Corrosion * Solutions containing are very corrosive. 4 Some of the measures to limit corrosion of the construction materials are: ¥ proper selection of construction materials, ¥ addition of a small amount of air to the carbon dioxide feed — by reaction of oxygen with the stainless steel, the protective metal oxide layer is kept intact; minimal exposure of materials to the corrosive carbamate solution —“The most important side reaction in the urea process is the formation of biuret 7 a 4 Even at very low concentrations, formation should be minimized. 4 In the urea reactor itself this is not @ problem, because of the high ammonia concentration, which shifts the reaction to the left ‘ However, in downstream processing, 4 To minimize biuret formation, itis essential to keep the residence times of urea containing solutions at high temperature as short as possible.Methanol J Demand and supply in india? ‘ There are 5 main producers of methanol in India - ¥ Gujarat Narmada Valley Fertilizer & Chemicals limited, ¥ Deepak Fertilizers, ¥ Rashtriya Chemicals and Fertilizers, ¥ Assam Petrochemicals and National Fertilizers Li Table 1: Source ~ Ministry of Chemicals and Petrochemicals Capacity Domestic | Consumption Capacity _Year (MT) _| Production(MT) |___(MT) Utilization (%) 2010-11 | 0.496 0375 20-12 | 0.496 0.360 474 0.255 0474 0307 0474 0.210 0474 0.163Year Imports (MT) | Exports (MT) 2010-11 081 (0.044 2011-12 1.20 0.120 iB 1.40 0. 2013-14 131 0.082 2014-15 Le 0.049 2015-16 1 0.084 India imports 99% of its methanol from Iran (1,31 MT) and Saudi Arabia (0.38 MT), where methanol is produced from natural gas which is abundantly available in latter countries at extremely low prices. eee ee ee ee ecValue of Methanol Imports Vs Exports (INR Cr) i - - a 2010-11 2011-12 2012-13 2013-14 2014-15 201 Imports (INR Cr) mlm Exports (INR Cr) —=Net Imports (INR CrSolvent or as an intermediate. * It is also increasingly used in the energy sector. + Methanol synthesis was the second large-scale process involving catalysis at high pressure and temperature (BASF. 1923). The same team that developed the ammonia synthesis process also developed a commercial process for the production of“ The main reactions for the formation of methanol from syngas are CO+2 Hy 2 CH;OH A, Hogs = —90.8 kJ/mol CO; +3 Hp CHOH + H,0 AcHHags = —49.6 kI/mol The two methanol forming reactions are coupled by the water-gas shift reaction, which has been discussed earlier: CO + H,0 2 CO; + Hr Ar Higa = —41 kJ/molCO and CO.equilibrium conversion data (CO conversion Presure bar) CO +2 Hy 2 CHjOH A, Hoos ( CO» +3 Hy & CHsOH + H20 A, Hag = —49.6 kJ/mol | COFMOCO+H: Ade =—A1 13/01}4 The original catalysts (ZnO) were only active at high temperature. Therefore, the pressure had to be very high((250-350 bar) to reach acceptable conversions. ‘+ Until the end of the 1960s basically these original catalysts were used in what are now call classical methanol processes “® More active catalysts (copper-zinc) were known, but these were not resistant to impurities in the feed such as sulfur, + In the late 1960s, the ability to produce sulfurfree syngas allowed the use of these very active catalysts and this has led to a new generation of plants, the “low-pressure plants”.Equilibrium CO conversion to methanol (feed Hi/CO = 2 mol/mol) classic) | At low pressure, processes maintaining the same conversion in the Medeen Processes \ classical process temperature is critical. > Catalyst sintering soo 6506000 Temperature (K) Development of catalysts that are active at lower temperature made it possible to operate at lower pressure (50100 bar).¢ The usual practice for restoring activity, + The temperature should not ex yecause then unacceptable ~ mt sintering of the cataly}t will occur, 7, ? [oul ah 7 (See + Compored-to-ammonia synthesis, catalyst development for metifinol synthesis was more difficult because, “It is not surprising that in the hydrogenation of carbon monoxide + That this Ts certainly possiCluster Particle Metal crystalite (2imensional) (Gdimensiona) atte — — veel a Carer —F “The selectivity of modern copper-based catalysts is over 99%, which is remarkable considering the large number of possible by-products.Synthesis Gas for Methanol Production syngas steam reforming of natural gas. “The ideal syngas for methanol production has a H,/CO of about 2 mol/mol.A H,/CO ratio ¥ lower than 2 mol/mol leads to increased by-product formation (higher alcohols, etc.) Y higher ratio results in a less efficient plant due to the excess hydrogen present in the syngas, which has to be purged. The composition of syngas depends on the feedstock used. ¥ When naphthyis the raw material, the stoichiometry is“A major breakthrough came in the late 1960s with the development of using the more active and selective copper-based catalysts. with plant capacities ranging from 150 to 6000 t/cfPalthough plants using remote natural gas may have a capacity as large as+ The Lurgi process is very similar to the ICI process. + The most important difference is the reactor. + In the Lurgi process, a cooled tubular reactor is used yet ‘© The Lurgi reactor is nearly isothermal & The heat of reaction is directly used for the ¢ Stoam out generation of high-pressure steam (~40 bar), which is used to drive the compressors I pew la and, subsequently, as distillation steam 4 Several adiabatic reactors are used, e arranged in series. Schematic