LITERATURE

SURVEY

1. LITERATURE SURVEY The large number of references used in this project were divided into subject categories according to the content of the articles and the type of information provided , this made evaluation easier. Six major categories were selected. These are listed below : 1. General Information (G) 2. Process Technology (PT) 3.process & equipment design(PD) 4. Cost Estimation (CE) 5. Market Data (MD) 6. Thermodynamic Data (TD) The references used have been catalogued according to the type of information they contain. Each category has been reviewed to highlight the most useful sources of information. 1.1 General Information (G) This category provides general information for the background of the industry and current process technology. The references tend to be broad but shallow in their coverage, their style being typical of an encyclopedia. The most comprehe-

sive reference in this group was undoubtedly encyclopedia of chemical technology .KIRK-OTHMER(Ref.G.1). It provides an excellent historical background into process development and Market characteristics , and also provides a broad coverage of the physical and chemical properties of acetaldehyde , its specifications, test methods, and health and safety factors. Second reference of importance is Petrochemical processes :major oxygenated, chlorinated& nitrated (Ref. G.2). This book excellently deals with all about Acetaldehyde, like that in an encyclopedia. Third reference is the general chemical technology book i.e. outlines of chemical technology: DRYDEN, C. E. (Ref.G.3). Fourth book concisely covers all about Oxidation of Ethylene to Acetaldehyde (Ref.G.4).The fifth reference is the web site WIKIPEDIA: The free encyclopedia (Ref.G.5).It is like a launching pad and touches all aspects of Ethylene to Acetaldehyde. Sixth in the series is catalysis in petrochemical.. by: Mirbach, M.J.& Tayim, (Ref.G.6). Here we get the description of present process, its comparison with other processes, reaction mechanism along with the quantity of the present catalyst. Seventh in this category is the paper Homogeneous stationary catalysis (Ref.G.7).

1.1a. INTRODUCTION:

Product

: Acetaldehyde

IUPAC Name Chemical formula Common name

: Ethanal : C2H4 : Acetaldehyde

Common synonyms : Acetic Aldehyde , Ethanaldehyde, Ethyl- Aldehyde, Diethyl Acetal,1,1-Diethoxy Ethane, Acetylaldehyde.

Chemical structure:

Lewis structure

Ball & stick model

CHEMICAL STRUCTURE :

space filling model FIGURE: 1a

H ' H-C-C=O ' ' H H

1.1b.HISTORY: Acetaldehyde ( Ethanal ) was first prepared by Scheele in 1774,by the action of manganese dioxide and sulfuric acid on ethanol . Liebig established the structure of Acetaldehyde in 1835 when he prepared a pure sample by oxidizing ethyl alcohol with chromic acid. Liebig named the compound aldehyde from the Latin words translated as al (cohol) dehyd (rogenated). Kutscherow observed the formation of Acetaldehyde by the addition of water to acetylene in1881. Acetaldehyde is an important intermediate in the production of Acetic acid, Acetic anhydride, Ethyl acetate, Peracetic acid, Pentaerythritol, Chloral, Glyoxal, Alkylamines, and pyridines . Acetaldehyde was first used extensively during World War I as an intermediate for making Acetone from Acetic acid.Commercial processes for the production of acetaldehyde include: the oxidation or dehydrogenation of ethanol, the addition of water to acetylene, partial oxidation of hydrocarbons , and the direct oxidation of ethylene . It is estimated that in1976, 29 companies with more than 82% of the worlds 2.3 megaton per year plant capacity use the Wacker Hoechst processes for the direct oxidation of ethylene. 1.1C.PHYSICAL PROPERTIES: Acetaldehyde is a colorless, mobile liquid having a pungent suffocating odor that is somewhat fruity and pleasant in dilute concentrations. Some physical properties of acetaldehyde are given in table:1.a.

The freezing points of aqueous solutions of acetaldehyde are as follows :4.8 wt %, -2.5C; 13.5 wt %, - 7.80 C, and 31.0 wt %,- 23.00C. Acetaldehyde is miscible in all proportions with water and most common organic solvents : acetone, benzene, ethyl alcohol, ethyl ether, gasoline paraldehyde,toluene, xylenes, turpentine, and acetic acid. Table:1.a: PROPERTIES Formula weight Melting point Boiling point at 101.3 kPa (1 atm), C Density, d4 d4 11 d4 15 d4 20 Coefficient of expansion per C (0-30 C) Refractive index, nD20 Vapor density (air = 1 ) Surface tension at 20 C,mN/m Absolute viscosity at 15 CmPa.s Specific heat at 0 C,J/(g.K) At 25 C = C p / C v at 30 Cand 101.3 kPa Latent heat of fusion, kJ/mol Latent heat of vaporization, kJ/mol Heat of solution in water at 0 C, kJ/mol At 25 C Heat of combustion of liquid at constant pressure, kJ/mol Heat of formation at 273 K, kJ/mol Free energy of formation at 273 K, kJ/mol Critical temperature, C Critical pressure, MPa (atm) VALUES 44.053 -123.5 20.16 0.8045 0.7901 0.7846 0.7780 0.00169 1.33113 1.52 21.2 0.02456 2.18 1.41 1.145 3.24 25.71 - 8.20 - 6.82 11867.9 -165.48 -136.40 181.5 6.40(63.2)

Dipole moment, C-m (debyes ) Ionization potential,ev Dissociation constant at 0 C, K Flash point, closed cup, C Ignition temperature in air, C Explosive limits of mixtures with air, vol % acetaldehyde

9.04 x 10 30(2.69) 10.50 0.7 x 10 14 -38 165 4.5 60.5

1.1d Chemical properties : Acetaldehyde is a highly reactive compound exhibiting the general reactions of aldehydes; under suitable conditions, the oxygen or any hydrogen can be replaced.Acetaldehyde undergoes numerous condensation, addition, and polymerization reactions. 1.1d.1 Decomposition: Acetaldehyde decomposes at temperatures above 400C, forming principally methane and carbon monoxide. The activation energy of the pyrolysis reaction is 97.7 kJ/mol (408.8 kcal/mol). There have been many investigations of the photolytic and radical induced decomposition of acetaldehyde and deuterated acetaldehydes. 1.1d.2 The Hydrate and Enol Form: In aqueous solutions, acetaldehyde exists in equilibrium with the hydrate, CH3CH(OH)2. The degree of hydration can be computed from an equation derived by Bell and Clunie. The mean heat of hydration is 21.34 kJ/mol (89.29kcal/mol); hydration has been attributed to hyper conjugation. The enol form, vinyl alcohol (CH2 = CHOH) exists in

