Urea Manufacture Plant

END SEMESTER PROJECT REPORT ON

UREA MANUFACTURING PLANT
(5th Semester Chemical Department)

Project Coordinator: Mam Maham Hussain Group Members: Nauman Hafeez 2K9-Che-120 Muhammad Bilal Chaudhry 2K9-Che141 Salik Mateen 2K9-Che-153 Jawad Mohsin 2K9-Che-139 Anum Maqsood 2K9-Che-134 Aisha Farid 2K9-Che-135

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Urea Manufacture Plant Hafsa Iqbal 2K9-Che-136

ACKNOWLEDGEMENT
All the praising leads to All Mighty Allah to whom gratitude is always least. We would like to grant our heartiest gratitude to our project coordinator, Mam Maham Hussain(lecturer- Chemical Process Technology, Chemical Department, Institute of Engineering and Technology Multan) for all the guidance and support that she has given us to complete this design project in a successful manner. Dear Madam, please expect our sincere thanks for your kind hearted support and genuine friendly attitude shown towards our work. Thank you very much for spending your precious time to share your knowledge & experience with us. Then again, we must not forget all the staff members of Chemical Engineering department, including the head of the department Sir Nasir Abdi , for all the assistance and support given us for accomplish the project. Without your support we may have not come this far, so please accept our sincere thanks. And finally, a special thank should be given to the staff of Pak-Arab Fertilizers Office who provide us data related to urea plant

Thank you, Nauman Hafeez Muhammad Bilal Chaudhry Hafsa Iqbal Aisha Faird Anum Maqsood Jawad Mohsin

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Urea Manufacture Plant

PREFACE
The Third year project is task, where we apply our knowledge & experience, gained throughout the past two year course, in a practical scenario. Here we have done it in our best capacity. It is a step which finally determines the capability to perform as chemical engineers. The ultimate goal of the third year design project on urea manufacturing plant is to find out the feasibility of setting up such a plant in Pakistan. In Pakistan urea is being used as a fertilizer in the agriculture sector. Other than as a fertilizer, urea is hardly used in any industry or any other sector even though urea has number of industrial and commercial uses. Pakistan imports urea from other countries such as Saudi Arabia, India, and China. The total import volume of urea is around 330,000 MT per annum. Pakistan government gives urea fertilizer in subsidized price for farmers. From the budget 2008, Pakistan allocated 15 billion rupees for fertilizer subsidies. However in the past with the establishment of The Urea Plant Fatima Fertilizer and Engro, Pakistan became self sufficient in fertilizer requirements of the country. Urea is produced from synthetic ammonia and carbon dioxide. Urea can be produced as prills, granules, flakes, pellets, crystals, and solutions. More than 90% of world production is destined for use as a fertilizer. Urea has the highest nitrogen content of all solid nitrogenous fertilizers in common use (46.7%).Urea is highly soluble in water and is, therefore, also very suitable for use in fertilizer solutions. Solid urea is marketed as prills or granules. The advantage of prills is that, in general, they can be produced more cheaply than granules, which, because of their narrower particle size distribution, have an advantage over prills if applied mechanically to the soil. In Pakistan establishing urea manufacturing plant has many advantages. It will have greater effect on countrys economy, development in agriculture sector, providing employment and other tangible and intangible benefits. But without having an ammonia Urea Manufacturing Plant production process from which in most cases raw materials for urea manufacturing (ammonia and carbon dioxide) is derived, it is rather difficult and unfeasible to establish a urea plant along considering the availability of raw materials. Considering the project it is presumed that ammonia and some instance carbon dioxide is imported. According to the current demand of Pakistan, the urea demand of the country with in next five years will be around 350,000 MT per annum. So we decided to design a Urea manufacturing plant to fulfill that requirement. Our plant is operated for 328 days per year. And rest of the year can be allocated for maintenance of the plant. Constructing of this kind of manufacturing plant will enhance the countrys development since the ultimate product urea is directly related with countrys economy and growth in agriculture sector and a utility for many other industries. On the other hand the global demand for urea is increasing rapidly; specially in Asian NFC IET MULTAN

Urea Manufacture Plant countries. Under those circumstances we present the final year comprehensive design project which would be beneficial for countrys development.

Table of Contents
1.0 Introduction to urea
1.1Urea 1.1 Synthetic urea 1.2 Commercial production of urea 1.3 Chemical characteristics of urea 1.4 Physical characteristics of urea 1.5 raw materials for urea manufacture 1.6 Ammonia 1.7 Ammonia production 1.8 Ammonia storage 1.9 Carbon dioxide 1.10 Applications of urea 1.11 Agricultural usage 1.12 Advantages of urea

2. 0 Manufacture Process of Urea

1.1 Selecting process background 1.2 Feasibility study 1.3 Introduction to plant components 1.4 Static equipments

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Urea Manufacture Plant

1.5 Rotary equipments 1.6 Process selection 1.7 Snamprogetti Ammonia and self stripping processes

3.0 Process Description and flow sheet

3.1 Process Description Snamprogetti Ammonia and self stripping processes 3.2 Reactor 3.3 Stripper 3.4 Carbamate Condenser 3.5 Scrubber 3.6 Medium Pressure Decomposer 3.7 Low Pressure Decomposer 3.8 Medium Pressure Absorber 3.9 Low Pressure Absorber 3.10 Lower Separator 3.11 Flash Separator 3.12 Upper Separator

4.0 Urea plant waste water treatment section

4.1 Sources of the ammonia and urea are

5.0 Mass Balance Calculation

5.1 Material Balance

6.0 Safety of the Urea Plant

6.1 Safety Factors Relevant to Ammonia 6.2 Stability and reactivity 6.3 Incompatible materials 6.4 Flammability 6.5 Hazard identification 6.6 Route of entry and health hazards

