Applied Catalysis A: General 280 (2005) 8388 www.elsevier.

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New diol processes: 1,3-propanediol and 1,4-butanediol

T. Haasa,*, B. Jaegera, R. Webera, S.F. Mitchellb, C.F. Kingb
b a ls AG, P.O. Box 1345, D-63457 Hanau, Germany Degussa-Hu DuPont, Experimental Station, Wilmington, Delaware 19880-0302, USA

Abstract More than 1000 t of polyester resins and bers are produced every hour in the world. The highest fraction of this amount is contributed by the oldest polyester, polyethylene terephthalate (PET). This material is based on the diol ethylene glycol (EG). Beside ethylene glycol butanediol (BDO) gained increasing demand in the polyester business, especially because of the use of polybutylene terephthalate (PBT) in the automotive industry as an engineering plastic. In the last 5 years also 1,3-propanediol (PDO) joined its homologues as an interesting polyester raw material. This development was caused by the nding of unique properties of the corresponding polyester, polypropylene terephthalate (PPT) in ber application. Because of the increasing new market demand for PPT and PBT new production technologies were developed for 1,3-propanediol and 1,4-butanediol. A review will be presented whereby the production of 1,3-propanediol via fermentation of glucose will be not considered. # 2004 Published by Elsevier B.V.
Keywords: Polyesters; Resins; 1,3-Propandiol; 1,4-Butanediol; Polypropylene terephthalate; Polybutylene terepththalate

1. Introduction PPT bers are characterised by much better resilience and stress/recovery properties than PET and PBT. These properties are due to the crystal structure of PPT. PPT chains are much more angular structured than PET and PBT chains. Therefore these chains can be streched up to 15% with a reversible recovery [1]. In the 1990s three technical processes for the production of 1,3-propanediol were developed. All three processes use different feedstocks. The rst process uses acrolein (Ac), the second ethylene oxide (EO), the third glucose as raw materials. The rst two processes are classical oleochemical processes, the third is a biotechnological process. The Ac process technology was developed by Degussa-Huels. In 1997 this technology was sold to DuPont. Shell developed the EO process technology. In parallel to the Ac process technology aquisition, DuPont is developing the newest PDO technology, the fermentation of glucose or sucrose to PDO. Production plants were built in recent years, using the Ac and the EO process in Germany and the US.
* Corresponding author. Fax: +49 6181 59 4403. E-mail address: dr_thomas.haas@degussa-huels.de (T. Haas). 0926-860X/$ see front matter # 2004 Published by Elsevier B.V. doi:10.1016/j.apcata.2004.08.027

1,4-Butanediol (BDO) is the most widely used of all the four carbon-based diols in industry today [27]. BDO is used predominately as a polymer feedstock. For example, it is used in the production of both polyurethanes and polybutylene terephthalate (PBT) [27,28]. PBT is growing in use in the automobile industry for the manufacture of engine and body components. BDO may also be converted to gamma-butyrolactone and tetrahydrofuran, which can be employed an intermediate for materials such as pyrrolidones and as a solvent, respectively. Additionally, tetrahydrofuran is also used as a feedstock for the manufacture of polytetramethylene ether glycol (PTMEG) a component of both urethane elastomers and spandex bers [28]. In this present paper an overview of current technolgies for the production of 1,3-propandiol and 1,4-butandiol developed in recent years will be presented. 2. PDO process based on acrolein Acrolein is easily accessible via selective air oxidation of propene. This technology is commercialized and mainly used to produce methionine and acrylic acid.

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Fig. 3. Reaction scheme of the 3-hydroxypropanal hydrogenation.

Fig. 1. Industrial 1,3-propanediol processes.

The Ac-based PDO process involves two reaction steps. At rst acrolein is hydrated in an aqueous solution to from 3-hydroxypropanal (HPA). HPA is consecutively hydrogenated to PDO. The overall yield is 8590%. The process is designed in a fully continuous mode. Both reaction steps run in adiabatic xed bed reactors. The only solvent is water. The reaction temperature of the Ac-hydration step has to be below 100 8C for thermodynamic reasons. Therefore a very active catalyst is necessary. To achieve high selectivities a buffer system in the pH-range 25 is needed (Fig. 1). Special ion exchange resins are suitable technical catalysts [2,3]. These resins are composed of basic and acid bifunctional groups, both in very high concentrations. Examples are iminodiacetic or phosphonic acid groups (Fig. 2). The Ac-hydration product stream contains secondary hydration products such as 4-oxaheptanedial in addition to water and 3-hydroxypropanal. This reaction mixture is hydrogenated in the presence of a hydrogenation catalyst after removal of unreacted acrolein and optionally part of the water [48]. Various catalysts, containing hydrogenation active group VIA-, VIII- and IB-metals are suitable for the hydrogenation of 3-hydroxypropanal to 1,3-propanediol [9] (Fig. 3). These catalysts may either be present in suspended form, or may be

