has played a major role in the development of oxidation processes. The catalytic effect of transition metal ions such as cobalt on oxidations had been known for some time (for example by the Du Pont work on the oxidation of toluene9). Whereas catalysis is important to the industrial process, adventitious catalysis, say by the reactor wall material and impurities in the chemicals used, can be a major problem in the understanding and interpretation of reaction kinetics. Twigg7 describes how, in the kinetic studies leading to the process development for phenol, the most elaborate purification procedures for cumene had to be followed in order to avoid adventitious catalysis. The role of wall catalysis had been recognized in the Russian work on cyclohexane oxidation,10 but the need for passivating reactor surfaces in kinetic work seems to have been recognized and procedures developed in the work of Winkler and Hearne11 on isobutane oxidation. Wall catalysis remains a problem with the interpretation of many kinetic studies reported in the literature and is especially a problem in laboratory reactors with large surface-tovolume ratios. Systematic studies of the industrially important homogeneous catalysis of oxidation processes began in the 1950s.2 The discovery of the (appropriately named) “Mid-Century” catalysts and the subsequent development of the Mid-Century (MC) process for the oxidation of p-xylene to terephthalic acid belong to this period.12 The impetus for the discovery of the Mid-Century catalyst was provided by the need for a cheap source of aromatic acids for the industrial production of aromatic polyesters, in particular, poly(ethylene terephthalate) (PET). In searching for an alternative to esterification (Witten process of 1951) for overcoming the inhibiting effect of the first carboxyl group on further oxidation, Landau and co-workers at Scientific Design discovered the promoting effect of the bromide anion13 and immediately obtained qualitative improvements in yield
over the norm using cobalt catalyst alone. Standard Oil of Indiana (later Amoco) purchased the patent rights to the new catalyst and proceeded to develop the oxidation technology. Landau14 has recently given a fascinating account of this development. In the subsequent decades, many aspects of the action of MidCentury catalysts have been clarified, and the principle has been extended to over 200 other aromatic, alkylaromatic, and other systems.12 In particular, improvements in the technology for purification have today put Pure Terephthalic Acid (PTA) in a dominant position in the world market as the preferred raw material for PET fiber.8 The processes for the oxidation of cyclohexane, like those for the oxidation of p-xylene, were driven by developments in the synthetic fiber industry, as raw materials for the manufacture of Nylon-6 and Nylon6,6 (caprolactam, adipic acid, and hexamethylenediamine) are derived from this route. van de Moesdijk15 has given an interesting account of the development of competing processes for caprolactam up to the late 1970s. Caprolactam came into prominence in the late 1930s when I. G. Farben synthesized a spinnable polymer (Nylon-6 or Perlon) from it. Early processes (1940s) for the manufacture of caprolactam were based on the hydrogenation of phenol [Allied Signal (U.S.) and DSM are still users of this route]: phenol f cyclohexanone f cyclohexanone oxime f caprolactam. Caprolactam production expanded in Europe after the war, when the I. G. Farben process was freed from patent restrictions. In view of long-range forecasts for caprolactam, (former) Dutch State Mines (now DSM) started research on the cyclohexane oxidation route in the 1950s even though the company was operating phenol-based plants. By 1959, the company had the designs of a plant ready, and the DSM caprolactam processes have since been licensed widely by Stamicarbon, a subsidiary of DSM. Other companies in Europe and the U.S. (Inventa, BASF, Snia Viscosa, Du Pont, Rhone Poulenc, Nitrogen Works in Poland, etc.) have also been active in this area and have developed their own processes. Even prior to the advent of Perlon in Europe, Carothers at Du Pont had produced the condensation polymer of adipic acid and hexamethylenediamine, which he called “Nylon”. In the late 1930s, the knowhow for Perlon and Nylon were exchanged between Du Pont and I. G. Farben, and industrial development of both were undertaken. Du Pont’s original development of a commercial adipic acid process dates from 1937. The basis for the industrially applied two-step process, with the oxidation of cyclohexane to cyclohexanol and cyclohexanone as the first step, was laid sometime during the war.16 A single-step process from cyclohexane to adipic acid makes obvious economic sense, and several attempts at developing such a process have been made. Asahi17,18 and Gulf research19 seem to have arrived at a feasible process using activated cobalt catalyst in an acetic acid medium, but these processes have not been commercialized. Patent activity has, however, been rife in the area. PPC ventures have developed a commercial route directly from cyclohexane to adipic acid up to pilot scale (Fluor Daniel offers this process). Also, Twentyfirst century research corporation is very active in this area and has filed as many as 17 patents recently (for example, see Vassiliou et al.20 and Dassel et al.21). Today, practically the entire world output of adipic acid is via the liquid-phase oxidation (LPO) of cyclohexane
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for example. Air oxidation for the second step has not found favor because of loss of selectivity and proliferation of secondary products. which itself is produced by a liquid-phase air oxidation step from a conveniently oxidized substance such as isobutane or ethylbenzene. One reason for this was probably that engineering descriptions of the kinetics (which were invariably of the “lumped” type) did not often account for features such as induction periods and autocatalysis. mainly because of the costs of handling the borate ester adducts and recycling the boric acid. albeit in a qualitative manner.8 ARCO is a world leader in this field..25). No.38 in which the possibility of the reaction becoming mass-tranfer-limited and the bulk becoming starved of oxygen was recognized. Although an awareness of the issues involved in mass transport with chemical reaction is evident in the early Russian work on organic oxidations (for example. however. These data demonstrated conclusively the importance of backmixing in the reactor. the models used in the early attempts were rather crude and did not pay adequate attention to the influence of mass transfer.26 In fact. These authors made an attempt to explain certain experimental observations that could not be explained on the basis of considerations of chemistry alone by invoking the role of mass transfer. in the late 1960s. The Celanese LPO process for acetic acid from n-butane is still operative. but a multiplicity of products is obtained because of the comparable reactivity of all the methylene groups. 2009 | http://pubs. A development that led to a technology and several process plants in the U. 11. However.S. most oxidation systems. starting with the work of Higbie in 1935. apart from tert-butyl alcohol. however. The desired specificity could.. and hence. the first attempt to explicitly acknowledge the role of mass transfer in organic oxidations was probably the work of Hobbs et al. Eng.and isobutane.10). and paraldehyde8 as co-oxidizing substances. hold the promise of a much more economical route to cyclohexanol and would seem to have the potential of displacing the direct oxidation of cyclohexane.28. Over the years. of Bashkirov’s method of using boric acid to convert the alcohol that forms from the hydroperoxide directly to the boric acid ester of the alcohol to prevent the overoxidation of the alcohol. Yet another illustration of the link between polymer feedstocks and organic oxidation is the development of the oxirane process. by Scientific Design. Methods of improving the selectivity have naturally been the focus of research effort over the decades. Another reason was the lack of data on the important mass-tranfer parameters in systems and under conditions of temperature and pressure which were of industrial interest.6). This process. reactor and process design aspects have received considerable attention.acs. Attempts to bring hydrocarbon oxidations within the ambit of the theories of mass transfer with
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. the route continues to occupy a dominant position today in the manufacture of the raw materials for nylon (both Nylon-6 and Nylon-6.39 In the 1960s.org Publication Date (Web): October 11.S. 2000 | doi: 10. 39. be obtained in small molecules such as n. and the high reactivity of the primary and secondary reaction products.8 A process that yields a small number of products is obviously desirable.19.27 acetaldehyde.16 The oxidation of cyclohexane must be one of the least efficient of all major industrial chemical processes.I. it must be said that the subject has received relatively little attention in the literature and has remained largely inconclusive. The functionalization of alkanes by treatment with oxygen has an obvious attraction for the industrial chemist and has been a recurring theme. ought to be treated as cooxidation systems because of the participation of the products. Berezin et al. methyl tert-butyl ether (MTBE). The development of paraffin oxidation began around 1930 in Germany.S. The features of co-oxidation are a direct result of the free-radical chemistry and had been studied in the 1950s.35-37 However.23 Although the Flixborough disaster of 1974 opened up important questions of safety24 in cyclohexane oxidation processes. The interest in isobutane oxidation in the context of the oxirane process has been mentioned earlier. van de Vusse40-42 applied the theory to complex reactions with kinetics of the type encountered in organic oxidations. the U. Oxygen is incorporated into the propylene molecule by reaction with a hydroperoxide. The process was of importance in Japan. and Europe in its wake was the application. the boric acid variant of the oxidation process seems to have largely given way to other processes in the following decades.1021/ie0002733
. The pioneering work of Winkler and Hearne11 on this reaction led to a number of patents. 2000
by air.S. Although not much of this was published in the open literature. The oxirane process accounted for more than half of the production of propylene oxide in the U. Meanwhile. However. the commercial success of such a process also depends on the market for the coproduct. Chem.R. although one can find studies delving into the question of mass-tranfer limitations in organic oxidations (summaries are available in Doraiswamy and Sharma43). and efforts to solve this saw the application in the 1980s of the emerging area of reaction in supercritical media. the process has not yet been applied outside Asahi.22 Although this process is still in use by Bayer in cyclohexane oxidation.S. The development of industrial processes naturally required that extensive engineering studies be carried out. Vol. uses an interesting cooxidation principle to oxidize propylene in an indirect manner.3 and research interest in the process continues unabated (see. Although this new route to adipic acid has been commercialized by Asahi. not considered. developed by Atlantic Richfield (ARCO). until the late 1970s8 and continues to operate in the C. Deliberate co-oxidation routes have also been attempted for the oxidation of p-xylene to terephthalic acid by using butane. Schuchardt et al. The possibility of reaction within the diffusion film was. followed by the further oxidation of the products using nitric acid.30-32 Interest in isobutane oxidation has been rekindled in recent years33 because of the possibility of its development for the production of the fast-growing petrochemical. however. A substantial selectivity to a mixture of secondary alcohols was
obtained by the use of boric acid in Bashkirov’s method. mention must be made of the work of Steeman et al. Recent developments in the selective hydrogenation of benzene to cyclohexene.S. the theory of gasliquid reactions had made significant strides. in 1991. Japan.29 The conflicting demands of rate and selectivity was again the major problem.. and hydrocarbon oxidations had been recognized as a major class of reactions of industrial significance falling within the scope of the theory. for the oxidation of propylene to propylene oxide.. and the U. except at very low conversions.. process development usually involved extensive experimentation at different scales.3962
Ind. Res.34 who reported the first comprehensive set of data on the oxidation of cyclohexane to the scientific world.
etc. these differences call for innovative technological developments. and experimental studies do show evidences of complex behavior. Suresh et al. depending on the place of the desired product in the reaction sequence (whether as a primary.1021/ie0002733
propylene oxide acetic acid
cyclohexane to cyclohexanone/ cyclohexanol (KA) and KA to adipic acid iso-butane to TBHP ethylbenzene to hydroperoxide butane/naphtha
BASF. for example. 11. at Monash University. The production volumes of the chemicals listed is impressive and serves to underline the importance of liquid-phase oxidations in industry. Dupont.35 on “critical conditions” in the oxidation of methyl ethyl ketone suggest hysteresis-type effects.6-dimethylnaphthalene two-step process or one-step process coproduct: acetone also applies to cresols.50 Cao et al. several studies.51. 39.38 (1995) 4. always of paramount importance in this field. diisopropylbenzenes also employed in the Snia-Viscosa route to -caprolactam and Henkel route to TA
0. A choice of hydrocarbons is therefore available (several have been suggested. the oxidation step leads directly to the product of interest. 2.8. hydrocarbon oxidation provides a convenient carrier of oxygen for the selective oxidation of propylene to propylene oxide. Although treatises on hydrocarbon oxidations underline the similarities that exist in the mechanisms that govern various organic oxidations.Ind. such as the process for caprolactam. pseudocumene. resin) PET (fiber. Stamicarbon Scientific Des. Major Chemical Processes Utilizing Hydrocarbon Oxidation1.5 (1998) oxidation step p-xylene to terephthalic acid p-xylene to p-toluic acid and monomethyl ester of pTA to DMT cumene to cumyl hydroperoxide important processes Amoco Mid-Century Witten.52 and other places.0b (1994)
toluene to benzoic acid cyclohexane to KA
DSM. Chem. UCC
K:A ratio depends on use of boric acid coproduct: tert-butyl alcohol (gasoline additive) phenyl methyl carbinol (dehydrated to styrene) main route is via carbonylation of methanol
propylene glycol. 2009 | http://pubs. A growing appreciation for the interaction between physical transport phenomena and chemical kinetics in organic oxidations has led to an examination of the possibility of using oxygen-rich gases for oxidation. etc. it is the differences that exist between hydrocarbons that is often of interest. oxirane oxirane Celanese. In the oxirane process. A Survey of Industrial Hydrocarbon Oxidations A broad survey of the commercially important processes employing liquid-phase hydrocarbon oxidations is presented in Table 1.. Eng.2 (1993) 4 (1993) 6.. Bayer. In some of the processes. 2000 | doi: 10.44-50 Twente. Recent developments in air separation technology have also contributed to the interest in this area. A quantitative assessment of the costs and benefits for such a changeover to oxygen-rich gases does not yet seem possible without actual experimentation for most hydrocarbon oxidations.) main application PET (fiber. polyols styrene vinyl acetate.
chemical reaction therefore met with limited success..acs. are being reexamined in this context. There are others. 2000 3963
Table 1. the review by Gray and Scott53). see Weissermel and Arpe8). Res. for example. Furthermore. It is interesting to note the different roles of the oxidation step in these processes. especially in combination with mass-transport influences. DuPont Hock (BP. The issues of safe design and operation of oxidation reactors. cellulose acetate. have attempted to address these gaps. BP.55 product purified terephthalic acid (PTA) dimethyl terephthalate (DMT) cumyl hydroperoxide (CHPO) benzoic acid capacitya 106 tpy 11. resin) phenol remarks applies also to other alkylaromatics such as m-xylene. b About 9% of the total production capacity shown is by the oxidation route. DSM. The observations of Hobbs et al.org Publication Date (Web): October 11. BASF. DuPont.6
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and simulation carried out on particular oxidations (see. and the market for the coproduct determines which hydrocarbon is chosen in a given context. from an engineering point of view. these authors suggested that industrial reactors should be operated “with a mass-transfer-limited zone present”. 4. Dow
phenol and salts. can. but much remains to be done. Vol. such as the Amoco process for the manufacture of PTA. The nonlinear kinetics of organic oxidations. secondary. esters of benzoic acid Nylon-6 (Perlon) Nylon-6.28 (1995) 3. in which oxidation is the step that produces a key intermediate that is then further processed to the product of interest. Because such situations can lead to unstable operation in practice. quantitative application of the theories to hydrocarbon oxidations is still to come. Stamicarbon Scientific Des. Kellogg. PTA.06 (1995) 6. lead to a rich variety of dynamic behavior with possible consequences for the safe operation of industrial reactors among other things.
a Capacities shown are worldwide figures and refer to the year indicated in parentheses.
. solvent.54 and Roby and Kingsley55). while theoretical aspects have received much attention in this area (see. resorcinol/hydroquinone from cymenes. film. Once again. Bayer. in principle. film. In the last two or three decades. No. BASF.
. Vol. As raw material for conversion to PET fiber. and Du Pont. the oxidation proceeds up to the stage of p-toluic acid (oxidation of one methyl group to -COOH). 11.1021/ie0002733
iso-butane air ethylbenzene air toluene air
cumyl 130-140 5 hydroperoxide TBHP 120-140 35 EBHP 120-140 35 benzoic acid acetic acid 110-120 2-3 165 9
stirred Amoco reactors.8. a procedure that allows oxidation to proceed. A fascinating account of the development of these technologies from early stages has recently been written by Landau. In 1998. but for reasons that are still a matter of debate. the esterification and the second stage of oxidation are carried out simultaneously. the bromide in the catalyst promotes the reaction sufficiently to give reasonable rates of oxidation even beyond the p-toluic acid stage. two approaches have been found to circumvent the problem. a partial oxidation product. the dominance of terephthalic acid has been continuously
increasing. the product of interest forms fairly late in the reaction sequence. would interfere with the polycondensation. the process needs tend to be very different.14 In the oxidation of p-xylene. In the manufacture of terephthalic acid. Chem. DMT is the product. This method uses less catalyst and provides higher rates12 than the first and is being increasingly preferred. The problem here is thus the presence of an intermediate. In either case.
or tertiary intermediate). Eng. 4. and selectivity considerations become extremely important.3 the resulting carboxylic group seems to confer resistance to further oxidation. or tetrabromoethane. In the older Witten method. when the final product is desired. 2009 | http://pubs.55 reaction conditions hydrocarbon liquid p-xylene air gas desired product PTA temp °C pressure bar medium acetic acid (90-95%) catalyst MC cata conversion 95% selectivity >90% reactor type process
monomethyl air ester of pTA p-xylene + air and DMT monomethyl methanol ester of pTA cyclohexane air KA oil cyclohexane cumene air air
p-toluic acid pTA DMT
140-170 4-8 140-240 40 100-200 5-20 125-165 8-15 125-165 8-15
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. 2000
Table 2.06 million tonnes.38 million tonnes and that of DMT. the selectivity with respect to the hydrocarbon is better in the single-step process (Table 2). In a majority of situations however. the share of PTA has further increased. as well as the conversion to which the reaction must be allowed to proceed. 4. p-Xylene and Other MC Oxidations In terms of tonnages. Res. process Ti/hastelloy lined Co and Mn Witten salts process pTSA or 85% Witten other acid process p-xylene 90% countercurr. the share of PTA in the PET raw materials went up from 29% in 1976 to 55% in 1988.. with improvements in the purification technology by high-pressure hydrogenation. Technologically. 2000 | doi: 10. In 1995. Montecatini. A single-step variant of the process is practiced by BASF. the conversion of p-xylene to PTA and dimethyl terephthalate (DMT) ranks as the highest among the oxidation processes. The presence of small amounts of 4-carboxybenzaldehyde.org Publication Date (Web): October 11. In practice. and significant differences between the various cases stand out. the worldwide production of PTA was 11. Du Pont and column one-step rxn prod process Co and Mn 5-8% 80-85% stirred salts reactors Co and Mn 12-13% >90% stirred salts with reactors boric acid CHPO 30% 93-95% bubble initiator column initiator 25% 60% oxirane initiator 15-17% 87% bubble cap oxirane trays Co salts 90% Dow Co acetate 90% Snia viscosa caprolactam process MC cata 99% 96% Amoco product mix Co acetate 10-20 Huls acetic acid uncat UCC
MC catalyst consists of Co and Mn acetate. 39. Whereas the two-step process gives a higher selectivity with respect to methanol (80% vs 60-70% in the single-step process8). the use of terephthalic acid lagged behind that of DMT in the past. No. the acid group is esterified with methanol. NH4Br.3964
Ind. are often determined by the selectivity-coversion relationships. Some Important Process Parameters in the Commercially Important Oxidations1.1. In the second method. the desired product is an intermediate susceptible to further oxidation. Choice of reaction conditions. it may in fact be considered as the end product. and. the difficulty of manufacturing terephthalic acid on a large scale at a purity sufficient for polycondensation has prevented its widespread use in the past.acs. which can be hydrolyzed to terephthalic acid or used directly in the manufacture of PET by transesterification. Table 2 provides some relevant details for the oxidations involved in the processes presented in Table 1. used in the Amoco (MidCentury) process. which converts the aldehyde to the easily separable p-toluic acid. However. Although direct esterification of terephthalic acid with ethylene glycol is chemically the simplest method for manufacturing PET. Thus. considering its resistance to oxidation. using countercurrent contacting of the p-xylene (and oxidation products) with a stream of air and methanol.
will briefly be discussed here. as in this case. was abandoned because of poor product quality. as usually practiced. it is the high reactivity of the intermediate. but also stood the test of time. boric acid is used to direct the reaction of the hydroperoxide toward cyclohexanol and protect the alcohol as its boric acid ester to prevent its over-oxidation. However. The latter problem is present to some extent whenever acetic acid is used as a solvent and is. 80-85 °C. and its application in PET resins is rising at an impressive rate. Chem. Vol.23 has not only become established in industry. Castellan et al. in passing. pseudocumene to trimellitic anhydride and trimellitic acid. Eng. Scientific Design has developed a process for a twostage autoxidation route to adipic acid. and produces a mixture of cyclohexanol and cyclohexanone. The former of these references also has an extensive listing of patents on the manufacture of adipic acid and summarizes the status of alternative routes for adipic acid.16 and Weissermel and Arpe57 have recently summarized the information available on the oxidation of cyclohexane and the manufacture of adipic acid and caprolactam. and a selectivity of over 97% has been claimed. a ketone-rich mixture is preferred. Thus. The second approach (Halcon and IFP) allows higher conversions to be used. less of a problem with the Mid-Century catalyst than with cobalt alone. catalytic air oxidation under milder conditions (acetic acid medium. The first of these is to maximize the selectivity to the hydroperoxide in the first oxidation step and achieve a selective conversion of the hydroperoxide in a second stage by employing milder conditions and special catalysts. m-xylene can be oxidized to isophthalic acid. Because of work carried out by Du Pont. Res. The former is engendered by the use of metal/bromide/acid mixtures. Amoco has manufacturing capacities of 2 × 105 tons/year of isophthalic acid (continuous process) and about 4. the route using oxidation with nitric acid as the second stage is preferred because of better selectivity. The MC method lends itself to batch as well as continuous processing.7 × 104 tons/year of trimellitic acid (batch process). 39. which have higher temperature ratings and better barrier properties than PET. to prevent their overoxidation. 2009 | http://pubs. Other processes for terephthalic acid have been discussed by Weissermel and Arpe. Other Saturated Hydrocarbons. The low conversion levels in the oxidation of cyclohexane with traditional cobalt catalysts have motivated a large literature on alternative catalysts. For caprolactam.2 and safety in section 11). Industrially. 11. both based on the MC process with yields of over 90%..56 The catalytic principle of the Mid-Century process and the process details have been discussed comprehensively by Partenheimer. selective decompositions of cyclohexyl hydroperoxide using homogeneous as well as heterogeneous catalysts has led to a rejuvenation of interest in this approach. (Also. DSM developed such a process and applies it on a large scale.
.8 Naphthalene-2. has been attempted with good results.5 in the presence of cobalt stearate4) and can be made to strongly favor the alcohol by the use of boric acid
(alcohol-to-ketone ratio of 9:1). It is interesting to note. Developments in the low-temperature. the conditions are milder (100-140 °C).acs.6-dimethylnaphthalene to naphthalene-2.1021/ie0002733
major disadvantages of the method are the need for special materials (Table 2) and the loss of acetic acid solvent through decarboxylation. Oxidation of Cyclohexane. The main problem in the oxidation of cyclohexane to cyclohexanol and cyclohexanone is one of selectivity and arises from the fact that these products are much more reactive with respect to oxidation than cyclohexane itself in the oxidation medium and under the conditions employed. 2000 | doi: 10. one of two approaches is followed in order to contend with the selectivity problem in the case of cyclohexane oxidation. in fact. The problem in the former case is the inhibiting effect of the intermediate (p-toluic acid). and Terpenes The oxidation of cyclohexane is notoriously inefficient. However.2. and 2. The principle of the Amoco process has been successfully applied in the case of other aromatics and alkylaromatics.12 Co-oxidation of p-xylene with various other substances. 2000 3965
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. although neither seems to have yet reached the stage of commercialization.12. although there are the additional problems of corrosion and recovery of the nitrogen oxides produced. an important greenhouse gas. has become a major concern with this process. based on autoxidation technology. whereas in the latter. 7 bar) has received some attention.5 in the uncatalyzed oxidation and 1. a use must be found for the coproduct. Two approaches in particular. No. The ratio of alcohol to ketone in the oxidation mixture depends mainly on the use of catalyst (the alcohol-to-ketone ratio being about 0. This oxidation.6-dicarboxylic acid. mesitylene to trimesic acid. trimellitic anhydride is emerging as an important component for the manufacture of extremely heat-resistant polyimides. Isophthalic acid finds application in polyesters and copolyesters.. in recent years. Practically all of the adipic acid16 and about 63% of the caprolactam57 produced in the world in 1990 used cyclohexane oxidation as the first step. In the further conversion of the KA (ketone-alcohol) mixture to adipic acid.S. such as acetaldehyde and paraldehyde in acetic acid solution (Toray process).org Publication Date (Web): October 11.8 One route involves the LPO of toluene and is discussed later. bromide corrosion is not a problem. Trimellitic acid is mainly used for the manufacture of esters for plasticizers. is carried out only to very small conversions (usually less than 8%). hence. 4.6dicarboxylic acid is now emerging as an important raw material in the manufacture of PEN resins as well as co-polyesters with PTA. The process economics still favors cyclohexane oxidation. a reaction that can be carried out with a selectivity in excess of 97% at 99% conversion. uses cobalt naphthenate or stearate as the catalyst.) Weissermel and Arpe8 report that the Rohm & Haas plant in the U. acetic acid. The first approach is to keep the conversion very low in order to keep the concentration of the products low in the oxidation mixture and. The conflicting demands of selectivity on one hand and safety and rate on the other are best reconciled by having several stirred reactors in series (reactor selection issues are discussed in section 8. The disadvantage of the method is the need to recycle large volumes of unconverted cyclohexane. It is therefore interesting that this process. The alternative route to cyclohexanol and cyclohexanone involves the hydrogenation of phenol. formation of N2O. which have been targeted for industrial development in cyclohexane oxidation. the widely divergent process needs in the cases of p-xylene and cyclohexane. Recovery and recycling of the boric acid used is the problem in this case. Cu or Mn acetate as catalyst.Ind. which offers selectivities no higher than 80% even at 4% conversion.