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Urea Manufacture Plant

6.7 Eye effects 6.8 Skin effects 6.9 Ingestion effects 6.10 Inhalation effects 6.11 Long term health effects of exposure to Ammonia gas 6.12 First aid (Emergency procedure) 6.13 Fire Extinguisher 6.14 Engineering controls

7.0 Flow sheet Diagram and Layout

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Urea Manufacture Plant

INTRODUCTION TO UREA
1.1 Urea Urea is an oraganic compound with the chemical formula (NH2)2CO. Urea is also known by the International Nonproprietary Name (INN) carbamide, as established by the World Health Organization. Other names include carbamide resin, isourea, carbonyl diamide, and carbonyldiamine. 1.1 Synthetic Urea It was the first organic compound to be artificially synthesized from inorganic starting materials, in 1828 by Friedrich Whler, who prepared it by the reaction of potassium cyanate with ammonium sulfate. Although Whler was attempting to prepare ammonium cyanate, by forming urea, he inadvertently discredited vitalism, the theory that the chemicals of living organisms are fundamentally different from inanimate matter, thus starting the discipline of organic chemistry. This artificial urea synthesis was mainly relevant to human health because of urea cycle in human beings. Urea was discovered; synthesis in human liver in order to expel excess nitrogen from the body. So in past urea was not considered as a chemical for agricultural and industrial use. Within the 20th century it was found to be a by far the best nitrogenic fertilizer for the plants and became widely used as a fertilizer. Urea was the leading nitrogen fertilizer worldwide in the 1990s.Apart from that urea is being utilized in many other industries. Urea is produced on a scale of some 100,000,000 tons per year worldwide. For use in industry, urea is produced from synthetic ammonia and carbon dioxide. Urea can be produced as prills, granules, flakes, pellets, crystals, and solutions. More than 90% of world production is destined for use as a fertilizer. Urea has the highest nitrogen content of all solid nitrogenous fertilizers in common use (46.7%).Therefore; it has the lowest transportation costs per unit of nitrogen nutrient. Urea is highly soluble in water and is, therefore, also very suitable for use in fertilizer solutions (in combination with ammonium nitrate).

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Urea Manufacture Plant 1.2 Commercial production of urea Urea is commercially produced from two raw materials, ammonia, and carbon dioxide. Large quantities of carbon dioxide are produced during the manufacture of ammonia from coal or from hydrocarbons such as natural gas and petroleumderived raw materials. This allows direct synthesis of urea from these raw materials. The production of urea from ammonia and carbon dioxide takes place in an equilibrium reaction, with incomplete conversion of the Urea Manufacturing Plant reactants. The various urea processes are characterized by the conditions under which urea formation takes place and the way in which unconverted reactants are further processed. Unconverted reactants can be used for the manufacture of other products, for example ammonium nitrate or sulfate, or they can be recycled for complete conversion to urea in a total-recycle process. Two principal reactions take place in the formation of urea from ammonia and carbon dioxide. The first reaction is exothermic: 2 NH3 + CO2 H2N-COONH4 (ammonium carbamate)

Whereas the second reaction is endothermic: H2N-COONH4 (NH2)2CO + H2O Both reactions combined are exothermic. 1.3 Chemical characteristics of urea The urea molecule is planar and retains its full molecular point symmetry, due to conjugation of one of each nitrogen's P orbital to the carbonyl double bond. Each carbonyl oxygen atom accepts four N-H-O hydrogen bonds, a very unusual feature for such a bond type. This dense (and energetically favorable) hydrogen bond network is probably established at the cost of efficient molecular packing: The structure is quite open, the ribbons forming tunnels with square cross-section. Urea is stable under normal conditions. 1.4 Physical characteristics of urea Urea is a white odorless solid. Due to extensive hydrogen bonding with water (up to six hydrogen bonds may form - two from the oxygen atom and one from each hydrogen) urea is very soluble. Density 1.3310 kg/m, solid Melting point 132.7 C (406 K) decomposes

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Urea Manufacture Plant Boiling point NA Solubility in water

1. 108 g/100 ml (20 C) 2. 167 g/100 ml (40 C) 3. 251 g/100 ml (60 C) 4. 400 g/100 ml (80 C) 5. 733 g/100 ml (100 C) Vapor pressure <0.1 hPa Bulk density 0.8 kg.m-3

1.5 Raw materials of urea manufacturing

1.6 Ammonia Ammonia, NH3, is a comparatively stable, colorless gas at ordinary temperatures, with a boiling point of 33 C. Ammonia gas is lighter than air, with a density of approximately 0.6 times that of air at the same temperature. The characteristic pungent odors of ammonia can be detected as low as 1-5ppm. Ammonia can be highly toxic to a wide range of organisms. In humans, the greatest risk is from inhalation of ammonia vapor, with effects including irritation and corrosive damage to skin, eyes and respiratory tracts. At very high levels, inhalation of ammonia vapor can be fatal. When dissolved in water, elevated levels of ammonia are also toxic to a wide range of aquatic organisms. Ammonia is highly soluble in water, although solubility decreases rapidly with increased temperature. Ammonia reacts with water in a reversible reaction to produce ammonium (NH4)+ and hydroxide (OH)- ions, as shown in equation. Ammonia is a weak base, and at room temperature only about 1 in 200 molecules are present in the ammonium form (NH4)+. The formation of hydroxide ions in this reaction increases the pH of the water, forming an alkaline solution. If the hydroxide or ammonium ions react further with other compounds in the water, more ammonia with react to reestablish the equilibrium.

