ETHANOL TO ETHYLENE (ETE) CASE STUDY
ETHANOL TO ETHYLENE (ETE)CASE STUDYYIM YUEN YANA project report submitted in partial fulfilment of therequirements for the award of Bachelor of Engineering(Hons.) Chemical EngineeringFaculty of Engineering and ScienceUniversiti Tunku Abdul RahmanApril 2012
iiDECLARATIONI hereby declare that this project report is based on my original work except forcitations and quotations which have been duly acknowledged. I also declare that ithas not been previously and concurrently submitted for any other degree or award atUTAR or other institutions.Signature :Name:ID No.:Date:
iiiAPPROVAL FOR SUBMISSIONI certify that this project report entitled “ETHANOL TO ETHYLENE (ETE)CASE STUDY” was prepared by YIM YUEN YAN has met the required standardfor submission in partial fulfilment of the requirements for the award of Bachelor ofEngineering (Hons.) Chemical Engineering at Universiti Tunku Abdul Rahman.Approved by,Signature :Supervisor : Dr. Low Chong YuDate:
ivThe copyright of this report belongs to the author under the terms of thecopyright Act 1987 as qualified by Intellectual Property Policy of University TunkuAbdul Rahman. Due acknowledgement shall always be made of the use of anymaterial contained in, or derived from, this report. 2012, Yim Yuen Yan. All right reserved.
vSpecially dedicated tomy beloved grandmother, mother and father
viACKNOWLEDGEMENTSI would like to thank everyone who had contributed to the successful completion ofthis project. I would like to express my gratitude to my research supervisor, Dr. LowChong Yu for his invaluable advice, guidance and his enormous patience throughoutthe development of the research.In addition, I would also like to express my gratitude to my loving parentswho always give me support and encourage me during the project period. Theirblessings and wishes for me have been the driving force for achieving my aims.Last but not least, I would like to thanks my friends who always give metechnical as well as moral support throughout my work. Their patience and interestintegrates me into the investigation of technologies about bio-based product.
viiETHANOL TO ETHYLENE (ETE)CASE STUDYABSTRACTInvestigation of Ethanol-to-Ethylene (ETE) process technologies for differentlicensors was carried out by collecting the related data such as the operatingparameters, product yield, selectivity, catalyst and reactor used as well as itsadvantages over the conventional technologies for ethylene production. Besides, theproject cost for ETE process was estimated. Simulation using Aspen HYSYS 7.1 wascarried out to assess the viability of ETE process. The results showed that Lummusfluidized bed technology combined with the use of HZSM-5 catalyst is the best interm of the overall performance. It gives almost 100 % of ethylene selectivity andyield at lower temperature. Furthermore, the simulation results showed that 100 400kg/hr of ethanol was required to produce 57 850 kg/hr of ethylene which isequivalent to 0.58 kg ethylene/kg ethanol and the energy required by the process was2.69 108 kJ/hr. In addition, the total investment cost for ETE plant and theproduction cost of ethylene through ETE route were estimated to be USD 196 776836 with USD 1299/ton of ethylene produced respectively. In such case, the return ofinvestment (ROI) of 20 % and the payback period of 5 years were obtained. Lot ofcompanies have started the production of ethylene through ETE route, especially inBrazil. However, the production cost is much higher than that of equivalentpetrochemical ethylene owing to the high ethanol cost which accounts 80 % of theproduction cost. In conclusion, the development of cheap and sustainable conversionprocesses of low cost lignocellulosic biomass is crucial to enhance the viability ofETE process.
