Esters to Alcohols and back again

Don McKinley

ESTERS TO ALCOHOLS AND BACK AGAIN

(first published in Hydrocarbon Engineering, April 2001) Hydrogenation of vaporised C18+ hydrocarbons at around 220C does not immediately spring to mind as being the most cost-effective processing route to alcohols. Don McKinley* describes how ten plants producing four very different alcohol products have proved otherwise. Recent research into the reverse process -dehydrogenation of alcohols into esters -has led to a process licensed to upgrade ethanol to more valuable ethyl acetate without using acetic acid. These plants supply products ranging from butanol (from C8 ester), through 1,4- butanediol (BDO) (from C6 or C8 esters) and 1,4-cyclohexanedimethanol (CHDM) (from C10 ester), to C12-C18 fatty alcohols (from C13-C19 esters). All but one of these plants have been licensed by Davy Process Technology (DPT), and capitalise on the discovery in the 1980's of the benefits of low-pressure vapour-phase hydrogenation of esters. With six plants licensed, Davys BDO technology is now the leading process available, and a licensing arrangement has recently been concluded which gives BASF non-exclusive rights to use Davy's BDO technology in their future plants. Meanwhile, a unique low-pressure vapourphase CHDM process was developed by DPT for Eastman Chemicals, the world's leading manufacturer of CHDM. Eastman have since successfully commissioned a plant in Spain using the Davy technology. Also in the Far East, two plants have been licensed to make fatty alcohols from coconut/palm kernel fatty acids using Davy's esterification and ester hydrogenation technologies. The first plant in the Philippines was fully accepted just one month after feed ester introduction. Early Days For nearly 100 years Davy Process Technology has been involved in syngas-based processes -initially the processing of coke-oven off-gas followed by the production of towns gas by naphtha steam reforming. The discovery of natural gas in the North Sea gave the impetus to develop other syngas-based processes. Principal among these is the long association that DPT have had with ICI (now Synetix) as their main methanol licensee. DPT has now built 85% of ICI's LP methanol technology licences, representing 42% of the world's installed methanol capacity. Next was the development and commercialisation of the rhodium-catalysed LP Oxo Process with Union Carbide Corporation and Johnson Matthey. This enormous step change in technology from the established HP cobalt-catalysed process gave such an economic benefit that many existing cobalt plants were replaced under "shut-down economics". In 1977 Union Carbide, Johnson Matthey and DPT (then Davy Powergas Ltd.) received Chemical Engineering's prestigious Kirkpatrick Award for outstanding group effort in new chemical engineering technology. The LP Oxo Process has been hugely successful. Together with Union Carbide, DPT continues to develop the process and has now granted 25 licences to 19 operators in 14 countries throughout the world. Over 90% of the world's oxo plants licensed in the last 25 years use this process. Main products are butanol and 2-ethylhexanol (2EH), both produced by the hydroformylation of propylene. One of the 2EH plants is also configured to produce 2propylheptanol (2PH) from normal butenes. Both 2EH and 2PH are plasticiser range alcohols used to produce plasticisers controlling flexibility in PVC products. The technology has now been extended to the production of detergent range alcohols (CIO to C18) following process design development and extended testing in a continuous mini-plant at DPT's new Technology Centre. The first licensed application to convert a higher olefinic feed to detergent alcohols will be brought on-stream by Sasol Chemical Industries in South Africa in 2002.

Problem Solved One of the early LP Oxo plants used a reactor configuration that resulted in a high level of one ester by-product during the hydrogenation of butyraldehyde to butanol. Hydrogenating this butyl butyrate ester to make more butanol was an obvious remedy. However, there was a site limitation of 40 bar and 250C for the reaction. Liquid- phase hydrogenation required high pressures. Vapour-phase hydrogenation was therefore investigated in 1981. A range of highly active non-precious metal catalysts were developed and tested in the desired operating range at DPT's own Technical Centre in Stockton-on- Tees. Reproducible results were obtained in a range of bench-scale tests and this information, together with tests on an 8 inch diameter pilot plant reactor, gave confidence to go directly to full scale. The reaction fluid, being a single vapour phase, meant that hydraulic scale-up problems were minor compared to liquid phase (trickle-bed) scale-up.

