one: Introducti pt 1.4 Importance and uses Ethylene oxide (EO) has been an important chemical substance until now. lls great importance stems fiom the reactivity of the oxirane ring, making it a Key substance for « multitude of other intermediates and final products. “! The majority of all ethylene oxide (EO) produced is used as @ chemical intermediate in the production of various compounds including ethylene glycol, glycol ethers, and non-ionic surfaciants. EO is also used as a fumigant for food and cosmetics, and in hospital sterilization of surgical equipment and heat scusitive materials such a3 plastics, ©! Other minor uses worldwide include its application in the manufacture of rocket propellant and petroleum demulsifiers Ethylene oxide is used for the control of insects in stored produets and for the control of bacteria in spices and natural seasonings. Ethylene oxide is also present as ¢ formulant or component of formulant in pest control products at concentrations up to 0.4%. ‘The formulants include fungicides, insecticides, herbicides and an adjuvant. 1.1 Ethylene glyeols Ethylene glycol, usuelly known simply as glycol, is the most important secondary product of ethylene oxide. “ The Ethylene oxide is converted by thermal hydration into mixture of glycols, namely moncethylene glyco! (MEG), diethylene glycol (DEG), triethylene glycol (LEG), and higher glycols. MEG has two main uses, in fiber manufacture in combination with dimethylicrephihalate, and in the cooling systems of motor vehicles where it acts as a [ree7ing point depressant, DEG is also used in the fiber industry and as a tobaeco humectant, ‘TEG and DEG are both used for gas treatment, TEG is also used int the manufacture of eellophane for food packaging, When VIEG and DEG are futher reacted with ethylene oxide and then polyzlyeols of specitie molecular weight are produced. These polyglycols can then be used in the cosmetic and pharmaceutical industry as base material for carrying the active ingredients, in the ink and printing industry, as antitoam agents in distillation processes, and in the textile industry as spinning lubricants, 1.4.2 Ethanolamines Bihylene oxide will react with ammonia to give « mixture of ethanolamines, and the mono-. di- an be separately recovered. Mono and diethanolamine are used as absorbents for the removal of acid gases from synthesis gas; triethanolamine is widely used in cosmetic and toilet preparations (ais shampoos). "7 and triethanolamines so produced 1.4.3 Glycol ethers Ethylene oxide will reget with alechols to produce glyco! ethers and, depending on the alcohol used, will yield, for example, methyl. ethyl-, isopropyl-, and butyl glycol ethers, again inthe mono, di, and tri forms, In particular the monoethers are the most important products and findapter one: Introduction and literature re applications as high-boiling solvents in the surface coating industry, the di- and triethers, either separated or as a blend, are used as components in hydraulic and brake fluids. 14.4 Ethoxylation of long chain Fihylene oxide is also used for the ethoxylation of long-chain alcohols and alkyl phenols. These products are used as the active ingredients in surface-active agents (detergents). "7 Ls Polyols Fthylene oxide will react with sucrose for the produetion of polyols, precursors fur the manufacture of flexible and rigid polyurethane foams. !7) 1.4.6 Medical use Ethylene oxide is widely used in hospitals as a gascous sterilant for heat-sensitive medieval items, surgical instruments and other cbjects and fluids that come in contact with biological tissues. Large sterilizers are found in ceatral supply areas of most hospitals, und smaller sterilizers are found in clinics, operating rooms, tissue banks and research facilities. 1.4.7 Other uses Pthylene carbonate and |,3-propanediol are two produets made from ethylene oxide which have not yet reached the production volumes of those elteady listed, Ethylene carbonate is an excellent solvent for many for niany polymers and resins; this particular property is utilized le Libers. | intermediate in organic syntheses. tn some eases cthylene carbonate ean replace ethylene oxide in ethoxylations, More recently ethylene carbonate has been used as an intermediate in the conversion of ethylene oxide f@ ethylene glycol. A second growing product is 1,3-propanediol, ‘which can be manulactured from acrolein as well as from ethylene oxide, industrially, for example, in Rumania in the manufacture of polyacrylon also an ethylene glyeotether 426 Polyels, 3% + polyetytene ziycols, 256 ea Gethylene glycoland twetieme sco 75 stiyenepyeoL or ig (1.2); Global industrial use of ethylene oxide in 2007. © 6Chapter one: Introduction and literature review 1.5 Production of ethylene oxide Ethylene oxide has experienced a dramatic expansion in production since its discovery in 1859 by A. Wurtz and the first industrial process in 1925, Ethylene oxide has been produced commercielly by two basic routes: 1. Ethylene ehlorohydrin. 