viiiTABLE OF CONTENTSDECLARATIONiiAPPROVAL FOR SUBMISSIONiiiACKNOWLEDGEMENTSviABSTRACTviiTABLE OF CONTENTSviiiLIST OF TABLESxiLIST OF FIGURESxiiiLIST OF SYMBOLS / ABBREVIATIONSLIST OF d11.2Problem Statement21.3Proposed Solution41.4Aims and Objectives4LITERATURE REVIEW62.1Cracking Technologies for Ethylene Production62.1.1Steam Cracking62.1.2Catalytic Cracking of Naphtha72.1.3Cracking of Vegetable Oils92.2Alternative Process Technologies for Ethylene Production 102.2.1Methanol-to-Olefins10
ix2.2.234Ethanol to Ethylene12METHODOLOGY203.1Data Collection203.2Data Analysis203.3Cost Estimation and Economic Evaluation213.3.1Total Capital Cost Investment213.3.2Operating Cost223.3.3Other Cost233.3.4Sales Revenue243.3.5Economic Evaluation243.4Simulation253.5Selection of Technology26RESULTS AND DISCUSSIONS4.14.24.34.44.528Foundation of Catalytic Dehydration of Bio-ethanol toEthylene28Licensors284.2.1Lummus Fluidized Bed Technology284.2.2Halcon Scientific/Chematur Engineering AB FixedBed Technology304.2.3SINOPEC Technology304.2.4Petrobras Technology31Comparison between Licensors Technologies334.3.1Process Main Characterization344.3.2Catalyst Characterization for ETE Process37Selection of Technology and Catalyst404.4.1Process Description414.4.2Catalytic Dehydration of Ethanol41Viability of ETE process444.5.1Availability of Ethanol444.5.2Economic Evaluation474.5.3Simulation51
x54.6Comparison between ETE and Naphtha Cracking564.7Commercial ETE Plants and Research Activities60CONCLUSION AND 63REFERENCES64APPENDICES72
xiLIST OF TABLESTABLETITLEPAGE2.1Typical Conditions for Naphtha Cracking62.2Products from Steam Cracking of Naphtha72.3Product Yields from Catalytic Cracking ofNaphtha82.4Ethanol Yield for Different Crops143.1Estimation of Labour-related Operating Cost andMaintenance Cost233.2Estimation of Fixed Cost244.1Operating Condition and Product Composition ofLummus Technology294.2Comparison between Licensors Technologies364.3Typical Composition of Polymer Grade Ethylene444.4Estimation of Total Capital Investment474.5Estimation of Production Cost484.6Economic Analysis Review514.7Material Balance by Stream534.8Material Balance by Component534.9Energy Balance by Stream534.10Summary of Simulation Results544.11Comparison between Naphtha Cracking and ETE59
xiiA.1Ethanol Production in Thailand73A.2Ethanol Production in Indonesia74A.3Ethanol Production in Philippine75A.4Ethanol Production in Vietnam76A.5Ethanol Production in Myanmar76
xiiiLIST OF FIGURESFIGURETITLEPAGE1.1Global Oil Supply and Demand, Hike in Oil Prices21.2Global Demand of Commodity Polymer32.1Flow Diagram of an Ethylene Plant Using LiquidFeeds62.2Products Yield at Different Feedstocks92.3Process Flow Scheme of MTO Process112.4Process Flow Diagram of UOP/HYDRO’s MTOProcess11Flow Chart with the Main Raw Material andProcess Used for Ethanol Production142.6Typical Flow Diagram of ETE Process152.7Ethanol ConversionDifferent Catalysts2.52.8overTemperaturefor16Catalytic Activity of SAPO Catalyst over LiquidSpace Velocity17Effect of Temperature and Space Time onSelectivity towards Ethylene and Diethyl Ether inDehydration of Ethanol182.10Effect of Feed Composition on Catalyst194.1Process Flow Diagram of Lummus’s FluidizedETE tur Engineering AB’s ETE Process302.94.2
xivProcess Flow Diagram of SINOPEC’s ETOProcess314.4Petrobras Adiabatic Fixed Bed Process324.5Block Diagram of Petrobras’s Co-processingProcess334.6Production Distribution of Different Catalysts404.7Lummus Fluidized Bed Reactor and Regenerator424.8Ethylene Column and Striper Section434.9World Ethanol Production454.10Production Capacity in South East Asia byCountry (million litres)464.11Breakeven Point Chart504.12Overall Process Design Diagram for EthyleneProduction from Dehydration of Ethanol55Total Energy Used for Different Routes ofEthylene Production57CO2 Emission for Different Routes of EthyleneProduction574.34.134.14
xvLIST OF SYMBOLS / ABBREVIATIONSCtotal production cost, USD/yrCalloccost of allocated plants, USDCDPIdirect permanent investment, USDCMmodule cost of equipment, USDCTBMtotal bare module investment, USDCTCItotal capital investment, USDCTPItotal permanent investment, USDDannual depreciation, USDF1, F2factors account for site preparation, service facilities, utilityfacilities and related facilitiesFMmaterial factorFpproduction rate of main product, lb/yrFPIfactor account for piping, instrumentation and automatic controls,and indirect costsFPRproduction rate factoriminminimum acceptable return of investment, %SSales revenue, USDtincome tax rate, %APECAsia Pacific Economic CooperationCTOcatalyst-to-oil ratioDW&Bdirect wages and benefits, USD/yrETEethanol-to-ethyleneFCCfluid catalytic crackingHChydrocarbonHVChigh value chemicalsIEAInternational Energy Agency