Ester Hydrogenation Column, Shinwha, Korea

The first commercial application came on-stream in October 1983. The initial catalyst charge not only performed as predicted but exhibited long life. Only one plant was actually built but a new catalyst and reaction system had been proved commercially - paving the way for further developments. The Next Step DPT then looked for other applications where these highly active catalysts could be used, especially where low-pressure vapour-phase ester hydrogenation would offer significant advantages. Several basic classifications of esters were examined: primary esters, e.g., laurates, stearates saturated di-esters, e.g., oxalates, succinates unsaturated di-esters, e.g.,maleates aromatic esters, e.g., benzoates.

In each case, hydrogenation of the esters produces the corresponding alcohols forming the ester. For example, alkyl maleates and succinates produce 1,4-butanediol while methyllaurate produces lauryl (C12) alcohol. C11H23 CO.OCH3 + 2 H2 = C12H250H + CH3 0H DPT has developed commercial capability for each of these four types of ester. Butanediol The first application to be developed after butyl butyrate was for 1,4-butanediol. This has also been the most successful so far, with six plants currently licensed. Combined licensed capacity confirms the DPT process as the most cost-effective BDO process available. All the plants use maleic anhydride feedstock (produced from cheap n-butane) which is first esterified to make di-alkyl maleates. The first two plants use ethanol to make diethyl maleate

with ethanol being recycled, while all subsequent plants use methanol to make dimethyl maleate. At the start of the development a review of six commercially available esterification processes revealed that none of them provided the desired high processing efficiency combined with low sulphur contamination of the esters and low environmental impact from catalyst disposal. The use of solid esterification catalysts was therefore investigated and developed as a separate technology area. The first two licensed plants were started up in Korea and Japan in 1992. Both have a capacity of 22,500mtpa of BDO equivalent (includes coproduct tetrahydrofuran, THF). A smaller 11,250mtpa plant was successfully commissioned in China in early 2000. This was the first to use methyl esters produced in an improved esterification process based on a resincatalysed reaction column. A similar larger plant for 33,750mtpa BDO was commissioned mid-2000 in Taiwan for TCC, and a 100,000mtpa plant for BASF Petronas is due to start up next year, 2002. A sixth licence for 50,000mtpa has been granted in Saudi Arabia and this is now proceeding through design, engineering and procurement.
Butanediol Plant, Chengli, Cina

For all of these licences, DPT has provided all the catalysts, a comprehensive Front End Engineering Package (FEEP) for the detailed engineer, FOB supply of certain critical items of equipment such as reactors, compressors, etc., comprehensive operator training, and full commissioning and laboratory advice and guidance. DPT stands alone as an independent technology company and is free to supply basic engineering packages to any competent contractor. Natural Detergent Alcohols In 1988, during BDO development, DPT actively started a full development programme to convert fatty acids into fatty alcohols. Traditionally this was a liquid- phase hydrogenation process using methyl esters (usually made by trans-esterification of fats and oils) or wax esters (made by reacting feed fatty acids with recycled product alcohol). All these processes used very high pressures (200 to 300 bar), and temperatures as high as 300C. Tests showed that DPT's vapour-phase hydrogenation could be operated at much lower pressures and temperatures. An optimum operating pressure of 40 bar was selected with reaction temperatures well below 250C. At these conditions, the hydrogenation section can be constructed in carbon steel, avoiding the alloy/stainless steels normally needed to minimise hydrogen embrittlement. Obviously, a large molar excess of hydrogen is recycled to ensure the C12-C18 esters in the hydrogenation reactor feed are fully vaporised. However, this has the advantage of a low temperature rise across the catalyst bed, allowing high selectivities to be achieved when operating at temperatures appropriate to throughput and catalyst activity. Optimisation of the heat exchangers and other equipment in the loop means that a very low head compressor is used to circulate hydrogen. A simple centrifugal compressor design can be used which combines easy operation and maintenance with reduced capital cost