Fig. 2. Ion exchange resins for the selective hydration of acrolein.

constituent of xed bed catalysts [10]. Catalysts of choice are Raney nickel, which may be doped with other components, as well as platinum or ruthenium supported on activated carbon or metal oxides such as titanium oxide, aluminium oxide or silicon oxide [4,6]. Catalytic hydrogenation of 3-hydroxpropanal entails the risk of small quantities of the catalytically active elements being discharged into the product stream in form of soluble compounds. This results in the necessity of further steps to separate the so formed contaminants and may be observed in particular with suspended catalysts such as Raney nickel. Nickel xed bed catalysts also entail the risk of product contamination with nickel compounds in small quantities [11,12]. Therefore the nobel metal-based catalysts are superior. The preferred design for 3-hydroxypropanal hydrogenation in industrial scale consists of a trickle bed reactor in which the liquid reaction mixture trickles over the xed bed catalyst together with the hydrogen introduced [1315]. The formation of by-products in contrast to the main reaction is exponentially dependend on temperature, doubled with every 10 8C rise in temperature. Increasing pressure has a positive effect on the selectivity by favouring the main reaction. However, this positive effect of an increasing hydrogen pressure is not sufcient to compensate the exponential negative effect of a rising reaction temperature on selectivity [13,16]. Accordingly, a suitable design of an industrial hydrogenation, including a high space time yield aims at highly active catalysts which allows conversions of almost 100% under mild reaction conditions (4070 8C), so to achieve 1,3-propanediol with a selectivity close to 100% [13]. In industrial scale it has been found, that even under such optimal reaction conditions, with conversion and selectivity being at almost 100% and using a careful work up of the reaction mixture, a pure product is obtained which still contains residual carbonyls in an extend of up to a few thousand ppm [13]. These carbonyls include saturated aliphatic carbonyls like propionic aldehyde as well as acetalization products like 2-(20 -hydroxyethyl)-1,3-dioxane (HED) (Fig. 3). This high carbonyl content is extremely troublesome in the production of poly-(1,3-propyleneglycolterephthalate) and its resulting bers [13]. Several patents deal with the problem of hydrolyzing and hydrogenating acetal rings [17,18]. In case of the particular problem within the hydrogenation of 3-hydroxypropanal it has been found, that the implementation of a second, high

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Fig. 4. Reaction scheme of the carbonyl cleavage.

acrolein, which can be hydrogenated to propanol or propanal. Or the 3-hydroxypropionaldehyde can undergo condensation reactions with other aldehydes to C5- or C6aldehydes which can undergo dehydration or hydrogenation reactions [20]. For this reason special precautions have to be taken in order to develop a suitable catalyst and process for the hydroformylation of epoxides. These are:  use of special promotors in addition to known ligandmodied precious metal catalysts;  use of suitable solvent;  close look at the reaction conditions. Temperature is especially critical. The balance between high catalyst activity and extent of undesired side- and consecutive reactions is important. In the beginning of the 1990s several companies started to develop the technology for the manufacture of 1,3propanediol starting with ethylene oxide as raw material. Most of the recent publications are limited to patent literature. A comparison of different processes could therefore give only a broad overview. Most companies use catalyst systems based on rhodium, only Shell has developed a cobalt catalysed process for the hydroformylation of ethylene oxide. It is likely that processes which produce 1,3-propanediol from ethylene oxide using hydroformylation catalysts, produce 3-hydroxypropionaldehyde as chemical intermediate. The 3-hydroxypropionaldehyde can either be hydrogenated in situ, or isolated in some manner and then hydrogenated in a separate step. Early work was reported by Hoechst Celanese starting in 1987 [21]. They were able to achieve 6578% yields of 1,3-propanediol in a single step process using a catalyst system consisted of rhodium, various phosphines and various acids and water as promotors. The patents granted by Union Carbide involve the hydroformylation of ethylene oxide in the presence of a phosphite-modied rhodium-catalyst [22]. A number of different promotors (tetrabutylphosphonium acetate, triphenylamine, 2,6-lutidine, etc.) are described. A maximum selectivity to 3-hydroxypropionaldehyde of 72% is achieved, if ethylene oxide conversion is limited to 25%. Induction times in the range of several hours are noticed for this process as well as for the Hoechst Celanese process. Eastman Kodak describes a process using a mixed phosphine-modied rhodium/ruthenium catalyst [23]. Ethylene oxide is employed as reagent and solvent. The single step process is characterised by yields up to 90% but poor catalyst activity. Table 1 gives an overlook over the rhodium catalysed hydroformylation of ethylene oxide. Shell has done some of the most recent work on 1,3propanediol and is the only company that has commercialized a process for the hydroformylation of ethylene oxide so