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Urea Manufacture Plant NH3 + H2O (NH4)+ + OH-

While ammonia-air mixtures are flammable when the ammonia content is 16-25% by volume, these mixtures are quite difficult to ignite. About 85% of the ammonia produced worldwide is used for nitrogen fertilizers. The remainder is used in various industrial products including fibers, animal feed, and explosives. 1.7 Ammonia Production Essentially all the processes employed for ammonia synthesis are variations of the Haber-Bosch process, developed in Germany from 1904-1913. This process involves the reaction of hydrogen and nitrogen under high temperatures and pressures with an iron based catalyst. This process also requires large energy consumption. Ammonia is generally produced at a few large plants with stream capacities of 1000 tonnes/day or greater. The formation of ammonia from hydrogen and nitrogen is a reversible reaction, as shown in equation. The fraction of ammonia in the final gas mixture is dependent on the conditions employed. Unreacted hydrogen and nitrogen gases separated from the ammonia and are usually recycled. In almost all modern plants, the ammonia produced is recovered by condensation to give liquid ammonia. H2 + 3N2 2NH3

The source of nitrogen is always air. Hydrogen can be derived from a number of raw materials including water, hydrocarbons from crude oil refining, coal, and most commonly natural gas. Hydrogen rich reformer off-gases from oil refineries have also been used as a source of hydrogen. Steam reforming is generally employed for the production of hydrogen from these raw materials. This process also generates carbon dioxide, which can then be used as a raw material in the production of urea. Trace impurities in the feed gases, such as sulphur compounds and chlorides, can have a detrimental effect on the production of ammonia by poisoning the catalysts employed. The feed gases, therefore, need to be purified prior to use.

1.8 Ammonia storage Anhydrous ammonia is usually stored as a liquid in refrigerated tanks at 33.3 C and atmospheric pressure, often in doubled-walled tanks with the capacity for hundreds or thousands of tonnes. The low temperature is usually maintained by the venting of ammonia gas. The vented gas is reliquefied for recycling, or absorbed in water to make aqueous ammonia. Relatively small quantities of anhydrous ammonia are sometimes stored under pressure in spherical vessel at ambient temperature. Ammonia is corrosive to alloys of copper and zinc and these materials must never be used in ammonia service. Iron and steel are usually the only metals used in ammonia storage tanks, piping and fittings. NFC IET MULTAN

Urea Manufacture Plant 1.9 Carbon Dioxide CO2 is a odorless and colorless gas which contain 0.03% in the atmosphere. It is emitted as a pollutant from number of industries. CO2 can be obtained from ammonia production process as a by product.

1.10 Applications of urea

1.11 Agricultural use More than 90% of world production is destined for use as a fertilizer. Urea is used as a nitrogen-release fertilizer, as it hydrolyses back to ammonia and carbon dioxide, but its most common impurity, biuret, must be present at less than 2%, as it impairs plant growth. Urea has the highest nitrogen content of all solid nitrogeneous fertilizers in common use (46.4%N.) It therefore has the lowest transportation costs per unit of nitrogen nutrient. In the past decade urea has surpassed and nearly replaced ammonium nitrate as a fertilizer In the soil, urea is converted into the ammonium ion form of nitrogen. For most floras, the ammonium form of nitrogen is just as effective as the nitrate form. The ammonium form is better retained in the soil by the clay materials than the nitrate form and is therefore less subject to leaching. Urea is highly soluble in water and is therefore also very suitable for use in fertilizer solutions, e.g. in foliar feed fertilizers. Commercially, fertilizer urea can be purchased as prills or as a granulated material. In the past, it was usually produced by dropping liquid urea from a "prilling tower" while drying Urea Manufacturing Plantthe product. The prills formed a smaller and softer substance than other materials commonly used in fertilizer blends. Today, though, considerable urea is manufactured as granules. Granules are larger, harder, and more resistant to moisture. As a result, granulated urea has become a more suitable material for fertilizer blends.

1.12 Advantages of Fertilizer Urea Urea can be applied to soil as a solid or solution or to certain crops as a foliar spray. Urea usage involves little or no fire or explosion hazard. Urea's high analysis, 46% N, helps reduce transportation costs over other dry N forms. handling, storage and

Urea manufacture releases few pollutants to the environment.

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Urea Manufacture Plant Urea, when properly applied, results in crop yield increases equal to other forms of nitrogen.

Nitrogen from urea can be lost to the atmosphere if fertilizer urea remains on the soil surface for extended periods of time during warm weather. The key to the most efficient use of urea is to incorporate it into the soil during a tillage operation. It may also be blended into the soil with irrigation water. A rainfall of as little as 0.25 inches is sufficient to blend urea into the soil to a depth at which ammonia losses will not occur. Urea breakdown begins as soon as it is applied to the soil. If the soil is totally dry, no reaction happens. But with the enzyme urease, plus any small amount of soil moisture, urea normally hydrolizes and converts to ammonium and carbon dioxide. This can occur in 2 to 4 days and happens quicker on high pH soils. Unless it rains, urea must be incorporated during this time to avoid ammonia loss. Losses might be quite low if the soil temperature is cold. The chemical reaction is as follows: CO(NH2)2 + H2O + urease 2NH3 +CO2

2.0 Selecting Process Background

2.1 Feasibility Study 2.2 Introduction Urea white crystalline solid containing 46% nitrogen is widely used in the agriculture industry as an animal feed additive and fertilizer. Agriculture forms the major sector in the national economy of the majority of the countries in the Southeast Asian region. As these countries try to expand the sector, through diversification of agriculture and extensive multiple cropping programs, the demand for agriculture chemicals growing day by day. Large population countries like China, India, Pakistan, and Bangladesh are largely manufacturing the Urea for Domestic consumption. Due to high cost of the production facility Government incentives are common in 3rd world countries. In Middle East Saudi Arabia developed the large production facility of Urea production as an allied industry of the petroleum product. The surplus amount is being exported to neighboring countries. In the present urea fertilizer prices in global markets are increasing and most countries establishing urea manufacturing plants to support growing agriculture sector while saving cost of urea fertilizer imports. It is necessary to establish urea manufacturing plant in Pakistan in order to meet growing demand for urea fertilizer and to save fertilizer subsidies given by the government. Apart from those benefits it can earn foreign exchange by exporting excess production and provide employment for local community.

