PRODUCTION OF AMMONIA BY HABER BOSCH PROCESS

A project report submitted in partial fulfillment for the award of degree of BACHELOR OF TECHNOLOGY IN PETRO-CHEMICAL ENGINEERING SUBMITTED BY
T.V.S.ANJANI (10021A2516) TEJA KRISHNA KADALI (10021A2547)

Under the Esteemed guidance of ______________ DEPARTMENT OF PETROLEUM AND PETROCHEMICAL ENGINEERING UNIVERSITY COLLEGE OF ENGINEERING, KAKINADA JNTU, KAKINADA 2010-2014

ACKNOWLEDGEMENT

I wish to express my sincere thanks to Dr. K. Padma Raju, PRINCIPAL of the college for providing me with all the necessary facilities. I place on record, my sincere gratitude to Dr. B. Balakrishna, Head of the Department, Department of Petroleum and Petrochemical Engineering, for his constant encouragement. I also thank Prof. K. V. Rao, Academic advisor & Programme Director for Petroleum Courses. I am extremely grateful and indebted to him for his expert, sincere and valuable guidance and encouragement extended to me. I would also thank my institution and faculty members without whom this project would have been a distant reality. I also extend my heartfelt thanks to my family and all who, directly or indirectly, have lent their helping hand in the completion of the project.

INTRODUCTION
Ammonia is a chemical compound with the formula NH3. At 20 Celsius and 1 atm pressure, ammonia is a gas with a characteristic pungent smell. Ammonia is a colorless alkaline gas, it is lighter than air and has a distinct pungent odor. Ammonia is found in small quantities as ammonium carbonate in the atmosphere, being produced from the putrefaction of nitrogenous animal and vegetable matter. Ammonium salts are also found in small quantities in rain -water, whilst ammonium chloride (salammoniac) and ammonium sulfate are found in volcanic districts; and crystals of ammonium bicarbonate have been found in Patagonian guano. Ammonium salts also are found in fertile soils, in sea -water, and in most plant and animal liquids, and also in urine. Ammonia was first prepared in the 16th century by distilling animal substances such as hoofs and horns in the form of a solution. Ammonia was first obtained in pure form in 1774 by an English chemist Joseph Priestley . He heated sal ammoniac (ammonium chloride) with slack lime (calcium hydroxide). The reaction 2NH 4 Cl + Ca(OH) 2 NH 3 + CaCl 2 is still used in laboratories if required a small quantities of this gas. Priestley collected the released ammonia over mercury. He called it "alkaline air" because water solution of ammonia had all attributes of alkalis. In 1784, a French chemist Claude Louis Berthollet decomposed ammonia into elements with the help of electric discharge and thus identified the composition of this gas. In 1785, it was shown by Berthollet to be a compound containing Nitrogen and Hydrogen. Ammonia received its official name as "ammoniac" in 1787 from the Latin name of ammonium chloride - sal ammoniac; because that salt was obtained near the temple of Egyptian god Amon. This name is still retained in the majority of West European languages (German Ammoniak, English ammonia, French ammoniaque); the abbreviated Russian name "ammiak" was introduced in 1801 by Russian chemist Yakov Dmitrievich Zakharov who was the first to develop the Russian chemical nomenclature system. The major use of ammonia and its compounds is as fertilizers. Ammonia is also used in large amounts in the Ostwald process (see Ostwald, Wilhelm) for the synthesis of nitric acid; in the Solvay process for the synthesis of sodium carbonate; in the synthesis of numerous organic compounds used as dyes, drugs, and in plastics; and in various metallurgical processes.

Manufacture of Ammonia:
The chief commercial method of producing ammonia is by the Haber-Bosch process, which involves the direct reaction of elemental hydrogen and elemental nitrogen. N2 + 3H2 2NH3 This reaction requires the use of a catalyst, high pressure (1001,000 atmospheres), and elevated temperature (400550 C [7501020 F]). Actually, the equilibrium between the elements and ammonia favours the formation of ammonia at low temperature, but high temperature is required to achieve a satisfactory rate of ammonia formation. Several different catalysts can be utilized. Normally the catalyst is iron containing iron oxide. However, both magnesium oxide on aluminum oxide that has been activated by alkali metal oxides and ruthenium on carbon have been employed as catalysts. In the laboratory, ammonia is best synthesized by the hydrolysis of a metal nitride. Mg3N2 + 6H2O 2NH3 + 3Mg(OH)2

WORLD SCENARIO OF AMMONIA MANUFACTURE

Ammonia Production by Country (Thousand metric tons of contained nitrogen)

