Ethyl Acetate Properties

ethyl group radical radical radical group ethanoate Properties ethyl radical ethanoate rayon is the around popular ester from neutral spirits and acetic acetous. It is fabricate on a massive scale for engagement as a solvent. ethyl radical acetate is a mode appreciately polar solvent that has the advantages of existence volatile, relatively non- noxious, and non-hygroscopic. ethyl group acetate rayon is an innate compound which likewise known as, ethyl ethanoate, usually abbreviated EtOAc or EA. Below is the table of Ethyl Acetate habitual data and physical propertiesFORMULACH3COOCH2CH3MOLECULAR WEIGHT88.10MELTING period-83.6CBOILING POINT77.15CINDEX OF REFRACTION nd201.372 compactness d200.902 g/mLSPECIFIC set off (20C)0.459 kcal/kg.CLATENT HEAT (bp)88 kcal/kgVISCOSITY (20C)0.455 cPEA SOLUBILITY IN pee (20C)7.7 wt.%WATER SOLUBILITY IN EA (20C)3.3 wt.%Table 1.1 Physical Properties of Ethyl AcetateEthyl acetate force out(a) dissolve up to 3% wet and has a solubility of 8% in irrigate at room temperature. At elevated temperature its solubility in water is heightser. It is unstable in the comportment of strong aqueous initiations and acids.Ethyl Acetate tail assembly be getd by several(prenominal) types of impact such as esterification, Tishchenkos response and groundbreaking Acetates by train addition (AVADA) technology. In 1985 it was nigh 400000 tones in stacks were produced yearly in Japan, North America, and Europe combined. The commercial Ethyl Acetate is a clear, colorless, sweet smell odor and has a minimum honesty of 99.8%, with water and fermentation alcohol non exceeding 0.03%.Historical Review of Ethylbenzene ProcessesEthyl Acetate is primarily produced by direct esterification of ethyl alcohol (e.g ethanol) with acetic acid, a deal which involves mixing acetic acid with excess of ethyl alcohol and adding a small tot up of sulphuric acid. This mixture returns rough 65% of ester (EA). Then the EA is calved and purified by distillate in exhibition to achieve commercial specification. This cognitive operation considers as ex othermic and safe where the groove of reply is -0.0114kJ/mol with no danger of decomposition.Other methods that often use in manufacturing ethyl acetate atomic number 18 based on Tishchenkos response. This response is by combining devil equivalents of ethanal in the presence of an alkoxide base as atom smasher. This way is a commercial method of producing ethyl acetate. ascribable to the observation and experiment by Tishchenko, the result shown that the regainable yield of ethyl acetate by adding aluminum ethoxide to ethanal at -20oC is 61%.In addition, new and interesting bear on of manufacturing ethyl acetate is Advanced Acetates by Direct Addition (AVADA) technology. This chemical reaction apply the reaction of ethene, acetic acid and water with the presence of heteropoly acid (HPA) accelerator. It then provide undergo reaction at vapor arrange before macrocosm fed into the insularity section where the major harvest-time and by- harvest being separated. This process can produce ethyl acetate at 99% concentration.The Uses of Ethyl AcetateEthyl acetate is employ as solvent in a wide range application especially in industries. It is one of the close popular solvent that utilise in surface coating and thinners manufacture such as nitrocellulose lacquers, varnishes and thinners. It exhibits high dilution ratios with both aromatic and open-chain diluents and is the least toxic of industrial organic solvents.Pharmaceuticals also required ethyl acetate as an superfluousction solvent for the concentration and civilisation of antibiotics. Manufacturing of mixed drugs also used ethyl acetate as an intermediate. High uprightness product can be used as a viscousness reducer for resins used in photoresist formulations in the electronics industry. Besides that, ethyl acetate acts as a solvent in the preparation of syn thetic output essences, flavors and perfumes.On the other hand, the extensive nubs of ethyl acetate atomic number 18 used in the manufacture of flexible packaging and in the manufacture of polyester films and BOPP films. It is also used in the discussion of aluminium foils. Ethyl acetate is used as solvent to dissolve the resin, control the viscosity and modify the drying rate in inks for flexographic and rotogravure printing.Based on ICIS article that has been updated April 2008, the orbiculate ingest is predicted to grow at 3-4%/year because of strong get hold of for surface coatings and as a replacement for restricted