equilibrium with acetaldehyde to the extent of approximately one molecule per 30,000. Acetaldehyde enol has been acetylated with ketene to form vinyl acetate. 1.1d.3 Oxidation: Acetaldehyde is readily oxidized with oxygen or air to acetic acid, acetic anhydride, and peracetic acid (see Acetic acid and derivatives). The principal product isolated depends on reaction conditions. Acetic acid is produced commercially by the liquid phase oxidation of acetaldehyde at 65C with cobalt or manganese acetate dissolved in acetic acid as a catalyst. Liquid phase oxidation of acetaldehyde in the presence of mixed acetates of copper and cobalt yields acetic anhydride. Peroxyacetic acid or a perester is believed to be the precursor of acetic acid and acetic anhydride. There are two commercial processes for the production of peracetic acid. Low temperature oxidation of acetaldehyde in the presence of metal salts, ultraviolet irradiation, or ozone yields acetaldehyde monoperacetate, which can be decomposed to peracetic acid and acetaldehyde. Peracetic acid can also be formed directly by liquid phase oxidation at 5 - 50C with a cobalt salt catalyst. The nitric acid oxidation of acetaldehyde yields glyoxal. Oxidations of p xylene to terephthalic acid and of ethanol to acetic acid are activated by acetaldehyde. 1.1d.4 Reduction: Acetaldehyde is readily reduced to ethanol. Suitable catalysts for vapor-phase hydrogenation are supported nickel and copper oxide. Oldenberg

and Rose have studied the kinetics of the hydrogenation of acetaldehyde over a commercial nickel catalyst. 1.1d.5 Polymerization: Paraldehyde,2,4,6- trimethyl 1,3,5 trioxan, a cyclic trimer of acetaldehyde is formed when a mineral acid, such as sulfuric, phosphoric, or hydrochloric acid, is added to acetaldehyde. Paraldehyde can also be formed continuously by feeding acetaldehyde as a liquid at 15 - 20C over an acid ion exchange resin. Depolymerization of paraldehyde occurs in the presence of acid catalysts. After neutralization with sodium acetate, acetaldehyde and paraldehyde are recovered by distillation. Paraldehyde is a colorless liquid, boiling at 125.35 C at 101 kPa (1 atm). Metaldehyde, a cyclic tetramer of acetaldehyde, is formed at temperatures below 0C in the presence of dry hydrogen chloride or pyridine hydrogen bromide. The metaldehyde crystallizes from solution and is separated from the paraldehyde by filtration. Metaldehyde melts in a sealed tube at 246.2C and sublimes at 115 C with partial depolymerization. Travers and Letort first discovered Polyacetaldhyde, rubbery polymer with an acetal structure, in 1936. More recently, it has been shown that white, nontacky, and highly elastic polymer can be formed by cationic polymerization with BF3 in liquid ethylene. At temperatures below - 75C with anionic initiators, such as metal alkyls in a hydrocarbon solvent, a crystalline, isotactic polymer is obtained

. This polymer also has an acetal structure [poly (oxymethylene) structure]. Molecular weights in the range of 800,000 3,000,000 have been reported. Polyacetaldehyde is unstable and depolymerizes in a few days to acetaldehyde. The methods used for stabilizing polyformaldehyde have not been successful with polyacetaldehyde and the polymer has no practical significance. 1.1d.6 Reactions with aldehydes and ketones: The base catalyzed condensation of acetaldehyde leads to the dimmer, acetaldol, which can be hydrogenated to form 1,3 butandiol or dehydrated to form crotonaldehyde. Crotonaldehyde can also be made directly by the vapor-phase condensation of acetaldehyde over a catalyst. Crotonaldehyde was formerly an important intermediate in the production of butyraldehyde, butanol, and 2-ethylhexanol. However it has been replaced completely with butyraldehyde from the oxo process. A small amount of crotonaldehyde is still required for the production of crotonic acid. Acetaldehyde forms aldols with other carbonyl compounds containing active hydrogen atoms. Kinetic studies of the aldol condensation of acetaldehyde and deuterated acetaldehydes have shown that only the hydrogen atoms bound to the carbon adjacent to the CHO group takes part in the condensation reactions and hydrogen exchange. A hexyl alcohol, 2-ethyl-1 butanol, is produced, industrially by the condensation of acetaldehyde and butaraldehyde in dilute caustic solution

followed by hydrogenation of the acrolein intermediate. (see alcohols, higher aliphatic) condensation of acetaldehyde in the presence of dimethylamine hydrochloride yields polyenals which can be hydrogenated to a mixture of alcohols containing from 4 to 22 carbon atoms. The base catalyzed reaction of acetaldehyde with excess formaldehyde is thecommercial route to pentaerythritol. The aldol condensation of three moles of form aldehyde with one mole of acetaldehyde is followed by a crossed cannizzaro reaction between pentaerythrose, the intermediate product, and formaldehyde to give pentaerythritol. The process proceeds to completion without isolation of the intermediate. Pantaerythrose has been made by condensing acetaldehyde and formaldehyde at 45 C using magnesium oxide as a catalyst. The vapor-phase reaction of acetaldehyde and formaldehyde at 475C over a catalyst composed of lanthanum oxide on silica gel gives acrolein. Ethyl acetate is produced commercially by the Tischenko condensation of acetaldehyde with an aluminum ethoxide catalyst. The Tischenko reaction of acetaldehyde with isobutyraldehyde yields a mixture of ethyl acetate, isobutyl acetate, and isobutyl isobutyrate. 1.1d.7 Reactions with Ammonia and Amines: Acetaldehyde readily adds ammonia to form acetaldehyde ammonia. Diethyl amine is obtained when acetaldehyde is added to a saturated aqueous or alcoholic solution of ammonia

and the mixture is heated to 50-75C in the presence of a nickel catalyst and hydrogen at 1.2 MPa (12atm). Pyridine and pyridine derivates are made from paraldehyde and aqueous ammonia in the presence of a catalyst at elevated temperatures; acetaldehyde may also be used by the yields of pyridine are generally lower than when paraldehyde is the staring material. Levy and Othmer have studied the vapor- phase reaction of formaldehyde, acetaldehyde, and ammonia at 360 C over oxide catalysts; a 49% yield of pyridine and picolines was obtained using an activated silica-alumina catalyst. Brown polymers result when acetaldehyde reacts with ammonia or amines at a PH of 6-7 and temperature of 3-25C. With acetaldehyde, a primary amines can be condensed to Schiff bases: CH3CH=NR, the schiff base rivets to the starting materials in the presence of acids. 1.1d.8 Reactions with Alcohols and Phenols: Alcohols add readily to acetaldehyde in the presence of a trace of mineral acid to form acetals; eg, ethanol and acetaldehyde form diethyl acetal. Similarly, cyclic acetals are formed by the reactions with glycols and other polyhydroxy compounds; eg, the reaction of ethylene glycol and acetaldehyde gives 2 methyl 1,3 dioxolane. Mercaptals, CH3CH(SR)2, are formed in a like manner by the addition of mercaptans. The formation of acetals by a noncatalytic vapor phase reactions of acetaldehyde and various alcohols at 350C has been reported. Butadiene can

