Building a Petrochemical Process Technology Portfolio Mike Ashley

Building a Petrochemical Process Technology Portfolio

Introduction The history of development of process technologies for oxo and detergent alcohols provides a classic demonstration of the benefits of a modern approach to research and development. From the outset, the discipline of intensive laboratory investigation of chemical properties, reaction equilibria and kinetics led to the derivation of novel process concepts. Then it is necessary to test process concepts in bench-top units to provide data to generate computer simulation models that will predict performance at industrial scale. This phase of investigation must be continued in order to construct simulation models that are sufficiently robust to be used to design Mini-Plants from which engineering design data is derived for the full-scale plant. During this time uncertainties are eliminated and confidence to embark on capital projects is firmly established. Using this disciplined protocol, process technology for oxo synthesis of propylene to form aldehydes followed by hydrogenation has been commercialised and proved to be a costeffective route to producing butanols. More than thirty world-scale plants have been built based on this technology. The development of ester hydrogenation by reactive distillation paved the way to new processes for butandiol and related products and this led on to improved technology for natural detergent alcohols. Another phase of research and discovery is now underway by applying the concept of reversing equilibrium reactions that were previously harnessed to make oxo alcohols and diols. This approach will be systematically investigated across a spectrum of petrochemicals to ascertain where there is economic potential for novel process technologies. Converting Concepts into Hardware Many organisations in the hydrocarbon processing industries support R&D activities in order to maintain a technical edge and thereby obtain market advantage. When a company decides that a novel processing concept or new product has the potential to be commercialised, one critical step may have already been taken, that is to have combined the complementary skills of chemists and chemical engineers. Together, they convert a novel chemical route into a process flowsheet and then into a rudimentary plant design. To progress further from technology concept to commercial exploitation usually involves the design and construction of a demonstration plant, followed by its operation to generate sufficient engineering data to commence the first industrial scale project. This step in a conventional development route for a typical chemical process takes more than two years and may well cost many millions of Dollars. Many production companies who have developed new products or novel processes for their manufacture know that the market will not wait for them and they want to proceed more rapidly. To make rapid progress, these producers are out-sourcing process development tasks to specialist companies who have pilot plant facilities. Recently, a new development tool has become available and this has proved to be a key differentiator in realising the objective of rapid progress to commercialisation. This has been the development of the Mini-Plant concept. This concept entails the inclusion of the major design details of a commercial scale plant into a pilot plant that is sufficiently small to be operated on a laboratory scale cost basis. A Mini-Plant is designed so all the fundamental design parameters can be confidently scaled to commercial size. Scale factors may be as high as 200,000:1 but even so these Mini-Plants include most of the instrumentation that will be implemented on the ensuing commercial plant. A Mini-Plant is flexible so that it can be operated in any of the possible design permutations of a commercial scale plant. The key process steps can be operated independently or fully integrated to allow the entire operating envelope to be evaluated. The Mini-Plant is very highly instrumented so that the maximum data is extracted over the widest possible range of operating conditions.

Oxo Alcohols The development in the 1970s of a rhodium-catalysed low pressure oxo alcohols process was the most significant step towards establishing and commercialising this technology. This enormous step change in technology from the established high pressure cobalt-catalysed process gave such an economic benefit that many existing cobalt plants were replaced under shut-down economics. In 1977 the developers Dow and Davy Process Technology (DPT) received the prestigious Kirkpatrick Award for outstanding achievement in chemical engineering technology. This has come full circle for DPT with another Kirkpatrick Award in 2003 for the new ethyl acetate process technology. It is the history of this consistent development work that forms the basis of this paper. 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. Vapour-phase hydrogenation was therefore investigated in 1981. A range of highly active nonprecious metal catalysts were developed and tested in the desired operating range. Reproducible results were obtained in a range of bench-scale tests and a 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. he first commercial application came onstream in October 1983. The initial catalyst charge not only performed as predicted but exhibited long life.

Jilin Butyraldehydes Plant

The resulting LP Oxo Process has been very successful and over 90% of the worlds oxo plants licensed in the last 30 years use this process. These plants supply n-butanol and 2-ethylhexanol (2-EH) that is used to produce plasticisers controlling flexibility in PVC products.