compared to other types of recycle compressor. In addition, the low operating pressure of 40 bar means that make-up compression is minimised, or not required as hydrogen can be made from methanol at this pressure in an integrated plant. Total power requirement (make-up and recycle) for the DPT NDA process is actually less than competing highpressure, liquid-phase processes which have relatively low hydrogen recycle flows, but high make-up hydrogen compression and feed pump power requirements. Two NDA plants have been licensed in the Far East, both based on fatty acids from coconut/palm kernel oil. A 30,000mtpa plant for Primofina in the Philippines was successfully commissioned in early 1998 and a similar plant for 50,000mtpa is being constructed for Dahin in Taiwan.
Natural Detergent Alcohol Plant , Primechem,Philippines

Both licences were sold with a full design package and supply of all catalysts, FOB supply of critical items of equipment (mainly from the UK), operator and analyst training at DPT's London office and Technology Centre, plus on-site pre- commissioning and start-up/analytical advice and guidance. For both projects, DPT worked closely with the Singapore office of the specialist oleochemical contractor, De Smet, who supplied the upstream fatty acid plant and acted as overall contractor. As part of the development DPT designed, fabricated and shipped a skid-mounted demonstration unit, which Unichema operated in Holland to produce around 200 tonnes of fatty alcohols, for downstream processing to surfactants for product application tests. Although Unichema did not take up their option to licence, the highly successful results of this demonstration programme assisted in gaining development agency funding for the first plant in the Philippines. Cvclohexanedimethanol This aromatic diol was also traditionally made by high-pressure (200 bar) liquid-phase hydrogenation of the corresponding di-ester. Tests showed that DPT's low-pressure vapourphase technology could be applied. Apart from reduced capital (low pressure, carbon steel loop) and improved economics, there was much more of the desired trans isomer in the product. Furthermore, the trans/cis ratio could be readily controlled to meet market demands. Eastman, the world's leading producer of CHDM, approached DPT to develop a vapour phase route. They subsequently signed a Development Agreement and thereafter were closely involved in monitoring DPT's test programme and process design developments. At the conclusion of the Development Programme, DPT granted Eastman an exclusive right to Davy's vapour-phase ester hydrogenation technology for the production of CHDM. With input from DPT, Eastman has since built a 30,000mtpa plant in Spain, which DPT engineers and chemists assisted in commissioning in 1999. High purity CHDM is now being produced.

Spin-off Technologies -Esterification Several technologies have evolved in the development of the different flow-sheets based around vapour-phase ester hydrogenation. As previously mentioned, DPT uses solid catalysed esterification in the NDA and BDO flowsheets. A number of different reactor types are used to shift the reaction equilibrium to the desired conversion. The heterogeneous resin catalyst is retained in all the reactors used and consequently esters can be fed directly to the hydrogenation vaporiser without further treatment. Other homogeneous esterification catalysts would require neutralisation -giving effluents and loss of yield -and/or separation by distillation to reduce contaminants such as sulphur from reaching the hydrogenation catalyst. However, it was found that available resins promoted significant etherification of the alcohol to di-alkyl ethers such as di-methyl ether and water. This by-product water influences the esterification equilibrium making it difficult to approach full conversion to esters. Because of this, DPT's catalyst manufacturer developed a new range of polymeric resin catalysts that feature a low make of by-product di-alkyl ethers. This means that near 100% conversion to esters can be achieved in a reactive distillation column where the resin remains on each tray and alcohol vapour passes counter-current to the feed acid. Water is stripped out overhead and esters accumulate in the sump. DPT developed the esterification reaction column design through many laboratory tests, multistage pilot plant trials and full-scale hydraulic modelling tests. A total of five of these commercial scale reactive distillation columns have been designed and supplied by DPT. All supply highly converted, low sulphur esters from the column swnp with no further processing directly to the hydrogenation section of either the NDA or BDO processes. There is essentially 100% utilisation of the feed acids/anhydride making this a highly efficient processing step with very low environmental impact. The reactive distillation column can be licensed for other reactions apart from esterification, some of which are under development in a multi-stage pilot unit at DPT's new Technology Centre. Spin-off Technologies -Alcohol Dehvdrogenation Critical understanding of the chemistry underlying the ester hydrogenation technology portfolio, specific experience of catalyst applications and design experience of pilot and commercial scale plants enabled DPT to explore the limits of flexibility. This has resulted in a process to manufacture ethyl acetate directly and solely from ethanol. This is a major development step as it adds value to ethanol co-produced in Fischer- Tropsch synthesis or surplus fermentation alcohol. It is obviously of particular interest where there is no local supply of acetic acid. For these reasons DPT and Sasol entered into discussions which led to the signing of an agreement at the end of 1996, in which Sasol would support the development of a new direct ethyl acetate technology. A very rapid development took place with parallel test-work and process development in Stockton and London such that within two years a commercial design was in place. Development work included generation of VLE data to support optimisation of a novel two column pressure-swing refining system. The process uses a catalyst similar to that used in the BDO process and operates at similar temperatures. Some of the evolved hydrogen is used in a selective hydrogenation step ahead of refining to remove