be made by the reaction of acetaldehyde and ethyl alcohol at temperature s above 300C over a tantala silica catalyst. Aldol and crotonaldehyde are believed to be intermediates. Butyl acetate has been prepared by the catalytic reaction of acetaldehyde with butanol at 300C. Reaction of one mole of acetaldehyde with excess phenol in the presence of a mineral acid catalyst gives 1,1 bis (p-hydroxyphenyl) ethane. With acid catalysts acetaldehyde and three moles or less of phenol yield soluble resins. Hardenable resins are difficult to produce by the alkaline condensation of acetaldehyde and phenol as acetaldehyde tends to undergo aldol condensation and self-resinification. 1.1d.9 Reactions with Halogens and Halogen compounds: Halogens readily replace the hydrogen atoms of the methyl group: eg, chlorine reacts with acetaldehyde or paraldehyde at room temperature to give chloroacetaldehyde; increasing the temperature to 70-80C gives dichloroacetaldehyde; and at a temperature of 80-90C chloral is formed. The catalytic chlorination with an antimony powder or aluminum chloride ferric chloride has been described. Bromal is formed by an analogous series of reactions. It has been postulated that acetyl bromide is an intermediate in the bromination of acetaldehyde in aqueous ethanol. The gas phase reaction of acetaldehyde and chlorine, has prepared acetyl chloride. The oxygen atom in acetaldehyde can be replaced by reaction of

the aldehyde with phosphorus pentachloride to produce 1,1 dichloroethane. Hypochlorite and hypoiodite react with acetaldehyde yielding chloroform and iodoform, respectively. Phosgene is produced by the reaction of carbon tetrachloride with acetaldehyde in the presence of anhydrous aluminum chloride. Chloroform reacts with acetaldehyde in the presence of potassium hydroxide and sodium amide to form 1,1,1 trichloro 2- propanol. 1.1d.10 Miscellaneous Reactions: Sodium bisulfite adds to acetaldehyde to form a white crystalline addition compound, insoluble in ethyl alcohol and ether. The bisulfate addition compound frequently is used to isolate acetaldehyde from solution and for purification; the aldehyde is regenerated with dilute acid. Hydrocyanic acid adds to acetaldehyde in the presence of an alkali catalyst to form the cyanohydrin; the cyanohydrin may also be prepared by reaction of sodium cyanide with the bisulfate addition compound. Acrylonitrile can be made by reaction of acetaldehyde with hydrocyanic acid and heating the cyanohydrin to 600 700C. Alanine can be prepared by reaction of ammonium salt and alkali metalo cyanide with acetaldehyde; this is the Strecker amino acid synthesis, a general method for the preparation of -amino acids. Grignard reagents add readily to acetaldehyde, the final product being a secondary alcohol. Thioacetaldehyde is formed by reaction of acetaldehyde with hydrogen sulfide; thioacetaldehyde polymerizes readily to the trimer. Acetic

anhydride adds to acetaldehyde forming ethylidne diacetate in the presence of dilute acid; boron fluoride is also a catalyst for the reaction. Ethylidene diacetate is decomposed to the anhydride and aldehyde at temperatures of 220-268C and initial pressures of 1.5 6.1 kPa (110- 160 mm Hg), or by heating to 150C with a zinc chloride catalyst. Acetone has been prepared in 90% yield by heating an aqueous solution of acetaldehyde to 410C in the presence of a catalyst. Acetaldehyde can be condensed with active methylene groups. The reaction of isobutylene with aqueous solutions of acetaldehyde in the presence of 1-2% sulfuric acid yields alkyl-m-dioxanes, the principal product being 2,4,4,6tetramethyl m dioxane in yields up to 90%. 1.1d.11 Uses: The manufacturers use about 95% of the acetaldehyde produced internally as an intermediate for the production of other organic chemicals. Figure 1 illustrates thesignificant variety of organic products ( and their end uses) derived from acetaldehyde. Acetic acid and acetic anhydride are the derivatives of acetaldehyde followed by n-butanol and 2-ethylhexanol. Twenty percent of the acetaldehyde is consumed in variety of other products, the most important being pentaerythritol, trimethylolpropane, pyridines, peraceticacid, crotonaldehyde, chloral, lactic acid.
1.1e Brief outline of the selected process:

Acetaldehyde is predominantly made by the direct oxidation of ethylene. Where-

by an aqueous solution of Cupric chloride containing traces of Palladium chloride is used as the oxidizing system. The process is single stage. In the reaction palladium chloride is first reduced to elemental palladium while oxidizing the Ethylene to Acetaldehyde and is promptly reoxidized to palladium chloride by Oxygen , the ultimate oxidizing agent. In the process, 99.8% Ethylene, air (as equivalent to 99.5% Oxygen), recycle gas are directed to vertical reactor where Intimate contact is made with the catalyst solution (containing 200 gm/lit of cucl2 & 4 gm/lit of Pdcl2 ) under 830 KPa and at 90C. The feed is preheated using the heat of reaction. The water evaporated during the reaction absorbs the exothermic heat evolved, and make-up water is fed as necessary to maintain the catalytic solution concentration. The reacted gas is first flashed in a flash drum and then water scrubbed. The resulting acetaldehyde solution is fed to a distillation column. The tail gas from the scrubber is recycled to the reactor and a stream is purged. Water and catalyst are recycled. steam is used in reboiler with column. The distillation column overhead stream is condensed and collected in an accumulator cum reflux drum as pure Acetaldehyde .The pure ACETALDEHYDE is sent to storage vessel. Reactions involved are as follows: C2H4 + 2CuCl2 + H2O PdCl2 CH3CHO +2HCl +2CuCl 2CuCl + 2HCl + O2 2CuCl2 + H2O

1.1f Specification of ACETALDEHYDE product : Specification of different grade of Acetaldehyde are give ahead :

A typical specification of Acetaldehyde of Eastman (company name): Specification no.: 00160-4 Effective date : 09/01/2010(table 1.1f.1)

Product name Eastman Acetaldehyde specifications property appearance Colour,PTCO Specific gravity@15.5/15.5C Acidity as Acetic acid,w% Purity,w%

Limits Clear, Clean liquid 10 max 0.780-0.790 0.1 max. 99.7 min.

