C

Cairo University Faculty of Engineering Chemical Engineering Department Senior year 2012

Urea Ammonium Nitrate Fertilizer (UAN)

Submitted to: Dr.Mohammed Ali

Prepared by: Alaa Mahmoud Samy Amira Mahmoud Badran Rasha Maher Edward Nihad Nasr El-Din Soliman Nehal Rizk Ahmed Yasmine Ossama El-Sergany

December, 2011

Abstract:
This report will cover the organic and inorganic fertilizers types, also it will cover fertilizers advantages and disadvantages .we are concerned with nitrogen fertilizers and its types and importance and the main project topic is talking about urea fertilizer. The raw materials used for urea production are ammonia and carbon dioxide, by knowing their conditions and how ammonia is synthesized from natural gas, and carbon dioxide is obtained as a by-product from any other plants so, urea is produced by optimizing reaction conditions. There are different types of technologies to produce urea, this report is focusing on the Stami-carbon technology and its modifications, as Stamicarbon is the most commonly used technology in Egypt. Other technologies for urea production also mentioned such as; TOYOs technology for urea production and Snamprojecttis technology, those types of technologies are commonly used world-wide. The project main concern is urea ammonium nitrate fertilizer (UAN) which could be considered as a modification for the urea fertilizer itself. This type of fertilizer is produced directly by mixing urea solution with ammonium nitrate solution.

Contents:
Chapter One: Introduction .............................................................................. 1 Chapter Two: Fertilizers ................................................................................. 3 I. II. III. IV. A. B. V. A. B. C. D. E. G. H. VI. I. A. B. C. D. E. G. H. I. J. K. L. II. A. B. History: ...................................................................................................3 Advantages and disadvantages of organic fertilizers: ............................... 3 Advantages and disadvantages of Inorganic fertilizers: ........................ 4 Nitrogen fertilizers: .............................................................................. 4 Importance of nitrogen fertilizers: ..................................................... 4 Advantages and disadvantages of nitrogen fertilizers: ....................... 5 Organic and inorganic chemical nitrogen fertilizers types: ...................... 5 Sodium Nitrate: ................................................................................ 5 Ammonium Sulfate: .........................................................................5 Ammonium Nitrate:.......................................................................... 6 Ammonium Sulfate Nitrate: .............................................................. 6 Ammonium Chloride: .......................................................................6 Ammonia: ........................................................................................ 7 Organic Nitrogen Fertilizers: ............................................................ 7 Future of fertilizers: ............................................................................. 7 Ammonia: ............................................................................................... 8 History: ............................................................................................ 8 Occurrence: ...................................................................................... 8 Physical Properties of ammonia: ....................................................... 8 Importance of ammonia: ...................................................................9 Process Steps of Ammonia Production: .......................................... 10 Feedstock Pre-treatment and Raw Gas Production: ......................... 11 Carbon Monoxide Shift Conversion:............................................... 12 Gas Purification: ................................................................................ 12 Methanation: ...................................................................................... 13 Ammonia Synthesis: ....................................................................... 13 Safety Features &health aspects of ammonia: ................................. 14 Carbon Di-oxide: .................................................................................. 14 History: .......................................................................................... 14 Carbon dioxide in the gas form: ...................................................... 14 II

F. Urea: ....................................................................................................6

Chapter Three: Raw Material of Urea production............................................ 8

F. Synthesis Gas Production:.................................................................. 11

C. D. E. 1. 2. I. II. III. IV. V. A. 1. 2. B. 1. 2. C. VI. A. B. C. I. A. B. 1. 2. 3. C. II. A. 1. 2. 3.

Carbon Dioxide in the liquid form: ................................................. 15 Gasification of coal: ....................................................................... 15 Properties of carbon dioxide: .......................................................... 16 CO2 Emissions: ........................................................................... 16 Greenhouse Effect:...................................................................... 16

F. Environmental hazards for CO2:......................................................... 16

Chapter Four: Urea Fertilizer ........................................................................ 17 History: ................................................................................................. 17 Importance of urea: ............................................................................... 17 Physical Properties of pure urea: ........................................................ 17 Advantages and disadvantages of Urea Fertilizer: .............................. 17 Modifications of the Stami-carbon CO2-stripping process: .................... 18 The Original Stamicarbon CO2-Stripping Process: .......................... 19 Main Reactions: .......................................................................... 21 Side reactions:............................................................................. 21 Urea 2000 plus: .............................................................................. 22 Urea 2000 plus with pool condenser: ........................................... 22 Urea 2000 plus with pool reactor:................................................ 23 The Avancore process: ................................................................... 24 Corrosion: .......................................................................................... 26 Role of Oxygen Content: ................................................................ 26 Role of Temperature: ...................................................................... 27 Material Selection: ......................................................................... 27 Technology for urea production (TOYO): ............................................. 28 History: .......................................................................................... 28 Process description: ........................................................................ 28 Ground Level Reactor: ................................................................ 28 Vertical Submerged Carbamate Condenser: ................................ 29 Optimum Selection of Synthesis Condition: ................................ 29 TOYOS Process Performance: ...................................................... 30 Snamprogetti Urea Technology: ............................................................ 30 Process description: ........................................................................ 30 Synthesis and High Pressure (HP) recovery: ............................... 30 Medium Pressure (MP) purification and recovery: ...................... 31 Low Pressure (LP) purification and recovery: ............................. 31