solvents. China and Southeast Asia atomic number 18 queen-sizest demand spot Western Europe is developed markets. Southeast Asia and China ar expected to become the most popular for ethyl acetate labor and consumption. The Southeast Asian paints and coatings market is expected to grow at 5-6%/year.Japans Daicel Industries is converting an acetic acid pl ant in Otake, Hiroshima to produce ethyl acetate by development bio-ethanol as the raw material. It will shoot a aptitude of 50,000 tonnes/year with labor expected to start in spring 2009.The global demand growth for US is about 2%/year to 2009. gibe to ICIS Chemical Business (ICB), US demand increased from 88,500 tonnes in 2005 to 95,300 tonnes in 2009. Around 60% of ethyl acetate is consumed in US as a solvent in a variety of coating formulations. These coatings are used for wood furniture and fixtures, agricultural, construction and mining equipment, driveers and closures, auto re complete, and sustentation and marine applications.Around 20% of the ethyl acetate is used as solvent-based architectural coatings for both exterior and interior use. This sector has been growing at approximately 6%/year. However, in industrial coatings the usage of ethyl acetate is decline because of environmental constraints has largely been completed and future growth in the US is estimated to be a healthier 2.5%/year up to 2009.OEM (original equipment manufacturer) solvent-based coatings bring forth been declining slowly in the US. The OEM sector, however, is the largest and represents 58% of ethyl acetates coatings use demand. The remaining sector, metier coatings, which allows marine coatings, has held steady.The European market is reported to be balanced with macroscopic supply and steady demand. However, future demand is expected to be forthwith and or even contract slightly as consumption by local paints and inks sectors shrinks as production moves eastwards.In the UK, INEOS has acquired BPs ethyl acetate business including a 250,000 tonnes/year plant in Hull. Future desegregation is seen as possible in Europe as ethylene-based producers struggle to make do against more competitive ethanol-based production. Europe could also become more dep removeent on imports. sour BACKGROUNDEsterificationEsterification is a chemical reaction process mingled with alcohol and carboxylic acid in the presence of accelerator that formed ester. This mixture converts to ester about 65% at room temperature. The commonly arduous sulphuric acid is acting as a esterification throttle to enhance the reaction. The sulphuric acid removes water to help shift the balance wheel towards forming more ester product. Water is a by- product and moldiness be take in tell to get the equilibrium in the desired direction. This process is a simple process, well known reaction, and moderately exothermic where the oestrus or reaction, H is -0.0114kJ/mol with no danger of decomposition reaction. The optimal temperature for this reaction is in the range of 363 K 400 K eon the optimum pressure is in the range of 20 bar 40 bar.Ethanoic acidulated + ethanol Ethyl Acetate + WaterCH3COOH + C2H5OH CH3C02C2H5The reaction between acetic acid and ethanol to produce ethyl acetate in the presence of concentrated sulphuric acid. This process is released a few amount of heat to the surrounding and classified as exothermic reaction. This reaction is called a homogeneous lucid grade. Water is formed in the reaction is removed continuously to ensure maximum conversion of acetic acid.The catalyst can be heteregenous and homogeneous. There are two categories of catalyst that can be used in this reaction, mineral acid catalyst and para toluene sulphonic acid or ion ex trade resins can serve as nonuniform catalyst.Process DescriptionEthanol and acetic acid together with scratchy ethyl acetate is fed into the nuclear reactor in the presence of concentrated sulphuric acid to produce ester and water. Then, the products are fed into the distillation editorial (DC1) to separate water and ester (ethyl acetate). The bottom product of DC1 is water and the overhead product is ethyl acetate. This part are taken by dehydration and azeotropic distillation of ethyl acetate and water. The overhead product is passed to the decanter to separate the organic phase and aqua se phase. The upper layer known as organic phase dapple lower layer known as aqueous phase. partly of organic phase is fed into the reactor and another potion of organic phased is passed into the wink distillation tower (DC2). The consequence column is a purify