Test methods ASTM D-2090 ASTM D-1209 ASTM D-891 ASTM D-2086 TXAL-A- XX-G-GC-044

Reagent grade acetaldehyde (source: wintersun chemical): (tab1.1f.2) 99% min. 0.5 % max 0.00005% max 0.00001% max 0.00001% max 0.00001% max 0.00001% max 0.00005% max

Assay by GC Acidity as CH3COOH iron cobalt Ni copper lead zinc Packing : 100ml or 1 lit

Technical grade acetaldehyde (source: wintersun chemical): (table1.1f.3)

Appearance Assay Non volatile Free acid Packing : In 200 Kg plastic drum

Colourless transparent liquid 40%min. 0.1%max 0.6% max

Food grade acetaldehyde (source: wintersun chemical): (table1.1f.4) Appearance Assay Relative density Heavy metal as Pb Colourless transparent liquid 40% min. 0.913-0.920 0.001 % max.

Packing : In 25 Kg plastic drum

Typical technical data of Acetaldehyde

(source: CELANESE CHEMICALS): Sales specifications (table1.1f.5) Acetaldehyde (DIN 51 405, determined by gas chromatography) Water (DIN 51 777, modified) Total Chlorine (DIN 51 408) Density at 10 C (DIN 51 757) 1.1g Transportation: Hazard class Packing group UN NO. (table1.1f.6) 3 I 1089 % (w/w) mg/kg mg/kg g/cm3 min.99.5 max. 200 max. 30 0,7904 0,7928

1.1h Hazard class 3 placard: given ahead

Product Name: Acetaldehyde(source: wintersun chemical)

WCode: CAS No. Molecular Formula: Formula Weight: Hazards: (source: Wikipedia) MSDS EU classification R-phrases S-phrases : : : :

01-002 75-07-0 C2H4O 44.05

External msds Very flammable (F+), Harmful(Xn) R 12 (S2) R36/37 S16 S33 R 40 S36/37

NFPA-704 Flash point

: : -39C

4 2 2

Auto ignition temperature : 185C

Identifiers:( source: Wikipedia) (table1.1f.7) CAS number ChemSpider UNII 75-07-0 172 GO1N1ZPR3B

1.2. Process Technology (PT) This category contains those references specifying process, process innovation, operating conditions, utility requirements, catalyst information, etc. All information relates directly to the process requirements. Again in this category encyclopedia of chemical technologyKirk- Othmer ..(Ref.PT.1) & Petrochemical processes:major oxygenated, chlorinated& nitra ted (Ref. PT.2) plays important role.Third in this category is the web site Science direct.com. This web site provides excellent collection of journals & research papers which may be used in the technological advancement & optimization of the present process & plant.(Ref. PT.3).other references are papers from various journals& are Ethylene oxidation on a supported catalyst (Ref.PT.4),Catalytic oxidation...palladium chloride- activated charcoal catalyst ,

(Ref.PT.5) , Wacker-type oxidation .liquid polymer medium supported on silica gel(Ref.PT.6), Real time optimization..Acetaldehyde production process (Ref.PT.7), & how to start manufacturing industriesunido (Ref.PT.8). 1.2a Manufacturing processes & selection: The economics of the various processes for the manufacture of acetaldehyde are strongly dependent on the price of the feed stock used. Since 1960, the liquidphase oxidation of ethylene has been the process of choice. However, there is still commercial production by the partial oxidation of ethyl alcohol, dehydrogenation of ethyl alcohol andthe hydration of acetylene. Acetaldehyde is also formed as a co product with ethyl alcohol and acetic acid. 1.2a.1 Oxidation of Ethylene: Wacker Chemie and Farbwerke Hoechst, developed the direct liquid phase oxidation of ethylene in 1957 1959. The catalyst is an aqueous solution of PdCl2 and CuCl2. In 1894, F.C. Phillips observed the reaction of ethylene with an aqueous palladium chloride solution to form acetaldehyde. C2H4+PdCl2 + H2O CH3CHO +Pd +2HCl The metallic palladium is reoxidized to PdCl2 with CuCl2 and the cuprous chloride formed is reoxidized with oxygen or air. Pd + 2CuCl2 PdCl2 +2CuCl 2CuCl+1/2 O2 + 2HCl 2CuCl2 + H2O

The net result is a process in which ethylene is oxidized continuously through a series of oxidation reduction reactions. C2H4 + O2 CH3CHO H = -244 kJ(102.1 kcal) Studies of the reaction mechanism of the catalytic oxidation have suggested that a cis hydroxyethylene palladium complex is formed initially, followed by an intramolecular exchange of hydrogen and palladium to give a gem hydroxyethyl palladium species which leads to acetaldehyde and metallic palladium. There are two variations for the production of acetaldehyde by the oxidation of ethylene; the two stage process developed by Wacker Chemie and the one stage process developed by Farbwerke Hoechst. In the two stage process ethylene and oxygen (air) react in the liquid phase in two stages. In the first stage ethylene is almost completely converted to acetaldehyde in one pass in a tubular plug-flow reactor made of titanium. The reaction is conducted at 125130C and 1.13 Mpa (150 psig) palladium and cupric chloride catalysts. Acetaldehyde produced in the first reactor is removed from the reaction loop by adiabatic flashing in a tower. The flash step also removes the heat of reaction. The catalyst solution is recycled from the flash tower base to the second stage (or oxidation) reactor where the cuprous salt is oxidized to the cupric state with air. The high pressure off gas from the oxidation reactor, mostly nitrogen, is separated from the liquid catalyst solution and scrubbed to remove

acetaldehyde before venting. A small portion of the catalyst stream is heated in the catalyst regenerator to destroy undesirable copper oxalate. The flasher overhead is fed to a distillation system where water is removed for recycle to the reactor system and organic impurities, including chlorinated aldehydes, are separated from the purified acetaldehyde product. In the one-stage process ethylene, oxygen, and recycle gas are directed to a vertical reactor for contact with the catalyst solution under slight pressure. The water evaporated during the reaction absorbs the heat evolved, and make up water is fed as necessary to maintain the catalytic solution concentration. The gases are water scrubbed and the resulting acetaldehyde solution is fed to a distillation column. The tail gas from the scrubber is recycled to the reactor. Inerts are eliminated from the recycle gas in a bled stream which flows to an auxiliary reactor for additional ethylene conversion. This oxidation process for olefins has been exploited commercially principally for the production of acetaldehyde, but the reaction can also be applied to the production of acetone from propylene and methyl ethyl ketone from butanes. Careful control of the potential of the catalyst with the oxygen stream induced commercially by a variation of this reaction. 1.2a.2 From Ethyl Alcohol:

1.2a.2a Acetaldehyde is produced commercially by the catalytic oxidation of ethyl alcohol. Passing alcohol vapors and preheated air over a silver catalyst at 480C carries out the oxidation. CH3CH2OH + O2 CH3CHO + H2O, H = 242 kj/mol (57.84 kcal / mol) With a multitubular reactor, conversions of 74-82% per pass can be obtained while generating steam to be used elsewhere in the process. 1.2a.2b Acetaldehyde also, produced commercially by the dehydrogenation of ethylalcohol.Reaction: C2H5OH CH3CHO + H2 Catalyst: Cu -Co-Cr2o3 Temperature: 280 350 C. Process description: The raw material i.e., ethanol is vaporized and the vapors, So generated, are heated in a heat exchanger to the reaction temperature by hot product stream. The product stream is cooled to 10 C and in doing it, all unreacted ethanol and acetaldehyde are condensed. The out going gaseous stream, containing hydrogen mainly, is scrubbed with dilute alcohol (alcohol + water) to remove uncondensed products and the undissolved gas. The remaining pure hydrogen (98%) is burnt in stack. Figure 2, shows the flow sheet of the process in which ethanol is vaporized in vaporizer and heated to the reactor temperature in heat exchanger. The heated vapors are passed through the

converter. The product stream is first cooled in heat exchanger and then in condensers using water and liquid ammonia. This condenses most of the unreacted ethanol and the acetaldehyde formed in reactor. The escaping gas, which is almost pure hydrogen, is scrubbed by ethanol to remove all the traces of the product. The liquid stream consisting of mainly ethanol and acetaldehyde, is distilled in distillation column to get acetaldehyde. 1.2a.3 From Acetylene: Acetaldehyde has been produced commercially by the hydration of acetylene since 1916. However, the development of the process for the direct oxidation of ethylene in the 1960s has almost completely replaced the acetylene based processes and in 1976 there was only small volume production in a few European countries. In the older processes, acetylene of high purity is passed under a pressure of 103.4 kPa (15 psi) into a vertical reactor containing a mercury catalyst dissolved in 18-25% sulfuric acid at 70-90C. HC = CH + H2O CH3CHO Fresh catalyst is fed to the reactor periodically; the catalyst may be added in the mercurous form but it has been shown that the catalytic species is a mercuric ion complex (100). The excess acetylene sweeps out the dissolved acetaldehyde which is condensed by water and refrigerated brine and scrubbed with water; the crude acetaldehyde is purified by distillation and the unreacted acetylene is recycled. The catalytic mercuric ion is reduced to catalytically inactive

mercurous sulfate and metallic mercury; this sludge, consisting of reduced catalyst and tars, is drained from the reactor at intervals and resulfated. Adding ferric or other salts to the reaction solution can reduce the rate of catalyst depletion. The ferric ion reoxidizes mercurous to the mercuric ion while it is reduced to the ferrous state; consequently, the quantity of sludge, which must be recovered, is reduced (81,101). In one variation, acetylene is completely hydrated with water in a single operation at 68-73C using the mercuric iron salt catalyst. The acetaldehyde is partially removed by vacuum distillation and the mother liquor recycled to the reactor. The aldehyde vapors are cooled to about 35C, compressed to 253 kPa (2.5 atm), and condensed. It is claimed that this combination of vacuum and pressure operations substantially reduces heating and refrigeration costs. Acetaldehyde may also be made from methyl vinyl ether and ethylidene diacetate, both of which can be made from acetylene. Methyl vinyl ether is made by the addition of methanol to acetylene at 1.62 Mpa (16 atm) in a vertical reactor containing a 20% methanolic solution of potassium hydroxide. Hydrolysis of the ether with dilute sulfuric acid yields acetaldehyde and methanol which are separated by distillation; the methanol is recycled to the reactor. Acetylene and acetic acid form ethylidene diacetate in the presence of mercuric oxide and sulfuric acid at 60-80C and atmospheric pressure. After

separation, the ethylidene diacetate is decomposed to acetaldehyde and acetic anhydride by heating to 150C in the presence of a zinc chloride catalyst (81). Acetaldehyde has been made from methyl vinyl ether and ethylidene diacetate in the past, but neither process is used today. 1.2a.4 From Saturated Hydrocarbons: Acetaldehyde is formed as a co product in the vapor phase oxidation of saturated hydrocarbons, such as butane or mixtures containing butane, with air or, in higher yield, oxygen. Oxidation of butane yields acetaldehyde, formaldehyde, methanol, acetone, and mixed solvents as major products; other aldehydes, alcohols, ketones, glycols, acetals, epoxides, and organic acids are formed in smaller concentrations. This is of historic interest. Unlike the acetylene route, it has almost no chance to be used as a major process. From synthesis Gas: A rhodium-catalyzed process capable of converting synthesis gas directly into acetaldehyde in a single step was reported in 1974 (84-85). CO + H2 CH3CHO + other products The process comprises passing synthesis gas over 5% rhodium on SiO2 at 300C and 2.0 Mpa (20 atm). The principal co products are acetaldehyde, 24% acetic acid, 20%; and ethanol, 16%. In the years 1980 an beyond, if there will be a substantial degree of coal gasification, the interest in the use of synthesis gas as a raw material for acetaldehyde production will increase.

1.2a.5 Specifications, Analytical, and Test Methods: Commercial acetaldehyde has the following typical specifications: assay, 99% min; color, water-white; acidity, 0.5% max (acetic acid); specific gravity, 0.790 at 20C; bp, 20.8 at 101.3 kPa (1 atm). Acetaldehyde is shipped in steel drums and tank cars bearing the ICC red label. IN the liquid state, it is noncorrosive to most metals; however, it oxidizes readily, particularly in the vapor state, to acetic acid. Precautions to be observed in the handling of acetaldehyde have been published by the manufacturing chemists association. Analytical methods based on many of the reactions common to aldehydes have been developed for the determination of acetaldehyde. In the absence of other aldehydes,it can be detected by the formation of a mirror from an alkaline silver nitrate solution(Tollens reagent) and by the reduction of Fehlings solution. It can be determined quantitatively by fuchsin-sulfiur dioxide solution (Schiffs reagent) or by the reaction with sodium bisulfite, the excess bisulfite being estimated iodometrically. Acetaldehyde present in mixtures with other carbonyl compounds, organic acids, etc. can be determined by paper chromatography of 2,4 dinitrophenylhydrazones polarographic analysis either of the untreated mixture or of the semicarbazones, the color reaction with thymol blue on silica gel (detector tube method) mercurimetric oxidation, argentometric titration,

