Acetaldehyde Synonyms ACETALDEHYDE ethanal, acetic aldehyde, ethyl aldehyde Historically, acetaldehy dehydrogenation of et WV wde was made by the silver gauze catalytic oxidation ot thyl alcohol using copper activated with chromium oxide. TREE routes replaced the easier acetylene based processes, and have, in their turn, been most! ly superseded by the direct liquid phase oxidation of ethylene, : The widescale availablity of ethylene, it lower price, and high selectivity of the catalyst used, which conserves raw materials, have ensured the success of tha route. Additionally, lower operating tempera significant energy savings, Today, world. Some acetylene based plant where available, fermentation 7 a tures and pressures have led to it is the principal process used in the Western ts are still in operation in Eastern Europe and ethyl alcohol is used in a few third world of Propane or butane or a mixture of the two is only economic if there ions demand for the range of oxidation products formaldehyde, methyl alcohol, i ‘acetone, and mixed solvents ~ which are formed, i Pisication of the end products is complex and expensive. Process conditions, : ‘aw materials and recovery procedures can be varied s0 that diferent teeny : end products can be produced, Mest tecent research hus involved the reduction of acetic anhydride with hydrogen over a platinum or palladium catalyst. Acetaldchyde is also obtained as a are the production of from propyiene 7 (Capacities range from 10,000-280,000 tonnes per year. by-product in a number of processes. These Vinyl acetate from ethylene, and acrolein and acrylic acid MLLLLLLLULLUDULAAAMA AAfremicals and Processes xe-stage process acess, high purity ethylene, 9.8%, and OXyBE" vine reactor at a pressure of 40 bar, An agueess catalyst per chloride CuCl, containing ‘small quantities of From ethylene by direct oxidation: The Or 99%, enter Inthe single stage P* into the lower part of solution, consisting of COPI pale ceive kes pace ea uses. contaning snes Thee, and uneacied eens pas (09 SE where lighter gases collected overhead ar cooled and separated by washing with water ‘Any . tunreacted gas, which contains ‘ethylene, is recycied tothe reactor Ikis necessary to purge the recycle gas t0 prevent he build up of inert gases, for example —— Shon dioxide, formed as a by-product (See Figure 1) = [GURE 1 ACETALDEHYDE FROM ETHYLENE BY DIRECT OXIDATION (ONE-STAGE PROCESS) Light Puntiation oactor Separator scrubber dstlation olumn ‘Exhaust 935 V ma ra Light ends \ estate: Regeneration ethylene omaer ‘Steam Steam Crude acetaldehyde is double distilled to give # PE Cigh water to eave Tower boiling point Product ‘and second by fractionation to remove higher boiling fractions: heated to 160°C in the regenerator, “The catalyst stream from the separator is —— vapose and the cuprous chloride i eoxidized PY PRE = where by-products deco nPottion of a bulfering agent, such a5 copper ssIPhat = fed into the system. The trevonts the formation of aid caused by the reducon ‘of palladium chloride to palladium. 2, The two-stage process _-where reduction and oxidation “Two stage versions of the process are on stream srrcarried out in separate tubular reactors, Airis iced instead of oxygen and theAcctaldehyde 3 ethylene reaction takes place at 110°C and 90 bar in the presence ofa solution of ‘cupric chloride containing palladium chloride which acts as the catalyst. The gaseous reaction mixture containing acetaldehyde passes to a flash tower where ‘an acetaldehyde-water mixture passes overhead. (See Figure 2) FIGURE 2 ACETALDEHYDE FROM ETHYLENE BY DIRECT OXIDATION (TWO-STAGE PROCESS) Reactor Oxiiser “Flash Crue Aldayde Lightends Final still tower cou asian Acetaldehyde ‘The catalyst solution is introduced into the second reactor where the cuprous chloride is oxidized to cupric chloride with oxygen at 100 bar. Exhaust gases are separated and the regenerated catalyst solution is recycled. ‘The acetaldehyde-water vapour is concentrated and double distilled to remove light and heavy by-products as in the one stage process, Because the reaction is carried out in two separate stages, ethylene obtained from naphtha cracking can bbe used