Rank 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Country China India Russian Federation United States Trinidad and Tobago Indonesia Ukraine Canada Saudi Arabia Germany Pakistan Egypt Iran, Islamic Republic Of Poland Qatar Netherlands Bangladesh Romania Australia Venezuela

World Production, By Country (Thousand metric tons of contained nitrogen) 42,290 11,200 10,441 7,704 5,100 4,600 4,200 4,000 2,600 2,362.55 2,300 2,000 2,000 1,990 1,800 1,800 1,300 1,300 1,200 1,160

INDIAN SCENARIO OF AMMONIA MANUFACTURE INDIA AMMONIA PRODUCTION BY YEAR

12,000

Thousand metric tons of contained nitrogen

11,500 11,000 10,500 10,000 9,500 9,000 2003 2004 2005

year 2006

2007

2008

2009

PROPERTIES STRUCTURAL PROPERTIES

Property Name Molecular shape Dipole moment Characteristic Trigonal pyramid 1.42 D

PHYSICAL PROPERTIES:

Property Name Molecular Formula Molecular weight Specific gravity

Characteristic NH3 17.036 g/ mol Gas 0.587 Liquid 0.682

Density

0.86 kg/ m3 (at 1.013 bar & at boiling point) gas at room temperature -33.35C (28.03 F) -77.7C (107.8 F) Alkaline Colorless Strong pungent odor 0.5967(air=1) Highly soluble in cold water (89.9 gm/ 100 ml at 0c)

Physical state Boiling point Freezing point Nature Color Odor Vapor density Solubility

Odor threshold: Air 25 ppm (18 mg/m3) 48 ppm (34 mg/m3) 53 ppm (38 mg/m3) Water Basicity (pKb) Critical temperature Critical pressure Viscosity of Saturated liquid 1.5 ppm 4.75 (reaction with water) 133c 5 kg/ cm2 0.25 cp at -15c 0.502 W/ m K at 0c 23.3 kilojoules per mole ( at its boiling point) 22 at 34 C [29 F]

Thermal conductivity of saturated liquid Heat of vaporization

Dielectric constant of ammonia Vapor pressure: Anhydrous NH3

8.5 atm (20 C) 10.2 atm (25 C)

Aqueous NH3 Auto ignition temperature

(28%) 2.9 atm (25 C) 651 C

CHEMICAL PROPERTIES:
Thermal stability Ammonia is highly stable. However, it can be decomposed into hydrogen and nitrogen by passing over heated metallic catalysts or when electric discharge is passed through it.

2NH3

N2+3H2

Combustibility Ammonia is combustible in air. However, it will burn in an atmosphere of oxygen 4NH3+3O2 2N2+6H2O

Nitric oxide is obtained when a mixture of ammonia and air is passed over platinum - rhodium catalyst at 800C Basic character Ammonia molecule has a strong tendency to donate its lone pair of electrons of nitrogen to other molecules. Thus, it acts like a strong Lewis base. In aqueous solutions, NH3 ionizes in accordance with the reaction.

The equilibrium constant for this reaction at 298 K is 1.8 x 10-5. Thus, ammonia ionizes to a very small extent in aqueous solution. The aqueous solution of ammonia acts as a weak base due to the presence of OH- ions therein. Therefore, ammonia turns red litmus blue and reacts with acids to form salts. For example, NH3+HCl NH4Cl

2NH3+H2SO4 With metal oxides

(NH4 )2 SO4

Ammonia gets oxidized to nitrogen, when passed over heated metal oxides. 3CuO + 2NH3 3PbO + 2NH3 With halogens Ammonia reacts with halogens but the type of halogen and reaction conditions determine the nature of products. Chlorine Nitrogen and ammonium chloride are formed with a limited amount of chlorine. In the presence of excess of chlorine, nitrogen trichloride is formed. 8NH3 + 3Cl2 (limited) NH3 + 3Cl2 (excess) Bromine It gives ammonium bromide and nitrogen 8NH3 + 3Br2 Iodine When rubbed with solid iodine, a dark colored precipitate of nitrogen tri-iodide is obtained 2NH3 + 3I2 NH3NI3 + 3HI 6NH4Br + N2 6NH4Cl + N2 NCl3 + 3HCl 3H2O + N2 + 3Cu 3H2O + N2 + 3Pb

After drying, if NH3.NI3 is struck against a hard surface or hit with a hammer, it explodes producing iodine vapors. 8NH3 .NI3 With alkali metals When ammonia is passed over heated sodium or potassium, amides are formed and hydrogen is set free. 2Na + 2NH3 2NaNH2 + H2 5N2 + 9I2 + 6NH4I

2K + 2NH3

2KNH2 + H2

Alkali metal dissolved in liquid ammonia gives a blue solutions, which upon standing slowly, liberate hydrogen. The blue color of such solutions is due to the presence of solvated electrons (e(NH3)n). For instance, with sodium 2Na + 2NH3 2NaNH2 + H2

Formation of complex compounds Ammonia forms complex compounds with the soluble salts of copper, silver etc. With copper sulphate solution, it gives a deep blue colored complex compound, tetrammine copper(II) sulphate.

USES:
Agricultural industries are the major users of ammonia, representing nearly 80% of all ammonia produced in the United States. Ammonia is a very valuable source of nitrogen that is essential for plant growth. Depending on the particular crop being grown, up to 200 pounds of ammonia per acre may be applied for each growing season. Ammonia is used in the production of liquid fertilizer solutions which consist of ammonia, ammonium nitrate, urea and aqua ammonia. It is also used by the fertilizer industry to produce ammonium and nitrate salts. Ammonia and urea are used as a source of protein in livestock feeds for ruminating animals such as cattle, sheep and goats. Ammonia can also be used as a pre-harvest cotton defoliant, an anti-fungal agent on certain fruits and as preservative for the storage of highmoisture corn. Dissociated ammonia is used in such metal treating operations as nitriding, carbonitriding, bright annealing, furnace brazing, sintering, sodium hydride descaling, atomic hydrogen welding and other applications where protective atmospheres are required. Ammonia is used in the manufacture of nitric acid; certain alkalies such as soda ash; dyes; pharmaceuticals such as sulfa drugs, vitamins and cosmetics; synthetic textile fibers such as nylon, rayon and acrylics; and for the manufacture of certain plastics such as phenolics and polyurethanes. The petroleum industry utilizes ammonia in neutralizing the acid constituents of crude oil and for protection of equipment from corrosion. Ammonia is used in the mining industry for extraction of metals such as copper, nickel and molybdenum from their ores. Ammonia is used in several areas of water and wastewater treatment, such as pH control, in solution form to regenerate weak anion exchange resins, in conjunction with chlorine to produce potable water and as an oxygen scavenger in boiler water treatment. Ammonia is used in stack emission control systems to neutralize sulfur oxides from combustion of sulfur-containing fuels, as a method of NOx control in both catalytic and non-catalytic applications and to enhance the efficiency of electrostatic precipitators for particulate control.

 Ammonia is used as the developing agent in photochemical processes such as white printing, blue printing and in the diazo duplication process. Ammonia is a widely used refrigerant in industrial refrigeration systems found in the food, beverage, petro-chemical and cold storage industries. Ammonia is used in the rubber industry for the stabilization of natural and synthetic latex to prevent premature coagulation. The pulp and paper industry uses ammonia for pulping wood and as a casein dispersant in the coating of paper. The food and beverage industry uses ammonia as a source of nitrogen needed for yeast and microorganisms. The decomposition of ammonia serves as a source of hydrogen for some fuel cell and other applications. Ammonia is used by the leather industry as a curing agent, as a slime and mold preventative in tanning liquors and as a protective agent for leathers and furs in storage.

Processes for Ammonia production

Ammonia is produced basically from water, air and energy. The energy source is usually hydrocarbon that provides hydrogen for fixing the nitrogen. The other energy input required is steam and power. This can be through coal or petroleum products or purchased power from a utility company. Steam reformation process of light hydrocarbon particularly Natural Gas (NG) is the most efficient route for the production of ammonia. The other routes are the partial oxidation of heavy oils if the available feedstock is residual heavy oil from a refinery. Coal has also been used to produce ammonia. The following is an approximate comparison of the energy consumption, cost of production and the capital cost of the plants for the three feed stocks. Natural Gas Energy consumption Investment cost Production cost 1.0 1.0 1.0 Heavy Oil 1.3 1.4 1.2 Coal 1.7 2.4 1.7

Natural gas is therefore the most appropriate source of feedstock on all the three accounts.