microscopic and spectrophotometric methods, and gas liquid chromatographic analysis.With the advent of gas liquid chromatographic techniques, this method has superseded most chemical tests for routine analysis. Acetaldehyde can be isolated and identified by the crystalline compounds of characteristic melting points formed with hydrazines, semicasrbazides, etc.; these derivatives of aldehydes can be separated by paper and column chromatography. Acetaldehyde has been separated quantitatively from other carbonyl compounds on an ion exchange resin in the bisulfite form; the aldehyde is eluted from the column with a solution of sodium chloride. In larger quantities, it may be isolated by passing the vapor into ether and saturating the ether with dry ammonia; the product, acetaldehyde ammonia, crystallizes from the ether solution. The reactions of acetaldehyde with bisulfite, hydrazines, oximes, semicarbazones, and 5,5dimethyl 1,3 cyclohexanedione (dimedone) have been used to isolate acetaldehyde from solutions. 1.2a.6 PROCESS SELECTION: Here, Single stage oxidation of ethylene is selected for the production of acetaldehyde. Because, this process is most economical one, uses less utilities with respect to other processes, heat given up in the reaction is used to pre-heat the feed, catalyst used is in the liquid phase & is regenerated easily, air is used as one of the raw material(i.e. free of cost) . Cost to electricity ,cost to steam, cost

to cooling water& cost to catalyst is less than that of acetylene hydration process & also than that of two stage ethylene oxidation. In Single stage oxidation of ethylene Catalyst is regenerated &its age is significantly more than that of any heterogeneous catalyst. Its advantage over two stage process is that the catalyst is regenerated simultaneously in the same reactor. Also, in Single stage oxidation of ethylene process the plant set up cost & maintenance cost is less than that of two stage ethylene oxidation process( for the same capacity). Some comparison ,in terms of table, are given ahead:

Table :1.2a.6a.: Acetaldehyde production economic data ( France condition mid-86) Production capacity 100000 tonnes/year
(Source: Petrochemical Processes Volume 2: Major Oxy- Genated, Chlorinated and nitrated derivative By Alain Chauvel, Gilles Lefebvre)

PROCESS Typical technology Battery limit conditions (106US $) Consumption per ton of Acetaldehyde Raw materials Acetylene(t) Ethylene(t) Oxygen(Nm3) utilities Steam (t) Electricity(KWH) Cooling water(m3) water@12c(m3) Process water(m3) Treated water(m3) Chemical & catalyst(us$) Hydrochloric acid(100% c),Kg Sulphuric acid,kg Labor(operators per shift)

Acetylene hydration CHISSO 17

Ethylene oxidation Wacker/hoechst Single step Two step 19 30

0.620 --------------2 350 250 -------1 -------20 5 4

---------0.675 280 1.2 100 200 ---------6 2 7 10 -------4

---------0.675 1.2 500 220 15 2 7 50 -------5

Comparison of ethylene oxidation with other known processes for manufacturing Acetaldehyde ( source : catalysis in petrochemical processes by : MATAR, S.

, MIRBACH, MANFRED J.& TAYIM, HASSAN A. ) is given below: table (1.2a.6b ): Table: 1.2a.6b
Starting material Process C2H5OH C2H5OH C2-C6 saturated hydrocarbons CH=CH Vap. Phase heterogeneous catalytic oxidation. Vap. Phase heterogeneous Catalytic hydrogenation. Vap. Phase non catalytic Catalyst temperature Ag, gauze 300-575C Cr/activated Copper, 260-290C ---------Yield % 85 -95 85-90 30-40 Conversion per pass 25-30 50 25 50-60

heterogeneous oxidation 100-450C Liquid phase homogeneous 18-25% aqueous Catalytic hydration. H2SO4 containing

~ 95

CH2=CH2

HgSO4+Fe2(SO4)3 Liquid phase homogeneous PdCl2/CuCl2, Catalytic oxidation. 100C

95

95-99

1.3.Process & equipment design(PD): Various books are available in this category. But best one, which has been used Extensively, is process equipment drsignJOSHI, M.V(Ref.PD.1). This book is of utmost importance & deals with the reactor & column design basics. Second in this category is Applied process design.Ludwig, Ernest E. (Ref.

PD.2). This is is an excellent book for a chemical engineer. It deals with the basics as well as advance level information regarding process designing. Next in the category is unit operationsMcCabe, L. & Smith, Julian C.(Ref.PD.3). The fourth one is outstanding book i.e.mass transfer operations..Treybal,R.E. (Ref.PD.4). The fifth book is like the Bible for chemical engineers. This is The Chemical engineers hand book.Perry,R.H. (Ref.PD.5). 1.3a Equipment: Here, reactor is a vertical tower type .since catalyst prescribed is aqueous solution of cupric chloride & palladium chloride, it is not possible to create a solid packed bed of catalyst (heterogeneous catalysis). However, it may be called a liquid packed bed reactor, because reactor is filled with liquid phase catalyst(liquid stationary catalysis) & gas is bubbling through the reactor .Thus it is a vertical tower type Bubble column reactor. Since reactor is operating at high pressure & the reactor outlet stream is a high pressure stream, it is necessary to reduce the head of the stream before it enters the scrubber & column. Otherwise, it will distort the downstream equipments . For this purpose a combination of pressure control valve & a flash drum will be used. Hence we will maintain the pressure of reactor & will reduce the head of the stream. Details of process &equipment will be discussed in the specific chapter .

1.4. Cost Estimation (CE): The ultimate book, of our use, in this category is the famous Plant design & economics for chemical engineers : Peters,M.S.&Timmerhaus, Klaus D. Details of cost estimation is given in the dedicated chapter(Ref.CE.1) 1.5. Market Data (MD): This group of references all contain information regarding the production (and producers) of Acetaldehyde both in INDIA and worldwide. No single reference was outstanding as each contained different statistics except that of planning commissions. The most relevant are of the Planning commission of GOVERNMENT OF INDIA. 1.5a Global scenario: Acetaldehyde is produced throughout the world primarily from ethylene, although some is still derived from ethanol and acetylene. Demand for acetaldehyde worldwide has continued to decrease primarily as a result of less consumption for acetic acid manufacture, as the industry continues to move toward the more efficient and lower-overall-cost carbonylation-of-methanol process. For example, all manufacture of acetic acid from acetaldehyde in North America has been discontinued and in Europe significant capacity for this process has been permanently shut down. Acetaldehyde use for acetic acid manufacture in Asia continues but is under pressure from the ongoing establishment of me-

thanol carbonylation technology. Demand has also significantly declined in the production of plasticizer alcohols, which has totally switched to oxo processes. As a result of these process replacements, acetaldehyde capacity has been shut down in Western Europe and in other areas, such as Mexico. In addition to the disappearance of use for acetic acid and plasticizer alcohols, acetaldehyde demand has also declined in the last few years because of mature end-use markets and the effects of the economic downturn on these acetaldehyde-derived products. There has also been continued substitution for acetaldehyde-based chemistries with other materials, which has further contributed to the drop in acetaldehyde use. The following pie chart shows world consumption of acetaldehyde:

Consumption in China is expected to grow over 5% annually in the next five years. Acetaldehyde use for acetic acid production will increase, although this will be more of a recovery back to the pre-2009 level. Actual growth might be

limited because of acetic acid production from the methanol carbonylation process. Strong growth of over 6% annually will actually occur in pyridine production and there will be moderate growth for use in pentaerythritol, as alkyd resin enamel and varnish production goes up. Other uses are generally mature, such as sorbic acid production. Indian consumption is anticipated to have moderate growth of over 3% annually in the next several years. Acetaldehyde demand for acetic acid production will grow 34% per year, while consumption for pyridines is expected to return to the 2008 level. Other uses for acetaldehyde will also increase 34% annually. Overall, the global market for acetaldehyde is expected to grow 23% annually during 20092014. However, some of this growth is actually a recovery from the significant decline experienced in 2009 (for example, China's use in the acetic acid market). Major regions including Japan, Western Europe and the United States will have low growth because of no use or no growth for acetic acid production, minimal growth in other acetaldehyde-consuming products, or continued product replacement of materials that consume acetaldehyde. (source: SRI consulting & Access intelligence LLC inc.) 1.5b INDIAN scenario: Apart from the Global trend, INDIAN trend is just reverse. Indian production & import has increased in the recent past. Also, we are exporting in order to grab the present & future market of Acetaldehyde. As according to planning commiss-

ionS report & data there was a growth of 13.9% in production with capacity utilization of 77.6% during 2005-06.The present installed capacity of acetaldehyde is 205060 MTs. All figures are from planning commissions Report. They are very authentic. Table: 1.5b.1: Indian production, capacity, export& import:

1.5d some more reports:

San Jose, CA (PRWEB) November 3, 2008

The downturn in the acetic acid industry, the largest end-use market for acetaldehyde, coupled with the phasing out of acetic acid production from acetaldehyde, are expected to result in huge declines in consumption. In North America, acetic acid manufacturers have shut down their operations, while in Europe, significant reductions in capacities are underway. Scaling back of production activities is expected in Latin America, and Asia Pacific in the upcoming years. Presently however, Asia-Pacific represents the largest market for acetaldehyde with growth stemming from the use of acetaldehyde in producing synthetic pyridines, pentaerythritol, glyoxal/glyoxylic acid, pentaerithryte, and crotonaldehyde. Within Asia, China has emerged into the largest consumer of acetaldehyde in the world, with the country representing the only market where new acetaldehyde capacity installations have occurred in the recent past. As stated by the recent report published by Global Industry Analysts, Inc., world acetaldehyde market is dominated by Asia-Pacific, and Europe, with a combined share of 68.4% estimated in the year 2008. World consumption of acetaldehyde in acetane hydride end-use market, and acetic ether end-use markets, is projected to decline by 2%, and 1.3% respectively during the period

2001 to 2010. Positive growth is expected to stem from 1,3 butanediol end-use market, with world consumption slated to rise at a CAGR of 2.7% during the period 2011 to 2015. In Asia-Pacific, consumption of acetaldehyde in crotonaldehyde end-use market is projected to grow at a CAGR in excess of 3.7% over the period 2011 through 2015. In Europe, Germany ranks as the largest market for acetaldehyde with a 30.9% share estimated in the year 2008, followed by France, United Kingdom and Italy. Leading global and regional players operating in the industry include Celanese AG, Eastman Chemical Company, Jubilant Organosys Limited, Showa Denko K.K., and Wacker-Chemie AG, among others. The report, titled "Acetaldehyde: A Global Strategic Business Report", published by Global Industry Analysts, Inc., provides a comprehensive review of market trends, issues, and challenges. Richly annotated with authoritative, and unbiased commentaries, and hard-to-find statistical facts, the report provides unequivocal views on future potential while throwing light on the prevailing climate in key regional markets. End-use markets analyzed in the report include Acetic Acid, Acetane Hydride, Acetic Ether, 1,3 Butanediol, n-Butyraldehyde, Crotonaldehyde, Glyoxal/Glyoxylic Acid, Penta-Erithryte, Peracetic Acid, and Pyridine. Latent demand patterns in end-use markets are quantified across major geographic market verticals including the United States, Canada, Japan, France,

Germany, United Kingdom, Italy, Spain, Russia, Asia-Pacific, Middle East and Latin America. Also provided in the report is an enumeration of recent mergers, acquisitions, and other strategic industry activities. (http://www.strategyr.com/Acetaldehyde_Market_Report.asp. 1.5e: Analysis: Background : The basic Organic chemicals and Intermediates Industry is one of the important sectors of the Chemical Industry and has made phenomenal progress since independence. This sector has played a very important role in the overall development by providing vital chemicals and intermediates to other sectors of the Chemical Industry like drugs and pharmaceuticals, dye stuffs and dye intermediates, leather chemicals, paints, pesticides and many others. With the substantial growth in the exports of the above commodities in recent years, the basic organic chemicals and intermediate industry is expected to have higher growth rate. WORLD SCENARIO The total global production of organic chemicals is 400 million tonnes per year. The annual world production of organic chemicals has increased from 15 to 400

million tonnes in the last 50 years.80% of the global production is in 16countries mainly in USA, Germany, U.K, Japan, China, India, etc. Since 1950, the number of known chemical substances has increased twenty fold. Production and capacity . Specific to Organic Chemical Industry - If the consuming industries are shifted out from India to other countries it would cause a shift in the consumption pattern for the manufacturers of the organic building blocks. It has to be recognized that demand for the end product drives the demand for intermediates and also the bulk chemicals. For example, if world scale capacity for Polyurethane and MDI comes up in our neighbouring countries, it will have an adverse impact on the demand growth for Aniline in India. - Most of the manufacturers in the unorganised sector need to be better informed about the pollution control measures, which could put a halt to their production activity at any time. - China, a major competitive challenger, is investing heavily in infrastructure (they are adopting the cost-effective German model). It has not only overtaken India in current export territories but could also inducted itself into the Indian market with cheaper imports Specific to Organic Chemical Industry. 1.5f Name of companies manufacturing acetaldehyde:

They are given ahead.

Company Eastman Celanese chemicals HULS LONZA Korea alcohol industries co. Kyowa yuka company Lee Chang Yung chem. Ind. Mitsubishi chemical corporation Showa Denko K. K. Jubilant Organosys, Nira-Baramati Trichy Distilleries & Chemicals Ltd. Dhampur Sugar Mills Limited Ankit Raj Organo Chemicals Ltd. Godavari Biorefineries Ltd Naran Lala Pvt Ltd. Ghaziabad Oraganics Ltd. Aeon India Corporation Private Limited

US/CANADA/EUROPE/ EAST ASIA US EUROPE EUROPE EUROPE EAST ASIA EAST ASIA EAST ASIA EAST ASIA EAST ASIA INDIA INDIA INDIA INDIA INDIA INDIA INDIA INDIA

1.6. Thermodynamic Data (TD):

Formula: C2H4O Molecular weight: 44.0526 Gasphase thermochemistry data: :(table:1.6a)

fHga -170.7 1.5s kJ/mol Chyd Wiberg, Crocker, et al., 1991

Constant pressure heat capacity of gas:(table:1.6b)

Cp,gas(J/mol*K) Temperature (K) 35.53 40.27 43.26 101.07 46.47 107.19 52.80 112.49 55.32 0.08 117.08 55.51 121.06 66.28 124.50 76.68 127.49 85.94 130.09 94.04 135.22 138.94 141.68 143.75 145.35 146.59

Reference

50. Thermodynamics Research Center, 100. 1997 150. 800. 200. 900. 273.15 1000. 298.15 1100. 300. 1200. 400. 1300. 500. 1400. 600. 1500. 700. 1750. 2000. 2250. 2500. 2750. 3000.