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Urea Manufacture Plant

2.3 INTRODUCTION TO PLANT COMPONENTS

2.4 Plant Components The components of a urea plant can be divided in to two categories 1. Static Equipment 2. Rotating equipment

1. Static Equipment Reactor: Reactor is the largest and heaviest key equipment in the urea plant. This is the place where Ammonia and Carbon di-oxide react together. The performance of the reactor influences the performance of the whole urea plant. The size of the shell depends upon the size of plant. For a plant of 2000 tons capacity the height of the shell will be around 30 Meters and Dia around 3 meters. Stripper Stripper is also a key component where the excess ammonia is separated. Carbamate Condensers They are relatively smaller in size HP Rotating Machines CO2 Compressors This is the largest and most critical rotating equipment. Very large compressors are used of approximate capacities of around 30,000 N cubic meter/hour capacity HP Ammonia pumps and Carbomate pumps piping Stainless steel 316 L pipes are utilized

HP Control Valves

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Urea Manufacture Plant Various control valves are required. The most critical is the solution feed control valve from the reactor to stripper. The material is stainless steel

2.5 Process Selection

Several processes are used to urea manufacturing. Some of them are used conventional technologies and others use modern technologies to achieve high efficiency. These processes have several comparable advantages and disadvantages based on capital cost, maintenance cost, energy cost, efficiency and product quality. Some of the widely used urea production processes are 1. Conventional processes 2. Stamicarbon CO2 stripping process 3. Snamprogetti Ammonia and self stripping processes 4. Isobaric double recycle process 5. ACES process

Process which we are going to use is: 2.6 Snamprogetti Ammonia and self stripping processes In the first generation of NH3 and self strip ping processes, ammonia was used as stripping agent. Because of the extreme solubility of ammonia in the urea containing synthesis fluid, the stripper effluent contained rather large amount s of dissolved ammonia, causing ammonia overload in down stream section of the plant. Later versions of the process abandoned the idea of using ammonia as stripping agent; stripping was achieved only by supply of heat. Even without using ammonia as a stripping agent, the NH3:CO2 ratio in the stripper effluent is relatively high. So the recirculation section of the plant requires an ammonia-carbomate separation section The process uses a vertical layout in the synthesis section. Recycle within the synthesis section, from the stripper via the high pressure carbamate condenser, through the carbamate separator back to the reactor, is maintained by using an ammonia-driven liquid-liquid ejector. In the reactor, which is operated at 150 bars, NH3:CO2 molar feed ratio of 3.5 is applied? The stripper is of the falling film type. Since stripping is achieved thermally, relatively high temperatures (200-210 0C) are required to obtain a reasonable

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Urea Manufacture Plant stripping efficiency. Because of this high temperature, stainless steel is not suitable as a construction material for the stripper from a corrosion point of view; titanium and bimetallic zirconium stainless steel tubes have been used Off gas from the stripper is condensed in a kettle type boiler. At the tube side of this condenser the off gas is absorbed in recycled liquid carbamate from the medium pressure recovery section. The heat of absorption is removed through the tubes, which are cooled by the production of low pressure steam at the shell side. The steam produced is used effectively in the back end of the process. In the medium pressure decomposition and recirculation section, typically operated at 18 bar, the urea solution from the high pressure stripper is subjected to the decomposition of carbamate and evaporation of ammonia. The off gas from this medium pressure decomposer is rectified. Liquid ammonia reflux is applied to the top of this rectifier; in this way a top product consisting of pure gaseous ammonia and a bottom product of liquid ammonium carbamate are obtained. The pure ammonia off gas is condensed and recycled to the synthesis section. To prevent solidification of ammonium carbamate in the rectifier, some water is added to the bottom section of the column to dilute the ammonium carbamate below its crystallization point. The liquid ammonium carbamate-water mixture obtained in this way is also recycled to the synthesis section. The purge gas of the ammonia condenser is treated in a scrubber prior to being purged to the atmosphere. The urea solution from the medium pressure decomposer is subjected to a second low pressure decomposition step. Here further decomposition of ammonium carbamate is achieved, so that a substantially carbamate free aqueous urea solution is obtained. Off gas from this low pressure decomposer is condensed and recycled as an aqueous ammonium carbamate solution to the synthesis section via the medium pressure recovery section. Concentrating the urea water mixture obtained from the low pressure decomposer is preformed in a single or double evaporator depending on the requirement of the finishing section. Typically, if prilling is chosen as the final shaping procedure, a two stage evaporator is required, whereas in the case of a fluidized bed granulator a single evaporation step is sufficient to achieve the required final moisture content of the urea melt. In some versions of the process, heat exchange is applied between the off gas from the medium pressure decomposer and the aqueous urea solution to the evaporation section. In this way, the consumption of low pressure steam by the process is reduced. The process condensate obtained from the evaporation section is subjected to a desorption hydrolysis operation to recover the urea and ammonia contained in the process condensate.

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Urea Manufacture Plant

3.0 Process Description and flow sheet

3.1 Process Description Snamprogetti Ammonia and self stripping processes Snamprogetti Ammonia and self stripping process consists of the reactor, stripper, two parallel carbamate condensers and a scrubber. All above equipments are operated at 175 bars.