Haber- Bosch process:

It is the main industrial route to ammonia. The Haber process now produces 500 million tons of nitrogen fertilizer per year, mostly in the form of anhydrous ammonia, ammonium nitrate, and urea. 35% of the world's natural gas production is consumed in the Haber process. Fertilizer generated from ammonia produced by the Haber process is estimated to be responsible for sustaining one-third of the Earth's population. In this process hydrogen and nitrogen are reacted in the presence of iron catalyst to form ammonia. The hydrogen is formed by reacting natural gas and steam at high temperatures (steam reforming) and the nitrogen is supplied from the air. Other gases (such as water and carbon dioxide) are removed from the gas stream and the nitrogen and hydrogen passed over an iron catalyst at high temperature and pressure to form the ammonia. The stepwise process is described below: Step 1 - Hydrogen production Hydrogen is produced by the reaction of methane with water. However, before this can be carried out, all sulfurous compounds must be removed from the natural gas to prevent catalyst poisoning. These are removed by heating the gas to 400C and reacting it with zinc oxide: ZnO + H2S ZnS + H2O

Following this, the gas is sent to the primary reformer for steam reforming, where superheated steam is fed into the reformer with the methane. The gas mixture heated with natural gas and purge gas to 770C in the presence of a nickel catalyst. At this temperature the following equilibrium reactions are driven to the right, converting the methane to hydrogen, carbon dioxide and small quantities of carbon monoxide: CH4 + H2O 3H2 + CO CH4 + 2H2O 4H2 + CO2 CO + H2O H2 + CO2 This gaseous mixture is known as synthesis gas. Step 2 - Nitrogen addition The synthesis gas is cooled slightly to 735C. It then flows to the secondary reformer where it is mixed with a calculated amount of air. The highly exothermic reaction between oxygen and methane produces more hydrogen. Important reactions are: CO + H2O CO2 + H2 O2 + 2CH4 2CO + 4H2 O2 + CH4 CO2 + 2H2 2O2 + CH4 2H2O + CO2 In addition, the necessary nitrogen is added in the secondary reformer. As the catalyst that is used to form the ammonia is pure iron, water, carbon dioxide and carbon monoxide must be removed from the gas stream to prevent oxidation of the iron. This is carried out in the next three steps. Step 3 - Removal of carbon monoxide Here the carbon monoxide is converted to carbon dioxide (which is used later in the synthesis of urea) in a reaction known as the water gas shift reaction: CO + H2O CO2 + H2 This is achieved in two steps. Firstly, the gas stream is passed over a Cr/Fe3O4 catalyst at 360C and then over a Cu/ZnO/Cr catalyst at 210C. The same reaction occurs in both steps, but using the two steps maximizes conversion. Step 4 - Water removal The gas mixture is further cooled to 40C, at which temperature the water condenses out and is removed. Step 5 - Removal of carbon oxides The gases are then pumped up through a counter-current of UCARSOL solution (an MDEA solution, see article). Carbon dioxide is highly soluble in UCARSOL, and more than 99.9% of the CO2 in the mixture dissolves in it. The remaining CO2 (as well as any CO that was not converted to CO2 in Step 3) is converted to methane (methanation) using a Ni/Al2O3 catalyst at 325C: 2

CO + 3H2 CH4 + H2O CO2 + 4H2 CH4 + 2H2O The water which is produced in these reactions is removed by condensation at 40C as above. The carbon dioxide is stripped from the UCARSOL and used in urea manufacture. The UCARSOL is cooled and reused for carbon dioxide removal. Step 6 - Synthesis of ammonia The gas mixture is now cooled, compressed and fed into the ammonia synthesis loop. A mixture of ammonia and unreacted gases which have already been around the loop are mixed with the incoming gas stream and cooled to 5C. The ammonia present is removed and the unreacted gases heated to 400C at a pressure of 330 barg and passed over an iron catalyst. Under these conditions 26% of the hydrogen and nitrogen are converted to ammonia. The outlet gas from the ammonia converter is cooled from 220C to 30C. This cooling process condenses more the half the ammonia, which is then separated out. The remaining gas is mixed with more cooled, compressed incoming gas. The reaction occurring in the ammonia converter is: N2 + 3H2 2NH3 The ammonia is rapidly decompressed to 24 barg. At this pressure, impurities such as methane and hydrogen become gases. The gas mixture above the liquid ammonia (which also contains significant levels of ammonia) is removed and sent to the ammonia recovery unit. This is an absorber-stripper system using water as solvent. The remaining gas (purge gas) is used as fuel for the heating of the primary reformer. The pure ammonia remaining is mixed with the pure ammonia from the initial condensation above and is ready for use in urea production, for storage or for direct sale.

The process flow diagram:

SCHEMATIC REPRESENTATION OF THE AMMONIA SYNTHESIS PROCESS: