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Polymer Reviews

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Bio-Ethanol Based Ethylene

Antonio Morschbacker a a Centro de Tecnologia e Inovacao Braskem, Braskem S. A., Triunfo, RS, Brazil

To cite this Article Morschbacker, Antonio(2009) 'Bio-Ethanol Based Ethylene', Polymer Reviews, 49: 2, 79 84 To link to this Article: DOI: 10.1080/15583720902834791 URL: http://dx.doi.org/10.1080/15583720902834791

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Journal of Macromolecular Science R , Part C: Polymer Reviews, 49:7984, 2009 Copyright Taylor & Francis Group, LLC ISSN: 1558-3724 print / 1558-3716 online DOI: 10.1080/15583720902834791

Bio-Ethanol Based Ethylene

ANTONIO MORSCHBACKER
Braskem S. A., Centro de Tecnologia e Inovacao Braskem, Triunfo, RS, Brazil
The use of bioethanol-based ethylene as raw material for chemical products, especially to produce polyethylene and other polymers, is being considered an effective way to capture carbon dioxide from the atmosphere and offer to the market an alternative of a commodity plastic with a wide range of applications and a low carbon footprint. The present article discloses the aspects relatives to the ethanol manufacture in Brazil using sugarcane as feedstock, the catalytic dehydration reaction, the plants operated in the past with this technology and the main characteristics of the processes. Keywords biopolymer, green ethylene, green polyethylene, biobased ethylene, ethanol dehydration

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1. Introduction
Ethylene is a chemical intermediate used to produce many different products, especially polymers as polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), and polystyrene (PS). Its current world production capacity is around 115,000 tons per year, mainly (>98%) through the petrochemical route based on steam cracking (thermal pyrolysis) of petroleum liquids (naphtha, condensate, and gas oils) and natural gas feedstocks (ethane, propane, and butane). The manufacture of ethylene by the catalytic dehydration of ethanol is restarting to attract more attention, mainly in Brazil, with the building of large-scale plants motivated by the Brazilian sugarcane based ethanol competitiveness and by the low carbon footprint of the product obtained by this route. Since 2007, Braskem announced their plans to start the manufacture of polyethylene on a large scale and Solvay announced an expansion in its PVC capacity, all of them based on Brazilian renewable ethanol.

2. Ethanol
The use of bio-ethanol as engine fuel has been practiced since the beginning of the last century. In 1975, Brazilian ethanol capacity started to rise in consequence of the National Alcohol Program. Almost thirty years later the United States started to grow its capacity very fast until it became the world leader in manufacture. Both countries are currently by
Received 14 December 2008; Accepted 8 February 2009. Address correspondence to Antonio Morschbacker, Braskem S. A., Centro de Tecnologia e Inovacao Braskem, III Polo Petroquimico, Triunfo, 95853-000, RS, Brazil. E-mail: antonio. morschbacker@braskem.com.br