instead of high purity ethylene. ‘The choice of route depends on the source of the ethylene, the availability of oxygen and energy costs, since production costs and yields are similar. Reaction Gili, + Pac + H,O + CHCHO + Pd + 2HCI Pd + 2CuCl, + PdCh, + 2Cu catalyst 2CuCl + 140, + ZHCI— 2CuC, + HO regeneration $e tiers nd tare ed re ti mre. og cu ate Gate ae Gata rack, tke ad 95%4 Handbook of Petrochemicals and Processes 3. From n-butane by oxidation ‘Butane or propane mixed with air and recycle gases (inthe ratio 12:7 by volume nd ata presoure of 7 bs) are passed through a tubular furnace where they are heated to 370°C, prior to entering the reactor. The exothermic reaction which takes place raises the temperature of the exit gases to 450°C. Any peroxides formed are decomposed by passing the hot gases through a ceramic packed tube. (See Figure 3) FIGURE 3 ACETALDEHYDE FROM BUTANE BY OXIDIZATION Reactor Quenchor Scrubber Fractionator Recycle 95 ‘Acotaldehyde {purification Furnace Formaldehyde ‘olution to purification unit “The reacted gases are cooled by passage through a quencher-scrubber through which dilute aqueous formaldehyde circulates. The gases are absorbed by water in the scrubber and any unreacted gases are recycled. Liquid from the bottom ofthe tower is fractionated to separate and recover the many compounds formed. n-Butane yields about 31% acetaldehyde, 33% formaldehyde, 20% methyl alcohol, 4% acetone and 12% of mixed solvents. ‘Yields from propane are similar. Other alcohols and aldehydes can be recovered ‘or hydrogenated to alcohols and paraffins. By using different raw materials, reaction conditions and recovery methods, varying ratios of products can be obtained. Reaction CiHyo + Or» CHCHO + mixed + CO2 HCHO organics. CO Na Yield 31%.ULQUALUDNNUNNUUONUU01000 000MM Acetaldehyde § 4. From ethyl alcohol by dehydrogenation Ethyl alcohol vapour is passed over a catalyst consisting of copper activated with ‘chromium oxide. External heating is used to maintain the reaction temperature ‘at 290°C. (See Figure 4) FIGURE 4 ACETALDESYDE FROM ETHYL ALCOHOL BY DEHYDROGENATION — =< istitaion a camer ee a ‘e A L { mae | X | Seem | - Washing alcohol return The exit gases from the reactor are cooled by scrubbing with cold ethyl alcohol Acetaldehyde and any unreacted ethyl alcohol dissolve and the remaining ‘gases, consisting mainly of hydrogen, are recovered and used as fuel The alcohol.acetaldehyde solution is distilled and acetaldehyde is collected overhead. The remaining ethyl alcohol can be recycled for further use. Conversion per pass is between 25% and 35%. Reaction (CH,CH,OH — CH,CHO + H ‘Raw material requirements and yield Raw materials required per tonne of acetaldehyde: Ethyl alcohol 100%. 1140, Yield 90-95% Other processes ‘Methyl alcohol can be hydroformylated with carbon monoxide and hydrogen in. the presence of bromides or iodides of copper, nickel or iron, or iron-cobalt. cok of Petrochemicals and Processes carbonyls. Alternative catalyst combinations are cobalt-nickel in the presence of testiary amines, phosphines or nitriles. Reaction conditions are a temperature of 180-200°C and a pressure in the range of 300-400 bar. Methyl acetate can be hhydrocarbonylated using catalysts based on palladium, thodium or iron salts, cobalt-nickel in the presence of tertiary amines, phosphines or nitriles, or cobalt- ruthenium catalysts promoted by methyl and sodium iodides. Most recent developments involve the reduction of acetic anhydride with hydrogen over 2 platinum catalyst. Although selectivities of up to 80% are claimed, none ofthese processes has yet been commercialized. Properties Mobile, colourless liquid with a strong pungent odour. Flammable, Soluble in water and most organic solvents. Molecule We 44.095 ash Pint Closed Cu arc Beaty at °C om Vapour Density (r=) 132 Mating Point me Exposure Limit ASE 150 ppm Boing Point aac Eetis 1 sminvtes ‘Autoignition 100 ppm “Temperate sc hour WA xpiosive lite in air Boposure Limit ACGIH 150, Tower 4 volt muv-SeL per S7vol% ito ppm aw-Wa Polymers of Acetaldehyde ‘Acetaldehyde forms two polymers - paraldehyde which is a cyclic trimer, and metaldehyde, a cyclic tetramer In the