Ester Hydrogenation In a parallel development several technologies have been evolved based around vapour-phase ester hydrogenation using solid catalysts. A number of different reactor types were used to shift the reaction equilibrium to the desired conversion and a resin catalyst was developed and tested so that esters can be fed directly to a hydrogenation vaporiser without further treatment. This made possible near 100% conversion to esters in a reactive distillation column The esterification reaction column design was developed through laboratory tests, multi stage pilot plant trials and full-scale hydraulic modelling tests. This technology is now firmly established and a number of commercial scale reactive distillation columns have been designed and installed. All supply highly converted, low sulphur esters with essentially complete utilisation of the feed making this a highly efficient processing step with very low environmental impact. The reactive distillation column may be used for a range of reactions and further processes are under development.

Butanediol and Cyclohexanedimethanol The first application to be developed using ester hydrogenation was for 1,4-butanediol (BDO). Traditionally, BDO and its derivatives were made by the Reppe process from acetylene and formaldehyde. The production of BDO and derivatives from maleic anhydride was demonstrated at laboratory and pilot plant scale in the early mid 1980's and commercialised in two industrial plants which started operation in 1992. Long term operation of these plants has demonstrated the process efficiency, product quality, ease of operation and catalyst life of the process. Continued development of the process and has significantly reduced the capital and operating cost of the process. Today, this process has an established reputation as the low cost, efficient, safe and reliable process that produces a high quality product that is well accepted by the derivative and polymer industries. Low pressure vapour phase hydrogenation results in extremely low by-product production giving high process efficiency and high product quality. The process can be easily integrated with maleic anhydride facilities using abundant, low cost butane feedstock. The first two licensed plants in Korea and Japan have a capacity of 28,000mtpa and a smaller 11,250mtpa plant was successfully commissioned in Shengli, China in early 2000.

Shengli Butanediol Plant

High purity tetrahydrofuran (THF) forms part of the product slate in BDO plants and the amount of THF relative to BDO can be varied. Resin catalysed dehydration/etherification of BDO was therefore developed to meet additional demand for THF which is used in elastomer production. It was realised that the combination of (transesterification and ester hydrogenation process technologies is generic technology and the next product to be investigated was cyclohexanedimethanol (CHDM). This aromatic diol was traditionally made by high-pressure liquid-phase hydrogenation of the corresponding di-ester. Tests showed low-pressure vapourphase technology could be applied and a fast-track development project led to the design of a 30,000mtpa plant in Spain which was commissioned in 1999

Natural and Synthetic Detergent Alcohols Traditionally, conversion of fatty acids into natural detergent alcohol (NDA) was a liquid- phase hydrogenation process using methyl esters and trans-esterification of fats and oils. These processes used very high pressures and temperatures. In 1984 the companys researchers evolved the concept of vapour phase catalytic hydrogenation of long-chain esters and work commenced on the development of generic technology for the manufacture of higher alcohols. This was painstaking work which culminated in 1989 with bench-scale verification of a flowsheet for esterification of carboxylic acids of natural oils and their hydrogenation to natural detergent alcohols. Tests showed that vapourphase hydrogenation could be operated at mild conditions so that this section can be constructed in carbon steel, avoiding the expensive alloy/stainless steels normally needed to minimise hydrogen embrittlement. The C12-C18 esters in the hydrogenation reactor feed are fully vaporisedwith a low temperature rise across the catalyst bed, allowing high selectivities to be

achieved. A simple centrifugal circulator was used which combines easy operation and maintenance with reduced capital cost compared to other types of recycle compressor. In addition, the low operating pressure means that make-up compression is minimised. By 1991 a pilot plant had proved the technology which operates with nonchromium catalysts at a sixth of the pressure of conventional processes and the first licences were sold. The use of methyl esters is the most widely practiced route to convert fatty acids to alcohols and reactive distillation eliminates many problems associated with traditional esterification processes as well as minimising recycle of high value fatty alcohol. There are virtually no reaction by-products so esters can be fed directly to hydrogenation without a processing loss. Due to relatively mild vapour phase hydrogenation conditions with a highly selective and active nonchromium catalyst, and a proprietary design of the reaction system, the process is highly efficient with very little by-product formation and so this process has virtually no effluents. Alcohols produced in the NDA process are used by the detergent industry as ethoxolates and sulphonates to produce laundry products, detergents and shampoos.