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far the global leaders in ethanol production with the United States producing 23 billion liters and Brazil producing 21 billion liters in 2007. In tropical climates, sugarcane is relatively inexpensive to grow. In addition to the high agricultural productivity and the relatively simple harvest methods, the growing season for sugarcane is longer than that of other crops, taking usually 6 to 7 months. It is harvested year by year during at least four years with no necessity to plant it again during this cycle. The mechanical harvesting that was scarce 10 years ago is much more efcient and did not emit carbon dioxide in consequence of the sugarcane burning practiced by the old method that was done by laborers manually. In Brazil, the water requirement for its production is to a large extent rainfed. In consequence of these aspects, recently the World Bank1 and FAO2 have stated that Brazilian ethanol has not raised sugar prices signicantly and that it is the only biofuel competitive with petroleum-based diesel or gasoline and which saves greenhouse gases. Ethanol can be obtained by the fermentation of a sugar source, mainly sugarcane juice and molasses (as in Brazil) and hydrolyzed starch from corn grains (as in the United States). Other possible crops, such as potato, wheat, manioc, and sugar beets can be used in some regions. The use of hydrolyzed cellulose and hemicellulose from low-cost biomass is a potential way to obtain cheaper ethanol but until now this technology is under development and it is has not been explored at a commercial scale. To produce the ethanol through fermentation, sugar is extracted from sugarcane by crushing the raw cane with water to extract the sugars. In a similar way, starch is obtained from corn by dry milling, then slurried with water, and hydrolyzed to glucose. The resulting solution of fermentable sugars obtained by both ways is fermented typically in batch or fed-batch by Saccharomyces cerevisiae yeast to produce a broth with 6 to 8% by weight of ethanol. The fermentation of the sugarcane juice is quite simple, because it can be fermented directly, and faster, taking in general less then 16 hours. The broth containing ethanol is distillated to produce hydrated ethanol, about 93% by weight. In the case when ethanol is used as a gasoline additive to improve the octane number, the ethanol must be produced anhydrously (100%), usually by azeotropic distillation, extractive distillation, or molecular sieves drying. The stillage, the bottom by-product stream of the distillation, is rich in nitrogen and potassium and is commonly recycled to the sugarcane crop by a practice called ferti-irrigation. A relevant fact related to the sugarcane feedstock is that it also produces a large amount of lignocellulosic material. For an average yield of 8085 metric tons per hectare and 14% by weight of sugars, it produces, and in addition, 28% by weight of dry lignocelluloses bers as bagasse and leaves. These bers can be used to supply renewable heat and electricity to the ethanol process. Its surplus of about 2040% is used normally to cogenerate renewable electricity to the grid and may also be used in other processes when integrated with the ethanol manufacture. If in the future the hydrolysis of hemicelluloses and celluloses is economically competitive these bers may be used as an additional source of sugars. As a consequence of these many aspects the Energy Balance of the sugarcane based ethanol is very favorable. This number is obtained dividing the fossil fuel energy input required by the entire manufacturing process, since the crop plantation, by the energy content of the biofuel output. For the Brazilian sugarcane ethanol the input/output energy balance is 1:9, while for the US corn ethanol this relationship is 1:1.5.

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3. Catalytic Dehydration of Ethanol

Before the explosive growth of the oil industry after the Second World War, a big amount of the chemical routes were based on agricultural crops. During the last years, the current demand for green products is bringing back the alternative use of biobased raw materials as chemical feedstocks for many different products. The rst report that was published in the literature about the catalytic dehydration of ethanol to ethylene3 dates from 1797. The start-up of the rst commercial plant in the beginning of the twentieth century motivated an increasing amount of research in this technology in many countries. The dehydration of alcohols, mainly ethanol, has been studied since then with different technologies and using a large variety of catalysts such as alumina, silica, silica-alumina, zeolites, clays, metal oxides, phosphoric acid, and phosphates. However, almost all processes operated on an industrial scale, have been based on vapor phase reaction using just two catalyst systems. Most old technologies were based on supported phosphoric acid but latter activated alumina became predominant. In particular for alumina, many factors were investigated for the catalysis of the ethanol dehydration, as the alumina crystalline form, the amount of hydration water, the use of promoters (mainly metal oxides and organic or inorganic acids), and the inuence of the catalyst acidity, texture (surface area, pore volume, and pore size), and morphology. The dehydration reaction is endothermic and requires 390 calories per gram of ethylene formed. In addition to the catalysis, the inuence of the main process variable, as pressure, temperature, liquid hourly space velocity (LHSV), and ethanol dilution with steam, were also studied.4 The ethanol conversion is controlled by a single-site surface reaction, strongly dependent on the diffusion of reagents and products inside the catalyst pellets. The most accepted mechanism for the ethanol dehydration considers a simultaneous reaction:

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Diethyl ether is considered an intermediate and not a byproduct. Its formation is favored mainly between 150 C and 300 C, while ethylene formation is predominant between 320 C and 500 C. With these operational conditions, acetaldehyde and hydrogen are obtained also by the reaction: CH3 CH2 OH CH3 CHO + H2 Other by-products formed by minor side reactions, or obtained from ethanol contaminants are: acetic acid, ethyl acetate, acetone, methanol, methane, ethane, propane, propylene, butane, butylenes isomers, hydrocarbons with 5 carbons or more, carbon monoxide, and carbon dioxide. A simplied generic process diagram of an ethanol-based ethylene plant, based on an isothermal or an adiabatic process, is represented by gure 1. Depending on the catalyst characteristics, its operational age and the dehydration process used, the ethanol conversion in one reactor is usually bigger than 95%, sometimes reaching as high as 99.5% and the reaction molar selectivity ranges from 95 to 99%. These parameters will have a direct inuence on the raw ethylene purity and on the purication steps required to produce polymer grade ethylene.