process where to give the pure ethyl acetate (bottom product). The top product is a mixture that lies of ethyl acetate, water and ethanol. this mixture is separated after cool down process and the light phase is fed prat to DC2 and the rest is transferred to the second decanter where its process is same as the first decanter to separate the organic and aqueous phase.Pipeline is used to combine the aqueous phase from the both decanters and distilled in the third column to give waste water at the bottom product and again ester, water and alcohol. This stream is cycled into the reaction column.Raw textileEthanolEthanol is one of the material that is being used in the esterification process. it is also known as ethyl alc ohol. ethanol is a volatile, flammable and colorless liquid. Ethanol can be obtain by fermentation of plants. Ethanol is relatively non-toxic and dissolve in water. It is a renewable cogency source and it has less harmfull effects on the environment. However, ethanol will also give an impacts to the environment. The use of ethanol is a trouble for conventional air pollutants. Ethanol used will increase the spark of chemicals that lead to the production of ozone.Ethanoic acidOne of the raw material necessitate to complete the reaction. Ethanoic Acid is one of the simplest carboxylic acid. it is a colourless liquid with an unpleasant pungent odour. ethanoic acid is produced by the oxidation of ethanol. Ethanoic acid is super black to the metals and it is also potentially harmful to our health.sulphuric acid (catalyst)Sulphuric acid is chosed as homogeneous catalyst in this reaction. this catalyst is real(prenominal) effective mineral acid catalyst. however, this sulphuric acid is strongly corrosive and leaves sulfate equilibriums. besides that, it is also generates large amount of heat.Tishchenkos ReactionTishchenkos reaction is a reaction that direct the presence of an alkoxide base while two equivalents of acetaldehyde is combining. This way is becoming commercial method of producing ethyl acetate in Europe since acetaldehyde become important intermediate on the basis of acetylene. Due to Tishchenko, the obtainable yield of ethyl acetate by adding aluminum ethoxide to acetaldehyde at -20C is 61%. The reaction is express by,catalyst alkoxide base (e.g Aluminum Ethoxide)2CH3CHO CH3COOCH2CH3(Acetaldehyde) (Ethyl Acetate)Figure 1.3 Tishchenkos processProcess DescriptionFor the process of Tishchenkos reaction, acetaldehydes will be introduced to the catalyst solution continuously. The catalyst is first need to be prepared by dissolving granular Aluminium in an ethanol-ethyl acetate mixture in the presence of aluminium chloride and small amount of zinc ch loride. This catalyst ( prefatorially Aluminum Ethoxide) is prepare uncontinuosly.In reactor, while acetaldehyde contact with the prepared catalyst, the ratio of the reaction partner must be adjust in order to obtain 98% transformation of acetaldehyde in one passage. A further 1.5% transformation is achieved in divine guidance vessels. Consecutively to make sure the reaction temperature is kept to 0C, douse with normally -20C will be used as the cooler. This reaction takes approximately 1 hour to completely mix before being transfer to resi repayable separation.Next, separator is needed to remove the residue that contain in the mixture. The distillable products are removed by evaporation. For the economic issue, the residue is handle with water to regain ethanol. For the residual slurry, it can either be minded(p) to biological degradation plant or it can be destroy together with other organic waste products.Subsequently, the distillable products need to be purging in so that it can achieve commercial purity which is approximately 99.8%. Therefore, distillation column is used. For the 1st series of distillation column, light end are separated and this steam is further distilled to take non-converted acetaldehyde, which is returned to reactor. Then ethanol that contain ethyl acetate is separated for reuse in catalyst preparation.The bottom of 1st column give the high quality or grade of ethyl acetate that only will obtain at the head of the next column due to the need of separation of high boiling condensation products in mixture with ethyl acetate which will be remove at the bottom. In addition, further small column is needed to recover another part of pure ethyl acetate to isolate acetaldehyde diethyl acetal. Hence, after elaboration is done the recover product can used as an important intermediate or hydrolyzed in an acid