Surprisingly. This process still operates in Japan and the C.1% KMnO4 and 4-5% metaboric acid. such an approach would obviously have the advantage of simplicity. considering the low solubility of oxygen in cyclohexane. Chem. choice of noncatalytic wall material. While on the whole. and passivation of the wall. Vol. Eng. in the oxidation step. some interesting chemistry has been brought out as a result of this research.8 Atmospheric operation at 140-190 °C.59. we mention the work of Iwahama et al. is oxidized to a mixture of cis. which. According to the Asahi work. The reaction is conducted in acetic acid medium with trace amounts of transition metal salts as acetylacetonates. was first developed for the oxidation of n-paraffins as one of the routes to linear secondary alcohols in the C10-C20 range.18 and Gulf64 have made attempts in this direction. Asahi17. derived from R-pinene (a plant product).63 In the second approach. Weissermel and Arpe8 discuss some process variants.17 are of interest for further development (see.36 At the same temperatures (150-160 °C) as employed for cyclohexane oxidation.12-Dodecanedioic acid is the second most important dicarboxylic acid after adipic acid. a total exclusion of circumstances that could lead to a decomposition of the hydroperoxide is needed. Alcohol-to-ketone ratios are similar to those in the analogous cyclohexane oxidation. judging from the large amount of patent activity in the area. Obviously. cyclododecane can be oxidized in the liquid phase at atmospheric pressure to a cyclododecanol/ cyclododecanone mixture. Typical reaction conditions quoted include temperatures of 70-100 °C and reaction times of 2-6 h. indeed. Gulf patents claim that the presence of water improves the adipic acid yields substantially.72 These authors have also studied the oxidation of R. is preferred over polycyclic musk for environmental reasons.and trans-pinane hydroperoxides. limonene can be converted.acs. yields linalool. made via esterification with ethylene glycol. The work of Twenty-first century research corporation was cited in section 3. The Bashkirov principle of using boric acid to produce alcohol esters. Ciborowski23 argues the case for this process alternative and discusses the possibilities of utilizing the hydroperoxide. A recent claim by Ube industries71 refers to the liquidphase oxidation of cyclododecane in the presence of mono(2-ethylhexyl) phosphate and di(2-ethylhexyl) phosphate at 160 °C. also see Park and Goroff65 and Vassiliou et al. with a cobalt salt as catalyst.8 and selectivities of about 80% are achieved at 25-30% conversion. 2000 | doi: 10. steps of importance in the manufacture of several flavor intermediates apart from hydroperoxides (which are used in free-radical polymerizations as initiators).S. to carvone and other products using a cobalt catalyst. a product of some importance in polyamides (Nylon-6.and
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. The borate esters are later hydrolyzed with NaOH. conditions that favor the formation of Co3+ in the reaction medium are to be preferred. overall selectivity in the oxidation step to (cyclohexyl hydroperoxide + cyclohexanol + cyclohexanone) can approach 90% under optimum conditions. These alcohols have application in detergent manufacture. Kulsreshtha et al. If reasonable selectivity can be achieved. The interest in homogeneous oxidation..58 describe a family of active and long-lived catalysts for selective conversion of the hydroperoxide. A novel feature of this claim is the use of phosphate ester. 39. This dicarboxylic acid has been attracting additional attention in recent years.12-dodecanedioic acid. cyclohexanol is not formed.. Cyclododecanol and cyclododecanone are also precursors to lauryl lactam (monomer of Nylon-12). it must be admitted that the results on single-step oxidation to adipic acid have been less than satisfactory. and thereby gain alcohol selectivity. and it is suggested that it is further converted under the reaction conditions. as an entire process step is eliminated. No transition metal catalyst is used. such as contacting liquid in atomized form with a stream of the oxidizing gas. Also allied to cyclohexane oxidation is the oxidation of p-menthane and cis-pinane. with the hydroperoxide constituting up to 80% of these products. They use aldehydes and ketones as promoters for this purpose.70 have reported selectivities of 77% at 85% cyclohexane conversion using a Co(III) catalyst at 100 °C.S. indicates a recognition of the possibility that the reaction can move into masstransfer-limited regimes. for example.I. to conversion levels of 15-25% is used. has been used by some researchers as a model system for studying the kinetics of cyclohexane oxidation.3 Apart from being a product of importance in its own right.67 for example) deal with unconventional contacting methods. The manganese salts
appear to yield the best selectivity to adipic acid.3966
Ind. on pyrolysis.68). Recent studies at Monash University on homogeneous oxidation in a variety of reactor types in aluminum and glass-lined reactors have produced encouraging results. The oxidation is carried out in acetic acid medium. Similarly. interest in direct routes to adipic acid would seem to have revived.61. Thus.59 homogeneous oxidation. Res. whose actual role is unclear. a direct oxidation to adipic acid is attempted. pinane. Boric acid is used in the industrial process.org Publication Date (Web): October 11.16 some of the principles recognized by the earlier work. where 73% selectivity to hydroperoxide at 12% conversion has been realized. Cyclohexanone and adipic acid are the main products. Some patents (Dassel and Vassiliou. Processes are operated by Huls in Germany ¨ and Du Pont in the U. in the presence of about 0. This mixture is in turn hydrogenated to a mixture of cis. which is relevant to adipic acid manufacture. However. Also. again in analogy with cyclohexane oxidation products. The oxidation yields sec-alcohols almost exclusively. 2000
Tolman et al. with a statistical distribution of OH groups. neither process seems to have been implemented industrially. linalool can also be readily isomerized to nerol and geraniol using an orthovanadate catalyst. 11. and claims of 70-75% selectivity to adipic acid at conversion levels of 50% and above have been made.59-61 and use of a second phase to remove the hydroperoxide by reaction as it is formed62 are some of the methods that have been claimed to offer high selectivities. In particular. 2009 | http://pubs. The oxidation of cyclododecane is analogous to the oxidation of cyclohexane and.66 The role of water and the solvent-to-hydrocarbon ratio would seem to be important from these patents. via air oxidation.and transpinanols.12) and polyesters. 1. as also would a careful regulation of temperature versus holdup time. such as the need to keep the transition metal in the higher oxidation state. and in the new generation of polycarbonates. According to this author.69 which demonstrates the oxidation of cyclohexane at 100 °C and atmospheric pressure using N-hydroxyphthalimide as a radical catalyst. Steinmetz et al. In another development. In recent years.1021/ie0002733
. as the macrocyclic musk. No. Further oxidation with nitric acid is used to convert the alcohol/ketone mixture to 1.
and carotenoids. Mn. apart from being a gasoline additive. 39. A range of processes are available for the oxidation of toluene. Two other processes are shown in Table 2.76 4. the hydroperoxide and the alcohol are substantially the only products formed. 50% being the selectivity to TBHP. Weissermel and Arpe8 and Kahlich et al. coproduct economics have meant that the oxirane capacity is split almost equally between isobutane. The presence. yield phenol and methyl ethyl ketone. citronellol. on cleavage. or the “indirect oxidation” routes to propylene oxide. although substances such as Cu. the former accounting for about 56% of the capacity. and other conditions are shown in Table 2. 11. the oxidation is carried out until the stage of cyclohexanol/cyclohexanone. the total selectivity to tert-butyl hydroperoxide (TBHP) and tert-butyl alcohol (TBA) is 96%. m-diisopropylbenzene has been converted to resorcinol and p-diisopropylbenzene and to hydroquinone in Japan (Mitsui and Sumitomo) and the U. 2009 | http://pubs.5. in the case of the diisopropylbenzenes. In the ethylbenzene-based process.8 The importance of the oxirane route in PO manufacture has been increasing through the years. For example. to 2-naphthol (a widely used dye intermediate) and acetone with a yield of about 95%. The oxidation of limonene in glacial acetic acid containing lithium chloride in the presence of PdCl2-CuCl2 gives trans-carveyl acetate as the major product. and Kellogg processes use an air/aqueous emulsion at a pH of 8. hydroquinone. either in a preliminary step or in situ. which is oxidatively decarboxylated to phenol. and resorcinol (combined world capacity of about 85 000 tons/year in 1994). cymene can be oxidized and cleaved to m. was recognized in the 1950s and came to fruition thereafter. Hercules. as total oxidation of phenol is preferred to partial oxidation of benzene. and hence. in isobutane oxidation. The coproduct tert-butyl alcohol in the isobutane-based process. however. in theory. The Oxirane Process: Oxidation of iso-Butane and Ethylbenzene The oxirane processes. The table reflects the more recent trend to reduce or even eliminate water from the reaction medium.74 The direct oxidation of benzene to phenol is highly unselective. Cumene is. via neat air oxidation to hydroperoxide and subsequent acid-catalyzed cleavage.S. while themselves being converted to the alcohol (or the acid). 2000 | doi: 10. By far the most important process is the Hock process. three involve a liquid-phase autoxidation. (Goodyear). more than 90% of the phenol produced in the world. Thus. even at 48% conversion. and these have real large-size oxidizers. The BP. The process is based on the oxidation of cumene to cumene hydroperoxide and the subsequent cleavage of the hydroperoxide in acidic media to phenol and acetone. requiring modifications to the cumene-phenol process. The first step of toluene oxidation in the second process is of some importance in its own
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. Another potential possibility is to use secbutyl benzene in place of cumene so that the corresponding hydroperoxide will. air/cumene contacting can be used at 120 °C (Hercules process). The hydroperoxide or the peroxy acid is produced. Indirect oxidations exploit the ability of hydroperoxides (or peroxy acids) to selectively transfer their peroxidic oxygen to olefins to form epoxides. none is used. 2-isopropylnaphthalene has been converted. Alternatively.5 million tons per annum. In the former case. Eng.and ethylbenzene-based plants. 4. first commercialized in 1953. Kalama USA (now Goodrich)].acs.8 The oxidate is worked up to 65-90% before being subjected to acid cleavage. which gives phenyl ethyl
. citronellal.S. it ranks 34th in terms of capacity in the overall list of industrial chemicals. Although a choice of hydroperoxides/peroxy acids is available (see. which is dehydrogenated to phenol at 400 °C. In a manner analogous to the Hock process. toluene is oxidized to benzoic acid. and Co salts can reduce the induction period at the start. In the U. Vol. LPO-Based Routes to Phenol and Benzylic Alcohols Phenol is another major chemical derived from a liquid-phase oxidation route.. The aim in the oxidation is to maximize the selectivity to the hydroperoxide. among them the Amoco Mid-Century process discussed earlier. at a level of approximately 6. The conditions of oxidation and typical conversion-selectivity figures are shown in Table 2. As oxidation catalysts encourage hydroperoxide decomposition (see discussion on cyclohexane oxidation above). is produced by this route. the synthetic routes mentioned above are far more important. can be dehydrated to isobutene and further converted to methyl tert-butyl ether (MTBE). with small amounts of acetone in the case of isobutane and acetophenone in the case of ethylbenzene.75 The oxidation takes place at 110 °C. Cumene was originally produced in World War II as an additive for gasoline. The other LPO-based routes to phenols8 are those using cyclohexane oxidation (Scientific Design) and toluene oxidation [DSM. In the latter. These products are also important as intermediates in the manufacture of other terpene products such as citral. Several single-stream plants producing phenol at 200 000 tons per annum exist. menthol.3.org Publication Date (Web): October 11.8 Of the five routes that have attained commercial significance.5-10. 2000 3967
β-pinenes. vitamins A and E. which are of interest in the context of liquid-phase autoxidations. Today.77). applicable to other feedstocks such as ethylbenzene (coproduct acetaldehyde) and cyclohexylbenzene (coproduct cyclohexanone). of two hydroperoxide groups after the oxidation leads to a greater number of byproducts and lower rates than are attained with cumene hydroperoxide. the coproduct phenyl methyl carbinol is converted to styrene. of the more important dihydroxybenzenes. ionones. These processes have been operated for over 25 years by Sumitomo and Mitsui. from diisopropylbenzenes.. No.and p-cresol (coproduct acetone).1021/ie0002733
right. Chem. The process is. only the indirect manufacturing processes have been implemented.73 Although some of these products can also be directly extracted from plant sources. for example. accounted for about 48% of the worldwide propylene oxide (PO) capacity in 1991. because of the various other uses of benzoic acid (as well as its salts). for example. as has been reported by Gusevskaya and Gonsalves.8 Again. Its potential for making phenol. Res. via the hydroperoxide.4. Under the conditions.Ind. Modified Hock processes are also used in the manufacture. A small amount of primary hydroperoxide of ethylbenzene is also formed. expected to remain the dominant feedstock because of the market for acetone. the former has established a dominant position in industry. as an intermediate (to caprolactam in the Snia Viscosa process and to terephthalic acid in the Henkel process) and as an additive in the rubber and food industries.
S. and the C. and although selectivities are similar. Byproduct recovery is important to the profitability of the process. While one considers the potential of developments cited in the previous paragraph. The byproducts are separated by distillation. etc. MTBE was expected to continue its growth at about 15% per year.5. some recent developments should be borne in mind.79). in 199674).S. Normally.77 Hence. Furthermore. so that anhydrous acetic acid is directly obtained. the traditional route based on isobutenesin most crackers.5 wt %) are used. TBA as an additive also seems to be safe. Grieken et al.57 This. Eng. with the current technology. Some of the recent literature (patent and published) that focusses on TBA rather than TBHP in the oxidation of isobutane (for example. The chemistry is.82 and is likely to continue. Ciborowski23). although at the expense of acetic acid. 39. TAME (tert-amyl methyl ether) is another gasoline additive with properties similar to MTBE. and its usage in motor gasoline is being phased out. the possibility of using cyclohexyl hydroperoxide to convert propylene to PO in a step analogous to the existing oxirane processes has also been commented upon (e. as in the commercial processes operated by UCC in the U. typical reaction conditions are indicated in Table 2. The Rhone-Poulenc/Melle Bezons process uses air instead ˆ of oxygen. 11. Vol.84) and patents dealing with the selective conversion of TBHP to TBA (for example. MTBE has come under a cloud. other plants have been put into operation.K. These plants use the acid-catalyzed reaction of isopentene with methanol.S. We have surveyed some of the more important LPO processes so far. 25-40 bar). and uses a mixed feedstock of crude oil distillates in the 15-95 °C boiling range (roughly C4-C7). H2O2 is expensive. The Huls process (Table 2) is a ¨ typical catalyzed LPO that produces. A feature of this process is that. Although the interest in isobutane oxidation has been in the context of the oxirane process. Daicel in Japan. possibilities for its development for MTBE production are being actively examined. It ranked 33rd in the list of U.83 and Fan et al. Chem. ethyl acetate medium. The Hoechst process8 uses oxygen. According to the projections made in 1993. As with isobutene in cracker streams. although they have been superseded in recent years by methanol carbonylation. byproducts are recycled to simplify product workup. in addition to acetic acid.acs. MEK. Careful temperature control is needed to limit degradation reactions and obtain the high selectivities shown. is used for TAME production. In the processes for acetic acid however. Acetic acid is one of the most important aliphatic intermediates and the first carboxylic acid used by man.S.1021/ie0002733
.) ETBE (ethy tert-butyl ether) is a possible replacement for MTBE. however. similar. interest in the autoxidation of isobutane has resurfaced33. a common disadvantage of all processes based on H2O2 is that. they accelerate the reaction by helping in radical generation and facilitating the decomposition of the peracetic acid. Under mild conditions (no catalyst..78 If this growth is sustained. as well as the individual peculiarities of the specific processes that lead to highly specific technologies. at 160-200 °C and 40-50 bar. However.3968
Ind. The unifying thread of the free-radical chemistry (modified in some instances by the action of the catalysts used) that runs through all these processes. (The state of California has banned the addition of MTBE to gasoline. Japan. industrial chemicals according to a recent survey
and was one of the few organics to register a doubledigit growth during 1994-1995. The Distillers-BP process operates in Europe. solutions of Co and Mn acetates at low concentrations (0. Some of these processes illustrate how. The spread of unleaded fuels and legislation such as the U. LPO routes with acetaldehyde and butane/naphtha as feedstocks accounted for about 32% of world production. with the free-radical mechanism producing peracetic acid as the primary product. therefore.. whereas selectivity to the product of interest remains a problem when a straight through-process from the alkane to the acid is attempted. Most recently. The complex chemistry of these oxidations makes them highly versatile and makes process optimizations toward a number of alternatives from a given feedstock become possible. the C4 stream containing isobutene is directly converted to MTBE with methanolsmay not be able to meet the demand because of problems of isobutene availability. and Weissermel and Arpe8 describe them in some detail.86) are also indicative of this trend. acetone. Clean Air Act have resulted in increasing demands for MTBE (12th in terms of capacity in the list of industrial chemicals in the U. isopentene. Res. as in other processes. No. It will be necessary to resort to other routes based on TBA and isobutane.S. which is also produced in small amounts during steam cracking. of relevance in the present context is the possibility of development of isopentane autoxidation for TAME. Although oxidation with hydrogen peroxide is a research focus (see.85. peracetic acid can be recovered as the main product in acetaldehyde oxidation. The first plant for TAME began production in 1987.I.g. 2000 | doi: 10. and since then. is a case of autoxidation of an oxygen-containing compound.81 Oxidation of isobutane followed by etherification of TBA with methanol seems to hold promise. and an interesting feature is that they serve as entraining agents for water. The process uses an uncatalyzed oxidation. as there does not seem to be any objection to its use.. safety considerations require H2O2 facilities to be restricted in size.
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. with the acetaldehyde-based process being the more important (23% of world capacity). In the context of the recent interest in the oxidation of cyclohexane to cyclohexyl hydroperoxide. Shen et al.74 In 1994. byproduct recovery can contribute to the overall success of the process when reasonable quantities can be recovered. are both evident in this broad overview. the greater amount of inert species in the gases requires washing of the gases to remove acetaldehyde and acetic acid. 2009 | http://pubs. for example. depending on the demand. other byproducts such as acetaldehyde.8 4. Various routes to the manufacture acetic acid from light paraffin feedstocks have been commercialized. Sanderson et al. 2000
alcohol (which has a high value as an aroma chemical). MEK can be manufactured at up to 17% of the plant capacity. Acetic Acid from Paraffin Oxidation Liquid-phase oxidation routes also account for a significant proportion of acetic acid produced in the world. -15 to 40 °C.79. in contrast to most oxidations discussed so far (with the exception of the oxidation of cyclohexanone). and British Celanese in the U.org Publication Date (Web): October 11. for peracetic acid. along lines similar to isobutane oxidation discussed above.
The degenerate branching reactions have been shown to be the cause of several features observed in hydrocarbon oxidations.87 These reactions are endothermic and quite slow.3 The rate of reaction 6 depends on the nature of the hydrocarbon as well as on the nature of the radical. Mechanism of Hydrocarbon Oxidation The chemistry of liquid-phase autoxidation of hydrocarbons. When the chains are long. e.1. Propagation The following two reactions represent the general chain-propagation mechanism:
R* + O2 f RO* 2 RO* + RH f ROOH + R* 2
RH + O2 f R* + HO* 2 2RH + O2 f 2R* + H2O2
or by the decomposition of an initiator such as a peroxide. the facility of hydroperoxide formation decreases in the order:2 tertiary C > secondary C > primary C. which are the “links” in this chain mechanism. for example. Therefore. 2000 3969
5. are all characteristics commonly observed. 5. Whether an initiator is used or not. The generic features exhibited by hydrocarbon oxidations in the liquid phase suggest similarities in the underlying kinetic mechanisms. The free-radical chain theory of autoxidation.2. A “kinetic chain length”.10 and Partenheimer12.g. the degenerate chain-branching reaction is usually important. in general increasing as the electron-withdrawing capacity of the R-substituent increases. we shall briefly consider the elementary processes in the free-radical chain mechanism. the multiplicity of products that form indicates a complexity of chemistry. Cyclohexanol shows evidence of both mechanisms. In what follows. are often unstable with respect to the formation of free radicals..1.2 as a general framework within which to interpret the kinetics of hydrocarbon oxidations in the liquid phase. and the chains are said to be long when the number of occurrences of reaction 6 per initiation event is large. Similarly. Eng.11 being itself a product.. TBHP might be used as an initiator in the oxidation of isobutane. the presence of an induction period. Thus. 5.
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. because the hydroperoxide molecules. and abstract preferentially only the most weakly bound hydrogen atom. if initiators are used. which is used as a solvent in these attempts. induction periods are often observed in oxidations without added initiators. and reaction 2 in the case of tetralin. For example. Often. Thus..2 Berezin et al. Thus. Vol. as described later.g. which is occasioned by the fact that the primary products of oxidation are themselves amenable to oxidation by mechanisms very similar to those that apply to the parent hydrocarbon. acylperoxy radicals are much
. and termination. Initiation The reaction may be initiated either by the hydrocarbon itself. the reactivity of the alkylperoxy radical strongly depends on its structure. these initiators are usually peroxides or hydroperoxides with reasonable rates of decomposition in the temperature range 50-150 °C.56). acetaldehyde has been used in studies on the oxidation of cyclohexane to adipic acid. 11. both catalyzed and uncatalyzed.1021/ie0002733
could be important in laboratory reactors in which considerable surface-to-volume ratios are present. This explains why reproducible kinetic behavior is observed in the post-induction period even when induction periods themselves may be irreproducible (see. The peroxy radicals are relatively stable. can be calculated as the ratio of the rate of the propagation reaction to the rate of the initiation reaction (assuming that each initiation event starts one chain).org Publication Date (Web): October 11. in the oxidation of cumene. When used. 2000 | doi: 10. Suresh et al. Use of initiators is favored in fundamental studies where it circumvents problems such as poor reproducibility of induction periods in batch reactors. only the important features and those relevant to the considerations of this paper will be summarized in this section. Res. Indeed. therefore. Emanuel et al. cumene. Thus. irrespective of the hydrocarbon.50 and Suresh88).1. the branching mechanism soon overtakes the primary initiation mechanisms in the generation of free radicals. reaction 5 (rate constants > 109 mol L-1 s-1. Therefore. and the overall reaction shows a zero-order behavior in oxygen. it would not lead to products that would otherwise be absent. autocatalytic behavior. which represents the average number of links per chain. and o-xylene.1 Sheldon and Kochi. According to this theory. oxidation is mediated by free-radical intermediates. the mechanisms shown above are of importance only in the initial stages of the reaction and are overtaken even at small conversions by the chain-branching reactions to be discussed later. with negligible attack on the ring or the methyl carbons. either or both reactions 1 and 2 may be important. Also.Ind. reaction 1 has been shown to be prominent in cyclohexane. propagation. Sheldon and Kochi2 opine that initiation from the hydrocarbon is kinetically and thermodynamically unfavorable and that initiation in the absence of added initiators is due to the decomposition of adventitious peroxidic impurities. 2009 | http://pubs. attack always occurs on the tertiary C in the isopropyl group. for example. even though no metal ions may be intentionally added. has been the subject of several monographs and reviews (see. Initiation from the hydrocarbon can be facilitated by the participation of metal ions. Rate constant information on some of the initiators commonly used in autoxidations is available from Sheldon and Kochi. they are usually chosen so as not to complicate the chemistry. and is characterized by the elementary processes of initiation.2 In industrial processes. being influenced by steric as well as polar effects. e. No. On the other hand. hydrocarbon consumption occurs essentially by reaction 6. for example. Each occurrence of reaction 6 represents the formation of a “link” in the chain reaction. For example. Again.
I f I* RH + I f IH + R
When no initiator is used. The kinetic chain length can be related to the efficiency of hydroperoxide formation. as its oxidation product is acetic acid. Sheldon and Kochi2) is usually much faster than reaction 6. 39. is now generally accepted.acs. so that the R* radicals are effectively scavenged. Chem. and zeroorder kinetics with respect to oxygen. and this factor
At oxygen partial pressures greater than about 100 Torr.
alkyloxy. such as autocatalysis. 11. aldehydes and ketones respectively).3 ROH can form from the attack of the primary alkoxy radical on RH. through β-scission reactions. Howard89 has some compilations of propagation rate constants at room temperature. These situations are not as well studied as the zero-order behavior at higher oxygen partial pressures. when chains are long. it can be calculated that. however. suggesting the predominance of mechanism 10. as the activation energies of the initiation and chain-branching reactions are usually comparable. for cyclohexane oxidation at 1500 °C. Vol. which are often operated with extremely low exit oxygen partial pressures in the interest of safety. 5.. The oxidations of cyclohexane and isobutane show a proportional relationship between the rate and total product concentration.
ROOH f RO* + *OH
a bimolecular interaction of a hydroperoxide molecule with the original hydrocarbon. As an example of the importance of the chainbranching process vis-a-vis initiation as a source of ` radicals under oxidation conditions. the rate constant for termination of primary alkylperoxy radicals is higher than those of secondary alkylperoxy radicals. when types of radicals other than peroxy radicals can also accumulate in solution.bond breakage. These are a unimolecular homolysis with -O-O.4. autoxidation rates (and selectivity.
ROOH + RH f RO* + R* + H2O
and a bimolecular mechanism involving association between two hydroperoxide molecules.. 2000
Downloaded by UNIVERSITA STUDI TRIESTE on September 1.acs.11. being in the range 25-35 kcal/mol.3
from the decomposition of the hydroperoxide. viz. except in the very early stages of the reaction. lead to similar products as would otherwise form (for example. alkylperoxy) of free radicals. The decomposition of hydroperoxides. to radical species can itself be a complex process. The free-radical population would be expected to become more complex with several types (alkyl. Propagation (and hence the overall reaction) kinetics at very low oxygen partial pressures.3. a progressive decrease in the kinetic chain length with conversion. Chem.. are expected to become first-order in oxygen. Similar is the situation with co-oxidations. Three mechanisms have been identified as being important87 in the breakdown of hydroperoxides to radical species. through chain length) depend not only on the nature of the hydrocarbon itself. Howard89 presents some data on these rate constants. Thus. The heat effects associated with the branching reactions are usually small and could be of either sign. the main source of free radicals in most liquid-phase organic oxidations are the so-called degenerate branching reactions in which the primary products of the chain mechanism participate. the primary oxidation products.91 In general. thereby lowering selectivities. there are several hydrocarbons and several types of peroxy radicals participating in reactions of the same type as 6 above. 2009 | http://pubs. Degenerate Chain Branching As mentioned earlier. termination mechanisms involving these species would be expected to become important.1021/ie0002733
more reactive than alkylperoxy radicals. the tetroxides derived from secondary and primary alkylperoxy radicals decompose by disproportionation to the correponding alcohol and carbonyl compound. the dominant mode of termination would be by (“Russell mechanism”) reactions of the type2. viz. Some of the reactions of the other radical classes do. 39. while secondary and tertiary alkoxy radicals can give. These reactions lead to a number of consequences in the conversion range of industrial interest. The situation is not much different in general at other temperatures. the C-H bond energies of the hydrocarbons and the relative reactivities of the peroxy radicals together determine the relative rates of oxidation of the different compounds in the oxidizing mixture and the selectivities that result. No. which again can perhaps be explained on the basis of such mechanisms.2 The concentration of these radicals can vary both spatially and temporally. the conversion at which the two mechanisms become competitive is as low as 0. depending on local oxygen concentrations. which are themselves much higher than those of tertiary alkylperoxy radicals. It is possible that such a situation arises in industrial reactors. 2000 | doi: 10. when reaction 5 begins to control the overall propagation rate. depending on the bond energies of the participating bonds.. Eng.