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Figure 1. Representation of a generic process diagram of an ethanol-based ethylene plant.

4. Commercial Processes and Plants

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The rst of the commercial plants to produce ethylene from ethanol was built and operated at Elektrochemische Werke G.m.b.H at Bitterfeld in Germany in 1913. It was a very smallscale plant that used alumina catalyst in isothermal conditions to produce ethylene for the preparation of pure ethane that was used in refrigeration. From 1930 until the Second World War, ethanol dehydration plants were the unique source of ethylene to the manufacture of mustard gas in Germany, Great Britain, and the United States. The process based on supported phosphoric acid was the basis for very primitive plants for all polyethylene production in England until 1951. Despite the many disadvantages of this catalyst, as low productivity and corrosion, its choice was based on the higher ethylene purity achieved by this catalyst that was required by high pressure polyethylene polymerization. During the 1950s, all ethylene needed for polyethylene and other chemical products started to be made from oil-based steam cracking plants. Since then and until the 1980s, Halcon/Scientic Design, ICI, ABB Lummus, Petrobras, Solvay, and Union Carbide, projected and built ethanol-based ethylene plants in India, Pakistan, Australia, Peru, and Brazil. The capacities of these plants were from 3,000 to 30,000 metric tons per year in general and the largest one was operated by Salgema (currently Braskem) in Brazil with a capacity of 100,000 metric tons per year that was used to produce ethylene dichloride to make PVC. Almost all of these plants were shutdown in the 1990s as a result of the drop in the oil prices and nowadays just one commercial unity is running in India to produce ethylene oxide. In 2007 Braskem started the operation of a pilot plant that is being used to make biobased ethylene to produce high density and linear low density polyethylene grades that have been distributed for many users around the world.

5. Process Main Characteristics

The ethanol dehydration reaction is conducted in the vapor phase through xed bed or uidized bed reactors with alumina or silica-alumina catalyst. For xed bed reactors, the operation can be isothermal or adiabatic. The uidized bed reactor operates usually in adiabatic conditions. 5.1. Isothermal Fixed Bed Reactor The isothermal process was most used in the ethanol dehydration since the early stages of the technology. It usually consists of a multitubular xed-bed arrangement where the catalyst is placed inside the tubes and a hot uid circulates in the shell to heat the endothermic

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reaction and maintain the catalyst temperature within a narrow range. Temperature control is important for the reaction. If the temperature is too high, acetaldehyde and decomposition by-products are formed and if it is too low, the conversion drops and diethyl ether formation is increased. Normally, the operating temperatures are between 330 and 380 C, with a LHSV of about 0.2 to 0.4 hr1 . The ethanol conversion is between 98 and 99%, and the ethylene molar selectivity is between 95 and 99%. The coke deposition on the catalyst demands a frequent regeneration with air diluted with steam. Depending on the process condition and the catalyst used, the regeneration procedure must be done in a frequency of between 1 month and 6 months. The scale up to large capacities is limited by the difculty of temperature control for bigger tubes and requires the use of multiple reactors in parallel.
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5.2. Adiabatic Fixed Bed Reactor The adiabatic technology was developed in the late 1970s. The reactor bed is packed with random catalysts and the endothermic heat of reaction is supplied by preheated steam as an inert heat carrying uid. Three xed-bed reactors in series are typically used, with additional ethanol make-up between each stage and intermediate furnaces to reheat the stream that feeds the next reactor. The typical LHSV is 0.15 to 0.5 hr1 in a water free basis. Feeding the reactor with a steam to ethanol weight proportion of 2:1 to 3:1 results in less coke, longer catalyst life, and higher yields. With an inlet temperature of about 450 to 500 C, the ethanol conversion is higher than 99% and the ethylene molar selectivity is between 97 and 99%. As another consequence of the steam usage, the coke build-up is smaller and the catalyst regeneration cycle is longer, usually between 6 and 12 months. 5.3. Fluidized Bed Reactor The rst uidized-bed to dehydrate ethanol was developed in pilot scale in the late 1970s5 . This process achieves nearly quantitative conversion of ethanol with very high selectivity to ethylene. However, no commercial plant using this technology has been built since then, in part because industry interest in ethanol dehydration technology declined after the decrease of the oil prices during the 1980s. The uidized-bed reactor permits an optimum temperature control and minimizes coke and by-product formation. The ethanol conversion at 400 C is 99.5% and the molar selectivity to ethylene reaches 99.9%. The endothermic heat of reaction is supplied by the hot feed and the recycle of the heated catalyst from the catalyst regenerator. Similarly to the adiabatic process, there is no need of external heating of the reactor. 5.4. Product Purication and Efuent Treatment After the dehydration reaction, the raw ethylene product is puried in a sequence of operations, starting with a quick cooling of the reaction stream and a water quench tower to remove most part of the water formed and the condensable polar substances, as the non reacted ethanol and small quantities of acetaldehyde and acetic acid. The crude ethylene, containing other minor contaminants, exits the top of the quench tower to be treated according to the purity desired for the nal product. In one preferred separation scheme, the crude ethylene stream is caustic-washed in a scrubbing tower to remove traces of carbon dioxide. After a compression, the ethylene stream passes through a desiccant drying bed with molecular sieves to produce a chemical