of Lurgi reactor for methanol production 11 noomesProduction of Formaldehyde in our country “ Constructions, furniture, paints & coatings, textiles, fertilizers & pesticides, etc., and is expected to increase at a CAGR of 3.9% during the forecasted period of 2016 to 2021. ‘A salurated water solution, of about 40% formaldehyde by volume or 37% by mass, called "100% formalinProduction of Formaldehyde “ One of the largest application of methanol, , is the synthesis Zz of formaldehyde, which is based on one of the CHjOH @ CH;0 +H; AcHigg = 85 kJ/mol CHOH + 1 02 > CH20 + H20 Has = —158 kJ/molProduction of Formaldehyde * One of the largest application of methanol, , is the synthesis of formaldehyde, which is based on one of the CH,OH 2 cH,0 £ Actag = 85 13 /mol | CHJOH + ' 0, > CHO + H,0 A,Hiss = —158 kJ/mol“In industrial practice + Dehydrogenation and partial oxidation are often carried Z out over ai: a single reactor. mo ** Heat produced by the exothermic partial oxidation reaction supplies the heat for the endothermic dehydrogenation reaction.shallow bed of catalyst ‘At adiabatic conditions : “heogiacaton SS, a contro i eitcal Achieved by the ¥ use of excess methanol, ‘which is recycled, and nox ¥ by the addition of ore steam to the feed scant Fonmalieyte solution (50 wt Vaporizer ‘ansorver) (‘Dieaton carn + Distillation yields a 40-55 wt.% formaldehyde solution in water% Processes for the conversion of syngas derived from coal or natural gas into liquid fuels such as and have been considered on and off for many years, usually + These processes are known as processes. + More recently, processes have been receiving more and more attention.cae {coat \ Biomass: *< Gasification Cm) =Franz Fischer (1877) “The best known of such processes is the Fischer-Tropsch (FT) process, named after & Fischer and H. Tropsch, the | German coal researchers who discovered, in 1923, that ** Before and during FT process was extensively used on a commercial scale in Germany for the production Coton star) “ After the war the plants were shut down because they became uncompetitive when large quantities of crude oil were discovered. * Coal-rich South Africa has used coal-based FT plants for the production of“A less known route is the conversion of “This methanol-to-gasoline (MTG) process was developed by Mobil (now Exxon Mobil) during the 1970s and 1980s in response to the critical energy situation in the Western world, +A natural-gas-based MTG plant was in operation in New Zealand from 1985 to 197.Until recently, these synthetic fuels have never been able to compete economically with oil-based fuels. +? However, in recent years these processes have come into the picture again, to convert natural gas from remote gas fields into liquid fuels. “The transportation of the gas to possible consumer markets, either by pipeline or as liquefied natural gas (LNG) in special tankers, is costly and logistically difficult.+ An interesting option then may be to Y convert this gas into more readily transportable liquids, {| such as the AL Us ee! “The latter have a much larger market and are, therefore, more attractive from the viewpoint of economy of scale.+ Characteristic of FT reactions is their high exothermicity. + The formation of one mole of —CH,— is accompanied by a heat release of 145 1. 4 The hydrocarbons are formed by a-chain growth process. + A mixture of hydrocarbons ¢ Thermodynamically ** The choice of catalyst and process conditions is very important“An appropriate choice of catalyst, temperature, pressure, and H,/CO ratio enables the value of the chain growth we probability (a) to be shifted, enabling different product ranges to be produced, Current catalysts used for FT synthesis are Bye “Cobalt catalysts are more active and Ox ek ekDiesel fuel consists mainly of paraffins enes. Diesel fuel contains hydrocarbons with approximately 12-20 carbon atoms and the boiling range is between 170 and 360°, @ “Thus, they are more suitable for the production of diesel (aad ue Gasoline a mixture of liquid aliphatic and aromatic hydrocarbons, berween C4 and Cl2 carbon atoms with the boiling range of 30-22:= 090 («= Chain growth probability (-) Classical catalysts * Novel catalystChain Growth Probability in Fischer-Tropsch Synthesis Product probabilty ch, women |e Coy aqt-a) won CHa Gite (14) Chain growth mechanism for FT ses ocean on emt+ Due tothe high exathermicty ofthe reactions, 2 ‘ Effient removal of the heat of reaction isa major consideration in the design of FT reactors (@) Multitubular fixed bed ( Gireulating fluidized bed reactor, @ (BPW = boiler feed water) (a) & (b) Le FT rea (2 & (@) high teMulti-tubular fixed bed reactor A high linear gas velocity is applied and unconverted syngas is recycled to enhance heat removal. Suitable at relatively low temperature (490-530 K). At >530 K, carbon deposition is excessive, leading to blockage of the reactor. This reactor can_be considered aCtrickle flow) reactor, since a large part of the product are liquigé (waxes: C194) yhat trickle df catalyst bed* Although the chemistry of the Fischer—Tropsch synthesis is rather complex, the fundamental aspects can be represented by the generalized stoichiometric relationships as shown in Table Main reactions Alkanes NCO4 (n+ 1) Hy > Cy Hop,2 +0 HO Alkenes nCO4-2n Hy > CoHan +n HO Side reactions Water-gas shift CO+H;0 2 CO) +H) Alcohols nCO+2nH; > Hick Boudouard reaction 2CO-+C+COz