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Urea Manufacture Plant

The reactor is operated at 1900 C and an NH3:CO2 molar feed ratio of 4:1. Liquid ammonia is fed directly to the reactor, whereas gaseous carbon dioxide after compression is introduced into the bottom of the stripper as a stripping aid. The synthesis mixture from the reactor, consisting of urea, unconverted ammonium carbamate, excess ammonia, and water, is fed to the top of the stripper. The stripper has two functions. Its upper part is equipped with trays where excess

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Urea Manufacture Plant ammonia is partly separated from the stripper feed by direct countercurrent contact of the feed solution with the gas coming from the lower part of the stripper. This pre stripping in the top is said to be required to achieve effective CO2 stripping in the lower part. In the lower part of the stripper (a falling film heater), ammonium carbamate is decomposed and the resulting CO2 and NH3 as well as the excess NH3 are evaporated by CO2 stripping and steam heating. The overhead gaseous mixture from the top of the stripper is introduced into the carbamate condenser. Here the gaseous mixture is condensed and absorbed by the carbamate solution coming from the medium pressure recovery stage. Heat liberated in the high pressure carbamate condenser is used to generate low pressure steam. The gas and liquid from the carbamate condensers are recycled to the reactor by gravity flow. The urea solution from the stripper, with a typical NH3 content of 15 wt%, is purified further in the subsequent medium and low pressure decomposers, operating at 17.5 and 2.5 bars, respectively. Ammonia and carbon dioxide separated from the urea solution here are recovered through stepwise absorption in the low and medium pressure absorbers. Condensation heat in the medium pressure absorber is transferred directly to the aqueous urea solution feed in the final concentration section; the purified urea solution is concentrated further either by two stage evaporation up to 99.7 % for urea prill production or by a single evaporation 98.5 % for urea granule production. Water vapor formed in the final concentrating section is condensed in surface condensers to form process condensate. Part of this condensate is used as an absorbent in the recovery sections, where as remainder is purified in the process condensate treatment section by hydrolysis and steam stripping, before being discharge from the urea plant. The highly concentrated urea solution is finally processed either through the prilling tower or via the urea granulator. Instead of concentration via evaporation, the ACES process can also be combined with a crystallization section to produce urea with low biuret content. 3.2 Reactor The reactor is operated at 190 C and 175 bars. NH3:CO2 molar feed ratio to the reactor is 4:1. One pass conversion rate of CO2 to urea is about 68%. NH3 is directly fed to the reactor. Following reaction occurs inside the reactor. NH2COONH4 + heat NH2CONH2 + H2O H = +23 kJ/mol 2NH3 + CO2 NH2COONH4 + heat H = -84 kJ/mol

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Urea Manufacture Plant 3.3 Stripper Carbon dioxide is introduced into the bottom of the stripper as a stripping aid. The synthesis mixture from the reactor, consisting of urea, unconverted ammonium carbamate, excess ammonia, and water, is fed to the top of the stripper. Medium pressure steam is supplied to the stripper. The stripper has two functions. Its upper part is equipped with trays where excess ammonia is partly separated from the stripper feed by direct countercurrent contact of the feed solution with the gas coming from the lower part of the stripper. This pre stripping in the top is said to be required to achieve effective CO2 stripping in the lower part. In the lower part of the stripper (a falling film heater), ammonium carbamate is decomposed and the resulting CO2 and NH3 as well as the excess NH3 are evaporated by CO2 stripping and steam heating. The overhead gaseous mixture from the top of the stripper is introduced into the carbamate condenser. Following reaction occurs inside the stripper. NH2COONH4 + heat 2NH3 + CO2 NH3(l) NH3(g) H = +84 kJ/mol

3.4 Carbamate Condenser Carbamate condenser is fed with overhead gaseous mixture from the top of the stripper, in this unit the gaseous mixture is condensed and absorbed by the carbamate solution coming from the medium pressure recovery stage. Heat liberated in the high pressure carbamate condenser is used to generate low pressure steam. The gas and liquid from the carbamate condensers are recycled to the reactor by gravity flow. 2NH3 + CO2 NH2COONH4 + heat H = -84 kJ/mol NH3(g) NH3(l)

3.5 Scrubber In the scrubber Ammonia and Carbon Dioxide coming from the reactor are absorbed to ammonia and ammonium carbamate solution which is going to Carbamate Condenser. 3.2.5 Medium Pressure Decomposer

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Urea Manufacture Plant The urea solution from the stripper, with a typical NH3 content of 15 wt%, is purified further in the medium pressure decomposer operating at 17.5 bars. No external heat supply. NH2COONH4 + heat 2NH3 + CO2 NH3(l) NH3(g) H = +84 kJ/mol

3.6 Low Pressure Decomposer After the medium pressure decomposer, further purification of urea solution occurs inside the low pressure decomposer which is operating at 2.5 bars. External heat supply is available. All ammonia and ammonium carbamate are removed by the Low Pressure Decomposer.

NH2COONH4 + heat 2NH3 + CO2 NH3(l) 3.7 Medium Pressure Absorber NH3(g)

H = +84 kJ/mol

In medium pressure absorber ammonia and carbon dioxide separated from the urea solution in medium pressure decomposer are recovered. Condensation heat in the medium pressure absorber is transferred directly to the aqueous urea solution feed in the final concentration section. 2NH3 + CO2 NH2COONH4 + heat 3.8 Low Pressure Absorber In low pressure absorber ammonia and carbon dioxide separated from the urea solution in low pressure decomposer are recovered. Heat release from that reaction is used to produce steam at 2 bars. This steam is used for evaporation process of lower and upper separator. 2NH3 + CO2 NH2COONH4 + heat H = -84 kJ/mol H = -84 kJ/mol

3.9 Flash Separator This unit is operated at 1.0 bar and 110 C. Here by reducing the pressure, let water to evaporate and concentrate the urea solution.