presence of mineral acids such as sulphuric or hydrochloric, acetaldehyde polymerizes to paraldehyde. The acid is neutralized with sodium acetate or sodium bicarbonate and any acetaldehyde is recovered by distillation. ‘Acetaldehyde will polymerize in the gaseous phase in the presence of Al:Os, SOs or ZnSO, which catalyze the reaction to give metaldehyde. Properties Paraldehyde Colourless with a pungent odour. Soluble in most organic solvents. Molecular Wt 13216 Melting Point nsc Density at 20°C 0992 Bolling Point ase Metaldehyde White crystals. Insoluble in water but soluble in acetic acid and carbon disulphide. Molecular WE 176.2 Grades ‘Technical > 98%WUUALUUMLLALLLALULAU ALU A ANAAMALALUUL Acetaldehyde 7 International classifications UN Number 09 Classification Flammable liquid CAS Reg No 410 Packing Grouy 1 EC Cassiication S-OS-O0-6 Hazchem Code aE Applications Acetaldchyde i 2 very reactive material and its main use is as an intermediate in chemical synthesis. Amongst the compounds that can be produced are: ‘© peroxyacetic acid, an intermediate in the manufacture of epoxides; ‘© pentacrythritol for the production of alkyd resins; ‘© 2ethyl hexyl alcohol, an intermediate for dioctyl phthalate used as a plasticizer for PVC: ‘© butyl alcohol which is converted to butyl acetate, a solvent for nitro-cellulose lacquers; ‘© polyvinylacetals, used in the manufacture of laminated safety glass and washable primer paints; acetic acid, whose main outlet is for the manufacture of vinyl acetate; © chloral, a raw material for the preparation of DDT. With phenol or urea, acetaldehyde forms thermosetting resins. It will react with ‘amines to produce compounds used in the rubber industry such as accelerators and antioxidants. Acetaldehyde is an effective disinfectant for the prevention of, mould growth on leather, and as a hardener for glue, gelatin and casein. It can be used as a denaturant for ethyl alcohol. ‘The need for acetaldehyde as an organic intermediate has declined in recent years because of the switch to Cl-based raw materials, This fact, together with the recovery of by-product acetaldehyde has led to the closure of a number of plants, a trend which is expected to continue. Health & handling ‘Acetaldehyde is iritating to eyes, nose and throat in high concentrations, and these effects usually serve as adequate warning of its presence in the atmosphere. ‘Adequate extraction systems must be provided. Contact with the eyes or skin should be avoided by the use of goggles and protective clothing, Any con: taminated clothing must be laundered before reuse, Containers should be constructed of stainless steel or aluminium and pressure tested because of vapour build-up caused by the low boiling point of acetaldehyde. Copper or mild steel must not be used due to the risk of corrosion from traces of acetic acid which are normally present. Acetaldehyde must be stored in a cool location under nitrogen at 1 bar pressure. Air must never be used because explosive peroxides may be formed. Storage tanks should be earthed to prevent static build-up. Spills can be absorbed by dry sand or earth, or if small, diluted with large quantities of water to reduce the potential risk of explosion. The liquid is a5 Handbook of Petrochemicals and Processes sion hazard. Clean-up personnel must wear full dangerous fire and explo: protective clothing. Fires should be blanketed ‘be avoided as it may spreat Jong distances, flashback is @ dothing and self-contained breathing monoxide and methane gases are given off by carbon dioxide, dry chemical or foam, Water must i the fire. Because acetaldehyde vapours can travel hazard. All firefighters must wear protective ‘apparatus because above 400°C carbon ‘Major plants Plants with capacities greater than 100,000 tonnes/year: Montedipe __Priolo Italy ‘Showa Acetyl Nomi Deak Germany) Chnmmel | Olea BE 10a Taragona Spain Japan Aldehyde Chiba Japan Hoechst-Celanese Kyows Yuka Yokkaichi Japan. Chemical Bay City US Mitsubishi Texas Eastman ‘Chemica! Mizushima Japan us Tokayama ‘hemi! Longview Pemex Ta Crangrejera Mexico ‘Pelrochemice!_ Shin Nanyo Japan Licensors Ethylene ‘Aldehyd (Hloechst-Uhde) Ethyl alcohol Veba Chemie j AWAY