2ROOH f RO* + RO* + H2O 2
RO* + RO* f RO4R f 2 2 O2 + non-radical products (7)
It is possible that mutual termination between different types of radicals becomes important under conditions of extremely low oxygen partial pressures.90 a summary is given in section 6. Res. most of the observed concentrations of alcohols and ketones in the reaction mixture derives
Alkenic hydrocarbons show a linear relationship between the rate and the concentration of the hydroperoxide. The isobutane data have been discussed recently by Suresh. and this situation is believed to lead to a much greater number of products than at higher oxygen concentrations. Under low oxygen concentrations. However. and a multiplicity of secondary and tertiary products. The tetroxide that forms in the reaction shown above undergoes decomposition in a manner that depends on its structure.01% even if reaction 8 alone is considered to operate among the branching mechanisms cited. 5. viz. as both nonchain and chain mechanisms have been implicated. but also on the structure of the peroxy radical derived from it. thus explaining the high rates and long chain lengths observed in the autoxidation of aldehydes. Some data available on the oxidation of isobutane31 suggest higher selectivities to TBHP under low oxygen partial pressures.org Publication Date (Web): October 11.3970
Ind. The termination mechanisms associated with t-alkylperoxy radicals lead to dialkyl peroxides.4. Termination Given the relative abundance of the peroxy type of free radicals under normal circumstances. when alkyl and alkoxy radicals can accumulate to some extent. In such cases. At moderate and high conversions. The relative importance of the three types of mechanisms described influences the overall kinetic
Mechanism 9 has been observed. whereas consensus has been reached on the broad features of the free-radical chain mechanism. decomposes to free-radical species. with hydroperoxides being used as initiators. see Berezin et al. Res. which are sometimes important from the industrial viewpoint. when hydroperoxide is the major product. Eng. and the low reactivity of p-xylene89 under comparable conditions. a mechanism that explains the occurrence of low-molecular-weight compounds even at early stages in some oxidations. in principle. The significant rate of termination of primary and secondary alkylperoxy radicals is the main reason an otherwise reactive hydrocarbon such as toluene has a rather slow rate of autoxidation. to treat oxidation kinetics directly from the mechanisms presented above. respectively. It is therefore clear that. for example. At moderate conversions. If initiation occurs according to reaction 1. the peroxy radical can itself isomerize and decompose into a smaller radical and a molecular product.87 Such unimolecular decomposition of the hydroperoxide is often catalyzed by metal surfaces. Overall Kinetic Features Based on the Mechanism The elementary processes involved in hydrocarbon oxidations have been established from extensive experimentation.2. in the case of tetralin and cumene and can often take precedence over the mechanism 8 because of bond energy considerations. 5. H2O2.87 that the rate of hydrocarbon consumption is given by
where rin is the rate of initiation and kp and kt are the rate constants for propagation and termination (eq 7). Chem. 11. the high reactivity of benzaldehyde. tractable models can be formulated with confidence only for the very initial stages of industrial oxidations. Cobalt has been the most prominent among
rRH ) kp[RH]
. in the case of isopropyl alcohol. Despite the shortcomings and limited scope of equations of this type. to obtain scale-independent kinetics. whereas the rate of reaction is seen to vary directly on rin. consistent with the above equation when the initiation is by homolytic decomposition of the hydroperoxide. Apart from the mechanisms discussed. The following equation has been derived2. For example. It is therefore possible. Vol. it can be shown2. at the conversions of industrial interest. The bimolecular mechanism 10 has been observed with. one would expect the reaction to show a half-order dependence on oxygen and a 3/2-order dependence on the hydrocarbon. the order with respect to the hydrocarbon is difficult to discern at the low conversions at which eq 11 applies.10 present various kinetic models for different combinations of the elementary processes discussed above.6. in part. the chain length varies inversely as its square root. but on the value of kt as well. and this explains.2 Oxidizability values can also be used to rationalize. Given that the rate of initiation can often be manipulated. No. particularly when catalysts are involved. and the order with respect to oxygen is more often seen to be zero. 39. First.5. The observed linear dependence of the oxidation rate on the product concentrations with species such as cyclohexane49. the hydrocarbons participating in these reactions at higher conversions could be the reactants as well as the intermediate products formed during the oxidation.3 to describe the rate of hydrocarbon conversion under these circumstances:
rRH ) nk2 p
where n is the number of radicals produced by decomposition of one molecule of the hydroperoxide and f is the fraction of RH consumed. Berezin et al. Second.87 Furthermore. a self-sustaining chain reaction becomes possible with ROOH as the radical source.92 and isobutane90 is perhaps indicative of this mechanism being important in these cases as well. there are others that often play a substantial role in radical generation after the induction period. because of the participation of the primary products in the various elementary processes. The kinetic features thus depend on the initiation mechanism. Thus. the different peroxide levels in cyclohexane oxidation in glass and stainless steel reactors. Because short chains are associated with a proliferation of products and hence with low selectivities. say by adding initiators.Ind. sometimes.1021/ie0002733
form. In practice however. was observed to be proportional to the square root of the hydroperoxide concentration by Farkas and co-workers (cited by Farkas6). the differences in behavior that are often observed between laboratory reactors made from different materials (for example.. Equation 11 does not explicitly account for the autocatalysis and accounts for it only indirectly if the products influence the rate of initiation. there are some difficulties with this approach in treating technical kinetics. Catalysis of Organic Oxidations It has been pointed out that the most important catalysts used in hydrocarbon oxidations involve transition metals. which is produced during the oxidation. These aspects are further elaborated in section 7. For example. For example. Some of the features anticipated from eq 11 have been experimentally observed. sharp controversies remain on various points of detail. Finally.10). this implies that addition of initiators to increase the rate can result in poor selectivities. Again. even for simple materials. However. the moderate reactivity of cumene. tertbutyl hydroperoxide and several alkenic hydrocarbons and is generally more important in cases where the hydroperoxides occur in reasonable concentrations.4 It is thus seen that the ease of oxidation of an organic depends not only on the value of kp. for example. the rate of hydroperoxide formation in the LPO of methylpentanes. nonradical pathways become important in intermediate product conversions and add to the complexity of the chemistry. the influence of wall catalysis is to be recognized and appropriate precautions taken. 2000 3971
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. 2009 | http://pubs. they are useful in comparing the susceptibility to oxidation of various substances. which disappears through alkylperoxy radical attack. At moderate to high oxygen concentrations and when branching is unimportant. showing perhaps the dominance of other initiation mechanisms even at a fairly early stage. as in the work of Farkas mentioned above.org Publication Date (Web): October 11. For a given oxidizability. a feature often observed. the chemistry gets complicated anyway. 2000 | doi: 10. the ratio kp/(2kt)1/2 is a measure of the intrinsic tendency of the compound to become oxidized and has been called the oxidizability. 5. for example.acs.
with the regeneration of the catalyst by reaction with oxygen or peroxidic intermediates (or manganese and bromide. selective route from the peracid to the acid. strictly speaking. they form the basis for some industrial production processes (for example.1).. 39. between one hydrocarbon and the alkylperoxy radical derived from the other hydrocarbon) and the cross-termination (between alkylperoxy radicals derived from different hydrocarbons) reactions. Metal catalysts are usually added in the form of hydrocarbon soluble salts such as stearates. Chem. p-xylene and paraldehyde or acetaldehyde. with the autoxidation being suppressed..94 It is possible that the direct attack on the substrate by the metal complex.e.26 and explained on the basis of the rates of the cross-propagation (i. such as acetic acid. 11. is important for several reasons. be considered as co-oxidation systems because of the participation of the products. the polarity of the solvent) in the oxidation medium is important. the ligand only has a marginal influence on the course of the autoxidations. Co-oxidations Consideration of co-oxidations. 2000 | doi: 10.2. It is also often observed that a large increase in the rate of oxidation of an unreactive component is obtained in the presence of a small amount of a substance easily attacked by alkylperoxy radicals.12 It is clear from the discussion above that the solvent has some role in catalytic oxidations.1021/ie0002733
is why solvents such as acetic acid are used when high catalyst loading is needed. the primary product in any autoxidation. induction periods and hydroperoxide levels are both smaller in cobalt-catalyzed oxidations. in which a mixture of two or more substrates is autoxidized. No. etc. alternative routes (to 14) for reducing the metal. The ease of reactions 13 and 14 depends on the redox potential of the Co(III)/Co(II) couple. This
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. Finally. Eng. in the oxidation of cyclohexane. The last property seems to play a particularly important role in oxidations in acetic acid medium as. The first two mechanisms can operate in all cobaltcatalyzed reactions. First. (c) It reacts rapidly and selectively with peracids. 2000
the transition metals used. and a catalytic process results.2 have shown that the commencement of the autoxidation virtually coincides with the conversion of cobalt to the III species.] The role of the solvent in MC oxidations is described in section 6. the metal acetate is commonly employed. among other things. and thus facilitates intermediate product conversion at advanced stages of oxidation. ketones. thereby enhancing the rate by participating in the initiation step (see eq 11). A phenomenon of some importance associated with the cobalt-catalyzed autoxidations is the “catalystinhibitor conversion”. Co(II) can exist as a dimeric species that provides a nonradical.68 that the ratio of Co(III) to Co(II) (which is influenced by.3972
Ind.17. The oxidation state of cobalt is readily recognized by the color of the solution. leading to a decrease in rate. These problems are much less significant in a polar protic medium.. It has been pointed out by several authors12. cobalt complexes are catalysts at low concentrations but inhibitors at high concentrations. this is one of the reasons for the autocatalysis commonly observed in organic oxidations. When reactions are carried out in acetic acid. Res. Methods of
. they provide the chemist with a tool for obtaining quantitative information on the relative reactivities of peroxy radicals on different hydrocarbons. sometimes operate to close the catalytic cycle. which are formed in the oxidation of aldehydes. 5. Normally.7. The decrease is attributed to the reduction to the II species by the aldehydic species generated in the oxidation. [During oxidation. the Co(III) level increases to a maximum and then decreases. Both of these features are observed in practice. an insoluble precipitate of cobalt adipate is sometimes formed. see section 4). Secondly. Third. and the transition seems to occur abruptly at some concentrations.2 In media of low polarity.12 cobalt performs at least three functions in the oxidation medium: (a) It quickly reacts with the primary peroxides via the Haber-Weiss cycle
ROOH + Co(II) f RO* + Co(III) + -OH ROOH + Co(III) f RO* + Co(II) + H+ 2
(b) It acts as a radical initiating species when in the higher (+3) oxidation state (i. These oxidations therefore show features not commonly expected from the free-radical mechanism.93 who observed the autocatalytic reaction to move from the bulk liquid into the film.2 With other metals (such as copper).e. at moderate to high conversions should. in reducing induction periods (Castellan et al.17 these rate ` expressions explicitly involve the concentrations of the catalyst in its different oxidation states.acs. becomes important in this case. Sheldon and Kochi2 cite several instances where dramatic effects have been observed by the addition of small amounts of a second substrate. The reason for the effectiveness of cobalt (and manganese) is the fact that the two oxidation states in its case are of comparable stability.) and the solvent also have some influence on this. under these conditions. Sheldon and Kochi2 discuss the mechanisms by which the direct interaction of strong metal oxidants with organic substrates can lead to the production of radical intermediates. Typical rate expressions for such mechanisms are given by Carra and Santacesaria4 and Tanaka. Vol.10 A striking observation is reported by Suresh et al. The drastic reduction in the rate of oxidation of cumene in the presence of readily oxidizable impurities has been well documented. Indeed.2 For example. quoted by Sheldon and Kochi. 2009 | http://pubs. The role of promoters such as aldehydes. as a result possibly of such catalyst deactivation.2 In other words. the presence of cobalt leads to a higher rate of initiation and a higher rate of decomposition of the hydroperoxide.. Careful studies.7. and then again from the film back into the bulk. fast. the nature of the ligand (acetate or bromide.16 give a summary of the use of promoters in cyclohexane oxidation to adipic acid) is also explained by their role in promoting the III species. When a material with a low oxidizability is co-oxidized with one of high oxidizability. the phenomenon of catalyst deactivation is sometimes observed. see section 6.17. such as hydrogen transfer by the solvent. etc. the mechanism of oxidation is believed to be different. naphthenates. etc. even other oxidation systems. The possibilities are discussed in Sheldon and Kochi. the former may oxidize faster than the latter if kp ratios favor the former. it generates R* radicals from RH). as the catalyst is extremely sensitive to polar substances formed during the reaction. According to Partenheimer. In nonpolar media.org Publication Date (Web): October 11. at high catalyst loadings. so that reactions 13 and 14 can occur concurrently.
It is instructive to observe the changes when bromine and manganese are added into a co-catalyzed oxidation of a methylaromatic. bromination of the ring to give undesired products is a problem. The relative rates of oxidation of methylaromatic compounds in MC oxidations (relative to toluene) have been correlated by the Hammett function
log(k/k0) ) σF
The particular kinetic features of these processes are essentially due to the catalyst used. The tertbutyl group will be oxidized.95 for the solvent and catalyst typical of industrial applications. 39. that of precipitation of the catalyst metal by the product carboxylic acid. and the relevant chemistry has been comprehensively reviewed recently by Partenheimer. where extensive treatises are available. ring carbons are left untouched. the discussion here is kept brief. The manganese is. 2000 | doi: 10. The negative sign indicates that the electron-withdrawing substituents are less active. σ is the Hammett constant characteristic of the substituent on the ring. the second methyl group. This combination offers a high activity as compared to other autoxidation catalysts. and the yield of the final product is about 90% (Table 2).3 In any case. recycled to the lower oxidation state by reaction with bromide. which is produced by the oxidation of Co(II) by the hydroperoxide.38 have developed procedures based on co-oxidation considerations to predict product distributions in hydrocarbon autoxidations. respectively. and this is one of the areas in which research efforts are active. decreases dramatically. Observable effects include a drastic increase in the rate and an equally dramatic decrease in the vent carbon monoxide and carbon dioxide (an indication of the higher selectivity). Thus. Bromine atom being a much better H abstractor from the aromatic methyl
where k and k0 are the rate constants for the disappearances of the hydrocarbon and toluene. if one wants to stop the reaction after the oxidation of a single methyl group. 6. An advantage incidentally arising out of the use of acetic acid solvent is that the carboxylic acid end products are usually insoluble in acetic acid at room temperature and precipitate out. in acetic acid). primary amines. The concentration of the higher-valency form of cobalt.12 Although several byproducts have been detected in MC oxidations.). cobalt acetate. one prefers a cobalt-catalyst system. a ratio of hydrocarbon to solvent of 1:3 is typically used. Vol. is oxidized from the +2 to the +3 state. in turn. manganese. and F. etc.. Co(II) exists as a dimer in acetic acid/water mixtures.Ind. this correlation anticipates that. Thus. and higher temperatures than applicable to co-catalyzed oxidations become available. in the process. A typical solvent composition might be 10% water/90% acetic acid. and Hobbs et al. 2000 3973
estimating such ratios are available. and finally. This latter problem can also be contained by a decrease in pH and an increase in bromide concentration. manganese acetate. Thus. in the oxidation of p-xylene. 11. benzylic methyl group is attacked preferentially to aliphatic methyl group (e. some combustion of the solvent acetic acid results. 6. sulfides. we will summarize the available information on some oxidations of commercial significance as well as some emerging oxidation systems. Anything that affects the steady-state concentrations of phenolic radicals. highly selective. In the oxidation of p-xylene. Co(III). According to a model described by Partenheimrer. Despite the features mentioned above.12 Acetic acid solvent is essential to the method. Thus. and bromide (for example. in trace amounts can deactivate
.position with respect to first. the Co(III). catalyst composition. and of the chemical form of the catalyst is a potential deactivating agent. it can be surmised that the reactive agents. p-toluic acid is about 10 times less reactive than p-xylene. and bromide become coupled to produce synergistic results. a constant that depends on the conditions of oxidation (such as solvent. Once again. However. will be much less reactive because of the reduction in the ring electron density. but at a much lower rate than the benzylic methyl group. which. the effect is seen to be much more pronounced in cobalt-catalyzed systems (as indicated by the higher value of F for these systems). The catalyst contains cobalt. has a value of -0.12 the efficacy of the MC catalyst is due to the fact that the catalytic cycles of cobalt. which provides for a nonradical. thus simplifying the downstream separation of the reaction product. Thus. No. manganese.. selectively abstract the most weakly bound H. indicating the availability of new catalytic pathways that recycle cobalt to the +2 state very efficiently. In the industrially important case of polymethylbenzenes. to show how the general mechanisms provide a backdrop against which the similarities as well as the differences among specific oxidation reactions can be understood. alkylperoxy radicals and bromine atoms. is less serious if water is allowed to accumulate. another intrinsic problem. These features make the catalyst suitable for a variety of oxidations. by Hobbs. Chem. for example. is recycled to the +2 state by redox reaction with Mn. one prefers an MC system. in a para. p-Xylene and Other MC Oxidations
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. on the other hand. Thus. the troublesome 4-carboxy benzaldehyde in the oxidation of p-xylene). phenols. Chemistry of Selected Oxidations Having given an overview of the general mechanisms that operate in autoxidations in the previous section.1% yield and include CO2 and methyl acetate intermediates from the oxidation of subsequent CH3 groups after the first (for example. any C atom attached directly is susceptible to attack. once the first methyl group is oxidized.1021/ie0002733
group than Co3+. Res. and if one wants the oxidation of all the methyl groups. In general. and hydrogen bromide) in solution in acetic acid. most form in less than 0.org Publication Date (Web): October 11. etc. Eng. 2009 | http://pubs. Another problem that is intrinsic to the method is that water (which is a reaction product) deactivates the MC catalyst. and high yields of p-toluic acid can be obtained before oxidation of the second methyl group commences. Induction times are generally reduced. of Co(III) and Mn(III).1. the net result is a much higher activity due to a higher rate of initiation) and selectivity (presumably due to increased chain length). it also offers a high selectivity over a wide temperature range.acs. Among other things. and very fast generation of acids from the peracids that form in these oxidations en route to the final products. Alternative explanations have also been advanced for the low reactivity of this intermediate. Continuous addition of acetic anhydride has been suggested12 as a way to reduce the problem. With naphthalene derivatives.g. the bromide is regenerated with the generation of a hydrocarbon radical of the R* type. in this section.
Cyclohexyl hydroperoxide is the sole primary product and its radical decomposition is responsible for most of the degenerate chain branching. 6. 27.4% precipitates at 100 °C. Furthermore.1021/ie0002733
hexanone. The aromatic acids also directly deactivate the catalyst.). In the medium of oxidizing cyclohexane. cyclohexanol forms from the start. Water. that is commercially practiced. as is to be expected from unimolecular branching and quadratic termination.
To avoid problems of leakage and the attendant problems of safety. as its addition at the start of the reaction actually retards the oxidation. 1. etc. Oxidation of Cyclohexane Because of the selectivity problems in cyclohexane oxidation. The role of wall catalysis must be duly considered in such process designs. Res. above this level. which traps cyclohexanol. The characteristic feature of cyclohexane oxidation is that the conversions are kept deliberately low. Berezin et al. 2009 | http://pubs. hence the beneficial effects of boric acid. the ratio of the rate constants for its formation and consumption has been estimated as 1:30. This result has been rationalized10 as being due to the fact that. The reagents that are themselves antioxidants must be masked for oxidation to proceed (acetylation of phenols and amines. whereas cyclohexanol is more reactive than cyclohexane. to cyclohexanone. oxidation is carried out at around 135 °C (see Table 2) and a pressure at the top of the reactor on the order of 3-4 atm. When oxidation is carried out in a solvent medium such as acetic acid. Typically. 96% terephthalic acid precipitates from pure acetic acid at 200 °C. decarboxylation of the solvent is a problem as in the case of MC oxidations. Although Berezin et al. under certain conditions. the rates of oxidation of pure compounds follow the ratio95 cyclohexane. thereby preventing its further conversion and all of the side reactions that thereby result.59 Oxidation in glass reactors follows the general radical mechanism outlined above rather closely. and in the recent past. At equal rates of initiation. the hydroperoxide levels in oxidation in steel vessels (as in the case of catalyzed oxidation) are much smaller than those in the case of oxidation in glass vessels. such oxidations are carried out in largesize bubble-column reactors (sparged reactors) that are jacketed.10 show that the product spectrum in glass reactors is quite different to that in steady-state reactors.. 2000 | doi: 10. The oxidation is carried out in 4-6-stage oxidizers to improve the selectivity. facilitating the heat removal problem.3974
Ind. The bubble-column reactors are staged. It is therefore the chemistry under these low-conversion conditions that is of interest.2. ketone and not the hydroperoxide has been implicated as the product mainly responsible for chain branching. It has been shown10 that up to 30% of the cyclohexanol forms directly from the cyclohexane. say in efforts to develop a single-step process to adipic acid.acs. the yield decreases because of side reactions associated with decomposition of the hydroperoxide to the carbinol. Some striking differences are observed when oxidation is carried out in a steady-state reactor. the radicals that form from it are less reactive than the cyclohexylperoxy radicals. but precipitation of acids from the acetic acid contains this problem. seems to have an inhibiting effect on the reaction and can. At extremely small conversions. It is therefore advisable to choose the minimum possible temperature for the oxidation so that the solubility of acid is kept small. liquid heights are typically 1015 m.3. The liquid circulation velocities in such bubble columns are remarkably high.org Publication Date (Web): October 11. etc. inevitably some oxidation at -CH3 occurs along with
. Vol. as the extent of liquid-phase backmixing in bubble columns is very high. even provided with coils inside the reactor. 39. In fact. Use of aluminum for the wetted surfaces in laboratory reactors is an innovation that has been tried recently with good results. it has an accelerating effect. taken to levels of conversion around 30%. The kinetic chains are usually reasonably long under such conditions.
At overall levels of conversion approaching 30%. There are few reports of MC catalysts having been tried for cyclohexane oxidation. The case of cyclohexanol is somewhat curious. the overall rate shows a square-root dependence on the hydroperoxide concentration. whereas 99. 2000
the catalyst (phenolic radicals are more long-lived than phenyl). For example. to cyclohexanol. The purity of the precipitated acid also depends on the temperature. Some metals are strong inhibitors. and fairly high values of the heat-transfer coefficient are realized even through the jacket. the rest coming via the hydroperoxide. Cyclohexanone is also a highly reactive compound in the oxidizing medium. Eng. 6. cyclohexanol is converted almost quantitatively to cyclo-
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. cause a second phase to form. 11. no clear evidence of this nature is seen in the available data. Chem. 40. the uncatalyzed oxidation to increase the hydroperoxide is a relevant process option. Both cyclohexanol and cyclohexanone are oxidized many times faster than cyclohexane itself. whereas if it is added during the oxidation. The hydroperoxide is no longer the sole primary product. as discussed in section 4. The loss of selectivity with conversion in the case of cyclohexane oxidation is because of the high reactivity of the oxidation products. This leads to obvious problems in translating the results from laboratory reactors to commercial-size reactors. An optimized overall level of conversion is about 30%. cleavage to acetophenone and methanol.10 claim from estimated values of activation energies of these reactions that higher temperatures should favor selectivities to the ketone. No. which forms late in the reaction. Oxidation of Cumene The liquid-phase oxidation of cumene is a unique example of “uncatalyzed” reaction.
but in subsequent years.. Res. as there is some oxidation at the methyl group as well. eventually leads to dihydroperoxides. 6. this volume has been reduced to only 1-2%. e. which. 39. However. because of a better understanding of the process. and of late even “dry” oxidations have been adopted. additional problems arise.. is used so that formic acid is instantaneously neutralized. obtained during acid-catalyzed cleavage of the hydroperoxide to phenol. and this. The cumene-based phenol technology has been adopted for making m. Although products are important themselves (e. The byproducts do have some commercial value. and this further complicates the separation train. on cleavage.and p. Vol. This formic acid catalyses the decomposition of the hydroperoxide to phenol and acetone. In the recent past. via clay-catalyzed reaction to convert AMS to higher-boiling alkylated products. 2009 | http://pubs. However. No. the dehydrated products of dicarbinols giving R-methyl styrenes have gained some importance. which gives a “bromine number” to cumene and is detrimental to the oxidation.Ind. a small amount of water. 2000 | doi: 10. MTBE can be produced conveniently by etherification of TBA with methanol. Oxidation of Isobutane The oxidation of isobutane in the liquid phase to tertbutyl hydroperoxide (TBHP) and tert-butyl alcohol (TBA) is widely practiced.and p. separated after the hydroperoxide is concentrated to about 80% (and of late even up to 90%). The oxidation of m. This cumene.g.e. To obviate this problem. 11. Chem. which can be separated by distillation because of a significant difference in boiling points.org Publication Date (Web): October 11. The
. give m-dihydroxybenzene (resorcinol) and p-dihydroxybenzene (hydroquinone). and as they can be converted to some value added substances.. in large plants. or even direct reaction with ammonia to give the corresponding amines. as shown below. This will also be the case for acetophenone-type products. since the switch over to the second isopropyl group starts when the first group is nearly fully converted to the hydroperoxide. a major application of the process in the past has been in the indirect oxidation process for the manufacture of propylene oxide. inhibits the oxidation. containing buffered carbonate-bicarbonate. will give -CH2OH. must be recycled and constitutes the major part of the feed to the reactor. has R-methylstyrene as an impurity.g.4.
some unique properties. and some formic acid is formed. upon cleavage. i. wherein TBHP is used to epoxidize propylene.diisopropylbenzene. which can be easily removed by fractionation.
The hydroperoxide on the CH3 group. in some respect like divinyl benzenes. as well as cumene obtained from cleavage of cumylphenol and R-methyl styrene (AMS) dimers.acs.1021/ie0002733
cleavage. 2000 3975
Downloaded by UNIVERSITA STUDI TRIESTE on September 1.. the aqueous-phase volume used was high (even 5%).cresols and follows similar plant practices. The array of products that can be formed has parallels with that encountered in manufacturing phenol. as they have
The deliberate desire to make the above R-methyl styrenes would benefit from this route in view of mildness of conditions and high yields.8 The recent interest in the possibility of developing isobutane oxidation for the production of MTBE and some related issues have been discussed in section 4. Catalytic dehydrogenation of two isopropyl groups is most unlikely to give a high yield of R-methyl styrenes. Originally. the level of carbinols that are formed will be relatively much higher than those obtained in the case of phenol. TBHP as an oxidizing agent and a free-radical initiator and TBA as a gasoline additive). use of water is rendered unnecessary because of better control of operating conditions. in turn. the remaining cumene. Eng. This side-product must be suitably removed. via reaction with HCN and conversion to the corresponding amines. Because the level of conversion of cumene is only up to 30%. via reaction with phenol to make a special bisphenol.
the rates and selectivity were significantly higher than those obtained in liquid-phase oxidation.