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Urea Manufacture Plant H2O(l) H2O(g)

3.10 Lower Separator This is a calendria type evaporator. This is operated at 0.55 bar vacuum pressure and at 110 C Here the purified urea solution is further concentrated and required heat is taken from 2 bar pressure steam produced in low pressure absorber.

3.11 Upper Separator This is evaporative type separator. This is operated at 0.55 bar vacuum pressure and at 112 C Urea solution coming from the lower separator is further concentrated. Output from that unit has 99.2% pure urea. After that urea solution is sent to granulation section.

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Urea Manufacture Plant

Referring to the drawing, stream 1 containing substantially molten urea at about 280.degree F is passed through spray heads 2, located in top section 3 of prilling tower 4. The molten urea sprayed into a stream of small liquid droplets through spray heads 2 is allowed to fall freely inside the prilling tower 4 counters currently to an uprising stream of ambient air introduced into the prilling tower at its bottom section 5. This ambient air, introduced into the prilling tower through lines 6 and 7, in its upwardly flow picks up heat from the molten urea which crystallizes in the shape of small spherical particles (prills). The hot solid urea prills are further cooled to about 10 degree 20 degree F above the ambient temperature of the air. The ambient air introduced into the prilling tower 4 is heated up by the equivalent amount of heat released by the urea prills during their free fall, and it is discharged from the prilling tower. The bottom section 5 of prilling tower 4 is provided with a hollow collecting trough 9 in the form of an inverted cone or frustum with sides 10 made of suitable material as concrete or metal. The sides 10 of the inverted trough 9 are solid and are at an approximate angle of about 20.degree.-30.degree. with the horizontal, and they are covered from the inside with fine wire mesh 11, which is held in place by means of

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Urea Manufacture Plant spacers 12. The wire mesh is provided to disperse the air which is passed there through; it has little surface area such that product cannot collect thereon. The surface area of the solid portion of the mesh is substantially smaller than the surface area of the openings therein. The dead air areas of the mesh are minimal. Free space 13 between the wire mesh 11 and the sides 10 is sealed at its ends 14 and 15, respectively, so as to form a sealed chamber all around the total surface of the sides 10. Further, vertical walls 16 and flat bottom 17 of the bottom section 5 of prilling tower 4 form a sealed chamber 18 with the sides 10 of the inverted trough 9. As shown in this preferred embodiment, a minor portion, from about 5 to about 30 percent by volume, of the total amount of ambient air fed to the prilling tower 4 is passed into sealed chamber 18 through line 7 and thence through openings 19 provided on the sides 10 into space 13 between the wire mesh 11 and the sides 10. It is to be understood that all of the air employed can be fed through line 7. The ambient air of line 7 is evenly distributed along the whole surface of the trough 9 by being passed through the wire mesh 11 and is finely dispersed as it passes through the wire mesh. As it leaves the wire mesh surface, the air is sufficient to divert the free falling solid urea prills from their vertical path to an oblique path which is converging toward bottom opening 20, located at the apex of the inverted trough 9. Thus, substantially all of the prills do not impinge upon mesh 11, but are diverted toward bottom 20. This prevents undesirable build up of the prills on the surface of mesh 11, which would impede upward air flow and reduce the efficiency of tower operation. Due to the fact that there is practically no upward air flow in the section just above the bottom opening 20, the solid urea prilled product falls through the bottom opening 20 onto belt conveyor 21, from which it is discharged at 22 ready for storage or bagging. As indicated, air is not introduced into bottom opening 20 counter current to the product passing there through. A rubber or other flexible skirt (not shown) can be located around the bottom opening 20 to seal the bottom product discharge area, and to minimize leakage of air from solidification. Urea dust present in the tower is removed through bottom opening 20 and can be separated from urea prills as undersized material in a commercial shaker or the like (not shown). In contrast to prior art towers, the dust is not blown upwardly and out of the tower. Thus, pollution problems are minimized. In this preferred embodiment, a major portion, from about 95 to about 70 percent by volume, of the ambient air fed to the prilling tower 4 is introduced into the bottom section 5 through lines 6 located above and preferably just above the inverted trough 9. This air is mixed with the smaller portion of the ambient air introduced into the prilling tower 4 through line 7; the total mixture of the two streams of ambient air rises through the prilling tower 4 and it is exhausted from the top section 3 of the prilling tower. In another embodiment, the major portion of ambient air can be introduced into the upper section 3 of the prilling tower 4 through the lines 8, passed downwardly and co-currently to the stream of free falling product and exhausted from the prilling tower 4 through the lines 6 on the bottom section 5 of the prilling tower 4 together

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Urea Manufacture Plant with the minor portion of air introduced into the prill collecting inverted trough 9 through line 7.

-Prilling Tower

4.0 Urea plant waste water treatment section

The process water in urea plants contains ammonia, carbon dioxide and urea. The concentrations of these components vary within a range depending on the operating conditions, On average, the concentrations in the process water are about 6 wt.% ammonia, 4 wt.% carbon dioxide and 1 wt.% urea. 4.1 Sources of the ammonia and urea are Condensate from the evaporators. Off-gases from the recirculation section, which are absorbed in the process water. Off-gases from the synthesis section, which are absorbed in the process water. Flush and purge water for pumps. Liquid drains.

The purpose of the process water treatment is to remove ammonia, carbon dioxide and urea from the process condensate. For every ton of urea produced, approximately 0.3 tones of water are formed. This water is usually discharged from the urea concentration and evaporation section of the plant. Removal of ammonia and urea from wastewaters can be a problem as it is difficult to remove one in the presence of the other. One method used to overcome this problem is the hydrolysis of urea to ammonium carbamate, which is decomposed to ammonia and carbon dioxide. These gases can then be stripped from the wastewaters. Urea plants are in operation that produces wastewaters with ammonia and urea levels below 1ppm.