Daqing 2-Ethylhexanol Plant

An excellent example of how a technology for one class of products may be applied to another class is the fast-track development for Sasol Technology of South Africa of oxo alcohols technology to convert Fischer Tropsch derived C11 to C14 olefin cuts available from a refinery to C12 to C15 alcohols. Current technologies for producing higher molecular weight alcohols are oleo chemical based and this development is the first commercially practised route to such alcohols based on coal. The plant was successfully started up in 2003 and the resulting C12 to C15 alcohol products are used as building blocks for surfactants, industrial and performance chemicals. Propanediol There has been considerable market interest in 1,3 propanediol (PDO) as it is a for the manufacture of polytrimethylene terephthalate (PTT) and so particular attention was given to PDO. A number of potential routes to PDO were investigated with various feedstocks including ethylene, aldehydes and ethylene oxide. A two year development programme resulted in major progress being made and currently a Mini-Plant capable of reproducing and testing the complete process technology is being operated. The process technology uses ethylene oxide, carbon monoxide to yield an intermediate which is hydrogenated to produce PDO. With a market for PTT that is predicted to exceed 1 million mtpa by 2010, there is a lot to aim for and it is anticipated that the first commercial licence will be granted within the next 12 months at a capacity of 50,000-70,000 mtpa.

Alcohol Dehydrogenation A recent development has entailed a return to studying the fundamentals of these equilibrium reactions and applying the same investigative protocols to develop process technology for reverse hydrogenation of alcohols to produce esters. This has resulted in the development of process technology to convert readily available ethanol to the more valuable ethyl acetate without using acetic acid. The history of this development provides clear evidence that a rigorous approach to research and development followed by Mini-Plant testing has clear benefits. Critical understanding of the chemistry provided the potential explore the limits of flexibility of the production of ethyl acetate from ethanol and this concept was quickly demonstrated. The process was scaled up from the laboratory via Mini-Plants without recourse to conventional pilot plant operations. Scale factors for unit operations varied from 80,000 up to 170,000. The first commercial plant was successfully started-up in 2001 since when interest has been shown by companies with access to fermentation ethanol derived from sustainable resources.
Sasol Ethyl Acetate Plant

Ethanol is vaporised before entering the dehydrogenation reactor where it is converted to ethyl acetate. Crude liquid product is separated from the cooled reactor outlet stream and the overhead vapour stream, containing mainly hydrogen, is scrubbed with part of the ethanol feed to recover organics before the major portion is exported. Liquid product and a small quantity of hydrogen are fed to a selective hydrogenation reactor, where the carbonyl impurities are hydrogenated to alcohols. The stream leaving the hydrogenation reactor contains mainly ethyl acetate, unreacted ethanol and small quantities of water. This is fed to a proprietary refining system in which unreacted ethanol is removed for recycle and impurities are removed to yield a high quality product. Consumption of ethyl acetate as an industrial solvent has increased in recent years, due in the main to it being preferred to Hazardous Atmospheric Pollutants such as MEK , MIBK and aromatics. As a growth product, it was a legitimate target for process development. There were a number of production routes available, all of which ultimately relied upon the use of nonrenewable feedstocks, primarily natural gas or ethylene. In addition these routes require several steps, each with its own inefficiencies and by-product issues and were not especially atom efficient. The major benefit of this new process is that it relies only upon the availability of ethanol, the majority of which is produced by fermentation. As fermentation ethanol is derived from biomass and this relies on atmospheric carbon dioxide, there is no net carbon dioxide contribution. The first EA plant with a capacity of 50,000mtpa was completed in Sasols Secunda complex in South Africa 2002. Future developments in Process Technology To maintain a competitive technology position it is necessary to continue to improve and develop existing processes as well as develop new applications. The foregoing sections have described how this portfolio of process technologies has evolved and indeed some of them are at their fifth stage of improvement in cost-effectiveness and energy efficiency. One area of particular interest, and currently the focus of an active R&D programme, is the production of C9 and C10 alcohols from commercially available feedstocks. Such alcohols are seeing more market interest because of regulatory issues linked to the use of alternative plasticisers in some soft PVC applications. Another departure is the application of BDO type technology to produce polydiols. In collaboration with Cyclics Corporation a new product that combines the best properties of