RO* + ROOH f ROH + ROO*
In any case. 39.04 mol % oxygen concentration leads to TBHP selectivity better than that obtained at a high concentration of oxygen (1% mol/mol) in the feed. as has been pointed out. and concluded that operation in supercritical phase at less than 0. and if oxygen concentrations are too low for the zeroorder behavior to be observed.acs. 11.and vapor-phase oxidation in a semibatch reactor. and the selectivity toward the hydroperoxide decreases with an increase in overall conversion. e. which appears in several patents subsequent to the work of Winkler and Hearne. The idea of using additives such as 2-propanol or water for improving the yield. as indicated by the high selectivity figures quoted above. The reaction is autocatalytic. Vol. in addition. Building on the work of Baumgartner.98 have examined the kinetics of isobutane in the liquid phase and under supercritical conditions. is discouraged by Winkler and Hearne11 because of the increased complexity of the oxidation reaction and subsequent product separation and recovery.32 They carried out detailed studies on batch and continuous reactors to identify the effect of the important operating variables on productivity and selectivity under supercritical conditions and concluded that operation in the supercritical phase gives TBHP productivities several times higher than those obtained with the conventional liquid-phase process. if any. and CO2. the consequences of catalyzed decomposition of tert-butyl hydroperoxide ensue. may be cheaper than catalytic dehydrogenation. Chem. which in this case include. higher levels of RO* decomposition products. and this permits a comparison of liquid-phase and supercriticalphase oxidation.3976
Ind. and catalysis by the metal wall of the reactor. which also results in better productivities. Baumgartner31 carried out a reaction of isobutane and molecular oxygen in a continuous stirred tank reactor (CSTR) with a residence time from 15 to 70 min. such as induction period. In both subcritical and supercritical oxidations. The decomposition is
. over a fairly wide range of conversion. 2009 | http://pubs. The reactions were also studied in a glass-lined continuous reactor using predissolved oxygen. If cobalt is used to catalyze the reaction. if the TBHP is used for epoxidation. autocatalysis.9 K). are evident in their work. it has been suggested that a reaction product consisting essentially of TBHP and TBA can be obtained in high yield by reacting isobutane with molecular oxygen in the liquid phase of a vapor-liquid mixture at a temperature in the range of 373-423 K and a pressure of at least 25 atm.g.11 does not seem to
have been established in industrial practice. The use of externally supplied reaction solvents. use of the initiator can have the undesirable consequence of reducing its concentration because of the reaction of the RO* radical with the hydroperoxide to produce the alcohol in a new propagation step.97 Surprisingly. it is necessary that the reaction be conducted in the presence of a relatively high boiling solvent. formic acid. data in the low-oxygen regime is far too minimal in the literature to permit firm conclusions. In view of recent interest in studying chemical reactions under supercritical conditions. 2000
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. CO. This is somewhat counterintuitive. TBHP has a tendency to decompose and react with isobutane to form TBA. probably for the same reason. The proposed reaction system envisages a cascade of several CSTRs with the supercritical isobutane moving from one CSTR to the next in series and the oxygen being fed in a crosscurrent manner. The methyl radical so produced leads to other products such as methanol. However.1021/ie0002733
production of isobutene from isobutane via oxidation to TBHP. Under these circumstances. However. The conditions under which the oxidation of isobutane is normally carried out in industry (temperature of 393408 K and pressure of around 35 bar) are quite close to its critical properties (Tc ) 406. a possibility that accounts for the presence of acetone in the reaction mixture. 2000 | doi: 10. Under supercritical conditions. decomposition of TBHP to TBA. of the stainless steel walls. If TBHP is the desired product.31 Foster32 employed a reactor configuration that keeps isobutane concentration high while keeping product and oxygen concentration low.84.org Publication Date (Web): October 11. radical initiation in the initial stages is likely to be by the decomposition of the peroxide
ROOR f 2RO* RO* + RH f ROH + R*
with R* taking part in the normal propagation reactions 5 and 6 (see section 5). Hence.. Res. The influence of supercritical conditions on the rate and selectivity of the reaction was investigated. The temperature and wall material exhibit a strong impact on the reaction kinetics. The levels of most of these are quite small. limited literature is available on isobutane oxidation under supercritical conditions. the total yield of TBHP and TBA is fairly constant between 90 and 96% at temperatures of 398 K and below. the influence of supercritical conditions was explicitly addressed by researchers from the Shell oil company through patents. temperature has an adverse effect on selectivity toward tert-butyl hydroperoxide. However. with proper precaution to prevent wall catalysis. Eng. No.30 A temperature range of 423-433 K has been claimed to be the best for high productivities. one only expects poorer selectivity because of the increased heterogeneity of the radical population. as hydrocarbon oxidations are usually zero-order in oxygen. and final dehydration.96 The first comprehensive work on isobutane oxidation was that of Winkler and Hearne. Shah et al.11 who carried out the liquid.30. Their results indicate that. organic acids. The prominent features of hydrocarbon oxidation. eliminates the catalytic effect. the RO* radical may decompose to acetone and a methyl radical. then the economics of producing isobutene from TBA improves dramatically.9 K and Pc ) 35 bar). However. The authors do not recommend oxidation in the vapor phase because of the formation of unacceptably large quantities of side products. Winkler and Hearne11 used di-tert-butyl peroxide as an initiator in most of their experiments. it can be expected that phenomena such as the clustering effect and the special ionization effects of the supercritical fluid would have a strong influence on the reaction mechanism. in addition to a faster rate of oxidation and more TBA. Winkler and Hearne11 proposed that the rate of the oxidation reaction in the liquid phase can be enhanced by carrying out the oxidation above the critical temperature of isobutane (407. This mode of operation allows kinetic studies without an intervention of gas-liquid mass transfer and.
does not induce any remarkable effect on either the rate of the reaction or the selectivity toward the desired products. Cyclohexene is emerging as an important raw material for cyclohexanol. An enhancement in the reaction rate is realized under supercritical conditions. the selective hydrogenation of cyclooctadiene yields cyclooctene. contrary to the claims of the authors. show a smooth transition in rate and selectivity as the temperature is increased at a constant (supercritical) pressure to go from liquid to supercritical state.102 in their lucid review of allylic oxofunctionalization of cyclic olefins. liquid-.90 in his analysis of isobutane oxidation under supercritical conditions. but the two are often competitive processes in practice. for which conversions of 3-5% are needed to ensure high selectivity. which the authors attribute to the action of acid sites on the catalyst surface. in some respects. and cyclooctene is the least reactive. Van Sickle et al. in fact.β-unsaturated ketones and alcohols of cyclic olefins) and epoxidation are two competing processes both in vivo and in vitro. The oxidation of cyclohexene is. The uncatalyzed reaction also yields cyclohexene oxide. which. and selectivity is only on the order of 50%.101 discuss some of the early work. The authors illustrate these points with the aid of examples taken from the industrially relevant cases of cyclohexene. Interest in this area can be discerned from some patents for the oxidation of cyclododecene106.. Chem. Although their data show the superior rate and selectivity of supercritical oxidation over gas-phase oxidation (as is to be expected). Among the cycloalkenes.4%. In the first of these.1021/ie0002733
highly influenced by the wall material. clearly demonstrated.2-cyclohexanediol.acs. on the nature of the olefin and the relative stability of the allylic radical formed. With the more complex cyclic olefins. approaching 20% conversion. can be conveniently made by the selective trimerization of butadiene.
RO* + R ) RO* + epoxide 2
Furthermore.Ind. Mahajani et al. Eng. phase separation occurs even at conversions as low as 0.
RO* + R ) RO2H + R* 2 RO* + R ) RO2R 2
Most of the cycloalkenes give the hydroperoxide as the primary product. Allylic oxidation (involving free radicals) is most likely in the presence of low-oxidationstate transition metal species. However. a key intermediate in the synthesis of carotenoids and flavoring substances). The promotional effect of the heterogeneous catalyst is. Fan et al. in turn. and it is at its maximum in the unpassivated stainless steel reactor. isophorone (to ketoisophorone. 2000 | doi: 10. presumably through the addition of the peroxy radical. than in the case of cyclohexane. The products obtained from cyclohexene allow a wider range of speciality chemicals to be produced.100 demonstrated that cyclohexene hydroperoxide has an open structure with the double bond retained. and epoxidation is to be expected in the presence of species such as Ru(VIII). cyclohexenone. The authors compare the performance of the reaction under gas-. 2009 | http://pubs. among other things. considered a suitable precursor to taxol). Furthermore. however. Figure 1 provides a schematic diagram of the various chemical pathways for cycloalkenes. similar to that of cyclohexane. cyclohexanone. similar to those realized in the oxidation of cyclohexene via the oxidation of cyclododecene rather than from cyclododecane. The oxidation of cyclohexene can be taken to much higher levels.104. has concluded that reaction kinetics in the liquid phase can be extrapolated conveniently in order to predict the kinetics under supercritical conditions. the modeling work indicates that this increase arises only because of the increase in temperature employed to bring the reaction mixture to the supercritical state. and supercriticalphase conditions and conclude that the rate as well as selectivity to TBA are superior in the supercritical case. Developments in both homogeneous and heterogeneous catalysis are reviewed. Early studies (see Kamneva and Panfilova99) were concerned with elucidating the structure of the hydroperoxide. The hydrogenation of benzene is the only viable route to cyclohexene. No. Oxidation of Cycloalkenes The interesting and diverse chemistry exhibited by the oxidation of saturated hydrocarbons is also seen in the oxidation of unsaturated hydrocarbons. there may be a distinct advantage in obtaining cyclododecanone and other products.107 using a ruthenium/cerium system as the catalyst.org Publication Date (Web): October 11. the oxide appears to be a primary product. etc. Res. Vol. cyclohexenol. cyclooctene differs from its analogues in that it gives high yields of the epoxide.49 for cyclohexane oxidation applies equally well for this reaction. cyclopentene is the most reactive. In the case of cyclododecene.. Murphy et al. 6. and cyclohexadiene. as such. The process that dominates depends. Moreover. The various chemical pathways for cyclohexene are shown schematically in Figure 1.103 have examined the kinetics of the oxidation of cyclohexene. 1. Suresh.5. 11. 2000 3977
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. point out that allylic oxidation (which preserves the unsaturation and results in R.β-unsaturated ketone. Cr(VI). 39. comparison with liquid-phase oxidation is less clear.84 have studied the oxidation of supercritical isobutane to TBA and have investigated the influence of silica-titania and palladium-carbon as heterogeneous catalysts. Similarly. but the exact mechanism for its formation from the hydrocarbon is not clear. almost quantitative yields can be obtained by the selective hydrogenation of cyclododecatriene. competitive isomerization and structural rearrangements often result in poor selectivity to the desired R. and R-pinene (to verbenone. The authors have emphasized that many olefins react partly or fully through addition of peroxy radicals to double bonds rather than through hydrogen abstraction (or transfer). However.106 a two-phase system
.. in the case of cyclooctene. Criegee et al. Some dehydration of TBA to isobutene was also observed in their work. The kinetic model proposed by Suresh et al. cyclohexene epoxide. as the latter was conducted at a lower temperature.105 The successful commercialization of the selective hydrogenation of benzene by Asahi chemicals provides a cost-effective route to this raw material. The uncatalyzed oxidation of cyclohexene yields large quantities of the hydroperoxide. The products formed from these oxidations depend on whether the hydrogen abstraction or the addition reactions dominate. Thus. their results. and its decomposition yields the alcohol and ketone. The fact that the rate expression used for predicting the liquid-phase kinetics works reasonably well under supercritical conditions indicates that the “supercritical” state of the substrate.
clearly establish the formation of the epoxide. using hydrocarbons such as ethylbenzene and tetralin as the hydrocarbon source under mild conditions. The autoxidation of the hydrocarbon was assisted by Nhydroxypthalimide (NHPI). Res. Indirect oxidations in two steps (that of propylene to propylene oxide is an example.101 have reported preliminary data on the noncatalytic oxidation of cyclododecene.and trans-2-octene) using molecular oxygen.
is used with ruthenium tetroxide in the organic phase as the oxidizing agent. Eng. Iwahama et al. it is suggested. Recent unpublished results from Monash University. The latter. The epoxidation of alkenes (cyclic as well as noncyclic) using molecular oxygen in a single step has remained a challenge in the field of oxidation chemistry.and transcyclododecene. there are clear
differences in the rate of oxidation of the cis. see section 4) are the rule in industry. Van Sickle et al. can be regenerated electrolytically in a separate step. Vol. 39. which contains cerium ions in the +4 state. 2009 | http://pubs. Prominent chemical pathways in cycloalkene oxidations.. 2000 | doi: 10. Recently. and the epoxidation of the alkene with the resulting hydroperoxide was catalyzed
.108 carried out in a way to obtain data of commercial importance. No. The tetroxide is regenerated in the second (aqueous) phase.org Publication Date (Web): October 11. Chem. The second patent107 provides a way of combining these steps in order to achieve simultaneous regeneration of the cerium (+4) species.acs.1021/ie0002733
Figure 1. where substantially high yields of epoxide have been indicated.3978
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. in addition to cyclododecenone. 11.109 reported a onepot epoxidation of alkenes (such as octene-1-cyclohexene and cis.
the following dominant products are obtained in equimolar amounts:
The other products are shown below.6. 11. as is obvious from the preceding discussion on the chemistry and kinetic mechanism of these reactions. With cyclohexene and cyclooctene.acs. Miscellaneous Oxidations Interest in the epoxidation of alkenes has been mentioned earlier (see section 6. it appears that there was mass-tranfer limitation and that the liquid phase was not saturated with oxygen. Although the rates were generally low under the conditions employed (6-12 h at 60-70 °C). but also serves to activate NHPI. to a ketonic compound. the C-H bonds in position 6 are preferentially attacked.112 have reported some interesting results on the oxidation of R-methylstyrene (AMS) at 110-160 °C.110 have studied the autoxidation of this olefin as well as vinyl cyclohexane. fortunately.. Between 100 and 120 °C and at atmospheric total pressure.1021/ie0002733
6. The quantitative analysis of the various products from a reactor is. among other things. The work of Iwahama et al. In addition. The selectivity to the epoxide depended. involving lumped models. Vol. This peroxide is reasonably stable at the temperature of oxidation but cleaves cleanly to acetophenone and formaldehyde at higher temperatures and reduced pressure.
The relative product distribution with respect to the cisand trans. at conversion levels of 80% and 89%.8). a function performed by cobalt acetate in the other oxidations. as in the case of cyclohexene. In vinyl cyclohexene. Chem.
.109 was discussed earlier and involves some interesting chemistry.111 Possibilities of heterogenizing the catalyst by encapsulation in modified zeolite cages have also been demonstrated. the epoxidation of allylic alcohol. Biela et al. One postulates a series-parallel reaction network that attempts to capture the essential features of the reaction depending on the purpose for which the kinetic model is intended. There is really scanty information on autoxidation of this important olefinic compound. 39. is thus usually followed.org Publication Date (Web): October 11. it is also probably unnecessary for engineering applications.Ind. in the presence of carbon monoxide and oxygen.isomers is not obvious (see also section 12. there are other issues to consider. even with very small amounts. 1-adamantane carboxylic acid was formed. ethylbenzene and tetralin giving good results whereas toluene gave poor results with oct-2ene. because the most convenient way for conducting the reaction is through contact of a liquid. Another recent development of interest in this area is the direct epoxidation of linear aliphatic olefins by molecular oxygen using Schiff base complexes. the principal product is the alternating polyperoxide. to epoxy alcohol was achieved in high yield when VO(acac)2 was employed instead. were obtained. although other allylic positions also undergo oxidation to give the products illustrated below. Second. on the hydrocarbon used. Oxidation of Vinyl Cyclohexene and Vinyl Cyclohexane These reactions are potentially attractive both scientifically and commercially.5) because of the importance of such a process from the synthetic and industrial points of view. respectively. although some information is available on Wacker-type oxidation. probably as a result of competing reactions in the case of toluene. 2000 | doi: 10. a significant challenge. or at other allylic positions. the results are interesting in view of the excellent selectivities reported. In the case of vinyl cyclohexane. as these versatile olefinic compounds are available in high yield from butadiene. trans-hex-2-en-1-ol. by itself. 7. In the case of vinylcyclohexane. Eng. These authors have demonstrated the Mocatalyzed epoxidations of a wide variety of alkenes with hydroperoxides generated in situ by the NHPI-catalyzed aerobic oxidation of hydrocarbons. 2009 | http://pubs. Kinetics of Hydrocarbon Oxidation The determination of kinetics of liquid-phase organic oxidations presents a nontrivial problem. For temperatures up to 100 °C and adequate oxygen. the principal products are AMS oxide and acetophenone. The use of NHPI seems to overcome the mismatch between the much higher rate of oxidation of the hydrocarbon to hydroperoxide as compared to the rate of epoxidation in conventional systems. and good selectivities in both configurations have been realized at reasonable conversions. 6. about 40% of the absorbed oxygen goes to the peroxides. In the case of adamantane. No. selectivities of 74% and 83%. Although Mo(CO)6 was employed as the epoxidation catalyst in most of their work. Mayo et al. with cupric chloride-PdCl2 catalyst. which can be obtained by selective ring hydrogenation of vinyl cyclohexene. Res. hydrocarbon under the appropriate conditions with a gaseous stream
In the case of vinyl cyclohexene. a detailed treatment of kinetics is usually not feasible. First.
Downloaded by UNIVERSITA STUDI TRIESTE on September 1.7. It is possible that VO(acac)2 not only catalyzes the epoxidation. An engineering approach to kinetics. the oxidation can take place at the olefinic double bond in the ring. 2000 3979
and the saturated liquid was pumped through the reactor. The cyclohexane was saturated with oxygen at room temperature at the required pressure (depending on the conversion desired). acievement of the oxygen requirement necessitates high pressures at the dissolution stage. measurable concentrations of dissolved oxygen could be detected only at conversions less than 5-7%. etc. However.49 developed a technique for measuring dissolved oxygen levels during reaction. 2000
containing oxygen. Reaction was stopped by plunging the reactor in a cold-water bath..49 used this principle to study cyclohexane oxidation in small batch reactors (“microautoclaves”). Second.3980
Ind. Chem. 11. These issues have resulted in several innovative approaches to the determination and interpretation of technical kinetics in the field of organic oxidations. At the outlet of the reactor. and extrapolation from data and correlations under ambient conditions is hazardous. Even at the rates of mass transfer that could be achieved in small mechanically agitated contactors with intense agitation. In their studies on cyclohexane oxidation. An appropriate choice of the model reactor must be made. Res. To determine the kinetics with reasonable accuracy.1. such as sparged and mechanically agitated reactors.) Thus. With sufficient care. Suresh et al. In such work. as the oxygen concentration need not be followed as long as it does not become so small during the reaction as to call into question the zero-order assumption. These authors observed that the reaction starts off being kinetically controlled (with the liquid being saturated with oxygen at the prevailing partial pressure) but gradually moves to other regimes because of autocatalysis. so that the right regime can be engineered and the reaction kinetics determined. wetted wall column. For example. An alternative strategy for circumventing the problem of mass-tranfer interferences in kinetic measurements is to eliminate the mass-tranfer step altogether by predissolving enough oxygen in the liquid before the start of the reaction and then to conduct the reaction homogeneously. it is important to reproduce induction periods exactly in a series of experiments by thorough cleaning between runs. although one would like laboratory reactors and their operation to be flexible in order to explore all the features of the reaction. even if the reaction is initially slow and kinetically controlled.1021/ie0002733
. the reactions are known to exhibit autocatalytic features. Wen et al. the influence of mass transfer can become important during the course of the reaction. the possible influence of masstranfer factors on the observed behavior must be considered carefully in interpretations of rate data. Because the mass-tranfer parameters needed to properly interpret reaction data from these reactors are usually not known with confidence (especially under the reaction conditions employed). Laboratory Reactors Early studies considered the reaction to be generally slow enough for intrinsic kinetics to control in any laboratory reactor that provides reasonable mass-tranfer rates. It is therefore preferable in such studies to rely on some direct indicator of the reaction regime.63 and Guo61 have used a similar principle to study cyclohexane oxidation in homogeneous continuous-flow reactors. the effect of agitation speed on interfacial
area is quite different at low and high speeds in pressurized contactors46. Therefore. for example. 39. (The available information on these aspects will be reviewed in section 9. No. it seems incorrect to assume the absence of mass-tranfer limitations in such reactions in general. Several arguments can be advanced against such an assumption. Eng. Oxygen was dissolved by equilibration at high pressures at room temperature. the pressure was allowed to decrease. Finally. The conditions of organic oxidations (elevated temperature and pressure) usually necessitate considerable design modifications if such model contactors are to be used. and the liquid contents of the reactor were analyzed for hydrocarbon conversion and product profile. is far from perfect. because each experiment gives a single conversion point. stirred contactor. if reasonable conversions must be achieved. 2009 | http://pubs. and the reaction rate increases as the products accumulate. the oxygen conversion was measured by slow depressurization and measurement of the volume of the oxygen released.48 For many systems.113 and not taking cognizance of such differences can result in erroneous conclusions being drawn. Most of the kinetic studies described in the literature have therefore been conducted in miniature versions of industrial equipment. Doraiswamy and Sharma43). Passivation of the walls by procedures similar to those used by Winkler and Hearne11 may also be necessary to prevent wall catalysis. The zero-order dependence of oxidation rates on oxygen is an advantage here. one must necessarily consider the implications of mass transfer with chemical reaction in designing kinetic experiments and interpreting data from them. considerations of safety impose restrictions on reactor design and operation. at the elevated temperatures and pressures necessary for these reactions.acs. 2000 | doi: 10. bubble columns. Wen et al. depending on the relative rates of mass transfer and chemical reaction. and the flow rates of the gas evolved and the liquid were separately measured. The theories of mass transfer with chemical reaction indicate that gas-liquid reactions can occur in one of several “regimes”. the reaction must take place in the slow-reaction regime with substantial kinetic control (in which case the overall rate is determined by the reaction rate in the bulk liquid) or in the fast-reaction regime (in which the reaction is complete in a very small region close to the interface). Several “model” reactors suitable for kinetic studies on gasliquid reactions have been described in the literature (such as laminar jet.org Publication Date (Web): October 11. Vol. it is hazardous to infer the regime on the basis of conventional tests such as the effect of agitation speed.63 used a CSTR constructed from a length of tube and stirred by a magnetic ball moved to and fro by the action of an
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. in which the mass-tranfer rates can be characterized with a high degree of confidence (see. Suresh et al. Therefore. and the part of the experiment in which kinetics had a role in determining the observed absorption rates could be identified. however. even properties such as solubility and diffusivity are not documented in the open literature and must be estimated for the conditions of reaction. First. and the temperature was rapidly raised by plunging the reactor in a fluidized bed maintained at the desired reaction temperature. etc). etc. even in laboratory reactors. depending on the velocity of the reaction being studied. The presence of measurable levels of dissolved gas shows that the reaction is in the slow-reaction regime with some degree of kinetic control. 7. reliable kinetic information can be obtained. the knowledge of mass-tranfer coefficients. This transition could be followed directly with the help of the observed variation in dissolved oxygen levels.
Res. on the other hand.116 have also used the same method to determine the mass-tranfer characteristics for the oxygen-cyclohexane system with two types of contactors. if at all.115) attempt to eliminate induction periods by the use of free-radical initiators. It is to be ensured that safety is not compromised in such designs. in cyclohexane oxidation. Under such circumstances.115 for ethylbenzene oxidation show no autocatalysis. whereas Guo61 used a glass-lined plugflow reactor. including the mechanically agitated reactor.114 The length of an induction period can be influenced by the presence of small levels of impurities. batch microautoclaves. a mixture of alcohol and ketone. the secondary oxidation products such as acids and other undesired compounds. Although the use of glasslined reactors. Kinetic Models from Laboratory Studies It is clear from the discussion of the mechanisms that operate in hydrocarbon oxidations that any attempt to adequately reflect all aspects of the mechanism in a kinetic model is bound to fail. Vol. If the ratio of alcohol to ketone is important. initiators could reduce the chain length (see discussion in section 5) to a point where initiation and termination mechanisms influence the overall behavior more than the propagation reactions. This was first demonstrated by Suresh et al. Eng. the data and model of Morbidelli et al. and C.2. but also because of the fact that not all pieces of the mechanistic puzzle are available yet.117 and isobutane28 are of this type. even if induction period variability is not totally eliminated. More recently. Winkler and Hearne11 and Morbidelli et al. B. If.49 have shown that good reproducibilty of post-induction-period behavior in batch experiments can be achieved with thorough cleaning of the reactor between experiments. and PFR. involving a series-parallel network of reactions have been written for a number of oxidations. Taken together. 39. to serve their purpose adequately. 2000 | doi: 10. etc.org Publication Date (Web): October 11.49. Some of the important considerations are summarized in section 11. then the kinetic model would reflect this by introducing the hydroperoxide as the primary product. Clearly. with the understanding that the model or the parameter or both may require modification as the needs change. 2000 3981
external magnet. Thus. However. the experimental plan to establish such kinetics could also be dictated by the modeling approach. Thus. and acids as the tertiary product. where A stands for cyclohexane. these studies49. a series scheme such as A f B f C might be considered (for example. This also means that. Suresh et al. see Spielman117). Tekie et al. therefore. Aspects of safety deserve the utmost attention in the design and operation of laboratory equipment for hydrocarbon oxidation studies. No. in which several experiments are necessary to construct a single time course of the reaction. one must be satisfied with empirically derived models of technical kinetics that are meant to address specific modeling or simulation needs.33 consists of a network of reactions whose kinetics are such that autocatalysis is indirectly the result. and it is difficult to be certain that the kinetics one obtains is not itself influenced.63 represent the most comprehensive studies on a single oxidation reaction of commercial importance. The reaction is slow enough to be neglected under these conditions. CSTR. the alcohol and ketone (either separately or as a lump) as the secondary product. Variability of induction periods is particularly important in laboratory studies.92 looking to include explicitly a term in the concentration of reaction products to explain autocatalysis in cyclohexane oxidation. the dangers inherent in hydrocarbon-air contact must be considered in detail. pressure-relief systems etc. The presence of an induction period can often be used to advantage in the measurement of various physical parameters in gas-liquid contact under the conditions of reaction. For example.1021/ie0002733
. autocatalysis.. The usefulness of these reactors is demonstrated by the internal consistency of the data obtained on the oxidation of cyclohexane from several types of reactors.61.36. 11. or passivation techniques to render the wall noncatalytic if steady-state reactors must be used. one sees several such models.acs. wall catalysis (in steady-state reactors). is only accounted for indirectly. perhaps as a consequence of the use of fairly high levels of azobisisobutyronitrile (AIBN) as an initiator. where the small volumes of reactors employed result in an exaggerated effect of such factors.49 who determined oxygen solubilities and mass-tranfer coefficients at reaction temperatures and pressures for the oxygen-cyclohexane system by taking advantage of the induction period. Attention was drawn earlier to the presence of an induction period in organic oxidations and some of the consequences that follow from it.. the model for isobutane oxidation proposed by Brejc et al. experimental reactors must be built so as to be flexible and allow operation over a wide and varied range of conditions. but (depending on the concentrations employed) such initiators could affect more than just the induction behavior. and one sees essentially a physical absorption behavior. the lump B can be further split up and the kinetics elaborated to include the formation of the ketone from the alcohol.. In many such cases. another commonly observed characteristic of most hydrocarbon oxidations. Chem. is recommended for complete reproducibility of batch data. 7. in flow reactors. in which the lumping follows the logic of process objectives. In literature. in batch microautoclave studies. found that an expression that was first-order with respect to (lumped) products was able to correlate the data well. Lumped kinetics. Indeed. the process objective is to stop at the hydroperoxide.49 further elaborated these kinetic expressions by invoking the free-radical mech-
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. not only because of the inherent detail and complexity of these mechanisms. if the emphasis is on producing a mixture of cyclohexanol and cyclohexanone in the first stage of air oxidation.93. absolute reproducibility of induction periods is a must. or at least not inconsistent. Suresh et al. Furthermore. The kinetic models of Morbidelli and co-workers54 for the oxidation of p-xylene and the early models for cyclohexane oxidation34. 2009 | http://pubs. Induction periods can be quite long in uncatalyzed oxidations and may not be quite eliminated even in the presence of some reaction products or dissolved catalysts.Ind. Botton et al. Apart from the usual precautions to be taken in the design and operation of
pressure vessels (provision of high pressure and temperature alarms. Although such models usually incorporate explicitly the observed zero-order behavior of the kinetics with respect to oxygen. whereas the early models for cyclohexane oxidation do not mention autocatalysis at all. Some authors (for example. with the basic free-radical mechanism. any differences in induction behavior do not influence steady-state behavior. an attempt is made to show that the kinetic model is consistent.).