temperature hydrogenation step (110150 8C) is suitable for substantially removing said carbonyls, while preventing a decomposition of 1,3-propanediol (Fig. 4) [13]. Thus by adjusting the space velocity in the catalyst bed to a substantially complete conversion of 3-hydroxypropanal throughout the lower temperature bed and an extensive removal of carbonyls within the higher temperature bed, a process is developed, which allows the production of polymer grade 1,3-propandiol from 3-hydroxypropanal at high space time yields.

3. PDO process based on ethyleneoxide The hydroformylation of epoxides provides an easy pathway to -hydroxyaldehydes which may be hydrogenated to 1,3-diols (Fig. 1). Because 1,3-propanediol has attracted considerable industrial interest as an intermediate in the production of polyester bers and lms, most work was concentrated on ethylene oxide (EO) as starting material for the hydroformylation of epoxides. In the early 1960s numerous attempts had been made to subject oxiranes to the hydroformylation reaction. On account of the great reactivity, not only of the epoxides but also of the resulting hydroxyaldehydes the hydroformylation of short chain epoxides generally led to numerous side- and consecutive reactions and thus poor yield and selectivity. That especially goes for the use of EO [19] (Fig. 5). The favoured side reaction is the isomerization of ethylene oxide to acetaldehyde which is sometimes further hydrogenated to ethanol. Furthermore ethylene oxide can undergo oligomerisation reactions to yield linear or cyclic oligo- and polymers. If hydroformylation to 3-hydroxypropionaldehyde is successful, the 3-hydroxypropionaldehyde can dehydrate to form

Fig. 5. Side- and consecutive reactions.

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Table 1 Rhodium catalysed hydroformylation of ethylene oxide Hoechst Celanese Catalyst Ligand Promotor Rh(CO)2acac PCy3 HI, H3PO4, hydrochinone, water Union carbide Rh(CO)2acac Phosphites [Bu4P][OAc], acids, water, nitrogen compounds Eastman Kodak HCORh(PPh3)3, Ru(III)-acac PPh3, NEt3

far [24]. Most of Shells patents describe Co2(CO)8 as catalyst precursor [25]. The use of numerous ligands (diphosphines, phosphines, arsines, etc.) and promotors (tetrabutylphosphonium acetate, butylpentylpyridine, dihydroxyarenes, etc.) for the hydroformylation reaction is claimed. Thereby MTBE was employed as solvent for the hydroformylation reaction and the resulting 3-hydroxypropionaldehyde is extracted in a second step using water as extractive agent. The promotors have two main functions:  Increase of activity by either generating a more active catalyst or accelerating the ring-opening of the epoxide.  Improvement of catalyst recovery during water extraction of 3-hydroxypropionaldehyde. The use of bimetallic catalysts and more complicated ligand-systems like porphyrines resulted in [26] recent process improvements. Yields are typically between 85 and 90% based on ethylene oxide.

recently been supplanted by the lower pressure, uid bed technology [27,31,34]. The reasons for this shift in process technology are centered around the desire to limit the operating pressure used for acetylene in this reaction, since acetylene is known to be very explosive at higher operating pressures (i.e. 1.4 bar and above) [27,34]. Fluid bed technology also offers the advantages of better heat transfer and limited pressure drop, concerns that result from the hydrodynamic stresses the catalyst experiences in xed bed tubes during two phase ow [34]. Typical reaction conditions used for this synthesis are 70100 8C, 16 bar, and a pH of reaction between 5 and 8 that is controlled via alkali addition [27,3234]. While the Reppe process still dominates the commercial production of butanediol, many alternative technologies have begun to appear [31]. The use of both acetylene and formaldehyde as feedstock chemicals is receiving increased scrutiny for environmental, safety and economic reasons [35]. These factors have led to the examination of the feasibility of alternative routes to BDO production.