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grade ethylene with purity higher than 99%. When polymer grade ethylene is desired, the chemical grade ethylene is fractionated in a cryogenic distillation/stripping system to remove heavy and light contaminants and obtain the nal product with a purity adequate for most kinds of polymerization catalytic systems. The efuent streams from the quench tower and the scrubbing tower will contain mainly acetaldehyde, diethyl ether and the non-reacted ethanol. These components could be easily removed by stripping and the remaining aqueous efuent may achieve a Chemical Demand of Oxygen lower than 100 ppm.

6. Conclusions
The ethylene manufacture through ethanol dehydration is a process that has a low investment per ton of product, even in small scales. The reaction step is the core of this technology. The maximization of the ethanol conversion and of the reaction selectivity has a direct impact on the yield and, consequently, on the costs of the process. A higher yield means mainly that the plant will be able to obtain a larger quantity of the product with the same consumption of raw material. In addition, the costs for the purication of the raw ethylene and for the treatment of the efuents obtained at the bottom of the quench and of the scrubbing tower will be decreased too. The versatility, the low cost, and the chemical stability of the resins are the main aspects that made the many different types of polyethylene the most commercialized resin in the world. The main characteristic of the biobased polyethylene is that it is a resin with all these advantages and with exactly the same properties of the wide portfolio of polyethylenes based in fossil feedstocks. Plastics converters will not need to invest in new equipments or even will not need to adjust the sets of their machines. The recognition by the users that renewability is a characteristic even more valuable and sustainable than biodegradability is supported by the ASTM D68666 standard that certies the amount of biobased carbon. This standard permits the traceability of the products in each step of the chain using just a small amount of the sample. The amount of biobased carbon, the energetic efciency of the processes used in the entire manufacturing cycle, and the use of green sources of energy will impact positively in the reduction of the CO2 emissions and contribute to a better Life Cycle Analysis of the nal product. And as an alternative to the end of the life of the plastic, the bio-ethanol based polyethylene will be able to be recycled mechanically or by incineration, releasing in this case a nonfossil CO2 that will be equivalent to the quantity absorbed by the sugarcane crop at the beginning of the cycle.

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References
1. Mitchell, D. A Note on Rising Food Prices. Policy Research Working Paper 4682, The World Bank, Development Prospects Group, July 2008. 2. Eide, A. The Right to Food and the Impact of Liquid Biofuels (Agrofuels). Right to Food Studies, FAOFood and Agriculture Organization of the United Nations, 2008. 3. Winter, O., Eng, M-T. Make ethylene from ethanol, Hydrocarbon Processing, November 1976. 4. Kochar, N. K., Merims R.; Padia. A. S. Ethylene from Ethanol, Chemical Engineering Progress, AIChE, 1981, 6, 6670, 77. 5. Tsao, U., Zasloff, H. Production of Ethylene from Ethanol, US Patent 4,134,926. April 1977. 6. ASTM D686608. Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis.