Introduction

Methyl methacrylate (MMA) is an importantmonomer, which is widely used for producing acrylicplastics (polymethyl methacrylate) or producing polymerdispersions for paints and coatings. The worldproduction capacity has been almost doubled in past15 years, and reached about 2.2 million tonnes peryear. The demand of MMA is still expected steadygrowth in the future. Methacrylic polymer, which hasthe characteristics of good transparency and weatherresistance, is used in many fields such as signboards,building materials, vehicles and lighting equipments.Methacrylic acid (MAA) and higher esters (such asbutyl methacrylate) derived from the acid, have notbeen produced in a large quantity, but are usefulco-monomers for various uses. The present, and proposed, manufacturing routes for MMA and MAA continue tobe based on natural gas or crude oil as the ultimate feedstock. They can be classified as propylene (C-3), ethylene (C-2), and isobutane/isobutylene (C-4).The commercial viability of a process is determined by the aggregate of raw material cost andutilization (ie, process yield), operating costs with particular attention toenergy-related charges, waste disposal costs, environmental impact, and plantcapital investment. Until 1982, almost all methyl methacrylate produced worldwide wasderived from the acetone cyanohydrin (derived from propylene) (C-3) process. However, MMA manufacturers were forced to develop new processes using alternate feedstocks due to the high costs for waste handling (ACH process makes 1.5 tons of ammonium bisulfate for every ton of MMA), the costs and corrosivenature of sulfuric acid and the anticipated tight supply for HCN as acrylonitrileproducers improve their process selectivity to decrease the level of this byproduct. Also, processes based on propylene suffer from raw materials limitation as it is difficult to get pure propylene feed. In 1982, Nippon Shokubai Kagaku Kogyo Co. introduced an isobutylenebased(C-4) process, which was quickly followed by Mitsubishi Rayon Co. in 1983.With the advent of using methyl tert-butyl ether (MTBE) as an oxygenated gasoline additive, there has been considerable emphasis on the synthesisof isobutylene or tert-butyl alcohol, which can be used as feedstocks for MTBEproduction.The use of isobutylene, isobutane or tert-butyl alcohol as a feedstock for MTBE production creates an economic disincentive for

their use as a raw material forMAA and MMA production, because MTBE is the product with the highervalue. Hence, the recent trend is to develop process based on ethylene. These processes involve minimum byproduct formation as selectivities are higher and the waste products are benign. They can be integrated with existing syngas plants as carbon monoxide is used as a feedstock which provides further incentive for coal gasification. BASF was first to commission MMA plant based on three step ethylene process having a capacity of 40,000 lbtonnes/annum. Recently RTI, Eastman and Lucite have developed 2 step direct processes based on ethylene but they have low conversion rates.

1. Methyl methacrylate Properties and Uses

Methyl methacrylate (CAS no. 80-62-6) is a colourless, volatile liquid with an acrid fruity odour. It has a relatively high vapour pressure and moderate water solubility. 1.1. Physical properties 1.2. Chemical reactivity Stability: The product is stable. Instability Temperature: Not available. Conditions of Instability: Not available. Incompatibility with various substances: Reactive with metals, acids, alkalis. Corrosivity: Non-corrosive in presence of glass. Special Remarks on Reactivity: Not available. Special Remarks on Corrosivity: Not available. Polymerization: Yes. 1.3. Uses of methyl methacrylate Global consumption of MMA today exceeds 2.5 million metric tons per year, of which more than two million tons is for MMA polymers. The other primary product of this industry is crude methacrylic acid (crude MAA), which is produced by similar technology but often in separate plant units 1.3.1. Polymer Industry Nearly all methyl methacrylate (MMA) is polymerised to make homopolymers and copolymers with the largest application being the casting, moulding or extrusion of polymethyl methacrylate (PMMA) or modified polymers. This acrylic sheeting has clarity, weather-resistance and light

weight properties making it a suitable substitute for glass in safety glazing, panels and illuminated light displays. Methylmethacrylate-butadiene-styrene (MBS) copolymers are used as an impact modifier for clear rigid polyvinyl chloride (PVC) and in food and pharmaceutical packaging. MMA can partially replace styrene in unsaturated polyester resins to give better weather resistance and longer life. A major application of MMA polymers and copolymers is in surface coatings and impregnation resins to give colour fastness and weather-resistance properties to latex paints, lacquer resins and stoving enamels. For example, exterior latex paint is based on emulsions containing MMA while other uses include industrial finishes, and metal and foil coatings. Over 80% of MMA consumption is accounted for in the construction and automotive industries and by original equipment manufacturers. Demand from these markets has slumped in the economic downturn. 1.3.2. Manufacture of higher methacrylate Transesterification of methyl methacrylate with the appropriate alcoholis often the preferred route for preparing higher alkyl and functional methacrylates as opposed to direct esterification of methacrylic acid with alcohols. Catalysts employed for transesterification include conventional acids and bases, where more recent work has shown lithium hydroxide and magnesium methoxide to be effective. In addition, transition-metal compounds exhibit goodactivity for transesterification and include complexes such as dialkyltin oxides, titanium(IV) alkoxides, zirconium acetoacetate, and ferric sulfate. The use of the transition-metal catalysts allows reaction under nearlyneutral conditions and is therefore more tolerant of sensitive functionality inthe ester alcohol moiety.