2. Direct oxidation process. 1.5.1 Ethylene chlorohydrin process The two step clilorohydrin process for te epoxidation of low olefins is rarely used with ethylene today, though it is still use with propene. In this process, the non-isolated ethylene chlorohydrin inlermediate was converted into ethylene oxide by heating with lime water: CHC + Cla + x0 > CICH,CHOH + HCL (sy 2CICH,CH, OH + Ca(OH }p > 2CHaCHsO + Calls + 21120 (6) The dirvet oxidation process Chemical principles The chlorohydrin process is not economically competitive, and was quickly replaced by the direct oxidation process as the dominant technology, "I In 1931, T.E. lefort first oxidized ethylene directly to ethylene oxide. This was transformed into an industrial process in 1937.1 AL present tine, all the ethylene oxide production in the world is achieved by the direct oxidation wh (he direct oxidation technology, as the name implies, utilizes the catalytic oxidation of ethylene swith oxygen over a silver based catalyst to yield ethylene oxide. "! Silyer maintained its po: as the most active and selective catalyst component, Partial oxidation of ethylene with silver ia catalysts is an exothermic reaction: Ext, + My 0, > Cat an It is normally accompenied by two even more exothermic side or secondary reactions. These are the complete combustion of ethylene, whieh is the main source of C2, and the further oxidation of ethylene oxide: !"!Chapter one: Introduction and literature review CyHy + 30, > 2Co, + 2120 (8) CHO +20, > 200, + 21,0 ay The loss of 25 to 30 percent of the ctiylene to cabon dionide and water by the second reaction is a major drawbzck of the oxidation process, This reaction also releases 13 times as much hest energy as does reaction of ethylene oxide formation, | tn all processes, inhibitors are used to prevent total oxidation, Several ppm of 1,2-Uichloroethane are often introduce to the reaction mixture for this purpose. The chemiabsorbed atomic ellorine ~ from the eaidation of hydrogen chloride oblained in the dehydrachlorination of 1.2-dichloroethane — hinders the dissociative chemiabsorption of atomic oxygen and therefore the combustion of ethylene to COz and HzO. ‘These reactions also produce small amounts of acclaldehyde (less than 1 pervent of the EO product) and trace amounts of formaldehyde. “I The specific O, activation on the metal surface of the silver is the fundamental reesan fur its catalytic activity. Initially oxygen is adsorbed molecularly on the silver and reacts in this form with ethylene to yield ethylene oxide. The atomic oxygen gentereted cannot produce more ethylene oxide; it oxidizes ethylene or ethylene oxide to CO and H20: 4 [Ag] + 02 > [Ag] -Orqas "8 ChigCH,0 + Ad-Ouas (419) 4[Ag].Oaas, + H2C = CH, > 20 + 2H20 + 4[Ag] (LL) AQ. Oxgas, + 2CO > 200, + [Ag] (1.12) Industrial catalysts generally contain up to 15% wt Ag as a finely divided layer on a support, All other specific catalyst characteristies are prapriatary and, together with technological differences account for the yatious processes in exisienee today. ‘The activity and selectivity of the catalyst is primarily influenced by the menufasturing process, the type of support and ils physical properties, and any promoters or activators. Reactor operating conditions Ethylene oxide eatalyst ‘There are four basic components in commercial ethylene oxide catalyst: (he active catalyst metal the bulk support: catalyst promoters that inercase selectivity andfor activity and improve catalyst life; and inhibitors or anticatalysts that suppress the formation of carbon dioxide and water without apprecisbly reducing the rate of formation of ethylene oxide. 8‘Chapter one: Introduction and literature review Operating pressure Operating pressure has a marginal effect on the economics of the ethylene oxide process. High- pressure increases production due to higher gas density; increases heat transfer, increases exhylene oxide and carbon dioxide recovery in the absorber, and lower the compression costs. Also, since the tolal number of moles decreases in the formation of ethylene oxide from ethyle and oxygen, high pressure is consistent with high conversion, However high pressures reduce the flammable limit of the process gas as well as increase equipment cusis. ‘Temperature and thermal effects Temperature is used to contro! two related aspects of the reaction: heat removal from the reactor ted and catalyst operating temperature. ‘The reactor temperature is controlled through the use of a heat-transfer fluid on the reactor shell. The coolant used in most recent designs is boiling water Roiling water provides good heat transfer and improved safety over previous reactor designs using either boiling or circulation organic heat tcansfer fluids, Control of the catalyst operating temperature is necessary to prevent catalyst damage such as sintering or tube damage resulting fiom excessive temperatures in the catalyst bed. Heat removal from ihe reactor is necessary for stable operation, The reactor stability is affected by the internal temperature profile in the tubular ceatalyst bed?! Raw material purily requis ments The process can be divided into wo caegories depending on the source of the oxidizing agent. ‘The air-based process anu the oxygen based process. In the fits, air or air enriched with oxygen is fed directly the system, In the second high purity oxygen siream (>98% mol) fom an air separation unit is employed as the source of the oxidizing agent.” Air was employed as the oxidizing agent in the first indusirial plants in USA, United Kingdom and Germany However, the No content interfered with the gas cycle and ked to ethylene losses, Therefore, oxygen is used for the oxidation of ethylene in almost all new units. Despite the investment anc operating costs for an air fractionating plan, the total ethylene oxide manufacturing costs are lower than those resulting from an air feed. However, in the (oxygen) eaidation process @ constant amount (about 50%) of a gas such as methane, ethane, or CO2 is employed as inter gas in a closed cycle. The main advantage of the process is the smaller amount of waste gas produced. The oxygen process has four main saw materials: oxygen, ethylene, nitrogen (cyclic diluent), and inhibitor ethylene dichloride. Oxygen must be 95 mel% pure and rest is assumed to be nitragen. Presence of argon is assumed to be negligible. ©!Chapter one: Introducti Ethylene Oxide Recovery An economic recovery scheme for a gas stream that contains less than 3 mol% ethylene oxide must be designed. It is necessary to achieve nearly complete removal since aay ethylene oxide reeyeled ta the reactor would be combusted or poison the carbon Uioside removal solution Commercial designs use @ water absorber followed by vacuum or low pressure stripping of ethylene oxide to minimize oxide hydrolysis. " Ethylene oxide purification ‘The main impurities in ethylene oxide are water, Iraces of carbon dioxide, acetaldehyde and formaldehyde. The water and heavy ends are removed in the distillation column, which works under atmospheric pressure. Acetaldehyde and formaldehyde are assumed to be present in PPM level, 1.5.3 Comparison between the vo methods ‘The main reasons for replacing the chlorohydrin process with the direc! oxidation were there Lor the high chemical feedstock requirements, is particular the cost of chlorine, “I direct oxidation eliminates the need for large volumes of chlorine, Also there are no chlorinated hydrocarbons by products to be sold, processing facilities can be mace simpler, and operating costs are lower. ‘The main disadvantage of the dirzet oxidation process is the lower yield or selectivity of ethylene ‘oxide per unit of feed ethylene consumed.” 1.6 Market s rvey 1.6.1 World production of ethylene oxide The world production of ethylene oxide was 19 million tonnes in 2008 and 18 million tonnes in 2007. This places ethylene oxide I4th most produced organic chemical, whereas the most produced one wes ethylene with [13 million tonnes. Socially responsible investing (SRI) Consulting forecasted the growth of consumption of ethylene oxide of 4.4% per year during 2008-2013 and 3% from 2013 to 2018" 10Chapter one: Introduction and literature review Table (1.2): The global production of ethylene oxide by region in 2004: Region, Number of major producers [ Production, thousand cones nied State 10 4009 Canada 3 1084 Mexica 3 350 Brezil 2 312 renea i 2, Belgium 2 770 Trance i 2i5 ‘Germany 4 995 Netherlands 2 460 | Spain) 1 100 Turkes i 115 United Kingdom 1 300 Tra 2 201 Kuwait 1 350) ShudiArabia 2 Tal Japan 4 949 Malaysia I 385 South Korea 3 740 Singapore 1 80 India zi 1 1.6.2 Consumption of ethylene oxide product in Sudan able (1.3): the ethylene oxide products imported 10 Sudan in 2012: '"! Products Mass] Customs | Customs | (inv/Ex) (kg) | value (ssd) | value (usd) | port Duty (sd Fiiylanegyeon | 893,495 | 487,522.) 19.590 99,885 Monoethanolamine | 43.376. | 378.348 L455 11.350 68,386 and its salts hanolamine || J5781 | 150,425 2.908 BO) ieaIs6 and its salts | |