Constant pressure heat capacity of gas:(table 1.6c)

Cp,gas(J/mol*K) Temperature (K) Reference 54.98 58.03 62.43 67.45 298.1 Chao J., 1986 322.9 372.7 422.4

Condensed phase thermochemistry data: (table 1.6d) Quantity Value Units Method Reference

fHliquid -196.4 1.5 Quantity Sliquid Value

kJ/mol Chyd Wiberg, Crocker, et al., 1991 Units Method N/A Reference Lebedev and Vasil'ev, 1988

117.3 J/mol*K

Constant pressure heat capacity of liquid: (table 1.6e)

Cp,liquid (J/mol*K) Temperature (K) 89.05 96.21

Reference

298.15 Lebedev and Vasil'ev, 1988 273. Connor, Elving, et al., 1947

Phase change data: (table 1.6f) Quantity Tboil Quantity Tfus Quantity Tc Tc Tc Quantity Value 293.9 0.8 Value 150. 3. Value 466.0 461. 454.7 Value Units Method K AVG N/A Units Method K AVG N/A Units Method K K K N/A N/A N/A Reference Teja and Anselme, 1990 Hollmann, 1903 Van der Waals, 1881 Reference Reference Reference

Units Method

6.49 mol/l

N/A

Teja and Anselme, 1990 Reference Majer and Svoboda, 1985 Wiberg, Crocker, et al., 1991

Quantity Value Units Method vapH vapH 26.12 kJ/mol 25.7 kJ/mol N/A N/A

Enthalpy of vaporization: (table 1.6g)

vapH (kJ/mol) Temperature (K) Method 25.76 25.7 0.2 293.3 294. N/A V

Reference Majer and Svoboda, 1985 Coleman and DeVries, 1949

Antoine Equation Parameters: (table 1.6h) Temperature (K) A B C Reference

293.3 - 377.4 3.68639 822.894 -69.899 Bull, Seregrennaja, et al., 1963 272.9 - 307.5 5.18830 1637.083 22.317 Coles and Popper, 1950
Enthalpy of fusion(table 1.6i)

fusH (kJ/mol) Temperature (K) 2.310

Reference

149.78 Lebedev and Vasil'ev, 1988

Enthalpy of fusion(table 1.6j)

fusH (kJ/mol) Temperature (K) 2.31 1.72

Reference

149.8 Domalski and Hearing, 1996 242.9

Entropy of fusion(table 1.6k) fusS (J/mol*K) Temperature (K) 15.43 Reference 149.78 Lebedev and Vasil'ev, 1988

Entropy of fusion(table 1.6l)

fusS (J/mol*K) Temperature (K) 15.42 7.06

Reference

149.8 Domalski and Hearing, 1996 242.9

Enthalpy of phase transition(table 1.6m)

Htrs (kJ/mol) Temperature (K) Initial Phase Final Phase 1.716 242.9 liquid liquid

Entropy of phase transition(table 1.6n) Strs (J/mol*K) 7.35 (sources: Temperature Initial (K) Phase 242.9 liquid Final Phase liquid Reference Comment

Lebedev and Lambda; DH Vasil'ev, 1988

Note: More data may be accessed in the web side of sources. All data cant

be given here.)

BIBLIOGRAPHY

1. General Information (G)

1. Kirk & Othmer : Encyclopedia of chemical technology. 2. Chauvel, A.& Lefebvre : Petrochemical processes :major oxygenated,

chlorinated& nitrated derivatives.

3. Dryden, C.E. :Outlines of chemical technology, Edited & revised by

Rao,M.G.
4. Speight, James G. : Chemical & process design handbook.

5. Wikipedia. 6. Matar, S. , Mirbach, M.J.& Tayim, H.A.: Catalysis in petrochemical processes. 7. Dykman, A.S. ,Imyanitov, N.S.& Polyakov, S.A. : Homogeneous stationary catalysis, Russian journal of applied chemistry. 2. Process Technology (PT)
1. Kirk & Othmer : Encyclopedia of chemical technology. 2. Chauvel, A.& Lefebvre : Petrochemical processes :major oxygenated,

chlorinated& nitrated derivatives. 3. Science direct.com.

4. Shaw, S. , J.S. Dranoff & J.B Butt.: Ethylene oxidation on a supported

liquid-phase Wacker catalyst.(American chemical society)

5. Fujimoto, Kaoru. , Hiroshi Takeda, & Taiseki Kunugi: Catalytic

oxidation of Ethylene to Acetaldehyde. Palladium chloride-Activated charcoal catalyst. University of Tokyo.

6. Okamoto ,Masaki & Yuichi Taniguchi :

Wacker-type oxidation in vapor

phase using a palladiumcopper chloride catalyst in a liquid polymer medium supported on silica gel.(Journal of catalysis).
7. Zhijiang, Shao. , Wang Jinlin & Jixin Qian (Institute of Systems

Engineering, Department of Control Science and Engineering, Zhejiang University, Hangzhou 310027, P.R. China : Real time optimization of acetaldehyde production process.
8. Unido : How to start manufacturing industries Acetaldehyde.

3.process & equipment design(PD) 1. Joshi, M.V.: Process equipment design. 2. Ludwig, Ernest E.: Applied process design for chemical & petrochemical plants.
3. McCabe, Warren L. & Julian C. Smith, : Unit operations of chemical

engineering. 4. Treybal, Robert E.: Mass transfer operations.

5. Perry, R. H. & C.H. Chilton : The chemical engineers Handbook. 6. Smith, J.M. : Chemical engineering kinetics. 7. Fogler, H. Scott & M. Nihat Gurmen : Elements of chemical recation engineering. 4. Cost Estimation (CE)
1. Peters,M.S.& Klaus D. Timmerhaus,: Plant design & economics for

chemical engineers. 5. Market Data (MD)

1. http://planningcommission.nic.in/aboutus/committee/wrkgrp11/wg11_chemical.pdf 2. SRI Consulting.

6. Thermodynamic Data (TD) 1. National institute of standard & technology