medium to give reusable acetaldehyde and ethanol.Raw MaterialAcetaldehydeIt is also known as ethanal. Acetaldehyde is one of the mo st important aldehyde and is being produced in a large scale industrially. This bosom can be produced by the oxidation of ethylene. Although it is not a expensive substance and it is real easy to get, acetaldehyde is a very toxic substance. It can give harm to living organisms and toxic substance is not an environmental friendly. It is an air pollutant resulting from combustion.Advanced Acetates By Direct Addition (Avada)In AVADA process, ethyl acetate is produced by reacting ethylene with acetic acid and water in the presence of heteropoly acid catalyst. The amount of water being used is in range from 1-10 mole% based on the total ethylene and acetic acid. The presence of water can reduce the amount of uncalled-for by-product that formed by the reaction. The mole ratio of ethylene to acetic acid in the fecundate stream is in range of 6.0 to 12.2, while for ethylene to water, the mole ratio is between 8.0 to 17.0 and the mole ratio of acetic acid to water is from 1.25 to 1.40.H eteropoly acidCH2 = CH2 + CH3C02H CH3C02CH2CH3(ethylene) (acetic acid) Water (ethyl acetate)The reaction is preferably carried out at a temperature in the range from 160C to 195C while the preferably pressure is between 1200 kPa to 1500 kPa.The catalyst used must consist at least one heteropoly acid salt of a metal such as litium, cuprum, and magnesium which supported on a carrier. The heteropoly acid used is phosphotungstic acid while the carrier is silica. Heteropoly acids usually have a high molecular weight in the range of 700 8500 and include dimeric complexes. They have high solubility in polar solvents such as water or other oxygenated solvents. In order to achieve optimum performance, the carrier should free from metals or elements which can affect the catalytic application of the system. To prepare the carrier, firstly the heteropoly acid is dissolved in distilled water, demineralised water, alcohols or other non-aqueous solution. Then the carrier is soaked in the acid so lution for several hours with periodic manual stirring. After that it is filtered exploitation Buchner funnel to remove either excess acid. The wet catalyst is then placed in an oven at elevated temperature for several hours to dry. Lastly it is allowed to cool to ambient temperature in desiccators. straight this supported catalyst is ready to be used in esterification process. raw material FLOW DIAGRAM OF ETHYL acetate PRODUCTION BY AVADAThe basic menstruum diagram of the unit is shown in the above figure. The unit consist of feed section, reaction section, and product and by-product separation section.The basic flow diagram of the unit is shown in the above figure. The unit consist of feed section, reaction section, and product and by-product separation section.The fresh feed which contain ethylene, acetic acid and water are fed into the vaporiser. Vaporiser is used to change the liquid phase feed into drying up phase as the reaction is preferably carried out in the vapour p hase. It also includes a recycle system for both unreacted feeds and all the major by-products.The combined feed vapour stream is fed to a reactor train comprising of four fixed bed reactors in which each reactor already filled with catalyst. The reactants are passed over the catalyst suitably at a GHSV (Gas Hourly position Velocity) of 300 to 2000 per hour. The first three reactors are fitted with acid/water injection to the exit streams. This is to facilitate independent control of reactor inlet temperatures and to honour the desired ethylene to acid ratio. The fourth reactor functions as finishing reactor where the final conversion of ethylene and acetic acid to ethyl acetate is achieved. There are four by-product formed from the reaction which are 2-butanone, acetaldehyde, ethanol and diethyl ether.The crude product stream exiting the last reactor is cooled before entering the flash drum where the separation of non-condensable ( waste) and condensable (liquid) phases occurs .The recovered gas is recycled back to the vaporiser while the liquid stream enters the product separation and purification system. In this system, series of distillation columns designed to recover and purify the final product. It is also to recover the unreacted acetic acid, water, ethanol and light ends streams for recycling back to the vaporiser.Advantages and Disadvantages of AVADAThe AVADA process is superior to other additional processes in terms of