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Urea Manufacture Plant This water can then be used for a variety of purposes depending on the required quality such as cooling water or Boiling Feed Water make-up. The recovered ammonia and carbon dioxide are returned to the process to be subsequently converted into urea.

5.0 Mass Balance Calculation

5.1 Material Balance

Urea production per day CO2 conversion CO2 requirement per day NH3 requirement per day

= = = =

1060.0 MT 68.00% 777.3 MT 600.7 MT

Compound

Chemical Formula

Molecular (kg/kmol)

Weight

Ammonia

NH3

17

Carbon dioxide

CO2

44

Ammonium Carbamate

NH2COONH4

78

Water

H2O

18

Urea

NH2CONH2

60

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Urea Manufacture Plant

Input ratio to reactor Molar ratio Weight ratio 4 : 1

NH3 : CO2

68 : 44

Reactions involved in the process

Sch Mass Wt%

2NH3 + CO2 2 34 0.4359 1 44 0.5641

NH2COONH4 + heat 1 78 1.0000

Sch: Mass Wt%

NH2COONH4 + heat 1 78 1.0000

NH2CONH2 + H2O 1 60 0.7692 1 18 0.2308

Sch: Mass

2NH3 2 34

CO2 1 44

NH2CONH2 1 60

H2O 1 18

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Urea Manufacture Plant Wt% 0.4359 0.5641 0.7692 0.2308

6.0 Safety Of the Urea Plant

6.1 Safety Factors Relevant to Ammonia 6.2 Stability and reactivity Ammonia has very low stability because it converts to ammonium hydroxide or other ammonium salt by combining with water or other salts. But it has no reactivity under normal conditions. 6.3 Incompatible materials Ammonia reacts vigorously with fluorine, chlorine, HCl, HBr, nitrosyl chloride, chlorine monoxide, aldehydes, boron, boron halides, calcium, amides, chromyl chloride, nitrogen dioxide, trioxygen difluoride, and nitrogen trichloride , halogens, heavy metals and many other materials. Hazardous decomposition products form with hydrogen at very high temperature. Hazardous polymerization will not occur. 6.4 Flammability Ammonia is slightly flammable material. Flash point: Not applicable Flammability limits: Not applicable Auto-ignition temperature: 1274oF 6.5 Hazard identification Irritating or corrosive to exposed tissues. Inhalation of vapors may result in pulmonary edema and chemical pneumonitis 6.6 Route of entry and health hazards Harmful if contact with eye NFC IET MULTAN

Urea Manufacture Plant Harmful if inhaled. Irritant if contact with skin and eye 6.7 Eye effects Mild concentrations of product will cause conjunctivitis. Contact with higher concentrations of product will cause swelling of the eyes and lesions with a possible loss of vision. Exposure to 50 ppm or less for 5 minutes was not considered irritating by volunteers, while exposure to 72 ppm was irritating to a few individuals and 134 ppm was irritating and caused tearing. At 700 ppm, the gas is immediately and severely irritating. Direct contact with the liquefied gas can cause frostbite and corrosive injury to eye. Permanent eye damage or blindness could result. Severe, permanent eye injury, including an almost complete loss of vision, has been reported following direct contact with liquefied ammonia gas. 6.8 Skin effects Mild concentrations of product will cause dermatitis or conjunctivitis. Contact with higher concentrations of product will cause caustic-like dermal burns and inflammation. Toxic level exposure may cause skin lesions resulting in early necrosis and scarring. High levels of airborne ammonia gas dissolve in moisture on the skin, forming corrosive ammonium hydroxide. At 10000 ppm, ammonia is mildly irritating to moist skin. At 20000 ppm, the effects are more pronounced and 30000 ppm may produce chemical burns with blistering. These same exposure levels would be almost certainly fatal due to inhalation health effects. Direct contact with liquefied gas can cause frostbite and corrosive burns. Symptoms of mild frostbite include numbness, prickling and itching in the affected area. Symptoms of more severe frostbite include a burning sensation and stiffness of the affected area. The skin may become waxy white or yellow. Blistering, tissue death and gangrene may also develop in severe cases. Corrosive burns of the skin have resulted from direct contact with a jet of liquefied ammonia. Permanent scarring of the skin may result. 6.9 Ingestion effects Since product is a gas at room temperature, ingestion is unlikely. 6.10 Inhalation effects Corrosive and irritating to the upper respiratory system and all mucous type tissue. Depending on the concentration inhaled, it may cause burning sensations, coughing, wheezing, shortness of breath, headache, nausea, with eventual collapse. Toxic effects to the respiratory system, senses, liver, kidneys and bladder observed in mammalian species from prolonged inhalation exposures at above 100 ppm Inhalation of excessive amounts affects the upper airway (larynx and bronchi) by causing caustic-like burning resulting in edema and chemical pneumonitis. If it

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Urea Manufacture Plant enters the deep lung, pulmonary edema will result. Pulmonary edema and chemical pneumonitis are potentially fatal conditions. 6.11 Long term health effects of exposure to Ammonia gas No significant differences in lung function were observed in workers exposed to 9.2 ppm ammonia for an average of 12.2 years compared to controls with very low exposure (less than 1 ppm). No conclusions can be drawn from one case report which described lung injury following long-term exposure to ammonia because the person was a long-term smoker. People with repeated exposure to ammonia may develop a tolerance (or acclimatization) to the irritating effects after a few weeks.

6.12 First aid (Emergency procedure) Eyes Flush contaminated eye(s) with copious quantities of water. Part eyelids to assure complete flushing.Continue for a minimum of 15 minutes. Persons with potential exposure to ammonia should not wear contact lenses.