4. BDO process based on formaldehyde and acetylene BDO has been manufactured industrially for the latter half of the 20th century via the hydrogenation of butynediol. This hydrogenation is typically accomplished through the use of either a nickel or palladium catalyst [27,29,30]. Butynediol is synthesized using a formaldehyde ethynylation process commonly called the Reppe process [27,31]. This process utilizes aqueous formaldehyde solutions into which gaseous acetylene is introduced. The reaction, as practiced industrially, is rst order with respect to formaldehyde and zero order in acetylene [24]. The catalyst most commonly used for this process is a silica supported copper(II) oxide (1015%) with 36% bismuth oxide added [27,32]. However, the literature reports the use of nonsupported copper catalysts as well [33]. The copper used in this reaction is converted to copper(I) acetylide by the reaction reagents. This compound further complexes with the additional acetylene present to form the active catalyst. Bismuth oxide is added to the catalyst to inhibit the formation of water-soluble cuprenes from the oligomeric acetylene complexes on the catalyst [27]. The Reppe process can be practiced either with a xed bed or uid bed reactor system. The xed bed system was the earliest version of the technology practiced and has

5. BDO-process based on acetoxylation of butadiene The rst alternative route to appear commercially was the oxidative acetoxylation of 1,3-butadiene developed by Mitsubishi Chemicals [3537]. This process, practiced by the Mitsubishi-Kasei Corporation of Japan, combines acetic acid with 1,3-butadiene over a palladium/tellurium catalyst at 3 bar and 80 8C to yield 1,4-diacetoxy-2-butene. This molecule is subsequently hydrogenated and nally hydrolyzed to BDO, while the acetic acid is recycled back to the front of the process.

6. BDO-process based on butane The production of BDO via the selective oxidation of butane to maleic anhydride (MAN) is also an area that has received renewed interest in recent years [38,39]. The reasons for this renewed interest are related to the increased abundance of butane as a feedstock that resulted from its decreased use in gasoline, and the much improved selectivities that are achieved with the newer generations of MAN catalysts [35,38]. These factors combine to provide a low cost, safe and environmentally advantageous route to BDO in comparison to currently practiced technologies. Additionally, the molecular structure of

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this cyclic, dicarboxylic acid makes it an attractive precursor for the production of BDO and its derivatives [36]. The production of BDO via butane begins with the selective oxidation of butane. This is accomplished in either a xed or uid bed containing a vanadium phosphorus mixed oxide catalyst. The catalysts active phase is thought to be a vanadyl pyrophosphate, (VO)2P2O7, and is used to oxidize butane in a one pass process with a conversion rate in excess of 80% and a yield between 50% and 60% on a molar basis [38]. The reaction conditions vary, but can be generalized to the following parameters: 390450 8C and 12 bar. The maleic anhydrid formed by this process can then be recovered as an aqueous solution or an anhydrous stream. The hydrogenation of maleic as an anhydrous stream or an aqueous acid has been the topic of much research [39]. The anhydrous route combines maleic anhydride with an alcohol, such as methanol, in a noncatalytic addition to form the mono-ester [28,35,40]. The subsequent addition of a second methanol to form the dimethyl maleate is accomplished over a solid acid resin catalyst at moderate temperatures and pressures (i.e. up to 5 bar and 150 8C). The dimethyl maleate is then vaporized and fed along with hydrogen into a xed bed catalytic reactor typically containing either copper chrome or copper manganese catalyst [28]. The copper to co-metal ratio in these catalysts is optimized for the maximum activity to BDO per unit cost of catalyst. During the hydrogenation, the alcohols are released and recycled to the front of the process while the remaining gamma butyrolactone is hydrogenated into BDO [28,35]. The hydrogenation of an aqueous maleic acid stream is also possible. This process typically involves the use of a precious metal catalyst such as a palladium on carbon with co-catalyst metals such as silver and or rhenium [41,42]. The aqueous route has the advantage over the anhydrous process of requiring no anhydrous recovery and/or rening of the maleic prior to its reaction as well as the complete elimination of the esterication process. DuPont has also used a similar type of process for the direct manufacture of tetrahydrofuran, which is one of the major end uses of BDO [38].

mylation technology is licensed from Kuraray for this purpose [36,43].

8. BDO process based on epoxidation of butadiene The last commercial route to BDO under exploration is based on the epoxidation of butadiene chemistry developed by Eastman Chemical Company [44]. The epoxidation is carried out over a silver catalyst to produce a 3,4-epoxy-1butene. This molecule is then hydrated using mixtures of hydriodic acid and organic soluble iodine salts as catalysts. It is further hydrogenated using a precious metal catalyst to BDO [45]. Dow Chemical has recently added to this area of research some work that reports on the isomerization of the hydrolyzed epoxide (i.e. 3-butene-1,2-diol) to 1,4-butenediol [46]. The catalyst used for this isomerization is a Zeolite-Y with approximately 10 wt.% rhenium oxide. The selectivity of this reaction is reported to be 86% [46]. However, is obvious from the patent literature that Dow Chemical is not alone in this area of research [45,47,48].

9. Outlook Although polyester polymers are very old, the world polyester market is still growing. More and more new applications are under development. This is caused by many reasons. In contrast to many other polymers recycling is easy. Polyesters contain only C, H and O. For that reasons it is likely that BDO and especially PDO will grow with high rates in the next decades. Concerning PDO, the Ac to PDO process as well as the EO to PDO process are technically proven. The advantage of the Ac-based process are much lower investment costs. The advantage of the EO process are slightly lower variable costs. It depends on where the market is growing how much and the infrastructure of the production site which process will grow faster. The bio route is a very interesting future option. The realization of this route depends on the progress of process development to obtain ber grade PDO quality and the carbohydrate/oil price ratio. Future growth of BDO as an intermediate in the production of polymer-based products look bright, too. However, the focus on technologies to produce BDO for these markets is shifting away from the acetylene-based Reppe process. Future production of this important intermediate will focus primarily on the C4 conversion chemistry. While there will certainly be BDO produced via other routes, such as Lyondells propylene oxide chemistry or the conversion of biomass materials such as pentosans and furfural [36], the stand alone economics of these processes remain unproven in the marketplace.

7. BDO process base on allyl alcohol Another alternative route to BDO is via the hydroformylation of allyl alcohol. This has been commercialized by Lyondell, formerly ARCO, and is based on their existing propylene oxide technology [36]. The propylene oxide is rst isomerized over a lithium phosphate, Li3PO4, catalyst to allyl alcohol. The latter is then hydroformylated to BDO using a rhodium catalyst having a large excess of triphenylphosphine and an equimolar amount of 1,4diphenylphosphinobutane to rhodium [43]. The hydrofor-

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T. Haas et al. / Applied Catalysis A: General 280 (2005) 8388 [27] H. Grafje, W. Kornig, H.-M. Weitz, W. Rei, G. Steffan, H. Diehl, H. Bosche, K. Schneider, H. Kieczka, in: W. Gerhartz, Y.S. Yamamoto, F.T. Campbell, R. Pfefferkorn, J.F. Roundsaville (Eds.), Ullmanns Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft, Weinheim, DE, A4455. [28] M.A. Wood, P. Willett, D.M. Sutton, J. Ladebeck, Shokubai 40 (1998) 298. [29] H. Mueller, H. Toussaint, J. Schossig, US Patent 4,864,066 (1989), to BASF Atkingesellschaft. [30] M. Irgang, V. Menger, E. Miesen, P. Stops, Peter, F.Graf, US Patent 5,714,644 (1998), to BASF Aktiengesellschaft. [31] E.V. Hort, P. Taylor, in: J.I. Kroschwitz, M. Howe-Grant (Eds.), KirkOthmer Encyclopedia of Chemical Technology, vol. 1, 4th ed. Wiley, New York, 1991, p. 202. [32] W. Reiss, H.-I. Joschek, R. Schnur, S. Winderl, J. Dehler, H. Hoffman, US Patent 4,093,668 (1978), to BASF Aktiengellschaft. [33] W. Reiss, S. Winderl, W. Schroeder, H. Hoffman, US Patent 4,067,914 (1978), to BASF Aktiengellschaft. [34] W. Reiss, R. Schnur, S. Winderl, H. Hoffman, P. Zehner, US Patent 3,957,888 (1976), to BASF Aktiengellschaft. [35] N. Harris, M.W. Tuck, Hydrocarbon Process. (1990) 79. [36] H. Mueller, Tetrahydrofuran, in: W. Gerhartz, Y.S. Yamamoto, F.T. Campbell, R. Pfefferkorn, J.F. Roundsaville (Eds.), Ullmanns Encyclopedia of Industrial Chemistry, B. Elvers, S. Hawkins, W. Russey (Eds.), VCH Verlagsgesellschaft, Weinheim, DE, A26, p. 221. [37] Chemical Week, Nov 19/26 (1997) 20. [38] T.R. Felthouse, J.C. Burnett, S.F. Mitchell, M.J. Mummey, in: J.I. Kroschwitz, M. Howe-Grant (Eds.), Kirk-Othmer Encyclopedia of Chemical Technology, vol. 15, 4th ed. Wiley, 1995, p. 893. [39] T.R. Felthouse, Chemist (1998) 22. [40] H.-M. Weitz, R. Schnabel, R. Platz, US Patent 4,361,710 (1982), to BASF Aktiengellschaft. [41] E. Nagahara, I. Yasushi, US Patent 5,426,246 (1995), to Arakawa Chemical Industries Ltd. [42] S.E. Pedersen, J.G. Frye, T.G. Attig, J.R. Budge, US Patent 5,698,749 (1997), to The Standard Oil Company. [43] E. Billig, D. Bryant, in: J.I. Kroschwitz, M. Howe-Grant (Eds.), KirkOthmer Encyclopedia of Chemical Technology, vol. 17, 4th ed. Wiley, 1995, p. 902. [44] J.L. Stavinoha, Jr., J.R. Monnier, D.M. Hitch, T.R. Nolen, G.L. Oltean, US Patent 5,362,890, to Eastman Chemical Company. [45] P.B. MacKenzie, J.S. Kanel, S.N. Falling, A.K. Wilson, US Patent 5,959,162 (1999), to Eastman Chemical Company. [46] CHEMTECH, December 1998, 32. [47] M. Fisher, US Patent 5,627,291 (1997), to BASF Aktiengesellschaft. [48] M. Fisher, C. Sigwart, US Patent 5,977,417 (1999), to BASF Aktiengesellschaft.

References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] Word, Wilding, Brody, J. Polym. Sci. Phys. Ed. 14 (1976) 263. D. Arntz et al., EP 412,337 (1990), to Degussa AG. Arntz et al., EP 487,903 (1991). Haas et al., WO 98/57913. Powell et al., US 5,786,524. Arntz et al., US 5,015,789. Arntz et al., US 5,171,898. Haas et al., US 5,276,201. Hatch et al., US 2,434,110. Eleuterio et al., US 3,536,763. Arntz et al., US 5,364,984. X.D. Zhu, H. Hofmann, Appl. Catal. A 155 (1997) 179. Haas et al., US 5,334,778. X.D. Zhu, H. Hofmann, Chem. Eng. Proc. 35 (1996) 1. X.D. Zhu, H. Hofmann, Chem. Eng. Technol. 20 (1997) 131. X.D. Zhu, G. Valerius, H. Hofmann, Th. Haas, D. Arntz, Ind. Eng. Chem. Res. 36 (1997) 2897. Fischer et al., US 2,888,492. Copelin, US 4,044,059. B. Cornils, New Synthesis with Carbon Monoxide, Springer-Verlag, 1980 p. 131. K.D. Tau, US 5,053,562 (1991). (a) M.A. Murphy et al., EP 0,257,967 (1987).; (b) M.A. Murphy et al., EP 0,343,944 (1989).; (c) M.A. Murphy et al., US 4,873,379 (1989).; (d) M.A. Murphy et al., US 4,935,554 (1990).; (e) K.D. Tau, US 5,053,562 (1991). (a) J.R. Briggs et al., US 5,030,766 (1991).; (b) J.R. Briggs et al., US 5,225,387 (1993).; (c) J.R. Briggs et al., US 5,210,318 (1993).; (d) J.R. Briggs et al., US 5,449,653 (1995). (a) W.A. Beavers, US 4,973,741 (1990).; (b) W.A. Beavers, US 5,043,480 (1991). Shell Chemicals Magazine, No. 10, 2nd Quarter, 1998. (a) L.H. Slaugh et al., WO 94/18149 (1994).; (b) J.P. Arhancet et al., WO 96/10550 (1996).; (c) D.C. Eubanks et al., WO 96/10551 (1996).; (d) J.P. Arhancet et al., WO 96/10552 (1996).; (e) D.R. Kelsey, WO 96/18596 (1996).; (f) K.T. Lam et al., WO 97/16250 (1997).; (g) J.P. Arhancet et al., WO 97/33851 (1997). (a) E. Drent, EP 0,478,850 (1992).; (b) P.R. Wieder et al., US 5,689,016 (1997).; (c) J.P. Arhancet et al., WO 97/45390 (1997).; (d) L.H. Slaugh et al., US 5,731,478 (1998).; (e) L.H. Slaugh et al., US 5,723,389 (1998).

[22]

[23] [24] [25]

[26]