environmental protection. This is because AVADA uses a unattackable acid catalyst. Therefore, there are fewer fates for the treatment and disposal of aqueous effluent canvassd to traditional esterification reaction that produces as much water as ethyl acetate. Since AVADA process eliminates the intermediate esterification steps and the need for ethanol, it save about 20% on energy cost compare to conventional routes. The AVADA process produces high purity (more than 99%) which reduces the production of by-products. hateful by products such as 2-butanone and acetaldehyde may be controlled by careful adjustment of feed composition and reaction temperatures while maintaining gratifying ethyl acetate yields. The production of c4 unsaturated hydrocarbons is significantly reduced. Therefore, the catalyst life sentence can be extended. The disadvantages of AVADA process is rapid catalyst deactivation soly disturbing the quality of the product. However, this problem can be solved using a bed porous silica beads with the heteropolyacid impregnated in the pores.PROCESS SELECTIONThere are three methods found in the production of ethyl acetate which are Tishchenko, Esterification and Advanced Acetates by Direct Addition (AVADA). By considering all of the advantages and disadvantages of each process, the Acetates by Direct Addition (AVADA) was chosen as the best alternative to produce ethyl acetate. The main author AVADA was chosen are because the catalyst used is environmental friendly.TICHSHENKOSESTERIFICATI ONADVANCED ACETATE BY DIRECT ADDICTION (AVADA)RAW MATERIALAcetaldehydeEthanolAcetic acidEthyleneAcetic acidWater atom smasherAlkoxide base (e.g aluminium ethoxide)Produced large amount of aluminium residue which is not easily separatedProduce large amount of wastewaterAcid catalyst (e.g Sulphuric acid)Very corrosiveProduce sulphate residueHeteropolyacid (e.g phosphotungstic acid)The catalyst life history can be extendedUsing solid catalyst- waste free and less requirement for treatmentOPERATING human body0C1 hour reaction90 0C 127C20 bar 40 bar160C 195C1200 kPa 1500kPaPURITYCrude ethyl 61 % purityCrude ethyl 55 % purityCrude ethyl 99 % purity proceeds OF EQUIPMENT USE5 equipments ( distillation column, feed surge drum, reactor, separator, mixer)3 equipments (reactor , decanter, distillation column)5 equipments (vaporizer, reactor, flash drum, distillation column, compressor)REACTION2Acetaldehyde Ethyl Acetateethanol + ethanoic acid ethyl acetateEthylene + acetic acidEthyl acet ateAVAILABILITY OF RAW MATERIALProduce in large scale in Europe due to the importance of acetaldehyde as intermediate on the basis ofacetyleneEasy to get in mainland ChinaTable 1.2 Comparison between all processesPROCESSADVANTAGESDISADVANTAGESAVADA (Advanced Acetates By Direct Addition)Undesirable by products such as 2-butanone and acetaldehyde may be controlled by careful adjustment of feed composition and reaction temperatures while maintaining acceptable ethyl acetate yields.The production of c4unsaturated hydrocarbons is significantly reduced.The catalyst lifetime may be significantly extended.The process economics are meliorate by a reduced requirement to operate process persecute streams to reduce the recycle of undesirable by-products and by the ability to de-bottleneck the product purification system.Very high purity (99%).Avoid environmental hazards by using heteropolyacids (environmentally friendly).More energy efficiency save 20% on energy costs.Using solid catalyst w aste free and less requirement for treatment and disposal of aqueous effluent.Rapid catalyst deactivation thus disturbing the quality of the product.EsterificationWell known reaction.Moderately exothermic reactions with no danger of decomposition of reactions.The reaction also exhibit second order ractions when no strong acid is present and a kind of autocatalytic behaviour when the acid is introducespurification system.Acidic feedstocksConcentrated sulphuric acid is a harmful chemical reagent.Generates large amount of heat.Tishchenkos ReactionThe raw materials are produced in large quantities.The price of the raw material is not very costly.It is an alternative way due to expensive price of ethanol.Produce large amount of aluminium residue which is not easily separated due to the use of aluminium ethoxide as a catalyst .The use of the catalyst can create a large amount of wastewaters and thus extra cost is needed to treat the waste.The raw material, acetaldehyde is a very toxic sub stance.Table 1.3 Advantages and disadvantages of each processes