close boiling aldehydes and ketones. The balance of the hydrogen is exported. The first EA plant with a capacity of 50,000mtpa has been completed in Sasol's Secunda complex in South Africa. Spin-off Technologies -Diol Dehydration Although high purity tetrahydrofuran (THF) forms part of the product slate in BDO plants, the amount of THF relative to BDO can only be varied within limits. Resin catalysed dehydration/etherification of BDO to THF was therefore developed to meet additional demand for THF, which is used in elastomer production. This add-on reaction system has been licensed to two BDO licensees. The Future Davy has maintained its technology position by continuing to improve and develop the BDO and NDA processes as well as develop new applications. Other applications of the low-pressure vapour-phase ester hydrogenation technology are being progressed. Most of these are directed towards other diols, which would be used in condensation polymerisation reactions to yield polyesters. These await market growth of enduse applications. Reactive distillation applications, including autocatalytic as well as solid and liquid catalysed reactions, are being investigated. Some show promise in the fine chemicals manufacturing sector where multi-stage batch operations can be replaced by a single reaction column. Finally, the application of Davy's alcohol dehydration technology may open some new opportunities such as methyl formate from methanol, and in ester solvent manufacture, for example, propyl propionate from propanol feeds. Mixed alcohol feedstocks are also being studied. Other possibilities include transesterification of ethyl acetate with butanol to produce butyl acetate. The liberated ethanol would be recycled to the EA plant. For proponents of renewable resources, this allows fermentation ethanol to be used as a building block to step off to other products, such as acetaldehyde, as well as being upgraded at low cost to a useful high-value solvent. Licensing and Development All these activities lead to licence agreements reflecting the history, aims and ambitions of the technology provider and user. Central to this is intellectual property and the reassurance provided by appropriate patents. As would be expected, DPT have been much more active in recent years in extending its patent portfolio. The income from licensing allows DPT to invest for the future as reflected in the new Technology Centre in Stockton-on-Tees, opened in January 1999, and from which more exciting technology developments are expected. *Don McKinley is a Development Manager with Davy Process Technology where he has been employed for the last fourteen years. A graduate of the University of Newcastle-upon-Tyne and a Fellow of the Institution of Chemical Engineers, he was responsible for process development of DPT's Natural Detergent Alcohols process and the associated Esterification Reaction Column design. He subsequently led the team that successfully commissioned the first commercial applications of these developments in the Philippines.

For further details please contact: Davy Process Technology Limited 20 Eastbourne terrace London W2 6LE UK Tel: +44 (0)20 7957 4120 Fax: +44 (0)20 7957 3922 Mail: dpt@davyprotech.com Web: www.davyprotech.com Davy Process Technology Limited Technology Centre Princeton Drive Stockton-on-Tees TS17 8PY UK Tel: +44 (0) 1642 853 800 Fax: +44 (0) 1642 853 801 Mail: tc@davyprotech.com Web: www.davyprotech.com

Davy Process Technology is a Johnson Matthey company