thermoset and thermoplastic resins has been developed and a plant is now being constructed. Finally, the application of alcohol dehydrogenation technology may open some new opportunities such as methyl formate from methanol. Other options include transesterification of ethyl acetate with butanol to produce butyl acetate. The liberated ethanol would be recycled to the ethyl acetate plant. For proponents of renewable resources, this allows fermentation ethanol to be used as a building block to step off to other products. Jilin Oxo Alcohols Project - a Case Study in Collaboration Exploitation of significant reserves of oil in Jilin Province led to the development of a world-scale fertiliser and petrochemical industry near to Jilin City. Production of synthesis gas, ethylene and propylene on this site made possible the manufacture of a range of added value products including oxo alcohols. This plant employed a high-pressure process using cobalt catalyst but suffered from poor isomer selectivity and also high operating costs. During early 1996 Jilin Chemical Industries Corporation (JCIC) called for tenders for a new oxo alcohols plant requesting that the plant be based on rhodium catalysis that operates at lower pressure. DPT was invited to offer its licensed process technology and after extensive negotiations a kick-off meeting took place at the plant site in Jilin in December 1996 with the contract being made effective in November 1997. The 140,250 mtpa capacity Jilin oxo alcohol plant shown here is based on the DPTs low pressure technology for producing n-butanol and 2-ethylhexanol.

Jilin Oxo Alcohol Plant

DPT, as process licensor prepared a process design in London and this was further developed as an Engineering Package. The Chinese engineering contractor, Huanqiu Chemical Engineering Corporation (HQCEC) undertook detailed design and construction. The main key to the successful outcome of this project was co-ordination between DPT and HQCEC concerning liaison with Chinese design institutes and familiarity with Chinese codes and regulations. Because of the simultaneous development of design and engineering packages in the UK, procurement of long lead items such as proprietary equipment and catalysts could take place early. This also allowed a fast track civil programme of five months to be undertaken by HQCEC. This was particularly important in order to plan construction works around the extended severe winter weather conditions in NE China. A team of Chinese engineers from JCIC and HQCEC spent many weeks in the UK reviewing the engineering documentation as it was being developed and seeking clarification on design issues before the final documentation was assembled and sent to China for detail engineering in Beijing. At predetermined times further review meetings took place in Beijing to finally approve HQCECs work before the start of construction. During the construction period representatives of DPT were resident on site in Jilin to provide technical advice and construction of the plant was completed in the early summer of 2000 when a team of DPT commissioning engineers then began the task of starting up the plant and putting it through its performance tests. As can be expected the difference in Chinese and English language and cultures has the potential to lead to misunderstandings but patience and objective analysis of problems as they arose resulted in mutual agreement and this positive approach by both sides eliminated

adversarial attitudes. The resulting co-operation was very rewarding and the commissioning programme proceeded very well so the plant was soon making the product in commercial quantities. The quality of final product and intermediate products during the performance test was consistently excellent; demonstrating the benefits of the LP Oxo technology when compared with the original HP cobalt based technology. JCIC and its customers were pleased with the quality of the products from the plant and the fact that the project has been successfully executed in good time with excellent co-operation during all phases. To achieve this level of success it was necessary to ensure accuracy and reliability of documentation, timeliness of its production and efficiency of information transfer. Moreover, the following of guidelines were adopted by JCIC, HQCEC and DPT: -. Common project procedures were used. To manage the difficult issue of change, ownership of data was agreed and regular updates on status were given and received. To ensure that the fastest schedule documents were prioritised to match input requirements. Common format, layout and software platforms were used to generate documentation to ensure smooth document transfer and update, with minimum rework. A standard numbering system was adopted in both the design and engineering packages.

