SECTION 1 PROCESS BACKGROUND PART 1 ( STUDENT 1 )

Urea occurs in nature as the end product of protein metabolism by mammals, including humans, which excrete urea as a waste product in their urine. It is highly soluble in water and is odourless in its purest state. First isolated by G.F. Rouelle in 1773, urea was then produced synthetically for the first time in 1828 in Germany, by F. Wohler. Manufactured urea is a harmless, non-toxic white crystalline solid made by combining synthetic ammonia and carbon dioxide (CO2). Its high nitrogen content (46.7 per cent) makes it an effective and popular fertiliser. Urea has the highest nitrogen content of all solid nitrogenous fertilisers in common use, and is used widely in agricultural food production. In fact, 90 per cent of the world's urea production is used for fertiliser. Other applications include urea formaldehyde resins, and engine exhaust systems. Method of Production (1) Urea production is a two-step process. One of the most common production process of urea is by reacting ammonia and carbon dioxide to form ammonium carbamate, which is then dehydrated to form urea. The urea solution is concentrated by evaporation or crystallization, and the crystals can be melted to produce pure urea as prills or granules.

The ammonia is produced using a primary and secondary reformer with a high- pressure ammonia converter. The carbon dioxide is recovered using either pressure swing adsorption or amine absorption. The carbon dioxide can be reused later in the urea production step. Method of Production (2) The synthesis of CO(NH2)2 in a discontinuous system involving a chemical reaction between CO (carbon monoxide), NH3 (ammonia), and S (sulfur) at a temperature of 100 C in the presence of CH3OH (methanol) is an alternative method for urea production compared to the conventional process.

Method of Production (3) Usage or application of biomass as feedstock is another great movement in manufacturing urea. Firstly, biomass (wood) consistently sized pieces similar to fuel pellets. Then it, fed into a syngas to produce clean syngas comprised of a mixture of CO and CO2. The clean syngas is fed into ammonia synthesizer to produce ammonia. Then, the ammonia is combined with air and water to produce urea.

Advantages and Disadvantages Method of Production ( 1 ) Advantages Sources of carbon dioxide is readily available. Purity of urea is higher. Disadvantages Production process more complex. Method of Production ( 2 ) Advantages Urea enriched with isotope N. Method of Production ( 3 ) Advantages Biomass source is available enormously. Manufacturing cost is low. Disadvantages Quantity of production is lower.

Disadvantages Cost of manufacturing is higher.

Method of production (1) by using carbon dioxide and ammonia is the most preferable method for high efficiency in the production of urea in terms of quantity and the quality. Other two methods is still new to urea manufacturing technology environment where the information regarding production process is under development. Hence, Method of production (1) is selected.

Figure 2: Process Flow Diagram of Urea Manufacturing

This process or production method is selected because this is the only method used by majority of industries around the world. Hence, the properties of feedstock is readily available out there. The information regarding quantity of urea to be produced and other related quantities can be calculate in a proper way due to the wide source of information provided by industries.

PART 2 STUDENT 2
The feedstock (raw materials) selected for this process is ammonia (NH3) and carbon dioxide (CO2). Physical and chemical properties of them are as follows; AMMONIA Physical Properties
Property Molecular Mass Colour Odour Physical State Melting Point Boiling Point Flash Point Decomposition Point Density (Gas) Density (Liquid) Vapour Density Critical Temperature Critical Pressure Heat of Fusion Heat of Vaporization Heat of Combustion Value or Detail 17.03 g/mol Colourless Sharp, Intensely Irritating Gas (at room temperature) -77.7C -33.35C 11C 500C 0.7710g/L 0.6818g/L 0.5697 (air has a vapour density of 1) 132.4C 111.3 atm 58.1 kJ/mol 23.3 kJ/mol -316 kJ/mol

Chemical Properties
Property Chemical Formula Type of Base Affinity (Water) Corrosiveness Oxidation Power Reactivity Volatility Value or Detail NH3 Weak High Corrosive to Some Metals Strong Reducing Agent Quite Reactive Increasing with increases in pH

CARBON DIOXIDE Physical Properties Molecular formula Molar mass Appearance Density Melting point Boiling point CO2 44.0095(14) g/mol colourless gas 1,600 g/L, solid; 771 g/L, liquid; 1.98 g/L, gas 56.6 C (216.6 K) 69.9 F (at 5.185 bar) 78.5 C (194.7 K) 109.3 F (sublimes)

Chemical Properties Solubility in water Acidity (pKa) Viscosity 1.45 g/L at 25C, 100kPa 6.35 and 10.33 0.07 cP at 78 C

Ammonia and carbon dioxide is the most common elements preffered in urea manufacturing industries. Source of ammonia production is found enourmously where it can be generated from natural gas and coal. While carbon dioxide is a waste gas that can be reused again for urea production. This is an economical way of producing urea. Therefore, ammonia and carbon dioxide is chosen as raw material for urea production.

Physical and Chemical Properties of Products and by-Products of Ammonia and Carbon dioxide
The commercial synthesis of urea involves the combination of ammonia and carbon dioxide at high pressure to form ammonium carbamate. (intermideate product). 2NH3 + CO2 NH2COONH4

Ammonium carbamate is further dehydrated by the application of heat to form urea and water. NH2COONH4 CO(NH2)2 + H2O

Properties of Ammonium Carbamate

Properties Molecular formula Molar mass Appearance Density Melting point Boiling point Solubility in water Solubility log P Vapor pressure CH6N2O2 78.0705 g/mol Colorless, rhombic crystals 1.38 g/cm3 (20 C) 152 C 251 C at 760 mmHg Freely soluble in water Soluble in alcohol 0.47 in octanol/water 492 mmHg(51 C

Properties of Urea

PART 3 STUDENT 3
Urea synthesis section that is the UREA SYNTHESIS REACTOR is the heart of urea plant, as urea is formed only in reactor. Remaining all section of plant is for concentration of urea. Liquid ammonia and gaseous CO2 at high pressure enter the reactor bottom and react to form carbamate which further decomposes to form urea and water.

1) 2NH3(l)
Ammonia

CO2(g)
Carbon dioxide

H2COONH4
Carbamate

2) NH2COONH4
Carbamate

CO(NH2)2
Urea

H2O
Water

Typical process conditions for the design:

Operating temperature Rate of Carbamate decomposition reaction increases with temperature. It is slow at < 150oC (NH3:CO2, stoichiometric) and quite rapid at 210oC. 180-210 oC in 0.3 to 1.0 hr is optimum for most process.At high temperature, corrosion rate is high.

Operating pressure Preferred pressure is 140 250 atm.

Inlet reactant and outlet products and by- product compositions Compositions of carbamate on mixing with NH3 are;

Composition of over flow stream;

Reactor Conversion

PART 4 STUDENT 4