An interesting observation made by Suresh et al. There are no reports of the MC method having been tried for adipic acid.g. For example.1-0. It is interesting to find that the oxidation reaction occurs mostly by the addition mechanism and that all oxidations give mostly acetone. 8. Recently. cL.103 have also shown the applicability of the cyclohexane oxidation model above for the oxidation of cyclohexene. as at small catalyst concentrations. Mayo et al. Bulygin et al. The temperature required for gas-phase oxidation to take place at appreciable rates (300-500 °C) is usually much higher than that for LPO (140-170 °C). however. the rate was observed to fall in the catalyzed case. In general. using the Mid-Century processes) are comparable to or exceed those obtained by using stoichiometric oxidizing agents.5 atm total pressure.. it is not out of place to consider briefly the relative merits and demerits of the various types of oxidations. the need to dispose of nitrated byproducts and handle nitrous oxide emissions has led to its displacement by autoxidation methods. VPOs are amenable to solid-phase catalysis. the question of selectivity is an important one in the consideration of LPO and VPO for a given substance. and low rates also mean that gas-phase processes tend to be more energy intensive. the use of stoichiometric oxidizing agents and oxidations in the vapor phase) also enjoy a significant presence in the chemical industry.1.. it is uncommon to find comparisons being made for oxidations in gas and liquid phases at comparable temperatures. and it causes autocatalysis and gives secondary products. oxygen. and cI are.5 ppm Co added as cobalt naphthenate) being the same as that of a 10 °C increase in temperature. Although. The poor selectivities of VPOs are often due to the fact that the conditions required are more severe than those required for LPOs (except in the case of lighter hydrocarbons such as isobutane). low concentrations of hydrocarbon normally employed (typically less than 3% in air12).027 M to 0. space time yields are often an order of magnitude higher for LPOs. 11. the qualitative features are similar in catalyzed and uncatalyzed oxidations. Thus. and a high-boiling residue. The next thing to consider is the case for liquid-phase oxidation (LPO) as opposed to gas or vapor-phase oxidation (VPO). the observed differences in selectivity can be attributed once again to density differences. The Case for Liquid-Phase Air Oxidation Although this review concerns liquid-phase air oxidations exclusively. Similarly. 39. the concentration of cyclohexane is essentially constant and does not figure in the rate expressions.1021/ie0002733
. at concentrations from 9 M in the neat hydrocarbon to 0.k02cI) (k01 + k02cp + k3cL)
Here. Suresh90 has shown that similar principles can be used to obtain rate expressions for the oxidation of isobutane in the liquid and supercritical phases. The equations were tested by fitting them to data obtained from two types of reactors in the kinetic regime and were found to provide a consistent explanation across both reactor types and a range of oxygen and product concentrations. the large surface areas that can be packed into a small mass of the catalyst make for good economy.10. 2000 | doi: 10. the effect of the catalyst (1. In general. It would be useful to look for similar correlations in other oxidations as well. dichromate. respectively. LPO gives the hydroperoxide in the latter case. Res. Often. etc. at late stages of oxidation (perhaps outside the range of industrial interest). radicalinitiated oxidations of cyclopentene were studied at 100 °C.12 Nitric acid
oxidations usually give good yields of aromatic acids. and intermediates. Mahajani et al. autoxidation yields (for example.17 but except in the case of adipic acid (where nitric acid oxidation of cyclohexanone has been preferred over the air oxidation in industry). VPO is more economical than LPO. As pointed out above.12 The other factor that makes for significant differences between LPO and VPO is the large difference in density between the liquid and vapor phases.056 M in the gas phase. Let us first consider the use of air (or oxygen) as an oxidizing agent as opposed to stoichiometric reagents such as permanganate. in some cases. 2009 | http://pubs. in the uncatalyzed oxidation of cyclohexane:
rc ) ro ) ri )
k01k3cpcL (k01 + k02cp + k3cL) k3cpcL(k01 + k02cp) (k01 + k02cp + k3cL) k3cpcL(k01 . Similar equations have been used to describe catalytic oxidation as well.112 have reported radical-initiated oxidations of isobutylene in benzene solution at 80 and 147 °C and several atmospheres of total pressure and compared the results with gas-phase oxidations at 147 and 197 °C and 0.112 found the rates and products of reaction to be similar in the two phases. The main product is cyclopentenyl hydroperoxide. because of the low conversions to which cyclohexane oxidation is usually run. It thus appears that some generalization of rate forms for hydrocarbon oxidation can be attempted along these lines.93 was that the (Co-) catalyzed oxidation retained all of the features of the uncatalyzed oxidation as described by the equations given above. Processing Options 8. Eng.118 find that selectivities are usually much better in LPO. Chem. the concentrations of (lumped) products. On the other hand.12 The higher temperatures. In most cases other than adipic acid. No. 2000
anism and obtained the following expressions for the rates of consumption of cyclohexane (c) and oxygen (o) and the rate of formation of the intermediates i (cyclohexyl hydroperoxide + cyclohexanol + cyclohexanone). Mayo et al. VPO of cumene is invariably accompanied by cracking (to benzene and propylene).025 M in chlorobenzene and from 0. Vol. in view of the fact that other types of oxidations (e. However. Although the rates are expected (from the mechanism) to be first-order in cyclohexane. The higher density of the liquid phase usually makes for better productivities in the case of liquid-phase oxidations. respectively. Any diffusion limitations would also be expected to be much less severe in gas-solid systems as compared to liquid-solid systems. The main problem with the latter reagents is the large amounts of byproduct salts that must be disposed of. as noted in section 4.16. poor selectivity prevents VPO from being economical. isobutylene oxide. there are
Downloaded by UNIVERSITA STUDI TRIESTE on September 1.acs. whereas VPO of oxylene to phthalic anhydride is much preferable to LPO (to phthalic acid followed by dehydration).org Publication Date (Web): October 11. under otherwise comparable conditions. perhaps because the catalyst was precipitated out as the adipate.3982
g. 2009 | http://pubs.2 However. as in mechanically agitated reactors. Fluidized beds are used in the oxidation of butane (as well as in the ammoxidation of propene to acrylonitrile) and exhibit excellent heat-transfer characteristics. in general.4 and 7. Catalyst composition can even be varied within limits during the oxidation. the liquid phase is essentially backmixed.org Publication Date (Web): October 11. and lower levels of partially oxidized impurities. Elimination of such surfaces therefore has an advantage.acs. on the issue of safe operation. It was shown that the rate of oxidation in the supercritical phase could be predicted from that in the liquid phase on the basis of the temperature effect.2. This would probably also explain why gas-phase oxidation has a greater chance of success with short-chain hydrocarbons. it is claimed that the oxygen absorption efficiencies are improved to a point where 90-99% of the oxygen entering is absorbed. 8. such as operation at lower temperatures and pressures. Reactor Configurations and Materials Most oxidations are performed under pressure. even jacket cooling may prove to be adequate.97. but the gas phase is largely in plug flow and. Catalyst deactivation and replacement can lead to additional constraints on the reactor design. large-size sparged reactors. Solid catalytic reactors for VPOs tend to be of the fixed-bed tubular type. and multitubular reactors are required in the interest of efficient heat removal. are widely used. coils can be inserted in sparged reactors. as in the case of oxidation of p-xylene to terephthalic acid (PTA) in acetic acid medium.55. Vol. reactions in supercritical media have been attracting some attention in the context of organic oxidations. Chem. in some cases. Furthermore. Because most organic oxidations are zero-order in oxygen down to very low oxygen concentrations. Here. 2000 | doi: 10.119 The case of isobutane in the liquid vs supercritical phase is referred to in sections 6. because oxidations are autocatalytic. and it would be useful to compare the benefits and shortcomings of sparged reactors versus mechanically agitated contactors. In view of the high heat-transfer coefficient. In particular cases. air has invariably been chosen for reasons of cost. namely. spectacular selectivity can be obtained in VPO through the use of highly specific solid catalysts. an example is the conversion of butane to maleic anhydride. LPOs are simpler.2. may even jeopardize the safety as the partial pressure of oxygen (pO2) at the outlet may not be in the desirable range. Catalyst concentration is also easily varied. products of combustion. e.. more smaller molecules are produced. CO and CO2. one would. control of LPOs is easier with little possibility of runaways. VPOs exhibit a much more complex behavior than LPOs with cool flames. which possess the advantage of superior heat-transfer characteristics for the exothermic LPO reactions. hot flames. relative proportions are easily adjusted in the liquidphase process. if conditions are such that the kinetic regime prevails. we must next examine the choice of oxidizing gas.120 has patented what it calls the “Liquid Oxidation Reactor” (LOR). In view of the above. there would appear to be several advantages in going to enriched air or even pure oxygen. the safety issues must be examined very carefully. Thus. 39. If the bulk liquid can become starved of oxygen. furthermore. Berezin et al. In the past. the relevance of masstranfer factors has been demonstrated in several cases (this is discussed further in section 9). Condensation of the hydrocarbon from the reactor exhaust gases is also facilitated if the concentration of noncondensables is reduced. Thus. it is possible for
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. one loses out on selectivity to the desired compounds. backmixing in the gas phase is pronounced. etc. it must be considered that the hydrocarbon inventory in VPO processes is much smaller than that in LPO processes. in the case of isobutane. which uses pure oxygen. Through careful design of the reactor internals (which include a draft tube to promote liquid circulation) and mixing devices. Thus. Although catalyst recovery presents problems and catalyst cost must be be borne in mind (especially where complex mixtures such as the MC catalyst are involved).1021/ie0002733
one of the mass-tranfer-limited regimes to arise as the reaction proceeds. In MC oxidations. with diameters up to 4-5 m. When the demand on the volumetric mass-tranfer coefficient (kLa) is not very high and heat loads are reasonable. LPOs are almost invariably homogeneously catalyzed. These are expensive to fabricate. Of late. However. such as in the oxidation of cumene. lower solvent combustion rates (such as of acetic acid in p-xylene oxidation).12 They are usually carried out in CSTRs or bubble columns. However. and this. Thus. the differences in the product spectra from gas-phase and liquid-phase processes can be narrowed down by diluting the liquid phase with CCl4 in the latter case and increasing the concentration of the reactant in the former.Ind. quite apart from excessive power consumption.10 have shown that the observed differences in the case of oxidation between LPO and VPO cannot be explained from considerations of density alone and that changes in reaction mechanism must be taken into account.90.12 From the point of view of engineering. it will provide additional advantage. a product. form in higher amounts. it is not surprising that gasphase oxidations have not been studied in the same detail as LPOs. unusually high gas velocities will be required for uniform suspension of particles. In any case. enriched air (up to 28% oxygen120) has been used also. and indeed. It is also claimed that the good mixing conditions inside the reactor and high extents of absorption before the gases leave the reactor ensure that safety is not compromised. the carboxylic acid product is often insoluble in the reaction medium and therefore precipitates out on cold surfaces. No. and hence. Having considered the case for liquid-phase oxidations.98. necessitating a frequent cleaning of such surfaces inside the reactor.. 2000 3983
others in which differences in chemistry also play a part. appropriate modifications in the reactor hydrodynamics120 make it possible that the heat of reaction is removed by evaporation of the hydrocarbon and that heat-transfer surfaces inside the reactor are rendered unnecessary. If substantially pure oxygen can be used under conditions such that most of the oxygen is absorbed. 11. There are other factors also to consider in chosing the oxidizing gas. should the rate be dependent on the partial pressure of oxygen. rate and selectivity characteristics would not be seriously affected by the choice of gas. On the other hand. Eng. Several advantages are claimed. then the volume of gases to be treated before venting decreases. Should there be a large loading of solids. Res. The higher temperature leads to more C-C bond scission than in the LPO case. Praxair Technology Inc. Furthermore. mechanically agitated reactors are used in PTA production
. expect that higher oxygen partial pressures would be beneficial.
in cyclohexane oxidation).127 Hence. such devices would push the reaction toward the diffusional end of the slow-reaction regime. which is.and agitated-type contactors for industrial oxidations. the near-interface region) and the bulk. Role of Mass Transfer in Liquid-Phase Oxidations The analysis of gas-liquid oxidation reactors requires separation of mass-transfer and reaction-kinetics effects and is complicated by the need to consider the coupling between mass transfer and chemical reaction. Most theories of mass transfer predict that
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. as occurs at low conversions in most cases) would suggest a gas-dispersedin-liquid mode of operation. liquid-in-gas. a more important issue is the selectivity of oxidation.2. but the autocatalytic kinetics (particularly in uncatalyzed oxidation) would call for a minimum backmixing for the reaction to get started. In this section. one anticipates that the masstranfer coefficient will increase with temperature. However.5 and 1. or bicontinuous). and determinations of the reaction locale with no accounting for the autocatalytic kinetics could lead to the wrong conclusions. 39. because of the autocatalytic nature of the kinetics. For a flatinterface reactor.. which. 11. The oxidation reactions discussed in this review take place at high temperatures and elevated pressures. difficulties arise in prediction of mass-tranfer rates. 2000
even though problems of leakage through shaft sealing and shaft mechanical soundness are possible problems. Thus. Different dispersion modes are associated with different ranges of the parameter aDA/kL.124 or a model chemical reaction.51. Furthermore. Thus. they suggest a decision on the dispersion mode (gas-in-liquid. It is not at all clear that extrapolation of such data to high temperatures and pressures is a valid exercise. Often. Although technical kinetics are usually determined under the (temperature and pressure) conditions of reaction. as in most oxidations. Res.acs. with the hydrocarbon moving from one stage to the next while the gas is fed to all stages in parallel in a crosscurrent manner.. The theory of simultaneous gas-liquid mass transfer and chemical reaction has been the subject of numerous theoretical and experimental investigations (a comprehensive review is available in Doraiswamy and Sharma43). some preliminary assessment of the effect of temperature and pressure on mass-tranfer parameters is now possible. The mass-tranfer coefficient depends on the diffusion coefficient and on a hydrodynamic parameter (variously described by the theories of mass transfer as a film thickness or a surface renewal rate). 2009 | http://pubs. Eng. in the case of gas-liquid systems. the type of operation used in industrial practice (for example. as conversion increases.5.org Publication Date (Web): October 11. For a bubbling reactor.6.52 Despite these difficulties. based on the reaction locale (as determined from Hatta number calculations). They recommend a three-level strategy for reactor selection. among other things. Considerations of safety would also require good mixing conditions in the reactor. 2000 | doi: 10.1021/ie0002733
kL ) D m
where the exponent m varies between 0. Chem. Mass-Transfer Rates at Elevated Temperatures and Pressures and under Actual Oxidation Conditions The mass-tranfer rate is determined by the product of the mass-tranfer coefficient (kL) and the interfacial area per unit volume (a).125. Vol. Krishna and co-workers121-123 have recently reviewed the strategies for multiphase reactor selection. The behavior of such reactors is dominated by the relative rates of mass transfer and chemical reaction. with the result that.45.126 The latter technique gives an average interfacial area.
9. would be influenced by properties such as surface tension. which is not dissimilar from the surface renewal theory prediction of m ) 0. there are only a few model reactions available for use at high temperatures and pressures. 9. Our knowledge base on mass transfer almost entirely rests upon experiments conducted under ambient conditions. Suresh et al. it does so at negligible oxygen concentrations with the possible consequence that the chemistry shifts to first-order mechanisms with an attendant loss of selectivity. the reaction could. This is because the selectivity to the intermediates is known to suffer in consecutive reaction schemes in the event of film reaction. a low value of the Hatta number (say.43 The measurement of interfacial area uses either a light-transmission technique46. indeed. These considerations thus help to rationalize the preponderance of bubbling. which determines the ˆ volume ratio between the film (i. it becomes important to choose reactors with high mass-tranfer rates so that the reaction can be made to occur in the bulk up to reasonable conversions. although the reaction occurs in the bulk liquid. Some additional considerations are warranted in the case of liquid-phase oxidations because of the peculiarity of the kinetics involved. kL
. the exponent m is found to be around 0. Liquid-phase backmixing is another consideration that merits attention in the context of hydrocarbon oxidation in view of the kinetic mechanisms involved. Some discrepancies between these techniques have been noticed for bubbling reactors. However. The location of the reaction and the impact of operating variables on the reaction are also dictated by these rates. Given that masstranfer coefficients in such equipment do not vary a great deal. a rational design of gas-liquid reactors is dependent upon an understanding of this complex interaction. At the first level. These diverse requirements can be reconciled by having several mixed reactors (or bubble columns) in series. The above considerations revolve mostly around the rate of oxidation. Selectivity considerations would normally dictate a reactor with minimum backmixing. the film-to-bulk volume ratio can be decreased by decreasing the gas holdup and the interfacial area.3984
Ind. If the desired products are the intermediates. we first review the status of data on mass-tranfer-related parameters and then consider theoretical advances in bringing organic oxidations within the ambit of the theories of mass tranfer with chemical reaction.46 In addition.e. one must be careful in extending the argument too far. Experimental techniques have been developed to measure both the product and the interfacial areas. particularly when the desired product is an intermediate prone to further oxidation. take place to a significant extent in the film.1. No. Aspects of mass transfer with chemical reaction in organic oxidations are discussed further in section 9. Temperature has a significant effect on the diffusion coefficient.48 present a detailed investigation of the effect of temperature on the mass-tranfer coefficient.
Other literature data128. this effect is somewhat modified by the coalescence rate. However. nonetheless indicate the need to adequately allow for these effects in data analysis.142 and Wilkinson et al.Ind. which do not contribute to the mass transfer. Note.116 have conducted experimental investigations on mass transfer under conditions of high temperatures and pressures in the cyclohexane oxidation process in agitated reactors.132 are in agreement with this reasoning. a combination of factors. 2009 | http://pubs. When this product exceeds 200 kg/m2s. The earliest study of pressure effects on interfacial area in stirred contactors is due to Sridhar and Potter.2. This surprising result is ascribed to the overlap of the diffusion boundary layers around bubbles. whereas Deckwer ct al. This implies that the average bubble diameter increases with pressure. at least up to 5 MPa. The experimental data130. 39. the gas holdup increases. especially surface tension. the large vapor pressures can cause the gas density to be large even at much smaller pressures. 2000 | doi: 10.52 The effect of pressure on interfacial area depends on the type of reactor used. and the other is an empirical factor depending on gas density. along with the differences between bubbling and flat-interface reactors mentioned earlier. Chem. There is a paucity of data on pressure and temperature effects. one would not expect the liquid-phase mass-tranfer coefficients to depend on pressure. concurrent changes in physical properties. The chemical method used to measure interfacial area gives a mass-tranfer-weighted area.46 Using the light-transmission technique. the early results of Yoshida and Arakawa133 show a small decrease in the mass-tranfer coefficient with increasing pressure. the geometric area could well be quite different from the mass-tranfer effective area. On the other hand.144 In gas-liquid stirred vessels. These papers also identified the gas density and velocity at the orifice as the dominant parameters. for reasons discussed under section 8. also see Oyevaar and Westerterp. This implies that bubbles. their paper demonstrates significant pressure effects under conditions relevant to the oxidation of hydrocarbons.. are not accounted for.136 that bubble formation at a single orifice is affected by pressure. The reduction in surface tension leads to a reduction in the surface renewal rates. 11. the gas-phase mass-tranfer coefficient decreases with pressure because of the decrease in the gas-phase diffusion coefficient. Tekie et al.130 suggest various values. Higher pressures lead to smaller bubble volumes and higher frequency of formation.138 claims that pressure has a significant effect on the gas holdup.46 Pressure effects in bubble columns are also discussed by Letzel et al. The earlier papers found no pressure effects at low pressures up to 2 MPa. the impact of hydrodynamics is even greater. Thus.. the more recent study at higher pressures of 8 MPa52 found a significant pressure effect.143. The available data. if temperature is varied. their reactors employ gas-inducing impellers or surface aeration. which is contrary to the single-orifice data cited earlier.1021/ie0002733
.51 and Oyevaar et al. These counteracting effects. It is therefore unwise to rely on such data in the analysis of oxidation reactors. A recent review by Oyevaar and Westerterp51 discusses the relevant issues. Oyevaar and Westerterp51 carefully discuss these contradictory results and show that at least some of these differences could result from the sparger design and from the superficial gas velocity employed. The picture is much clearer on the effect of pressure on mass-tranfer coefficients. However. On the other hand. although insufficient for design purposes. Influence of Mass Transfer on Liquid-Phase Oxidations The need to account for possible mass-tranfer influences in organic oxidations (considering that these reactions are usually carried out by bubbling an oxygencontaining gas through liquid hydrocarbon) has been generally appreciated even in early literature. such as the lack of an adequate theoretical analysis and the lack of adequate information on the magnitudes of mass-tranfer parameters under the conditions of oxidation. There is general agreement135.141 Krishna et al.145 Oyevaar and Westerterp. No. Eng. that in organic oxidations. Recently. a significant increase in area is observed. Oyevaar et al. are responsible for the contradictory results in the literature. which depends on physical properties and the hydrodynamic conditions. This paper also presents data on interfacial areas in bubble columns.. Because pressure. These are extremely low values and are well out of the range of Schmidt numbers found in the reported studies on mass transfer. Vol. but the
influence of pressure is not as large as on gas holdup.134 The situation is very similar with interfacial area. The lowering of surface tension at high temperatures and the presence of any adventitious surface-active impurities may also contribute by suppressing surface renewal rates. different measurement techniques could easily lead to different results. Hence.52 used the chemical method to probe pressure effects in stirred contactors at room temperature. and hence. the mass-tranfer coefficient decreases. which could be significant at large dispersed-phase volume fraction and at high diffusivities. The results indicate that the area increases with pressure. For bubble-column reactors. 2000 3985
is found to be nearly independent of temperature. However. However. However. The use of different gases does not give adequate variation in D and could lead to erroneous conclusions. Pressure effects were found to be uniquely dependent upon the product of the gas density and the gas velocity at the orifice. has only a minor effect on physical properties in the liquid state. the typical Schmidt number varies from 10 to 300. This contradictory state of affairs results at least partly from the method used to change diffusion coefficients. Such reactors are not common in industry. and hence.139 show that pressure has no effect on gas holdup. A tentative correlation developed by these authors ascribes the effect of pressure to two sources. the specific form suggested by Sridhar and Potter was not found to be supported by these experiments. It is therefore not
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. a group of investigators137. 9. also result.org Publication Date (Web): October 11.acs. mass transfer under conditions obtained in oxidation reactors is determined by several factors. the bubble sizes formed at the distributor have a major influence. with Kishinevsky and Serebryansky131 even suggesting zero. however. Smaller bubble sizes lead to a reduction in rise velocity. As a result. Res. One is the relative contribution of the energy input because of the gas (kinetic energy).140 show large increases in holdup with pressure. has forced researchers to correlate observed rate data in terms of “overall” kinetics in many instances. especially if the superficial velocity is high. the early Russian work10 or the work of Hobbs35 are examples. In summary. Oyevaar et al.. Under the conditions for organic oxidations. However.
39. and even these have led only to partial results. Froment and Bischoff151). on the other hand. taking first-order reactions in general. involve approximations and often do not consider the concentration profile of the dissolved gas. the autocatalytic nature of the reaction makes such a conclusion hazardous when applied over a conversion range. the zeroorder behavior with respect to the dissolving species (oxygen). They therefore developed50. Ultimately. where they are attributed to temperature feedback effects. and the free-radical chemistry and consequent autocatalysis. the role of reaction regime in modifying selectivities is usually inadequately appreciated (see Cao et al. in which the reaction came to a standstill as the temperature was lowered to a certain value and could not be re-started until the temperature was raised much beyond this value.148 were the first to consider the effect of autocatalysis within the framework of the film and penetration theories and showed that much larger enhancements result through the accumulation of the product in the diffusion film and consequent acceleration of the reaction there. For example. Steeman et al. The way commercial reactors are operated (with negligible oxygen concentrations in the reactor off-gases). Hronec and Ilavsky152 reported oscillations in the isothermal catalyzed oxidation of a mixture of p-xylene and p-toluic acid and of n-dodecane in an air sparged reactor. Although early theoretical work on hydrocarbon oxidations tended to classify these reactions as slow and hence occurring in the slowreaction regime. with easily oxidized feedstocks such as p-methoxytoluene. However.acs.54 for example). Darde et al. but that it accelerates as products accumulate. The kind of selectivities for which the kinetics inherently provide. The authors assumed masstranfer limitations to be absent. the locale of reaction. No. these authors found. Hobbs et al. The oscillations were observed in the concentration of oxygen in the exit gases and were reported as being aperiodic. However. Vol. leading to dimerization of R* radicals. such conditions could well prevail in a number of cases. o-xylene. Suresh150 has subsequently shown. Confusion also results from an insufficient knowledge of mass-tranfer parameters under conditions of reaction. This behavior is reminiscent of the “ignition-extinction” behavior that has been theoretically predicted and experimentally observed in such nonlinear chemical systems as exothermic CSTRs (see. This has been because of certain difficulties with treating liquid-phase oxidation reactions within the well-established framework of gasliquid reactions. and the ways in which they are modified by mass-tranfer limitations. Chem. for example. The theoretical analyses. such as the consecutiveparallel nature of the overall reaction network.50 on cyclohexane oxidation clearly showed that the reaction is slow enough at the beginning that dissolved oxygen concentrations in the bulk attain saturation. catalyzed by cobalt/bromide. and mesitylene).org Publication Date (Web): October 11. It is possible that the mass-tranfer parameters (especially interfacial area) could undergo changes during oxidation because of the changing composition of the liquid (especially. that swarm effects should not be expected to lead to predictions different from the traditional local-rate models (such as film and penetration theories).50 the whole question would still seem to be somewhat open. 10. are questions of some importance that still await answers.35 described some hysteresis-type effects in the oxidation of MEK.39. for example. producing enhancement of mass-tranfer coefficients. In their review of the literature on the selectivity of gas-liquid reactions. Rate Oscillations and Other Nonlinear Phenomena Considering the complexity of the chemistry that governs organic oxidations.. Suresh88 does report some visual observations that suggest that such may have been the case..34). depending on conditions such as the oxygen partial pressure and conversion level. the reaction can get fast enough to take place partly or wholly in the film. Eng. insufficient oxygen diffusion rates may result in depletion of dissolved oxygen. The authors speculated that the observed discrepancies could. much remains to be done in this industrially important and intellectually challenging area. Mann and co-workers147. 11. and attributed the oscillations to kinetic phenomena. One aspect that has hardly received any attention at all is the change in chemistry that one obtains under oxygen-deficient conditions. on the basis of which enhancements are calculated. as shown by the declining oxygen levels in the liquid. as high stirring rates were used. where some effort has been made to apply film and penetration theories to delineate regimes (Doraiswamy and Sharma43 provide a summary). Even in work where the mass-tranfer step is included in the rate model.. is also determined under similar swarm conditions. rate laws are invariably nonlinear.1021/ie0002733
mass-tranfer coefficients were determined in the work of Suresh et al. The most systematic effort to bring organic oxidations within the ambit of the theories of mass transfer and chemical reaction is probably to be found in the case of cyclohexane oxidation. 2000
surprising that the “reaction rate parameters” in several published accounts of kinetics are functions of such physical variables as the gas flow rate (see.48. which appeared to provide a better explanation. The experimental work of Suresh et al. which can change to first-order behavior at low concentrations. These authors developed a film theoretic approach to the treatment of cyclohexane oxidation. therefore. Low yields and dark-colored products are often the result (there might be a clue here to understand the inferior optical properties of the product in batch as compared to continuous operation in the oxidations of p-xylene. caused by the high diffusivities and large gas holdup. In summary. In the case of other oxidations. be due to interfering concentration fields around bubbles. 2000 | doi: 10. at least in part. Because this is the way in which physical
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. and its influence on the selectivity to the intermediates is often not appropriately brought out. Partenheimer12 points out that. at least in a part of the reaction volume.146 concluded that there were only a few experimental investigations of selectivity.154 describe oscillations in the air oxidation of benzaldehyde in acetic acid medium. the enhancement factors predicted by the theory (using independently determined kinetics and mass-tranfer parameters) were much smaller than those observed experimentally.43 There are several factors that the modeling must address. production of products which lead to foaming and so on). Jensen153 and Roelofs et al. 2009 | http://pubs. The oscillations were observed as coincident variations in the color
. and one should not be surprised to see some exotic phenomena associated with nonlinear kinetics. the importance of the regime.3986
Ind. Res.149 a bubble-swarm model that accounts in an approximate manner for these phenomena. provided that the physical masstranfer coefficient.