By adopting these recommendations, projects with fast-track programmes are delivered on schedule and to the optimal satisfaction of clients. Plant Installations in China The Chinese petrochemical industry has kept pace with many of the developments described in this article as can be seen by the illustrations. China has demonstrated a ready acceptance of recent advances in process technologies for the production of commodity peterochemicals. The following table lists companies that have licensed one or more of these technologies and gives brief details of the plants that have been installed over the last eighteen years. Plant Location Product Capacity MTPA Daqing Petrochemical Heilongjiang Province 2-Ethylhexanol 50,000 n-Butanol iso-Butanol Sinopec Qilu Shandong Province 20,000 7,200 1987 Start-up Date 1986

2-Ethylhexanol 50,000 n-Butanol iso-Butanol 20,000 7,200

Sinopec Qilu Plant Expansion

Shandong Province

2-Ethylhexanol 85,000 normal Butanol 50,000 iso-Butanol 14,600 11,250

1998

SEFC Shengli

Shandong Province

Butanediol

2000 2000

Jilin Chemical Industry Jilin Province

Butyraldehydes 140,250 n-Butanol 70,000

2-Ethylhexanol 60,000 Shanxi Sanwei Sinopec Qilu Petrochemical Co. PetroChina Jilin Jilin Province Shanxi Province Shandong Province Tetrahydrofuran 15,000 2-Ethylhexanol 171,000 i-Butryaldehyde 19,600 n-Butanol 128,000 2004 2002 2004

Conclusion Thirty years of consistent development has generated a family of commercially attractive process technologies. The aim was to start with natural gas or synthesis gas as the basic building block for petrochemicals and to systematically add further processes with increasing product values. This article has concentrated on the development of oxo synthesis, hydrogenation and dehydrogenation reactions but they use upstream products from natural gas and synthesis gas processing as their feedstocks. Each of these technologies is available from a single source and they have been developed to global scale so that they may be combined in a sequence of integrated processes. In recognition of their commercial importance, many operating companies around the world have licensed the process technologies that are listed in the table below: Feedstock Natural Gas Syngas Olefins + Syngas Propylene + Syngas Aldehydes + Hydrogen Butyraldehyde + Hydrogen Maleic Anhydride + Methanol Fatty Acid + Methanol Fischer-Tropsch Olefins Ethanol Conversion Process Steam Reforming Methanol Synthesis Oxo Synthesis Oxo Synthesis Hydrogenation Hydrogenation Ester Hydrogenation Ester Hydrogenation Oxo Synthesis Dehydrogenation Product Syngas Methanol Aldehydes Butyraldehyde Butanols 2- Ethyl Hexanol Butanediol Natural Detergent Alcohol Synthetic Detergent Alcohol Ethyl Acetate

The criteria for embarking on projects that include these technologies may be summarised as: Operational safety - simple, reliable processes with mild non-aggressive operating conditions, Logical Progression starting with natural gas as a feedstock, each stage adds value, Product flexibility - acids, esters and alcohols of different chain lengths can be produced to suit market conditions, Cost effectiveness - simplified flowsheets with recycle optimise conversion efficiency to give the lowest investment and operating costs, Low environmental impact - by-product recycle with chrome-free catalyst virtually eliminates effluent discharges. Market advantage - flexibility to use the most appropriate process route consistent with available low cost feedstocks Up-to-date - capability to retrofit improvements as and when they become available. The benefits that have resulted from the highly disciplined approach to technology development that is described in this article are a secure place in the market and the opportunity to continue to exploit developments in these leading-edge technologies. These benefits have been passed on to licensed operators, many of whom have modernised their plants with improvements to the processes as and when they become available. Davy Process Technology has a global business in petrochemicals technology development and technology licensing. The company has headquarters in London, a subsidiary company in Switzerland and a Technology Centre in Stockton-on-Tees. It owns a range of proprietary process technologies including: Methanol, Gas Conversion, Butanediol, Natural Detergent Alcohols, Oxo Alcohols, Industrial Amines, Ethyl Acetate, Fertilisers, Loop Reactors, Fluorine Chemicals, Phosgene and Carbon Anodes. For further information, visit the companys website at www.davyprotech.com

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