Skin Remove contaminated clothing as rapidly as possible. Flush affected area with copious quantities of water. In cases of frostbite or cryogenic "burns" flush area with lukewarm water. Do not use hot water. A physician should see the patient promptly if the cryogenic "burn" has resulted in blistering of the dermal surface or deep tissue freezing. Ingestion Not specified. Seek immediate medical attention. Inhalation Prompt medical attention is mandatory in all cases of overexposure. Rescue personnel should be equipped with self-contained berating apparatus. Conscious persons should be assisted to an uncontaminated area and inhale fresh air. Quick removal from the contaminated area is most important. Unconscious persons should be moved to an uncontaminated area, given mouth-to-mouth resuscitation and supplemental oxygen. Keep victim warm and quiet. Assure that mucus or vomited material does not obstruct the airway by positional drainage. 6.13 Fire Extinguisher Extinguisher media NFC IET MULTAN

Urea Manufacture Plant Water fog and foam. Use media suitable for surrounding fire. Fire extinguished instruction If possible, stop the flow of gas. Since ammonia is soluble in water, it is the best extinguishing media not only in extinguishing the fire, but also absorbing the escaped ammonia gas. Use water spray to cool surrounding containers.

Handling & Storage Earth-ground and bond all lines and equipment associated with the ammonia system. Electrical equipment should be non-sparking or explosion proof. Gaseous or liquid anhydrous ammonia corrodes certain metals at ambient temperatures. The presence of oxygen enhances the corrosion of ordinary or semi-alloy steels. The addition of water inhibits this enhancement. Keep anhydrous ammonia systems scrupulously dry. Use only in well-ventilated areas. Valve protection caps must remain in place unless container is secured with valve outlet piped to use point. Do not drag, slide or roll cylinders. Use a suitable hand truck for cylinder movement. Use a pressure regulator when connecting cylinder to lower pressure (<500 psig) piping or systems. Do not heat cylinder by any means to increase the discharge rate of product from the cylinder. Use a check valve to trap in the discharge line to prevent hazardous back flow into the cylinder. Protect cylinders from physical damage. Store in cool, dry, well-ventilated area away from heavily trafficked areas and emergency exits. Do not allow the temperature where cylinders are stored to exceed 125oF (52oC). Cylinders should be stored upright and firmly secured to prevent falling or being knocked over. Full and empty cylinders should be segregated. Use a "first in-first out" inventory system to prevent full cylinders from being stored for excessive periods of time. Never carry a compressed gas cylinder or a container of a gas in cryogenic liquid form in an enclosed space such as a car trunk, van or station wagon. A leak can result in a fire, explosion, asphyxiation or a toxic exposure. Engineering controls Use local exhaust ventilation to reduce concentrations to within current exposure limits. A laboratory type hood is suitable for handling small or limited quantities. Personal protection Eye/face protection Gas tight chemical goggles or full-face piece respirator.

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Urea Manufacture Plant Skin protection Protective gloves made of any suitable material. Respiration protection Respiratory protection with full face piece or self-contained breathing apparatus should be available for emergency use. Air purifying respirators must be equipped with suitable cartridges. Do not exceed maximum use concentrations. Do not use air purifying respirators in oxygen deficient immediately dangerous to life and health (IDLH) atmosphere. Consult manufacturers instructions before use. Other general protections Safety shoes, safety shower, eyewash "fountain". Disposal Considerations Do not attempt to dispose of residual waste or unused quantities. Return in the shipping container properly labeled, with any valve outlet plugs or caps secured and valve protection cap in place to BOC Gases or authorized distributor for proper disposal.

REFERENCES
Book References Urea manufacturing processes in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A27 Perry's Chemical Engineers' Handbook - Perry, R.H. and Green, D.W. (Editors) MARTYN S. RAY; DAVID W. JOHNSTON Project: A Case Study Approach - Chemical Engineering Design

World Wide Web references Ammonia and Urea Production http://www.nzic.org.nz/ChemProcesses/production/1A.pdf -

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Urea Manufacture Plant Urea - http://www.stamicarbon.com/urea/_en/index.htm Urea - www.epa.gov/ttn/chief/ap42/ch08/final/c08s02.pdf www.icis.com/v2/chemicals/9076560/urea/process.html Urea Wikipedia, the free encyclopedia - en.wikipedia.org/wiki/Urea Fertilizer Urea www.extension.umn.edu/distribution/cropsystems/DC0636.html UREA - www.jtbaker.com/msds/englishhtml/u4725.htm Urea - www.3rd1000.com/urea/urea.htm MSDS safety data sheets for ammonium carbamate, urea, and ammonium from http://msds.chem.ox.ac.uk/ MSDS urea - http://www.sciencestuff.com/msds/C2950.html - Science Stuff Inc.,1104 Newport Ave, Austin, TX, USA MSDS urea - http://www.pusri.co.id/data/MSDS-urea.PDF -

E-book References The Environmental Impact of a Stamicarbon 2000 mtpd Urea Plant Authors: Will Lemmen (Licensing Manager) and Hans van Baal (Licensing Manager) Latest Urea Technology for Improving Performance and Product Quality by EIJI SAKATA (Senior Process Engineer),TAKAHIRO YANAGAWA (PROCESS ENGINEER) --- TOYO ENGINEERING CORPORATION , TOKYO JAPAN Escalating worldwide use of urea a global change contributing to coastal eutrophication by PATRICIA M. GLIBERT, JOHN HARRISON, CYNTHIA HEIL and SYBIL SEITZINGER

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Urea Manufacture Plant

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Urea Manufacture Plant

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Urea Manufacture Plant

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