Vol. 11. in about one-third of the cases where the source was known.org Publication Date (Web): October 11. At the exit of the reactor. After storage vessels. they conducted an experiment in which. Hence. Good mixing conditions should be provided in the reactor so that good heat-transfer conditions prevail. is clearly needed to clarify these aspects. for example. and static electricity were among the other common causes. Suresh et al. a short interruption in oxygen supply would somehow “inactivate” the liquid. In these runs. as the concentration of dissolved oxygen neared zero in a normal oxidation. about 10% were due to the formation of flammable mixtures in the vapor space. thereby lowering oxygen consumption rates and allowing oxygen levels to increase.1021/ie0002733
. many bromate-driven oscillators have been reported. the equipment most often involved was pressure vessels.Ind. the dissolved oxygen levels rose nearly to saturation again. Mecklenburgh156) contains much valuable information to guide future designs. and the whole cycle repeats. this was autoignition. for example. and they concluded.155 Although it is thus possible that the nonlinearity of the kinetics is solely responsible in the case of organic oxidations also. the gas-vapor mixture is usually above the upper flammability limit. It would be interesting to see whether the selectivity of the oxidation is any different under these conditions. Suresh et al.114 investigated the effect of mass transfer through simulations of the kinetic model they had developed earlier. the usual situation is that the gas-vapor mixture passes through the flammable region as it passes through the reactor and the hydrocarbon vaporizes into the gas bubbles. Designs are usually to be based on very conservative estimates. To experimentally test such a hypothesis. Kletz157 lists the use of the wrong materials of construction as accounting for 7% of the incidents.88. The evidence presented in that case to the court of enquiry24 and the post-enquiry discussion (see. The evidence that a variety of nonlinear phenomena occur in organic oxidation is thus compelling. isothermal reactors have also been shown to exhibit a rich array of nonlinear behavior. Their simulations did not show any oscillations under the conditions employed. provided heat transfer is good enough to prevent the formation of local hot spots. the autoignition temperature is 523 K. Again. in which the oxygen levels went all the way to zero before coming up to about 25% of saturation. the most celebrated being the Belousov-Zhabotinsky reaction. Of the incidents in storage and blending areas. In the case of most of the hydrocarbons of relevance to this review. Although this has long been recognized.
For one thing. Suresh et al. Again. one can assume that the mixtures of air and hydrocarbon resulting under normal conditions are incapable of spontaneous combustion. 11. In the case of cyclohexane. 2000 3987
of the solution and the oxidation potential. provided that there is an autocatalytic step (with certain kinetic features) in the reaction mechanism (the extensive work of Gray and co-workers in this area is summarized by Gray and Scott53). thus necessitating a short “induction” period before the original reactivity could be restored. before immediately decreasing to zero. sparks. observed the alcohol-to-ketone ratio to be different under conditions of oscillation. In the work of Jensen. which incorporates the zero-tofirst-order transition at low oxygen concentrations. in later years. these oscillations also occurred as the dissolved oxygen declined in the batch oxidations. When dry air is used as the oxidizing gas.. dangers of ignition from an external source remain. there sometimes has been a tendency to regard the dangers involved as being somewhat exaggerated (see Berezin et al. consuming oxygen. Eng. No. aspects of reactor control must consider the variety of dynamic behavior that is possible. However. under both catalyzed and uncatalyzed conditions. 2009 | http://pubs. safety considerations are of utmost importance. Although mechanisms implicating the Co2+ f Co3+ transition have been proposed in the benzaldehyde work cited earlier. 39.153 the air flow rate was found to be an important parameter affecting the oscillations. Among primary causes. More work. Here.. The dangers of explosion are very real in hydrocarbon-air contact. they found that. Although the possibility of these and similar nonlinear phenomena is of obvious academic interest. As in the case of benzaldehyde oxidation. Some of the statistics provided (based on an analysis of about 500 incidents) are of relevance in the present context.10 for example). on switching back to oxygen every time. the active free radicals are inactivated (either through termination or through conversion to less-active free radicals). possible changes in reaction chemistry at low oxygen levels also could play a part. therefore. The reaction then accelerates.114 observed oscillations in dissolved oxygen in their studies of the oxidation of cyclohexane.acs. particularly as many of the reports seem to suggest that these phenomena are coincidental with low oxygen levels in the liquid. and hence. because of the change in chemistry associated with low oxygen levels in the liquid. and this is usually not a problem in agitated
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. Chem. Although early analyses of such exotic behavior were more or less restricted to the exothermic CSTRs. In 23% of the cases where the cause was ascribed to ignition.. Res. under the low dissolved oxygen concentrations that occur when some product concentration has been accumulated. It thus appears that. Oscillations in the dissolved oxygen concentration were also reported. whereas oxidation temperatures are on the order of 423 K. such mechanisms cannot explain the observed oscillations in uncatalyzed oxidations. Safety Issues in Organic Oxidations Oxidations being mediated by highly reactive species such as free radicals.114 for example. The whole subject was brought into sharp focus by the Flixborough explosion of June 1974 involving a cyclohexane oxidation plant. The range of flammable compositions expands with elevation and temperature. the source was unknown. However. both experimental and theoretical. that the explanation for the oscillations had to be sought in the kinetics. the main difficulty is that the flammability limits for mixtures of hydrocarbon in air are hardly ever available under the conditions of temperature and pressure employed in the oxidations.49. although the reactivity of the liquid is high during oxidation because of the products in solution. the explanations for these phenomena are still lacking. They proposed a mechanism in which. 2000 | doi: 10. caution is necessary in using data available under ambient conditions. implications for industrial operations are no less significant. the autoignition temperatures are much higher than the operating temperatures. the role of mass-tranfer limitations also must be keenly examined. Hot surfaces. the oxygen supply was periodically switched with nitrogen and back every 5 min. Kletz157 discusses this and other case histories of major industrial disasters in order to glean the lessons learned. Exhaust oxygen levels below 8% are generally considered safe.
12. 12. Biphasic Mode of Operation Several authors have studied oxidation in two-phase (biphasic) systems. 2009 | http://pubs. laboratory reactors sometimes have features in the interest of acquiring useful and comprehensive data that call for additional considerations. the design of the condenser is important. once the liquid is saturated with oxygen at the desired pressure. laboratory reactors must often operate with significant outlet oxygen levels so that absorption rates can be determined independently from gas-phase measurements. The products remain in the organic phase. hydroperoxides can form in nonnegligible concentrations in the reactor and can be carried downstream as entrainment.1) are ideal in this regard. When the second phase is water. the semibatch equipment used in the studics of Suresh et al.157 Alexander158 cautions that bad dispersion could lead to a buildup of free radicals. Although the remarks made above in regard to the good heat. the necessity for adequately addressing these issues is no less in laboratory reactors. Downstream of the reactor. Therefore. as the liquid holdup in these equipment is usually much larger. The possibility of liquid entrainment in the leaving gases must also be considered. because pure oxygen is used. High selectivities are reported. 39. by its very purpose. In general.
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. There is the further advantage in such equipment that the oxygen supply can be isolated before the actual experiment. Furthermore. whereas the industrial reactor operates in a narrow window. 11. although every care must be taken to eliminate possibilities of buildup of static electricity. adequate precautions are to be taken during the saturation step. therefore. Although industrial reactors usually operate with negligible oxygen levels in the gases leaving the reactor. the design of gas lines should ensure that no dead pockets are possible. it also increases the hydrocarbon holdup in the experimental rig. calls for a much greater consideration of the safety issues. Chem. Suresh et al.1021/ie0002733
The design of gas-liquid contactors. Vol. It is possible for the condensation to become mass-transfer-controlled and a mist to form. especially during start-up. Thus. The microautoclaves49 or the flow reactors of the type employed in the studies of Wen. 2000
vessels and bubble columns.. there is a case of condensation of the hydrocarbon from its mixture with a noncondensable (nitrogen). New Developments in Organic Oxidations The commercial importance of organic oxidations and the intellectual challenges they pose remain a potent driver for new research. situations could occur under which the exit oxygen levels are higher than those found in steady operation. it is good practice to keep the volume of the liquid hydrocarbon handled to a minimum in laboratory reactors. Although the liquid holdup in any experiment is just the reactor volume in the case of microautoclaves. this mist can prove to be a hazard.acs. Gas inlet and sparger designs should therefore ensure that stagnant pools of liquid do not collect at any point.63 and Guo61 (see section 7.. the laboratory reactor.49 worked with a system that avoids the formation of flammable mixtures in the reactor altogether by using a nitrogen stream that was presaturated with the hydrocarbon upstream of the reactor and mixing the desired (small) percentage of oxygen into this stream at the reactor inlet.org Publication Date (Web): October 11. Suresh et al. Fluid backing up into the gas lines can cause this. A demister should.59 Wen et al.161 used ruthenium trichloride for the oxidation of cycloalkanes with tert-butyl hydroperoxide
. Similarly. 2000 | doi: 10. The above are general considerations that apply equally well to industrial and laboratory reactor systems. Although safety issues are addressed in the industrial scenario through methodologies such as HAZOP. An example is provided by Chung et al. Parenthetically. and the fluorous phase containing the catalyst can be recycled. Care must be taken to avoid dead spots and regions where a buildup of such compounds can take place. apart from the need for loss prevention. On the other hand. about half of which would be at reaction temperature and pressure during an experiment. must be operated under a variety of conditions.48 housed all equipment containing hydrocarbon at or near reaction temperature inside a cabinet filled with carbon dioxide as a precaution. even with flow reactors of similar volumes. However. Eng. as the reactor holds only about 30-35 cm3 of liquid. but also must be an essential part of experiment planning. Fires have sometimes been observed in the gas lines. in the condenser. In uncatalyzed oxidations. Furthermore. One must then provide for efficient demisting because. Launay et al. we note that R-tetralone can be efficiently dehydrogenated to R-naphthol. Consequently. Furthermore. Sridhar159 and Suresh88 have discussed in detail the safety considerations in the design of such equipment. we illustrate some of the new processing options that have been considered recently. the hydrocarbon must be condensed out of the gas and returned to the reactor. Although the reactor designs are usually such that the oxygen level by this stage is very small (in steady-state operation). This approach has the additional advantage that vaporization inside the reactor can be neglected in interpreting the data using the theories of mass transfer with chemical reaction. Wen59 and Guo61 housed their equipment in an enclosure that could be flooded with carbon dioxide in case of an emergency. and this is another place where the mixture could pass through the flammability range.and mass-tranfer conditions inside the reactor (where flammable compositions could occur) are even more likely to be valid in laboratory reactors than in industrial reactors.49 had a holdup of about 20 dm3 of cyclohexane. on the other hand. and the reaction can be carried out at 60 °C. Thus. Res. although this step is carried out in the cold. The presence of moving parts such as mechanical agitators calls for precautions in preventing an accumulation of static electricity or the generation of hot spots.1. For one thing. oxygen or an oxygen-containing gas was continuously passed through the liquid. In this section. Because such liquid is likely to contain reactive hydroperoxides. Despite all of the advantages of small liquid holdup. resulting in fires well below auto-ignition temperatures.160 who oxidized tetralin to R-tetralone with a nickel complex of a surface-active ligand in the presence of an emulsifier. the comments made earlier in connection with the design of condensers to recycle the hydrocarbon are of even greater importance here. safety considerations not only are important in the design. be provided downstream of the condenser. No. an experiment for 10-20 residence times can be carried out with fairly small volumes of liquid. the catalyst can be drawn to the organic-water interface by a surface-active complexing agent.3988
169 have shown how. whereas it shows a maximum in the absence of ultrasound. At 3.e. SC CO2 is an attractive solvent for catalytic oxidations because it is noncoordinating and inert toward any further oxidation. There is a claim181 that. The rates in supercritical medium are three times faster than those in hexane (see section 12.177. The Role of Ultrasound in Oxidation Reactions The role of free radicals and their impact on reaction pathways has been detailed in section 5. conditions in SC CO2 (Tc ) 30. octene-1. the reaction mixture again forms two phases: the organic phase contains the products. in the Wacker process for the conversion of R-olefins to the corresponding carbonyl compounds. Matienko and co-workers172-175 have studied a number of related issues. but a recent claim from Bayer170.acs. Pc ) 217. Under reaction conditions. However. This is particularly relevant as cavitation can be employed in large-scale operations.6 atm) and has found it to be promising (cited by Haas and Kolis180). The use of a two-phase system prevents nonselective oxidation of the diols and permits the recycle of the catalyst. may well offer some advantages.at 135-160 °C and 12-15 atm pressure.167 However. The use of phase-transfer catalysis in enhancing air
oxidation of hydrocarbons has received attention. a 36 mol % selectivity to PO was obtained. Res. In contrast to SC water. Macrocyclic polyether 18-crown-6 changes the selectivity. 11.178 is known to create free radicals.
Downloaded by UNIVERSITA STUDI TRIESTE on September 1.165 An additional advantage of this system is that. The structure of the cage is reported in this paper. Dobler et al. colloidal ruthenium is formed and remains at the interface.6 °C. 2000 3989
(TBHP). recently. 12. Pc ) 72. 2009 | http://pubs..3. thereby facilitating rapid reaction. Microemulsions are thermodynamically stable and. The MnBr2-catalyzed reaction of p-xylene giving terephthalic acid has been reported. but higher olefins (C12-C14) do not react. Homogeneous ruthenium complexes with fluorous phosphines are being developed as catalysts.163 carried out the Wacker-type air oxidation of styrene and its derivatives to the corresponding acetophenone using (en)Pd(NO3). The catalysts are stable and can be recycled. we anticipate that this technique will continue to attract attention.4). cyclohexene.g.3 K.183 has claimed that propylene can be converted to PO by oxygen in a cascade of reactors using dichlorobenzene as a reaction medium. when propylene is oxidized under supercritical conditions (T > 91.171 reveals a Wacker process in a microemulsion medium with olefins such as cyclopentene. 39. Vol. the use of R-cyclodextrin can make a remarkable change. and as such. The solvent is environmentally friendly. Thus. Pesiri168 demonstrates the epoxidation of alkenes in dense-phase CO2 using oxo vanadiumtriisopropoxide.2. There is very little information in the literature.166 studied the oxidation of alkenes and obtained high conversions and selectivity to the epoxide using a cobalt complex of tetraarylporphyrin. Some reports have appeared on oxidations in supercritical media in the literature.164 show that osmiumcatalyzed dihydroxylations are facilitated by operating in a two-phase system. Environmental considerations have created a large interest in aqueous biphasic catalysis. water only thermally stable olefins undergo this type of reaction. these systems can generate some aqueous solutions as a waste stream. The oxidation rate under these conditions does not vary with time. Sulman179 has cited the effect of ultrasound on the liquid-phase oxidation of n-tetradecane at 385 K in the presence of 0. using a water-soluble palladium complex of bidentate amine ligands such as bathophenanthroline disulfonate for the Wacker-type conversion of terminal olefins (e. cleavage occurred). There is scant literature on the oxidation of hydrocarbons under conditions of industrial importance. This has motivated the search for the use of a dense-phase CO2-based system. simple nonconjugated olefins such as 1-octene and cyclohexene decompose in the harsh environment of SC water.) to the corresponding ketones.1021/ie0002733
. Chem. The inertness of the fluorocarbon and the high solubility of oxygen in this phase are additional advantages. Fluorous biphasic systems have also been developed wherein a perfluorinated solvent replaces water.8 atm) are milder and benign. This is an improvement over the conventional Wacker process. Ultrasound appears to increase the production of oxygenated compounds by 15-30%. In SC. propylene oxide (PO) is obtained. ten Brink et al. Oxidation in Supercritical Media A thesis from Clemson University has covered oxidation of alkyl aromatics to aldehydes and acids in supercritical (SC) water (Tc ) 647. Ito et al. the reaction mixture becomes homogeneous. The method is an improvement on the well-known Sharpless dihydroxylations. The oxidation of alkenes in the presence of Mo(CO)6 to form enols and epoxides is also cited in this work. C8-C10 olefins give the corresponding methyl ketones. hexene-1.org Publication Date (Web): October 11. The fundamental aspects pertaining to the prediction of rate and selectivity remain to be studied. This complex facilitates the transfer of organic material into the aqueous phase in a reverse phasetransfer catalysis. etc. including through cavitation. Eng. There is also a claim176 for the liquid-phase air oxidation of toluene to benzoic acid using cobalt catalyst and a phase-transfer catalyst like [Me(CH2)-9]2N+Me2Br. Harada et al. Dow182. and the aqueous phase containing the catalyst can be recycled. It is surprising that oct-2-ene gives poor results...3% cobalt stearate as a catalyst. P > 46.4 K. 12. Thus. and the corresponding ketone was obtained as the predominant product. On cooling. at temperatures around 60 °C.6% conversion. Ultrasonication. These authors carried out the liquidphase oxidation of ethyl benzene with Ni(acac)2 as a catalyst. The oxidation of stilbene with O2 and MoO2(acac)2 or VO(acac)2 gave benzaldehyde and benzoic acid (i. The maximum acceleration of the oxidation is reached at a frequency of 300 kHz. Several cycloalkanes were studied. These authors report the oxidation of various olefins to the corresponding ketones in the presence of a palladium catalyst with TBHP as an oxidant. and this can also be realized using quaternary salts such as Me4NBr and n-C16H38Me3NBr. No. we expect that the air oxidation of dissolved organics in wastewater would be favorably influenced by ultrasonic treatment during oxidation. 2000 | doi: 10. for sparingly soluble hydrocarbons. Haas and Kolis180 have reported that Mo catalyst can oxidize toluene to benzaldehyde in 25% yield in SC CO2. Pozzi et al.Ind.162 have adopted the biphasic system. etc. in connection with the oxidation of ethylbenzene.1 atm) with silver catalyst.
Thus. The engineering aspects of such aerobic fermentation reactions require further attention. may emerge. which has potential to be commercial. 39. which are potent inducers of cytochrome P450 activity. Photochemical Activation of Oxidation Reactions The role of photocatalysis in realizing the selectivity for the desired product in the oxidation of hydrocarbons has attracted attention in recent years. cyclooctane. Cytochrome P450 functions to activate molecular oxygen by iron porphyrin to generate an oxo iron porphyrin while transferring oxygen atom to the substrate. The photosensitizer is protected from attack by hydroxyl radicals because of its location within the pores of the zeolite.org Publication Date (Web): October 11.12-dodecanedioic acid for making modified polycarbonates has been reported. dodecanedioic acid from cyclododecane etc.189. For example. which. Eng.188 The catalyzed photooxidation of cyclopentene189 gives the following products:
droquinidine chiral ligands. It is known that brassylic acid is commercially manufactured (in Japan and China) by the aerobic fermentation route.195 have reported biocatalytic asymmetric hydroxylation of hydrocarbons with the microorganism Bacillus megaterium. that is obtained as a byproduct of cumene oxidation (see section 6.196 Dicarboxylic acids such as adipic acid. which. should give the optically active 2-aryl propanoic acid..187 describe a photocatalytic system consisting of an organic dye trapped in Ti-zeolite pores..13-tridecanedioic acid) is used to manufacture the corresponding nylon. the reaction of 1. etc.191 The catalytic asymmetric dihydroxylation of R-methylstyrene (AMS) by air under visible irradiation is a fascinating example of oxidation of a relatively cheap hydrocarbon.4. For example. The dye absorbs energy from light and generates hydroxyl radicals from water. 2009 | http://pubs. No.6%. and brassylic acid (1.
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. using a 400-W sodium lamp. The same enzyme also assisted in the regiospecific introduction of oxygen into alkanes. is through the oxidation of cyclic compounds (adipic acid from cyclohexane. 12. azelaic acid. 2000 | doi: 10. Blatter et al.3). to the corresponding hydroperoxides. Salycilate phenobarbitols.12dodecanedioic acid. Li et al. In such cases. at about 8% conversion. Decalin. Chem. Brassylic acid and 1. These acids are useful intermediates in the production of polyamides. These radicals react with olefins in the presence of molecular oxygen to form allylic hydroperoxides. and cyclooctene in dichloromethane medium containing tetraphenylporphyrin. this reaction can be conducted in the presence of catalytic amounts of Os(IV).197 An important commercial route. for some of these dicarboxylic acids. The simulation of these enzymatic functions with transition metals has received much attention. Highly dispersed titanium oxide on silica has been reported to catalyze the photooxidation of propene to propylene oxide using molecular oxygen. This synthesis in zeolite environments offers an opportunity for in situ use of the HPO as an oxidizing agent without isolation and storage. sebacic acid.185 have given an overview of photocatalyzed oxidation of hydrocarbons in zeolite cages with examples of toluene to benzaldehyde.5. Other enzyme catalysts have also been developed.184 Thus.186 have done some ingenious experiments in which isobutane and O2 gas were loaded in a single-photon process (monitored in situ by FTIR).194 Adam et al. Liquidphase air oxidation of saturated hydrocarbons such as decane. the oxo metal complex is generated without porphyrins. AMS. cyclohexene. 12. and lately. Res. Sanjuan et al. dodecanedioic acid. The liquid-phase oxidation of isobutane was referred to in section 6. Under visible irradiation.197 Similarly. Details of these approaches are contained in a report on the 4th Japanese-Swiss Meeting on Bioprocess Development. It is noteworthy that the selectivity to the hydroperoxide (HPO) was 98% even when more than 50% of the loaded reactants had reacted. see section 4). The optically active dihydroxy compound can be selectively hydrogenated to the optically active monohydroxy (primary) species.3990
Bloodworth and Eggelte190 have reported photooxidation. phthalazine dihy-
These reports have significance in the pursuit of a direct oxidation process for PO from propylene.12-dodecanedioic acid are preferred raw materials for making environmentally friendly musks as aroma compounds through esterification with ethylene glycol. and brassylic acid are commercially important. suberic acid. enzymes such as cytochrome P450 catalyze the oxidation of various organic compounds. The photocatalytic oxidation of hydrocarbons in the aqueous phase in the presence of finely divided TiO2 has been reported by Gonzalez et al. for which typically. of cyclopentene. Enzyme-Catalyzed Reactions In living organisms. the use of 1. to optically active 2-aryl propanoic acid like S-ibuprofen and S-naproxen.acs. Alkane hydroxylase from Pseudomonas oleovorans has been used to produce optically pure epoxides from terminal alkenes. Although Sharpless’ method of asymmetric dihydroxylation is known. low-valent ruthenium complex can react with a hydroperoxide. cycloheptene. These dicarboxylic acids are useful for making polyesters. facilitate the epoxidation of the alkene at the Ti sites.193 have used vesicles to direct the photosensitized oxidation of olefins either toward the singletoxygen-mediated or the superoxide-radical-anion-mediated products by controlling the status and location of the substrate and sensitizer molecules in the reaction media. on carbonylation. conversion about 90% selectivity to benzaldehyde was obtained. fermentation of n-dodecane can give 1. a new route. the work of Krief and Colaux-Castillo192 yields a new perspective by using air as an oxidant.4. toluene was oxidized to benzyl alcohol. Optically translucent zeolite membranes will have to be used.12. changed the regioselectivity of the microbial CH insertion without an effect on enantioselectivity. under photochemical activation has been reported by Nekhaev et al. we get 75% selectivity with respect to the hydroperoxide. Frei et al. and subsequent cleavage yields an oxo ruthenium (IV) species. and at 11. which can then be used to oxidize hydrocarbons. 11. This strain carried out the hydroxylation chemoselectively and enantioselectively in the benzylic and nonbenzylic positions of a variety of unfunctionalized aryl alkanes (the phenyl ring was unaffected).12-dodecanedioic acid with hexamethylene diamine gives Nylon-6. in turn. with O2. Vol.
Chem. Soluble heteropolyacids (HPA) and palladium acetate have been used for the direct oxidation of benzene to phenol. Vanoppen et al.7.6. No. The terminal methyl group in dodecane is able to access the active catalyst sites.201 With cyclohexane oxidation.202 have attempted heterogenization of the conventional cobalt catalyst by incorporating it into the framework of aluminophosphate molecular sieves. and hence. selectivities are not reported at the higher temperature. have yielded some significant improvements in rate and selectivity for cyclohexane oxidation with tert-butyl hydroperoxide. or vanadium-substituted aluminophosphates have been shown to be active (for example. The reaction was carried out at room temperature with an oxygen partial pressure of 40 atm. which subsequently epoxidizes propylene.1021/ie0002733
catalyst deactivation in the case of oxidation of ethylbenzene. indeed. The selectivity arises from the pore dimensions that govern the access of the hydrocarbon. The rates are. 2000 3991
12. Meiers and Holderich199 have used PddPt in TiSilicalite for a “one-pot” conversion of propylene to propylene oxide using H2 and O2.Ind.207 have designed a molecular sieve catalyst for the extremely difficult air oxidation of n-hexane to adipic acid. one of the prime motivating forces for catalysis research has been environmental concerns: increased efficiencies lead to reduced effluent volumes. Catalyst Developments As in the other areas reviewed in this section. heterogenization facilitates catalyst recycle and reuse. 39.acs. either in zeolite-type cages or in membranes. Chisem et al. The catalyst was prepared by a sonochemical method. however. long-term stability. This difference is apparently due to cyclohexane being much more confined in the case of FeAlPO-31. A development of some interest is the demonstration of catalysis by nanostructured amorphous metals such as cobalt and iron and alloys. This addresses the problem of selective oxidation of linear alkanes. 12. The latter catalyst showed selectivity to adipic acid as high as 65%. In an earlier work from the same school. 2009 | http://pubs.211 cited
. a selectivity of 80% (to cyclohexanol-cyclohexanone) at a conversion as high as 40% was realized with amorphous cobalt. 11. Passoni et al. whereas the molecular sieves retain the catalyst. problems associated with leaching. the diffusion of cyclohexane and cyclic intermediates is limited. whereas the former gave a maximum selectivity of 31%. further oxidation to linear products such as adipic acid is facilitated. Low-efficiency processes such as cyclohexane oxidation have naturally been at the forefront of research attention. These authors show that small amounts of leached metal could homogeneously catalyze the reaction and suggest ways of testing these catalysts. and the oxidation was carried out in an acetic acid medium. unlike in the case of the process based on the oxidation of cumene. Khenkin et al. Vanoppen et al. These catalysts are shown to facilitate the epoxidation of cyclohexene with excellent selectivity and also to assist in the oxidation of ethylbenzene to acetophenone. the structure of the acid site. Other studies in which similar principles have been applied to other metal catalysts with encouraging results are reviewed by Langhendries et al. Efficient removal of water is necessary to prevent
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. too low under these conditions for commercial exploitation. The HPA leaches out of the former support. and a catalytic amount of acetic acid was also added. Thus. However. Isobutyraldehyde was used as a co-reductant. which has proved to be useful for conversion of ethylbenzene to acetophenone. This has the effect of keeping the cobalt dispersed so that there is no deactivation due to either precipitation or clustering. Recently. particularly in the terminal position.200 have recently reviewed developments in providing clean catalytic technology for liquid-phase hydrocarbon oxidations. Use of O2 + H2 and O2 + CO as Oxidants Several unusual oxidations have been reported recently. whereas the carbon atoms along the dodecane backbone are protected when the pore diameter is small enough. change the fundamentals of the business of producing primary alcohols and dicarboxylic acids such as adipic acid. A palladiumruthenium catalyst was used. The poor accessibility of the reactants to the catalyst results in low reaction rates. Das and Clark204 have reported a complex form of Co(III) immobilized on a chemically modified silica substrate. and the method has the added advantages that no coproduct acetone is formed. Researchers at Tosoh in Japan198 have demonstrated the oxidation of benzene to phenol using mixtures of oxygen/hydrogen and oxygen/CO.203 have developed chemically modified mesoporous silica with metal ions immobilized on a hydrophobic chain. The catalyst has also been found to be effective for the epoxidation of alkenes with air. and additional studies are needed.210 report on attempts to heterogenize these catalysts by encapsulating them in MCM-41 or microporous AlPO4-VPI-5 molecular sieves.206 designed a heterogeneous catalyst for air oxidation of cyclohexane to adipic acid based on FeAlPO-5 and FeAlPO-31.. in the work of Khenkin et al. Chromium-. Tailored molecular sieves have been put forward as oxidation catalysts. cobalt-.org Publication Date (Web): October 11. and selectivity require further investigation. high selectivity for cyclohexanol from cyclohexane is obtained over an FeIIIAlPO-5 catalyst. Although rates were better at 70 °C. Attempts to mimic enzyme action using iron catalysts. A notable feature was the high ratio of alcohol to ketone (as high as 5:1). Along similar lines. This probably implies in situ production of hydrogen peroxide. Vol. It is even more remarkable that Raja et al. Lempers and Sheldon (1998) question whether some of these catalysts truly function as heterogeneous catalysts. Eng. Kraushaar-Czarnetski208). The rates appear to be promising. 2000 | doi: 10. Res. although the catalytic activity was somewhat reduced. Raja and Thomas205 replaced a portion of the aluminum ions in molecular sieves with Mn(III) ions and demonstrated regioselectivity in the air oxidation of linear dodecane.200 Functionalized heterogeneous catalysts for the oxidation reaction have also been developed. but catalyst deactivation through the irreversible reduction of HPA remains a problem. The authors obtained selectivities to hydroperoxide + alcohol + ketone that are better than those obtained with homogeneous catalysts at similar conversion levels.211 report a vanadomolybdophosphate polyoxometalate supported on mesoporous MCM-41 with which they were able to get product selectivities in the oxidation of alkanes and alkenes similar to those obtained via homogeneous oxidation. Langhendries et al.209 used zeolite Y ion exchange with alkali metal ions to study the oxidation of cyclohexane. The catalyst is based on a CoIII framework-substituted AlPO. Dugal et al. to alcohols and carboxylic acids and can. However.