2. Process selection
MMA can be produced using ethylene as a feedstock from the following three processes depending on the intermediates. 1. Propanalroute (BASF process) 2. Propionic acid route (RTI, Eastmen and Betchel process) 3. Methyl propionate route (Lucites Alpha process) All the ethylene based process used syngas as feedstock thus ethylene base production of MMA provides incentive for gasification of coal which is economically beneficial for Indian Companies as India has large gas reserves 2.1. Propanal route -BASF process BASF was first to produce MMA using ethylene as feedstock taking advantage of availability of feedstock at the plant site at Ludwigshafen, Germany, with a capacity of 36,000 tons of MMA. The process consist of three stages 1. 1st stage Oxo process It involves conversion of ethylene to propanal using oxo or hydroformylation process over triphenylphosphinemodified rhodium catalystat 7-30 bar pressure and temperature of 80-120C (LP Oxo process) H2C=CH2 + CO + H2 2. 2nd stage Methacrolein production Propanal is then reacted with formaldehyde in the presence of a secondary amine and, optionallya carboxylic acid (liquid-phase reaction) to form methacrolein. Alternatively, a gasphase reaction between propanal and formaldehyde catalyzed by molecular sieves may beemployed to produce methacrolein. CH3 CH2 CHO+ HCHO CH2=C (CH3) CHO +H2O CH3 CH2 CHO

3. 3rd stage Oxidation of Methacrolein to MAA The methacrolein is then oxidized to MAA over phosphomolybdic acid-based catalyst, usually with copper, vanadium, and a heavy alkali metal additive. MAA is then esterified to MMA. CH2=C (CH3) CHO + 0.5O2 CH2=C (CH3) COOH

CH2=C (CH3) COOH + CH3OH

CH2=C (CH3) COOCH3

2.2. Propionic acid or propionic anhydride route (RTI, Eastmen and Betchel process) It is a two stage process 1. 1st stage Hydrocarbonylation Propionic acid or propionic anhydride prepared by the liquid-phase hydrocarbonylationof ethylene over halide-promoted Cr-group (Group 6) metals, preferably in the form of iodidepromoted Mo catalysts as discovered by Eastman. Earlier nickel carbonyl catalyst was used which is toxic and required high pressures (>180 atm) and high temperatures (>270C). Alternative catalyst which may operate at substantially lower pressures and temperatures, generally require expensive metals, such as Rh, Ir, or Pd, and nonehave been commercially employed.Iodide-promoted Mo catalysts proceed at high rates and at moderate pressures (25 to 70 atm) and moderate temperatures (150 to 200C). The condensation of propionic anhydride rather than propionic acid or methyl propionate has the advantage of producing one less mole of water, which can kinetically inhibitthe reaction, hydrolyze the product, and make separation of the product more costly. Propionic anhydride:H2C = CH2+ CO + EtCOH (EtCO)2O

Propionic acid: H2C = CH2+ CO + H2O 2. 2nd stage HCHO and Propionate Condensation

EtCOOH

Vapor phase condensation of formaldehyde and propionic anhydride is carried out on fixed bed of catalyst. (EtCO)2O + HCHO MAA is then esterified to MMA using methanol. CH2=C (CH3) COOH

2.3.Methyl propionate route Lucites Alpha process Lucites alpha process consist of two stages however does not involve esterification reaction in the final stage as MMA is directly obtained. 1. 1st stage Hydrocarbonylation Ethylene + Carbon Monoxide Methanol Methyl Propionate

The first step in the process, the MeP synthesisreaction, is done in a continuous-stirredtank reactor under moderate conditions oftemperature and pressure.The catalyst for the first step is a palladium bisphosphinedisplays enzyme-like selectivity (>99.9% to methyl propionate from its raw materials)with excellent activity. Because thereaction is highly selective, no by-productsare formed. This makes the separationand purification of methyl propionatestraightforward. The catalyst is fully solublein the reaction mix so it can be continuouslyrecycled to the reaction stage, while pureMeP (>99.9% purity) can be produced.To ensure high selectivity to MMA andto avoid excessive ageing of the catalyst,the formalin used in the process must bedehydrated to give an anhydrous feed. 2. 2nd stage HCHO and methyl propionate Condensation The subsequent MMA synthesis from MeP and formaldehyde takes place over a fixedbed of catalyst. This catalyst has caesiumoxide on silica as its active component and it achieves a selectivity to MMA fromMeP of approximately 93% and 85% onformaldehyde to MMA. Two parallel MMAreactors are needed because of the formationof a small amount of heavy,relativelyinvolatilecompounds. These form coke (solidcarbonaceous material) on the catalyst thatcauses some loss of activity and selectivity.The coke is easily removed and catalyst activity and selectivity restored by controlled,in-situ regeneration whilst maintainingproduction through the other reactor.The reactor product stream is separatedin a primary distillation so that a crude MMAproduct stream, free from water, MeP andformaldehyde, is produced. Unreacted MePand water are recycled via the formaldehydedehydration process. Pure MMA (>99.9%) is produced from the crude MMA in a series of vacuum distillations and one proprietary reactiveseparation. In all cases, the separated streams are returned to the process;

there is onlyone (small) heavy ester purge stream. This isreadily disposed of in a thermal oxidizer withheat recovered for use in the process. The processes 2.2.and 2.3. give very low conversion per pass in the second stage. This requires complex separation systems and large recycle streams for unreacted feedstock. Also these process require that formaldehyde used for condensation in 2nd stage be free of water for god catalyst performance. This requires additional separation units and the technology for the same is protected by patents. On the otherhand, the BASF process is generic with every step in the process is well established and the technology to carry out the process is easily available. Hence BASF process is much more economically more favorable than the other two presently.