xviLHSVliquid hourly space velocity, hr-1MmaintenanceM&O-SW&Bmaintenance and operation salaries, wages and benefits, USD/yrMTOmethanol-to-olefinMW&Bmaintenance wages and benefits, USD/yrNETLNational Energy Technology LabOoperationalPBPpayback period, yearRCCresidual catalytic crackingROIreturn of investment, %ROWrest of WorldSDScientific DesignSECspecific energy consumption, GJ/tVPventure profit, USD/yrWHSVweight hourly space velocity, hr -1
xviiLIST OF APPENDICESAPPENDIXTITLEPAGEAEthanol Production in South East Asia72BSimulation Results77
CHAPTER 11 INTRODUCTION1.1BackgroundEthylene is the simplest olefin and the most important base product in manufacturingpetrochemicals. It is the largest volume of organic chemical worldwide which isconverted into a range of solid and liquid products with a wide range of applications.For instances, ethylene is used to manufacture ethylene derivatives and polymerssuch as ethylene oxide, ethylene dichloride, polyethylene and polyethyleneterephthalate (PET) (ICIS, 2011). The global demand of polymers which accountsfor approximately 59.3 % of total ethylene market is expected to continue to growover the next 10 years based on Nexant Chemsystem report (2011). Besides, SRIconsulting report (2011) estimated that the consumption of ethylene is continuouslyrising at an average rate of 3.5 % per annum.The most common used commercial methods for producing olefins is steamcracking whereby naphtha cracking and ethane cracking represent about 45 % and35 % of world ethylene production capacity respectively (Gielen, Bennaceur, & Tam,n.d.). This process uses the steam as the diluting agent and heat the feedstock infurnace without the presence of oxygen to break down the large hydrocarbon into thesmaller ones. The major concern of this technology is coke formation duringcracking process and it consumes large amount of energy which in turn, the energycost for production has increased. Therefore, it is necessary to produce ethylene atlow energy cost by adopting the alternative routes over the conventional methods.
21.2Problem StatementCrude oil, the raw materials of fractions that used to produce light olefins, is a nonrenewable resource. However, the oil demand is increasing due to the economicgrowth of developing countries even though the crude oil is depleting. Based on theOil Market Report from International Energy Agency (2009), the oil productionworldwide has always been unable to meet the increasing oil demand and the oilprices are increasing as shown in Figure 1.1. In fact, oil supplies have alwaysremained constant in terms of volume for years.Figure 1.1: Global Oil Supply and Demand, Hike in Oil Prices[Source: Peak Oil Consulting, 2008; IEA, 2009]
3Besides, the pressure arisen from oil depletion and escalating oil demand hasresulted in the hike in oil prices to reach the equilibrium in demand and supply.Currently, the oil prices are above 100 per barrel which has significantly burdenedthe investment and manufacturing sectors. As illustrated in Figures 1.2, the globalcommodity demand of polymers is growing and this has revived a strong interest inproduction of bio-based petrochemicals which is produced by using renewablefeedstock to avoid the negative impact on economics and business.Figure 1.2: Global Demand of Commodity Polymer[Source: Nexant, 2011]In addition to the crude oil issues, the technologies used for ethyleneproduction have significant impact on the environment. Steam cracking is the mostenergy consuming process in the chemical industry and it currently accounts forapproximately 180 to 200 million tonnes of CO2 emissions worldwide (Neelis, Patel,Blok, Haije, & Bach, 2006). Goals to develop alternative routes for ethyleneproduction which have favourable energy consumption and greenhouse gasesemission have been brought up.
4In a nutshell, from both environmental and economic perspectives, it istherefore of interest to study alternative sources for ethylene production as well asenergy saving potentials offered by alternative processes.1.3Proposed SolutionCatalytic dehydration of ethanol to ethylene so called Ethanol-to-Ethylene (ETE)was first reported since 1979 (Morschbacker, 2009). This process utilizes ethanol asfeedstock which is obtained through fermentation process using agricultural productssuch as sugarcane, corn and biomass. Compared to the petrochemical equivalent, themain advantages of bio-ethylene are that it can reduce greenhouse gas lifetimeemissions and the dependence of the chemical industry on fossil-fuels (Neelis et al.,2006).1.4Aims and ObjectivesIn this study, the alternative route to be investigated is dehydration of ethanol forethylene production, i.e., ETE process.The objectives of the study are as followings: To study and compare the licensors technologies for ETE process in term oftheir efficiency and propose the best technology. To study the feasibility of the project in term of economic worth, availability offeedstock, and practicability based on simulation results. To study the market distributions and market activities of the ETE process. To compare the ETE process with the naphtha cracking process.
CHAPTER 22 LITERATURE REVIEW2.1Cracking Technologies for Ethylene Production2.1.1Steam CrackingSteam cracking of hydrocarbons has been the major source of light olefinsproduction for more than half a century. The current feedstocks for olefin productionare derived from crude oil and natural gas such as naphtha and ethane. Theavailability of feedstock depends on the composition of crude oil and natural gas andtheir production volume (Rahimi & Karimzadeh, 2011). For instance, steam crackingof light naphtha produces about twice the amount of ethylene obtained from steamcracking of vacuum gas oil under nearly similar conditions.The typical process of steam cracking and the typical operating condition areshown in Figure 2.1 and Table 2.1, respectively.
6Figure 2.1: Flow Diagram of an Ethylene Plant Using Liquid Feeds[Source: Matar & Hatch, 2000]Table 2.1: Typical Conditions for Naphtha Cracking[Source: Matar & Hatch, 2000]ConditionTemperature, CPressure, atm.800atmosphericSteam/HC, kg/kg0.6-0.8Residence time, s0.35Generally, liquid feed are cracked with lower residence times and higher steamdilution ratios than those used for gas feedstocks. Besides, maximum olefin yieldscan be obtained at lower hydrocarbon partial pressures, pressure drops, and residencetimes for liquid feeds (Matar & Hatch, 2000). Cracking process operated at higherseverity increases the ethylene product and by-product methane and decreasespropylene and butylenes. Table 2.2 shows the product distribution at low and highseverity condition.
7Table 2.2: Products from Steam Cracking of Naphtha[Source: Matar & Hatch, 2000]Cracking SeverityProducts, wt 12.1Butadience4.54.2Butenes7.92.8BTX1013C5 179Fuel Oil36Other5.56.6The largest energy component is the heat used in cracking which is necessaryto provide the heat of reaction and the sensible or latent heat to bring the reactants tothe desired reaction temperature of 750 C to 900 C (Gielen et al, n.d.). It accountsfor 40 % of the total energy consuming every year in the entire petrochemicalindustry and results in high amount of CO2 emission (Rahimi & Karimzadeh, 2011).In addition to high energy consumption and CO2 emission, a typical steamcracking process which cracks the naphtha into smaller molecules in gaseous statehas a problem of coking that will cause inefficient of steam cracker (Tao, Patel, &Blok, 2006). Great efforts have been dedicated to the researches on developing anovel process that can overcome the deficiencies of steam cracking.2.1.2Catalytic Cracking of NaphthaThe current method of producing olefins via steam cracking of naphtha has severaldrawbacks such as the high energy consumption, the deposition of coke in the tubes,and the relatively low selectivity in ethylene from heavy feeds. This leads to catalytic
8pyrolysis has been studied extensively to overcome the shortcoming of steamcracking.Catalytic cracking is a process in which the heavy hydrocarbon molecules areconverted into lighter molecules by contacting the heavy hydrocarbon with thezeolite catalyst. From the Table 2.3, it was noted that the ethylene yield is lowerwhile the propylene yield is higher in comparison with conventional steam crackingprocess (Nexant, 1997).Table 2.3: Product Yields from Catalytic Cracking of Naphtha[Source: Nexant, 1997]Patent NumberFeed 97.1619970795.9Ethylene, wt %2222.821.922.321.8Propylene, wt %22.224.52320.822.4C4 – C6 aromatics, wt %26.420.320.222.821.3Total, wt %70.667.665.165.965.5The performance of fluid catalytic cracking (FCC) unit is dependent on alarge number of parameters which influence the conversion process in their own way.The parameters studied include the feed composition, residence time, temperature,catalyst-to-oil ratio (CTO), hydrocarbon partial pressure, catalyst properties, andriser hydrodynamics in order to find out the optimal condition for conversion process(Dupain, Makkee, & Moulijn, 2006).There are several studies on the optimization of FCC processes. Lid andStrand (1997) reported the implementation of on-line optimization and modelpredictive control to a residual catalytic cracking (RCC) unit. While Ellis, Li &Riggs (1998) presented an optimization model by combining an empirical yieldprediction model for cracking products with macroscopic mass and energy balancesfor the unit.