2%). and Fe2(SO4)3. Cr. taking into consideration aspects of chemistry. and phenazines. albeit for restricted olefins. and reaction temperature. possibly as a result of access limitations in the zeolite cage.5 and 6. Conclusions Liquid-phase air oxidation of important bulk raw materials like p-xylene. As the size of the olefin increases. etc. the cis isomer can be obtained predominantly. Chauvet et al.. 2000 | doi: 10. cis-Cyclooctene was oxidized in 100% yield to its epoxide with no sign of hydrolysis in contrast to.4-diacetoxy2-cyclohexene in high yield was obtained at room temperature. will be different.1021/ie0002733
. convert strained norbornenes to the epoxide. Higashijima213 claims that their method of hydrothermal synthesis is more effective and practical in comparison with the earlier methods. At 99% conversion. 13. the products consisted of terephthalic acid (58. No. on which the work of Iwahama and co-workers (section 6.4-dioxane-water in the presence of PdSO4. 2009 | http://pubs. [SiW11O39Ru(III)(H2O)]5-. In the case of 1. there are cis and trans configurations. This development is of interest in the context of the current search for environment-friendly processes and is an example of a “green” oxidation catalyst. A number of claims have been made in which porphyrin complexes are used as catalysts to convert olefins such as propylene. Higashijima213 has reported a novel water-soluble oxidation catalyst that is a ruthenium-substituted heteropolyanion. indicating interactions among several phenomena. V.. 39.3. in SC CO2 and Mo(CO)6 catalyst precursor with t-BuOOH. metal ion. because the entrapped complexes are prevented from dimerizing and degrading. W. the oxidation of cyclohexene where epoxide is converted to diol as well.8%). whereas trans-alkenes were considerably less reactive. trans-oct-2-ene was epoxidized almost exclusively to trans-2. such as pinane.
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. Olefins such as 1-octene. p-toluic aldehyde (0. 1 and 2-butene. etc. etc. Res. p-toluic acid (17. The oxidized H2A is reduced by hydrogen to regenerate the single oxygen acceptor. cyclooctene. in which a mixture of cis. This is an important result as it demonstrates that molecular oxygen can be used for epoxidation with low-valent transition metals from the Pt group and in the complete absence of any peroxidic structure element. There is very little information in the literature on this aspect. p-xylene at 200 °C in water as a solvent. A number of modifications have been claimed for conversion of olefins to ketones with Pd-based catalysts. The anion was salted out as the cesium salt from the hydrothermal solution. vinylcyclohexane. cyclohexane. type of reactor. in a nonhalogen-containing water solvent system. For examrple. Thus. and carbon dioxide (20%). which is shown to be effective for the oxidation of. butylene. The authors have investigated the effect of several parameters such as zeolite type. 12.214 have studied cobalt salophen catalyst encapsulated in zeolites. In the case of cyclooctene for instance. Woltinger et al. n-butane. reference was made to the selectivity of oxidation of cis. Mo. cumene. 2000
above. unlike the common Wacker cata-
lysts based on PdCl2 and CuCl/CuCl2. Methods of synthesis of these heteropolyanion catalysts are also simultaneously attracting a great deal of interest. It is expected that rates of oxidation of cis and trans isomers. In particular. as would be the case with the usual Wacker catalyst. These results are in contrast to the metal-catalyzed epoxidations of cis-olefins using an aldehyde and oxygen. Haas and Kolis180 have reported oxidation of cyclohexene. by manipulating the catalyst and the conditions of the hydrogenation of cyclooctadiene. no leakage was observed and the solid catalyst could be recovered and reused without loss in activity.3992
Ind. cyclooctene.. etc. are converted to the corresponding ketone.7). which is both scientifically interesting and commercially important. Chem. Similar results were obtained with the cis isomer as the starting material. cyclooctene. A recent patent from China212 refers to the epoxidation of olefins with oxygen in the presence of a single oxygen acceptor H2A. in the presence of the palladium-quinone system for the air oxidation of 1. where only the cis isomer reacts. can be analyzed on a fairly rational basis.and trans-stilbene. cyclopentene. Eggersdorfer216 shows that the air oxidation of pinane at 95 °C gives 2-pinane hydroperoxide.3-cyclohexadiene.3-epoxyoctane with a selectivity of 88% at 78% conversion. menthane. The product can be epoxide or alcohol when 70% aqueous t-BuOOH is used. cyclohexene. to industrially important products. ethylbenzene/isobutane. Mitsui Toatsu claims conversion of cyclooctene to cyclooctene epoxide. Wang et al. styrene. selected from diazo compounds. engineering kinetics. under similar conditions. in section 12.109 on the epoxidation of alkenes with a hydroperoxide generated in situ was discussed earlier (sections 6.7) and have obtained good activity and selectivity with many olefins. A notable feature of the results reported is the excellent stereospecificity of the epoxidation. the small pore sizes usually make them unavailable for large complexes. However. say. transStilbene does not undergo the oxidation reaction. the catalyst activity decreases.215 have shown that catalysts such as (CH3CN)2PdCl(NO2). etc. 1-octene. Stereospecificity in Organic Oxidations In the case of several hydrocarbons of industrial importance. H6PV3Mo9O40.org Publication Date (Web): October 11. even at 25 °C. etc. Similarly. A small amount of the diol was formed (about 4%). cyclododecene.versus transstilbene. probably because of steric effects.6%). The highest yields and fastest rates of diol and epoxide formation were observed with cis-alkenes.8. Cyclic olefins such as cyclohexene react relatively very rapidly. Eng. In this reaction the cis isomer reacts more rapidly than the trans isomer. for instance. Zeolites are interesting supports for oxidation with metal complexes. etc.and trans-epoxides is usually obtained. and a transition metal selected from Ti.acs. 1. if not exclusively. The work of Iwahama et al.3dienes. 11. the influence of temperature was found to be complex.111 have used new zeolites in which the cage size had been expanded as supports for encapsulating their Schiff base complexes that show good activity in oxidizing linear aliphatic olefins to their epoxides (see section 6. Idemitsu and Kosan have claimed conversions of 1-butene to methyl ethyl ketone in 1.. vinylcyclohexene. quinones. Vol.6) has been discussed earlier. cis. Another development of significance in the quest for direct air oxidation routes for olefins to epoxides is the use of N-hydroxyphthalimide (NHPI). which is used as a radical initiator for polymerization reactions.
Autocatalytic oxidation of cyclohexane mass transfer and chemical reaction. 1988. Prog. This is also the case for cyclooctene and cyclododecene where uncatalyzed oxidation gives high yields of epoxide. Eng.). Hofmann. 47 (9-11). U. A. C. In Kirk-Othmer Encyclopedia of Chemical Technology. J. No. (E. E. Emanuel.. G.-Sci. L. Hearne. D. Ind. There is considerable scope for further work. Liquid-Phase Oxidation of Hydrocarbons. 220. Ed.. 1979. 139. (Gulf Research and Development Co. 23. D. 1958. 209. 1988. Her Majesty’s Stationery Office: London. G. Untersuchungen zu einem alternativen syntheseweg fur mtbe.. J. J.058A1. (47) Sridhar. A. 317. 1974.. G. S. F. Chem. C. E. Eng. (10) Berezin. O. 1977. Technische Hogeschool Eindhoven. W. Sridhar. (44) Wild.. O. W.). translated by K..408. R. (49) Suresh. 1988. Process Des. T. Carvalho. R. 75. K.S. Solubility of nitrogen and oxygen in cyclohexane. efficient processes for making cyclohexanone and speciality chemicals through cyclohexene epoxide. Schultz. Eng. W. 21 (2). H. 1980. (16) Castellan. Ind. R.K. The Oxidation of Cyclohexane.). O.. W. Adipic acid in one step. Today 1991. DeCoster. A. 11 (2).. G. A. 1995. (19) Onopchenko.. Gas holdup and bubble diameters in pressurized gas-liquid stirred vessels. 1999. Sci. H. (26) Russell. G. J. Hydrocarbon Process. O. (17) Tanaka. E. E. J. M. R. Van’t Hof. Chemicals and long-term economic growth. Pergamon Press: Oxford. (4) Carra. Patent 4. V. Kaarsemaker. Moniuk. E. Patent 2.. 183.. 69. Methodology and scope of metal bromide catalyzed autoxidations of hydrocarbons.. K. (31) Baumgartner. Heterogeneous Reactions: Analysis.. Autocatalytic oxidation of cyclohexane modelling reaction kinetics. 59. Eng. 114. Chem. H. cyclohexenone. Chem. V.... (30) Lutz. Chem. Eng. 47 (12). Sci. P. Landau. E. Cavallaro. Asselineau. K.. 1970. Catal. 22 (1). Jones. J..S.. Sridhar. Horlenko. 39. (25) Schuchardt. Ind. Potter. Eng. II. Eds.907.). translated by C. K. (50) Suresh.. (6) Farkas. Petrochem. Fundam.. 1974. U. Santacesaria. O.. A. J. Product sequences in liquid-phase oxidation of paraffins.. 19..-Chem. L... Reaction engineering of emerging oxidation processes. L. 34. E. Lindley. T. 1994.. 1980.. Am. Simo. T. Baldyga. Ph. etc. 11 (1).). Eng. E. Trambouze.. 1972. John Wiley: New York.S.
(24) The Flixborough cyclohexane disaster: Report of the court of enquiry. Weber. van Landeghem. (48) Suresh. I.. Wojcik. Seekircher.-J. Simandi. Designing a cyclohexane oxidation reactor. Chem.. Res. I. 1961.. T. S. VCH: Weinheim. 1968. Eng. J. J. Catal. Patent 3. 11. Plenum Press: New York. 655. 1991. P. U. AIChE J. Saffer. 64. Mesich.528. 1966. My fifty years in catalysissThe Eugene J. D. Eng. G. U.. 1983. 21. Why is it interesting to study cyclohexane oxidation? Synlett 1993. (28) Winkler. Ind. U. K. Rostami. Allen. J. L. 1998. (Shell Oil Co. The effect of mass transfer on selectivity. 1983. Chem.. K.512. p 33. A. 1999. translated by B.. (38) Hobbs. M. Hydrocarbon oxidation. Westerterp. M. A. 34. Erdoel Kohle.. 21. U. oxidation under biphasic conditions. 645. Process for converting butane to acetic acid. 1981.. Eng. J. 33. J. 69. Oxidation of isobutane in the dense phase and at low oxygen concentration. Soc. (5) Mills. 1347. Engineering aspects of gas` liquid catalytic reactions. Today 1999..902.406. Chem. as in the production of benzoic acid from toluene. T. Ind.. E. 1978.942. 66.. (34) Steeman. Bart. 20. 1961. V. 78. 44 (11). W. G. (8) Weissermel. Thesis. 15.. M. E. Influence of order of reaction rates on selectivity. K. DuPont de Nemours). Houdry Award Address. 1984.. Busson. Chem.. M. Patent 3.. E. Hydroperoxides in hydrocarbons liquidphase oxidation. J.K. (35) Hobbs. Arpe. H. Clarendon Press: Oxford. K. 1989. Rate of oxidation of aralkyl hydrocarbons. 21. Eng. D. 51. Denisov.. Sridhar. E. 1972.. O. Sci. C. 2nd ed. 17. 13. 1975. (7) Chemistry and Industry.032. 131. Bedford. Vol. Storm. D. R. 2559. Industrial production and use of adipic acid. 53 (8). T. G. (51) Oyevaar. 13. 2691. G. Kochi.. A. Process for oxidation of isobutane.082. Krzysztoforski. A. Development of M-C process.).S. 47 (2). suggest new directions. Mass transfer and solubility in autocatalytic oxidation of cyclohexane. (14) Arora. J. Elsevier: Amsterdam. 23 (2). 1968. N. L.S. Selectively oxidise cyclohexane. Wiley: New York.. Denisov.845. D. Method for the production of tertiary-butyl hydroperoxide.Ind.430A1. 237. Potter. Oxidation of isobutane under supercritical conditions. (39) Danckwerts. G. J. (11) Winkler. K. H. Dev. (46) Sridhar. WO Patent 9.. C. Catal. Polar effects in free radical reactions. Rev. 34. Res. Prod. Gottlieb. Spinace. Patent 2. 1978. 1967. Vol. Chem. A. R. Industrial Organic Chemistry. Patent 4. (Atlantic Richfield Co. S. 2: Fluid-FluidSolid Reactions.. 2000 | doi: 10. 21. Chem. U. F. (12) Partenheimer. E. P. Sci. J. S. T. Vassiliou. (29) Grane. Vol. E. Mass transfer with chemical reaction... Consecutive reactions in heterogeneous systems.. Erdgas. 2009 | http://pubs. Process for treating cobalt catalyst in oxidation mixtures of hydrocarbons to dibasic acids. 1961. J.. T. Dev. 555. Hazzard. (33) Brejc. 4. tert-Butyl hydroperoxides. H.. R. O. (3) Hobbs. J. Chem. Catalytic oxidation of alkyl substituted aromatic compounds.570. Chem. (45) Sridhar. 9. (36) Alagy. References
(1) Emanuel.. Interfacial area measurements in gas-liquid agitated vessels. A pilot plant study of the oxidation of cyclohexane with air under pressure. J. Hearne. Metal-Catalyzed Oxidations of Organic Compounds. J.. P. Germany. C. 1993... AIChE J. Gas-Liquid Reactions. Cha. D. M. (Shell Oil Co.. A. Hoftyzer. E. C. Strategies such as oxidation of isobutane under supercritical conditions. 1983. Eng. A. J. (22) Alagy.S. E. V.D. 590. K. Potter. Potter.. G. cyclohexenol. Rostami. Predicting diffusion coefficients.
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. D. C. A. (Shell Oil Co.. M. Examples and Reactor Design. Patent 4.-Sci. M. AIChE J. G. Sharma. (43) Doraiswamy.940. E. 1975.. Onore. M. (Gulf Research and Development Co. D... A. H. (15) van de Moesdijk. J.461. Oxidation of cyclohexene may well open up new. 631. (18) Tanaka. Z. Chaudhari.. Rev. 1967.245.. Kroschwitz. Consecutive reactions in heterogeneous systems. Hydrocarbon Process. R.). L. Sci. (21) Dassel. F. Sci. R. H. Eng. Eng. H. E. Chem. C. Sridhar. (Twentyfirst Century Research Organization). D. Ed. Potter.. The Catalytic Reduction of Nitrate and Nitric Oxide to Hydroxylamine: Kinetics and Mechanism. J. U. Academic Press: New York. H. (42) Van de Vusse. T. S.S. R. 1956. T. Potter. G. (27) Schultz. photooxidation.acs. Mass transfer rate-limitation effects in liquid-phase oxidation. E. (41) Van de Vusse. Liquid-phase oxidation of cyclohexane modeling and industrial scale production simulation. Converting butane to acetic acid. I. Catal.org Publication Date (Web): October 11... Sci. H. The use of the chemical method for the determination of interfacial areas in gas-liquid contactors. U.S.. (20) Vassiliou. Methods and devices for separating catalyst from oxidation mixtures. Dudgeon. U. etc. Chem. Liquid-phase oxidation of isobutane. Mesich.. D. 4th ed. 1941. 1992. Patent 4. Vol. 1966. K. 2000 3993
There is potential for improving industrially important reactions/reactors.644. The Netherlands. (Shell Oil Co. CHEMTECH 1974. Maizus. R. B. Drew.. WO Patent 9. (37) Pohorecki. J. Process Des.. T. A. Dev.. Catal. Ed. 14. Brennst.. (32) Foster. M. 713. 16.404. N. Seekircher. Eindhoven. 1977. AIChE J. Rosenberg. 1047. (Twenty-first Century Research Organization). 1972. Today 1995. 1980.408. Eng. Chem. John Wiley and Sons: New York. (9) Loder. 55. Sandler. 1966. Chem. (40) Van de Vusse.. C. Foster. (2) Sheldon.081.. 48. Gerberich. (23) Ciborowski.1021/ie0002733
. McGraw-Hill: New York. Eng. Studies in Surface Science and Catalysis Series. Dudgeon. In Dioxygen activation and homogeneous catalytic oxidation. Z. Potter. A. (13) Landau. 81. A. Adipic acid by single stage. U. Dassel. R. Eng. Van Duyne. 53. N...
M.245. (Twenty-first Century Research Organization). 55 (1). translated by A. Ber. Patent 5. P. 17. Org. O. Une analyse generale et quelques exaples vecus.1021/ie0002733
. J.. Fujimoto.).. 137. (56) Partenheimer. R. Commun. L. Hofmann. M. (63) Wen. N. U. Use of titania or zirconia in the preparation of tertiary butyl alcohol from tertiary butyl hydroperoxide. J. 12. (95) Hendry. (59) Wen. A. U. Pergamon Press: Oxford. K.
(52) Oyevaar.. In Ullmann’s Encyclopedia of Industrial Chemistry.221. 12. 1988. Res.). J. A.. M. 1217. 1995.. 2. Germany. JP 2000. Henn and I. DuPont de Nemours). Cosserat. Propylene oxide.244. Kokai Tokkyo Koho. In The oxidation of hydrocarbons in the liquid phase. Industrial Organic Chemistry. Patent 6.. McHugh. Chem. Abstr. J.. Eng. Preparation of tertiary butyl alcohol by catalytic decomposition of tertiary butyl hydroperoxide over aluminasupported palladium/gold. 203105. B. P. Shen. Preparation of cyclododecyl hydroperoxide. J. (98) Shah. 1988. Air oxidation of supercritical phase isobutane to tert-butyl alcohol. Kingsley.. 1992.acs. Process for converting cyclohexane to adipic acid. O. O. H. S. Free-Radical Chem. Chem.. Commun. Herrmann. E. Seidel. 1996. P. 13. Pergamon Press: Oxford. 165. I.. 2000. Germany.. 1995. cyclohexanol and cyclohexanone by saturation of cyclohexane with oxygen and reaction in a tubular reactor. Ph. Chem. (57) Weissermel.org Publication Date (Web): October 11. Charpentier.. Sci. (84) Fan.D. 1984. The cobalt/zirconium-catalyzed oxidation of cyclohexane to adipic acid.. Krokoszinski. Ed. Vol. 52 (24). S. Sentenac. Clayton. A22. Melero..1 to 8..S. 49. M. Master’s thesis. Hirofumi. W. (62) Reimer. C. 4... D. R. Continuous preparation of cyclohexyl hydroperoxide.. Australia. Supercrit. N.414. 1939. 121 (2/3).. Eng.. (80) Nelson. Wiley: New York. 74.. Ein verfahren zur herstellung von tertiarem butanol aus Isobutan... M. Dev. 1994. (70) Kulsrestha. N. Marcel Dekker: New York. 1993. Westerterp. Chem. 25... Chemical oscillations and instabilities: nonlinear chemical kinetics. P. U.... G. Elvers. (91) Andrigo. (73) Gusevskaya.. Eds. Zaikov. 1995. Sanderson. E.S. Jpn. 1145..S.. Sridhar. (BASF AG). 26. Mayo..441. Direct conversion of cyclohexane into adipic acid with molecular oxygen by N-hydroxyphthalimide combined with mn(acac)2 and co(oac)2. 4593. (53) Gray. On the mechanism of autoxidation of cyclohexene.. translated by C. Singh. 255. Hydroquinone. M. (Amoco Corp.163.. Ravenscroft.220. Serrano. U. Potter. Catalytic conversion of cyclohexyl hydroperoxide to cyclohexanone and cyclohexanol. (90) Suresh. (79) Grieken. I. Monash University. Chem. Grosskinsky. (74) Production growth sputtered in most sectors. German Patent DE3403410. S. Vergnes.. L.... Rostami. L. (Texaco Inc. Synthesis of carvone from limonene by one-stage process.. A. Sci. S. A. Palladium(ii) catalyzed oxidation of naturally occurring terpenes with dioxygen. R. J. Sanderson. Smith.-M. Methods of making intermediate oxidation products by controlling transient conversion in an atomized liquid. Scott. G. B. (68) Steinmetz.S. Ovejero. One-step air oxidation of cyclohexane to produce adipic acid. 4th ed. Chem. E. Springer-Verlag: Berlin. 2000 | doi: 10. Entropie 1983. 25 (1). Patent 4.. E. VCH: Weinheim. Interfacial areas and gas hold-ups in gas-liquid contactors at elevated pressures from 0. Fluids 1998. Yamanaka. Chem. (82) Witzgall. Electron transfer with aliphatic substrates oxidation of cyclohexane with cobalt(III) ions alone and in the presence of oxygen. Pontal.. (83) Shen. 1996. (60) Brunner. K. Dev. 49. D..800. J.. Abstr. High rate process for preparation of cyclohexanol and cyclohexanone.. 842. 1973. A.453. News 1996. Ishii. C. Absolute rate constants for reaction of oxyl radicals. H. Vol. Clayton. Biotechnol. Challenges for the crude C4 stream.. U. M. (London) 1993. Mol. 57. D. J. (61) Guo. Ed. Emanuel. 2000. Williams. C. E. Monash University. A. (67) Dassel. V. S. Sci. Patent 5. Stadelhofer. 1984. 46 (5/6). (94) Onopchenko. Chem. A lumped kinetic model for liquid-phase catalytic oxidation of p-xylene to terephthalic acid. H. R. J. (87) Emanuel.. Bos. Chem..491.). Oxidize safely with pure oxygen. J. J.K. C.K. 132. (100) Criegee. 2009 | http://pubs. H.. U. Eng. An. Uncatalyzed oxidation of cyclohexane in a continuous reactor. (58) Tolman. K.. A. In Catalysis of organic reactions. Catalysed oxidation of cyclohexane in the liquid phase. 1972.. (93) Suresh. A. Sci. Maizus. (64) Schulz. D. Chem. W. (69) Iwahama. Sridhar. (54) Cao. Eng.K. T. M. Chem. p 321. In Kirk-Othmer Ency-
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. (Texaco Chemical Co. Ges. 1991. (92) Botton. R. G. T. (86) Sanderson. P. 1965. Eng. A. Schulz. Lafferty. I. J...M.-J.502. M. Chem.). 48. J. 2000
clopedia of Chemical Technology. 1993. Onopchenko.S. 1.. Adv.889. 1986. W.. Oxidation of Organic Compounds: Medium Effects in Radical Reactions. 1993. 49758. 11. T. K. Victoria. (78) Torck. E.. Unterzuchungen zur flussigphasenoxidation von ¨ ¨ isobutan zu tertiarem butanol.. Nappa. Patent 5. A. 2000... Victoria.. 61 (10). Potter. Marquis. Dassel. 41 (1). Druliner. U. J.D... K.. Conception.3994
Ind... AIChE J. Homogeneous Kinetics of Cyclohexane Oxidation. U. J.. Syz.. One-step oxidation of cyclohexane to adipic acid. Arpe. Chem. N.. D. Erlangen. M. 1993. G. T. R. J. Mahajani. (96) Brejc. 18 (2)..145. J. Clayton. U. H. Effect of supercritical conditions on the oxidation of isobutane.). Shankar. E.). Technol.D. M. 1994. J. Mol. Sumner.. G. Sharma. Panfilova.. DeCoster. Catal. S. Nakayama.. J. R. A. Catal. (Texaco Chemical Co. Tartari. Caimi. Catal. A chemical model for the Amoco “MC” oxygenation process to produce terephthalic acid. (76) Krumenacker. Org. 742. P. J. Clarendon Press: Oxford. Lindley. 50. G. C. K. M. J. S.. Universita Erlangen¨ ¨t Nurnberg. 4. J. E. (RPC Inc. 1993. P. Mol. Morbidelli. Kinetics of Liquid-Phase Oxidation of Cyclohexane... Ed. (72) Wang. A. D. (65) Park. Roberti. Sharma. K. (Gulf Research and Development Co. W. Australia. J. Pisu. Chem. A. 1990. (71) Kuroda. (99) Kamneva. Ind.-Ing. Uguina.. Wiechern. Chem. cf. E. 1991. R. 72. Eng. M. 1995. G.. Preparation of MTBE from TBA and methanol. M. Patent 4. Ind.. B. Miller. Dtsch. D. 36 (1).037. G. R.. 1997. K. 1997.S. Monash University. 3rd ed. 39. 5th ed. A. H. C. Ph. G. Hawkins.206. Y. Chem.. Magnussen. D.. 1998.. 1976. Yamazaki.01473. 40. F. T. K. Reactions in supercritical fluids. N. Autoxidation of cyclohexane and its autoxidation products. Process Des. 1990. resorcinol and catechol. Y.. 38 (21). Org.. N. (Texaco Chemical Co. Lindner... Sci. Vassiliou. Thesis. Process Res. 1989. J.. Onestep synthesis of MTBE from t-butanol and methanol using fluorophosphoric acid-modified zeolite catalysts. Schulz. (E. U.. A.. R. M. U. Thesis. Y.-G. 1799. K. G.263. O. ¨ (97) Subramaniam.. Y. U. Gonsalves. (66) Vassiliou. ref 99.S. (85) Sanderson. K. S. F. U. H. A. Australia.918. Fait. 2511. p 219... U. D. Chem. Y. Vol. J. Chem. Schuetzle.-M. Ph. (75) Franck. 39. Mueller.S. A 1997.. M. W.401. 1981.. VCH: Weinheim. J..414. Sridhar. Y. 129. Constantini.). A. Ittel. (81) Knifton. R. 129. G.. E. D. 3729. Methods and devices for controlling hydrocarbon oxidations to respective acids by adjusting the solvent-tohydrocarbon ratio. R. (88) Suresh. Gould. F. F. H. Victoria. J. A.-C. 2000.. A.. S. Pilz.). R. Jr.S. (Texaco Chemical Co. L.S. No. CHEMTECH 1996.. Z. Phenolacetone process: Cumene oxidation kinetics and industrial plant simulation. 131. Y. (77) Kahlich. Kroschwitz. M. 1986. Goroff. S. Germany. Linchan Huaxue Yu Gongye 1997. J. R. X.. patent 5.-Tech. D. J. Patent 5. D. 49 (24B). Syojyo. H. Blackburn. 5775. 1992.. 1990.. D. 1998. J. Storm. (89) Howard.. Evans. U.. Mass Transfer and Chemical Reaction in the Oxidation of Cyclohexane. S. Industrial Aromatic Chemistry. E.0 MPa.. (55) Roby.. U. Thesis. 47 (9-11). D. Synthesis of MTBE from isobutane using a single catalytic system based on titanium-containing ZSM-5 zeolite. Patel. A. G. Isobutane oxidation in the liquid and supercritical phases: Comparison of features. 1990. d’Oro. K. extrapolation et ameliorations potentielles de certainsreacteurs de l’industrie chimique. V. Aldrich. 1988. Krusic. Sakaguchi. Knifton. Patent 5.. L39. Cheng. Eng. Eng. Z.078. E. M. Flygare. Production of tertiary butyl alcohol from isobutane. 1179. 1997. C. Patent 5. A. J.
. Ponzi.. Eng. O.. (122) Krishna. Mallat. Y. Mashelkar. M. Van Dierendonck. 197. Eng. (110) Biela.-M. Soc. Potter.. (105) Ishada. Gas-liquid au´ toxidation reactors. Sci. G. 1974. Process development strategy and methodology. Academic Press: New York. Ralek. G. Ishii. S. Reaction rate pulsation during ´ liquid-phase oxidation of hydrocarbons. Determination of nitrogen diffusivities in cyclohexane over a wide temperature range. Ilavsky. D. AICHE J. 1978. M.. 12 (1). Karandikar. L. J. Chem. Pressure dependence of liquidphase mass transfer coefficients. Silverstein. Part I: The interfacial area in gas-liquid contactors with mechanical agitation. I. N. Haringa. Eng. Chem.. H. M. A. Chem. Eng. 1982. 522. Mass transfer parameters of O2 and N2 under elevated pressures and temperatures: A statistical approach. Danckwerts.. Krishna. (106) Davis. N. W. Sci. D. Chem. Chemical Reactor Analysis and Design. Interfacial areas in agitated gas-liquid contactors. Eng. Res..87. T. Hatta. W. (146) Darde. 33. 1970. Carr. Coulaloglu. M. 3879. Ed. Sharma. C. Paludetto. 2639. 1992. Eng. Process. 26. Eng. B. Wilkinson.. P. Chem. J. Wiley: New York. R. Bell. Eng. Sci. 151. M. 43. (119) Occhiogrosso. Chem. (135) Kling. Ind. M. Strategies for multiphase reactor selection. 1983. Vol. Process for the preparation of dodecanedioic acid. Eng. 22. Models for mass transfer with chemical reaction in concentrated fluid-fluid dispersions. de Kraa. (152) Hronec. O. Gas holdup and mass transfer in bubble column reactors operated at elevated pressure. T. 42.. Fukuda. 1987.Ind. 1. AIChE J. R. (148) Florez-Fernandez. Blauwhoff..026. Kokai Tokkyo Koho JP 09.. Eng. T. 443. L. (E. H. Zaidi. 2000 | doi: 10. Eds. R. R. 87 (21). 496. T. Eng. Spek. G. I. E. Chem. 889.. (120) Kingsley. 18.. Vol. H. 78. 1990. E. Mill.. Int. 2478. 57. R. Z. Chem. De La Rie. Van Swaaij. Chem. Effects of pressure on liquid-phase mass transfer coefficients. (134) Versteeg.S. The kinetics of the reaction between CO2 and diethanolamine in aqueous ethyleneglycol at 298 K: A viscous gas-liquid reaction system for the determination of interfacial areas in gas-liquid contactors..236. F. Serebryansky. 1242. (114) Suresh. (107) Wilhoit. 4824. Chem. Patent 5. J.-F. He. Eng. 1974. 223. (109) Iwahama. Res. Eng.... Blyumberg. A. 50. John Wiley: New York. Ind. 1986. R. A. Sridhar. Chem. L. M.. Wei.. M. S. T. Shah. In Advances in Chemical Engineering. M. D. 157.. Patent 5. N. Appl. Preparation of high purity 1. T. 1994. R. R. S. T. R. 1541. B. U. K. Eng. A. Sharma. Z. (144) Wilkinson.. 2009 | http://pubs. (113) Sridhar. Chem. Process for the preparation of dicarboxylic acid.-C. P. 1994. 1999. Today 2000.S. 19. Eng.. Van Dierendonek.. 1983. Westerterp. 1997. 4029. L. K. R. Al’tshuler. 52. M. L. (132) Teramoto. Terephthalic acid production using evaporative cooling. 1972.). M. P. Commun. Sci. Baiker.-G.. Eng. Chem. Ono. (E. T. T. (112) Mayo. (130) Deimling. D. Trans. 38 (4). (137) Tarmy.-X. Inst.. 2299. R. Br. (116) Tekie. 544. 1974. J. Chem. I. M. O. (141) Letzel. (123) Sie. Process development and scaleup: 1. J.. 115. P. A.. M. Sakaguchi. 52 (9). Eng. Ikeda. Y.523. Chem. M. 39. Chem. Tai. Sci. F. W.. Eng. K.. Mass transfer coefficients and solubilities in for hydrogen and carbon monoxide under Fischer-Tropsch conditions.3cyclohexadiene from cyclohexene. F. L. R. Physical rate processes in industrial fermentation. 1994. (140) Oyevaar. 105. Vladimir.219.. 893.. A. M. 1984. J. Eng. Chem. Chem. H. M. Arluck. 465. Patent 5. A. Potter. R. J.. L. 1978. H. Allylic oxofunctionalization of cyclic olefins with homogeneous and heterogeneous catalysts. 42 (10). S. 1991. G. D. 1984. 1991. M. U. J. I. 905. 46. van den Bleek. Li.. (104) Ishada. 962. 1987. The effect of diffusivity on gas-liquid mass transfer in stirred vessels. R. K. Nishi.. 54. Inst. 253. P. Chem. Selectivity in hydrocarbon oxidation. N. 1995. 1968. Westerterp. Heat Mass Transfer 1962. J. K. M. 36. Sci. M. J. Hydrodynamic characteristics of three phase reactors. Kokai Tokkyo Koho JP 07. Wang. Charpentier. T... B. 1990. H. Mann. Epoxidation of alkenes using alkyl hydroperoxides generated in situ by catalytic autoxidation of hydrocarbons with dioxygen. McHugh. Int. Feng. Xia. (151) Froment. 15. (153) Jensen. 1995. P. Bischoff.-P. (128) Tekie. C. 1965. 1998. vinylcyclohexane and 4-vinylcyclohex-l-ene. Rate oscillations in cyclohexane oxidation.. (102) Murphy.. 14. 468.. Chem. E.-D. O. 1984. 3283. Chang. 54 (18). Chem.. (145) Oyevaar. A. K. J. Carra. 2000. Am.. A systems approach to multiphase reactor selection. L. M. A.165. USSR 1956. Morsi. 1975. M. Kulkarni. F. M.. R.. (124) Calderbank. Sie.. E.. 11. 29. (142) Krishna. Teranishi. L. Design parameters estimation for scale-up of high-pressure bubble columns. P. M. A new type of oscillating reaction: Air oxidation of benzaldehyde. K.. 39 (5). Vol.. Eng. p 201. 45 (11). Eng.. 1103. A. 47. 49 (24A). 29. 699. K. Uber die dynamik der blasenbildung beim begasen von flussigkeiten unter druck. Sci.. (136) La Nauze. Sullivan. 1996. 10 (4). 35. 3967. E.. B. J. J.. 1993. Unpublished work. L. U. P.. Des. 337. T. M. Inc. T. II. R. 1215. Chem. 2237. Org. The liquid-phase oxidation of propane. Carr. No. Y. Soc. 1980a. (121) Krishna. Harris. Hydrodynamic properties of the Fischer-Tropsch slurry process. (125) Westerterp. W. Van der Sluijs. J. J. Eng. Pritzkow. 221.. Sci. Commun. Morssinkhof. (Praxair Technology. Gas absorption with radical multiplying chain-type reaction. E...S.. Chem. Chem. V.. Part I. G. F. C. Chem.-Y. 1997. Proc. (150) Suresh.461. SchmidtRenner. A. A. (149) Suresh. Sridhar... (126) Sharma. J. Mol. R. G. Mass transfer and bubble size in a bubble column under pressure. Eng. 1545. Sci. (143) Wilkinson. Mann. 1989. Y. (131) Kishinevsky. 2000 3995
(101) Van Sickle. H. Sci. 683.. 1964.. Eng.acs. Chem. 1991. Gas-liquid mass transfer in cyclohexane oxidation process using gas-inducing and surface aeration agitated vessels.. M. U. Castleman. Critical-mixture oxidation of cumene. (108) Sridhar. Mayo. (139) Deckwer. Roby. K. M. K. 211. Liquid-phase oxidation of cyclic alkenes.. J. Potter. Shah. 1986. Sci. Potter. 2000... Eng. Interfacial area and gas hold-ups in bubble columns and packed bubble columns at elevated pressures. R. H. Rev. 49 (9). 26.. In Recent Trends in Chemical Reaction Engineering. J. AIChE J. Sharma. L. Catal.. Morooka.. M.474. 325.. J. Mahajani. DuPont de Nemours). (117) Spielman. S. T. Louisi. L. Contribution to the analysis of selectivity in gas-liquid reaction. J. W. (127) Lynch. AIChE J. 37 (8). p 83. 1999. P. experiments at atmospheric and elevated pressures. M. J. Chem. 1958. Sci. A. Chem. (118) Bulygin. Trans. K.1021/ie0002733
. Sci. E. Sci. Chem. A: Chem. J.
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. (138) Idogawa. Autoxidation of vinylcyclopentane. 1980. 1417. 1963. Dev. 2491. Li.-R. E. 127. Chem.. M. C. L. Sridhar. Trans. M. 39.S. 41 (9).. T. O. 5. K. Chem. Eng. Rodin.. Preparation of 2-cyclohexen-1-ol by hydrogenolysis of cyclohexene hydroperoxide in the absence of hydrophilic solvents. Eng. 18. Chem.. Preparation and catalysis of NaY-encapsulated Mn(III) Schiff-base complex in the presence of molecular oxygen. 1983. R. Literature and theory.. 8. H. Chemical methods for measuring interfacial area and mass transfer coefficients in twofluid systems. I. M. 73A. Catal. Eng. 14. M.. (133) Yoshida. W. Chan. B. J. K. M. Chem. 1987. T. Cyclohexane oxidation: Interaction of mass transfer and chemical reaction. S.. Jpn.. D. R. R. Chem. Gas bubble formation at elevated pressures. 519.. (103) Mahajani.. Inst. B.. A. Sci. (129) Albal. K.. Uncatalysed oxidation of cyclohexene. Suo. 30.. Jpn. 1999. F.. H. 1992. S. S. Solubility and mass transfer of CO and H2 in Fischer-Tropsch liquids and slurries. The mechanism of mass transfer at the gas-liquid interface with vigorous stirring.org Publication Date (Web): October 11. (111) Wang. Chem. J. Eng. P.. 36. S.561. Int. Eng. 15 (4). Behaviour of bubbles of the air-water system in a column under high pressure. L...622. Van Dierendonck. Narasimha. Interfacial areas in gas-liquid stirred vessels.. Oxidations of R-methylstyrene at 110-160°. S. Gas absorption with autocatalytic reaction. Eng. Morsi. (115) Morbidelli. T.. 163. Midoux. W.. M.. R. Arakawa. DuPont de Nemours). Y.. Shouten.. C. (147) Sim... A model for gas holdup in bubble columns incorporating the influence of gas density on flow regime transitions. Catal. Van Dierendonck.. Chem. M. Ihsan.. Ono. Prakt. D. 19. Chem.. Krishna.. Am. Y.
Clean Prod. Tumas. Chem. (176) Dakka. Wacker oxidation of alkenes using a fluorous biphasic system.. 26 (6)... D. Effects of ultrasound on catalytic processes. Quaternary ammonium salts. CHEMTECH 1995. Catalytic direct oxidation of propylene to propylene oxide. Rev. 69. 2000. 17.. Sels. (197) Johnson. P. Chem. Cantrell. L.
(154) Roelofs. H. Jacobs. (159) Sridhar. (163) Ito. Process for the manufacture of benzoic acid and salts by phase transfer catalysed oxidation of toluene. (201) Kesavan. (187) Sanjuan.. M. Selective oxidation of ethylbenzene by dioxygen. Russ.1021/ie0002733
. Kurusawa. 8. Eickhoff. (200) Langhendries. Jensen. (175) Matienko. W. Kumar. A. E. Roucoux. 2083. (194) Murahashi. I. K. 3521. R. (164) Dobler. F. L. G. Aerobic oxidation of terminal olefins to methyl ketones catalysed by water soluble palladium complexes. Chimia 1995. 11. John Wiley: New York. 1641. 658. Improve reactions with hydrodynamic cavitation. 1. 598. B.. Chem. Nov 28-29. 1995. 43 (8). Genet. 129. 41. Catal. Mehltretter. A. Saha-Moller. J.. Sivanand. PCT Int. M. Catalytic asymmetric dihydroxylation of R-methylstyrene by air. Soc. Daun. I. Eur. L. I. Catal. L. Vol. J. 1999. W. A. (202) Vanoppen. E. Wasserman. H. 159.. Org. CHEMTECH 1996.. 372. 2359. Tetrahedron Lett. Kolis. 38. Wertgen.. I. Vesicle controlled selectivity in photosensitized oxidation of olefins.
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. A. Rouxlet. L. Organometallics 1998. A. Schrier.. Chem. 46 (4). Ruthenium colloids: A new catalyst for alkane oxidation by TBHP in a biphasic waterorganic phase system. Bull. P. P.. G. Chem. Eng.. I. C. 1998. 45.. (192) Krief. Koltypin.. Processes 1998. Commun.. 38 (23).. Chem. Topics in Current Chemistry 1983. 1242. P. (198) Otake. Appl. R... Chem.. Gedanken. H. 1998. 1998. J.3996
Ind. 1993. C.. Int.. J. New types of catalytic oxidations in organic synthesis. M. W. Atom efficient oxidation of alkenes with molecular oxygen: synthesis of diols. Symp. 1997.. G. Chem. Tetrahedron Lett. 1999. R. I. M. Chem. 3026. Ed. Takahasi. Chem. 2(4). (193) Li. TX.. V. M.. 126. Soc. Patent 717025A2. (190) Bloodworth. (170) Imre. 173. Epoxidation of propylene and direct synthesis of hydrogen peroxide by hydrogen and oxygen.470. 43 (8). Matienko. Glaze. 1999. Catal. H. Bull. B. Highly selective formation of tert-butyl hydroperoxide from the reaction of isobutane and O2 in a zeolite under visible light.: Houston.. D. New catalytic system for selective oxidation of olefins to ketones.. A. Int. 2000
(177) Pandit. Wertgen. (166) Pozzi. E. Catal. 445. 118. H.. G. A. D.. Chem. Kroschwitz. Selective oxidation of ethylbenzene by dioxygen in the presence of complexes of nickel and cobalt with macrocyclic polyethers. A. Mosolova. Ger. H. De Vos.. 1974.. H. 48 (22). G. 38 (1). Quici. A. Macrocyclic polyethers. Patent 717025A3. 95187. (174) Matienko. (179) Sulman. P. Organic-water interfacial synthesis of R-tetralone using nickel-tetraethylenepentamine complex catalysts. J. Russ. Chem.org Publication Date (Web): October 11.2. Russ. L.. Catalytic aerobic oxidation of cycloalkanes with nanostructured amorphous metals and alloys. Angew. Angew. H. R. L. G. M.. 43. A. Vol. Mass Transfer in Cyclohexane Oxidation. Part 1. Ser.. Russ. S. D. G. A. Gulf Publishing Co. 1995. T. Catalytic conversion in water. 2. L. Morita. Jacobs. R. 1998. G. R. G. Chem. Cobalt tetraarylporphyrin-catalysed epoxidation of alkenes by dioxygen and 2-methylpropanol under fluorous biphasic conditions. 1337. Int. 165. 293. Arends. 1983. 6667. T. 49. A one-pot conversion of olefins to R. 46. Pandit. C. (171) Imre. F.. What went wrong?. H. (165) Betzmeier. N. A. 1989. M. J. M. A mild preparation of polyfunctional ketones. (180) Haas. Japan. (188) Yoshida. W. C.. Composition catalysts of ethylbenzene oxidation based on bis(acetylacetonato) nickel(II) and phase transfer catalysts as ligands. L. T. B. R. Baron. Mosolova.. Chem. (195) Adam. Holderich. A.. Chem. Int. Liquid-phase oxidation of olefins to olefin oxides with improved product separation. 1996. Y. 36. 6329. 4th ed. Engl... (157) Kletz.. Lhermitte. J. Europe J.. 59 (2/4). Eng. Pollock. 560. G. Photocatalyzed oxidation of hydrocarbons in zeolite cages. 1015. Eur. (172) Skibida. 1999. Int. 1085. Abstr. (162) ten Brink. (182) Lindner. Mosolova. (178) Gogate.. Process for the preparation of carbonyl compounds by catalytic oxidation of olefins and catalysts in microemulsion. Res.. K. 339. F.. (186) Blatter. R. D. Eur. Eng. I. A.. C. 445. Bull. 1995. Schomacker. Neftekhimiya 1998. 1996. Sasson. Angew. 4189. Sun. Direct oxidation of olefins to olefin oxides using less solvent. Types of oscillations in chemical reactions. E. Ed. Sivakumar. R.. No. Zoran.. T. Chem. P. H. Thesis. M. Bull. Commun... (183) Lindner. H. Australia. 1998. 1999. Russ. Am. V.469.. H.. 1998. 24. M.. Garcia.. A. S. Colaux-Castillo. 111. B. T.. M. Gurel. Eng.. Synthesis of (n+5)-bromodioxabicyclo[n. 1332. S. Abstr. 40. 1996. W. Perkin Trans.. I. 1477.1] alkanes. W. (196) Leuenberger.: M. Commun. 385. S. DeVos.. 1375. an easy synthesis of 2-cyclopentenone and related compounds. Papadogianakis. Ed. 4th ed... J. P. A. Clayton. V.. 1978. Taeuber. F. The hazard of gas-phase oxidation in liquid-phase air oxidation processes. Photocatalytic selective oxidation of hydrocarbons in the aqueous phase. Montanari. Daun. P. P. Knochel. 65. Today 1998. L. G. 69.. (184) Gonzalez. L. 210. 39. (155) Gurel.. G.-J. Y. 23218. Matienko.. Lessons from the post-enquiry discussion of Flixborough. Composition catalysts of ethylbenzene oxidation based on bis(acetylacetonato) nickel(II) and phase transfer catalysts as ligands. 1. I. R. 238799. D. In Kirk-Othmer Encyclopedia of Chemical Technology. Mosolova.32.32. D. An organic sensitizer within Ti-zeolites as photocatalyst for the selective oxidation of olefins using molecular oxygen and water as reagents. Prostaglandin endoperoxide model compounds. K. A. (169) Harada. M. Cobalt-containing molecular sieve catalysts for the low conversion autoxidation of pure cyclohexane. 1999.. 1994. Komiya. 48 (1). E.. R. PCT Int. H. AIChE J. Harmsen. H. Appl. W. Wacker oxidation in an aqueous phase through reverse phase-transfer catalysis of a selfassembled nanocage. F. Corma.. J. 183. G.. 1997.. D. Schomacker.. S. Y. Emerging Japanese catalytic technologies. J. Fujita. J. H. 25.. W.. J. W. (156) Mecklenburgh. H... 2009 | http://pubs. Chem.. 1353. Lett. J. W. Alvaro. Cyclodextrin-Palladium chloride. (Bayer AG).acs. J.. Wu. F. (160) Chung. Chem. C. A.β-unsaturated carbonyl compounds..... Chandrasekaran. WO 99. S. Process for the preparation of carbonyl compounds by catalytic oxidation of olefins and catalysts in microemulsion. 39. 1999. 4135. Z. Hattori. Lett. A. I. S. Chem. J. Eggelte. (191) Nekhaev. Patent DE19529679. Part 10. Bagrii. J. Tung.. Sun. O.. Chem. Nader.. 21. (Bayer AG). Towards greener chemistry. Sikdar. Kyoto. 2000.. 1983. 34 (5). (168) Pesiri. 2000. Clean catalytic technology for liquidphase hydrocarbon oxidation. Beller. C. Prog... 2000 | doi: 10. Lim. (161) Launay. H. (185) Frei. Z. Zaikin. Chem. E. Commun. Photocatalytic epoxidation of propene by molecular oxygen over highly dispersed titanium oxide species in silica. the effect of the chelate center on catalysis by bicyclic nickel complexes. Chem. R. Chem. C. 1981. 1986. In Proceedings of the Symposium on Chemical Process Hazards with Special Reference to Plant Design V. (173) Skibida. E. 1994. Engl. Frei.. I. (158) Alexander. A. P. W. 1999. Photoinitiated liquid-phase oxidation of saturated hydrocarbons by oxygen of air... (167) Baker. (181) Mueller-Markgraf. Science 1999. Lett. S.. Ph. W.. (199) Meiers. Mechanism of an oscillating organic reaction: Oxidation of benzaldehyde with O2 catalyzed by Co/Br. Blatter. 1999. Monash University. Abstr. Commun. H. Biocatalytic asymmetric hydroxylation of hydrocarbons with the topsoil microorganism Bacillus megaterium. Victoria. (189) Mihelich. 1551.-J. Ying. Murata. 2000. 9. Chem. 22. Chem. Ahn. Tumas. P.. Chem. 157. Chem. A. S. Chem. 4th Japanese-Swiss Meeting on Bioprocess Development. Widmer. Venkelecom. 878. Sonnleitner.. D. 1998. 1999. Org. 1999. L.D. Taeuber. J. Patin. J. W. R. 105. WO 99. 1976. 39. J. 284. Dicarboxylic acids. B. Oxidation of alkenes in supercritical carbon dioxide catalysed by molybdenum hexacarbonyl. Howell. Tetrahedron Lett. 1989.. Sheldon. 55.. 161. Ed. 1994. Patent 300921. Commun. Selective epoxidation in dense phase carbon dioxide. F. 2000. Lukacs. Engineering design method for cavitation reactors I: Sonochemical reactors.
5. Jacobs. A manganese containing molecular sieve catalyst designed for the terminal oxidation of dodecane in air.. S. Luna. (209) Vanoppen. VCH: Weinheim. Chem.
Downloaded by UNIVERSITA STUDI TRIESTE on September 1. CN Patent 1203231. M. Sorokin. H5PV2Mo10O40. Catal. J. 2310.. 39. Abstr. J. Ionexchanged y-zeolites as catalysts for liquid-phase autoxidation of cyclohexane. 2313.. No. 1998. Eng. Res.. R. Germany.. Chem. 2000. E. (208) Kraushaar-Czarnetski. H. Sankar. Terpenes. 2000 3997
(203) Chisem. M. A. DeVos.. Wallau. G.. Commun. Sankar. R.. Angew.. Chem. B. (207) Raja. Chem. M. L. 1999. Zsigmond. Eindhoven. A. C. U. Engl. Ed. R. 2000 Accepted August 5. J. Epoxidation reaction of olefins using molecular oxygen as oxygen source. Wang. reactivity of bis((µ-chloro) bis[exo-3-(nitrosooxy)bicyclo[2.. J. 229. Clark.. I. 39. H. Chisem...1]-hept-2-yl-[n] palladium: Cleavage of the C-Pd bond. D. J. F. (212) Xi. The Netherlands. Thomas.. A novel immobilized cobalt(III) catalyst. Eindhoven University. Hawkins.. In Ullmann’s Encyclopedia of Industrial Chemistry. (204) Das. (206) Dugal. Mol. (215) Chauvet. (205) Raja. Commun. Chem.3-dienes.. 1999. Angew. Thesis. A26. Liquid phase oxidations using novel surface functionalised silica supported metal catalysts. Org. Macquarrie. 1998. P. M. Eur. M. Lett. 2000. 52. 1916. D. Designing a molecular sieve catalyst for the aerial oxidation of n-hexane to adipic acid. (214) Woltinger. Schuchardt.. B. Chem. J. Z. Commun. A. E. 2000 | doi: 10. Engl.. 132. M. Blackwall. Schulz. Ravenscroft. F. Tuel..1021/ie0002733
Received for review February 21. Aerobic hydrocarbon oxidation catalyzed by the vanadomolybdophosphate polyoxometalate.. B.acs.. J. 1998. J. Chem. 2000. J. Int. Heumann.D. Wang.org Publication Date (Web): October 11. 2009 | http://pubs. J. 2000 Revised manuscript received August 4. K. M. B. 11. Chem. Thomas.. Buffron. 22. M.. Rafelt. Vol... Chem. D. A.4-oxidation of 1. 605. J. G.. X. 1998. Int. (210) Passoni. 134. 1841. 2203.. 1997.. A.. Waegell.. Ed. 189... J. 1999. Catal. Chem. 1989. 177 (1).. Elvers. B. Hai. 1093. Heterogenization of H6PMo9V3O40 and palladium acetate in VPI-5 and MCM-41 and their use in the catalytic oxidation of benzene to phenol. A. R. 63. R. H. (216) Eggersdorfer. Catal. 5th ed.2. Oxygen transfer reactions catalyzed by nitropalladium (II) complexes. [SiW11O39Ru(III)H2O]5. 1987. M. M.. 252767. Cao. Neumann. L. J. (213) Higashijima.. Lett. G...Ind. Hydrothermal synthesis of rutheniumsubstituted heteropolyanion. Zeolite encapsulated cobalt salophen complexes as efficient oxygen activating catalysts in palladium catalyzed aerobic 1. S. 1460. 39. 2000 IE0002733
. Li. G. (211) Khenkin. Vol. Y.. Eds. 1995. J. Designing a heterogeneous catalyst for the production of adipic acid by aerial oxidation of cyclohexane. Ph. Sun. G. 1998.as a water soluble oxidation catalyst. J. Thomas. Raja. Clark. supported on mesoporous mcm-41.. C.