92.1.3Cracking of Vegetable OilsResearches on various alternative sources as crude oil substitute for ethyleneproduction were carried out to avoid the problems associated with crude oil.Zamostny, Belohlav, & Smidrkai (2011) have disclosed the use of vegetable oilswhich is one of the premium renewable resources as crude oil for short alkenesproduction via steam cracking. Figure 2.2 shows the product yield obtained based ondifferent feedstocks used in steam cracking process.Figure 2.2: Products Yield at Different Feedstocks[Source: Zamostny et al., 2011]Vegetable oils form the similar products as traditional crude-oil-basedfeedstocks under the condition matching with the gas oil steam cracking. Besides, thelong linear chain of vegetable oil leads to comparatively high content of ethylene aswell as propylene and butadiene in a product mixture. Since the mechanisms ofpyrolysis reactions of both the rapeseed oil and crude oil fractions are similar, itwould be possible to employ well-known hydrocarbon pyrolysis technologies tovegetable oil cracking (Zamostny et al., 2011).In addition, multiple studies regarding the topic have been published. Forinstance, Bielansky et al. (2010) and Dupain, Costa, Schaverien, Makkee, & Moulijn(2007) have studied on catalytic cracking of rapeseed oil to high octane gasoline andlight olefins. The researches again found that the vegetable oils can be used in fuel
10production and petrochemical industries and form similar products as traditionalcrude oil feedstock under the comparable operating condition. Furthermore, thevegetable oil can be blended with the feed of an existing FCC uni
production cost of ethylene through ETE route were estimated to be USD 196 776 836 with USD 1299/ton of ethylene produced respectively. In such case, the return of investment (ROI) of 20 % and the payback period of 5 years were obtained. Lot of companies have started the production of e
The overall function of the distillation column is to separate the ethanol from the water. We want the bottom of the column to be only water and the top of the column to be only ethanol. Li id 20% Vapor, 60% ethanol Individual tray from previous slide Liquid, 15% ethanol Liquid, 20% ethanol Vapor, 51% ethanol Liquid, 10% ethanol Liquid, 5% ethanol
ethanol-to-ethylene dehydration plant. The results are for a process that obtained produces 100 kt ethylene/yr and has an operating time of 8000 h/yr. A lignocellulosic ethanol plant producing the feedstock (174 kt ethanol/yr) to an ethanol-to-ethylene plant has an energy surpl
Oxygen, the combustion products of ethanol are considered to be "eco-friendly". Anhydrous ethanol, also known as absolute ethanol, is the standard ethanol used in vehicle fuels. It consists of at least 99.5% ethanol by volume. Presently, Brazil and the United States are the top two producers of ethanol.
Jan 27, 2005 · The Ethylene Oxide Product Stewardship Guidance Manual was prepared by the American Chemistry Council’s Ethylene Oxide/Ethylene Glycols Panel (Panel). It is intended to provide general information to persons who may handle or store ethylene oxide. It is not i
quire ethylene in quantities of 100 103 – 200 103 t/a only and ethylene supply from standalone crackers of this size is not feasible in most cases. 2. Physical Properties Ethylene is a colorless flammable gas with a sweet odor. The physical properties of ethylene are as follows: mp
DPCV/CRD/BI – IEA BIorefinery March 3rd 2010 - Lestrem 37 Chemical and Agro Industrial players have started to form partnerships to build biorefineries Some Emblematic Examples Product Volume kt Announced Timeline Ethylene/VCM (from ethanol) 360 VCM 2010 Ethylene (from ethanol) 350 2011 Ethylene
production Production of second-generation ethanol by biochemical conversion of lignocellulosic biomass Production of bio-ethylene from ethanol Production of bio-ethylene from ethanol
Abrasive jet Machining consists of 1. Gas propulsion system 2. Abrasive feeder 3. Machining Chamber 4. AJM Nozzle 5. Abrasives Gas Propulsion System Supplies clean and dry air. Air, Nitrogen and carbon dioxide to propel the abrasive particles. Gas may be supplied either from a compressor or a cylinder. In case of a compressor, air filter cum drier should be used to avoid water or oil .