Chapter Five: Other technologies for urea production ................................... 28

Chapter six: Urea-Ammonium Nitrate (UAN) .............................................. 33 III

I. II. III.

Overview of UAN Process Technology:................................................ 33 physical properties of Urea ammonium nitrate solution: ........................ 33 Description of Production Processes: ................................................. 33

References: ................................................................................................... 35

IV

Lists of Figures:
Fig.1 Block flow diagram for ammonia production Fig.2 Process flow diagram for ammonia production Fig.3 Block diagram for Stami-carbon CO2 stripping Urea Process Fig.4 Flow diagram of Stami-carbon CO2 stripping urea process Fig.5 Process flow diagram for Stami-carbon urea 2000plus with pool condenser Fig.6 Process flow diagram for Stami-carbon urea 2000plus with pool reactor Fig.7 Process flow diagram for Avancore Urea Process Fig.8 Process flow diagram for TOYO Urea Process Fig.9 Block flow diagram for Snamprojectti urea process Fig.10 Process flow diagram for Snamprojectti urea process Fig.11 Block diagram for Urea ammonium nitrate process Fig.12 Block diagram for partial recycle CO2 stripping Urea Process for Urea ammonium nitrate production 9 10 19 21 22 24 25 29 32 32 34 34

List of Tables:
Table.1 Physical properties of ammonia Table.2 Feedstock distribution of world ammonia production capacity Table.3 Properties of Carbon dioxide Table.4 Physical properties of pure Urea Table.5 TOYO s process performance Table.6 Physical properties of Urea ammonium nitrate solution 8 11 16 17 30 33

VI

Chapter One: Introduction

Fertilizer is any organic or inorganic material of natural or synthetic origin. It is added to a soil to supply one or more plant nutrients essential to the growth of plants. Soil amendments are made by adding fertilizer to the soil. There are different types of fertilizers; bulky organic fertilizer such as cow manure, bat guano, bone meal, and organic compost and green manure crops. There is also chemical fertilizer which is inorganic fertilizer and is made up with different formulations to suit a variety of specified uses. Many governments and agricultural departments want to increase the supply of organic fertilizers, as they are not enough to meet the existing and future fertilizer needs. Compared to organic compost, chemical or inorganic fertilizers also have the added advantage of being less bulky which makes chemical fertilizer easier to transport, because they are available to the plant relatively quickly when incorporated as part of the plant-food constituents. The different types of chemical fertilizers are usually classified according to the three principal elements, namely Nitrogen (N), Phosphorous (P) and Potassium (K).we are concerned with nitrogen fertilizers and its types and importance, and urea is one of the most important nitrogen fertilizers. The main raw materials used for urea production are ammonia and carbon dioxide. The complete process of industrial ammonia production may be subdivided into the following sections: Synthesis gas production including; Feedstock pre-treatment and gas generation, Carbon monoxide conversion, and Gas purification. The remaining sections are Compression and Synthesis and purge gas management. Carbon dioxide enters the reaction in the gas form, CO2 is produced as a by-product from many industries such as; the production of ethanol by fermentation and manufacture of ammonia. Urea fertilizer is also known as carbamide. It is organic chemical compound containing about 46% nitrogen. Urea is widely used in the agriculture sector both as a fertilizer and animal feed additive; this makes the production of urea considerably high in comparison to other fertilizers. The consumption of fertilizers in Egypt is around 9.2 million tons per year and the local production of fertilizers is estimated at 8.3 million tons. This means that there are annual imports of around 900,000 tons. Urea is the worlds most produced chemical at around 140 million tons per year. Demand for urea is growing at 3.7% globally higher even than the rise in population. In fact, around 90% of the worlds urea is used to fertilize crops and more than 40% of all food grown in the world is fertilized by urea. There are different types of technologies producing urea; one of these technologies is the Stamicarbon technology and its modifications as Stamicarbon is the most commonly used technology in Egypt, NH 3 and CO2 are converted to urea via ammonium carbamate at a pressure of approximately 140 bar and a temperature of 190 C. The molar NH 3/CO2 ratio applied in the reactor is 3:1. This results in a CO2 conversion of about 60% 1

and an NH3 conversion of 41%. The reactor effluent, containing unconverted NH3 and CO2 is subjected to a stripping operation at essentially reactor pressure, using CO2 as stripping agent. The stripped-off NH3 and CO2 are then partially condensed and recycled to the reactor. The heat evolving from this condensation is utilized to produce 4.5 bar steam, some of which can be used for heating purposes in the downstream sections of the plant and urea is produced. The other technologies concerning urea production are TOYO and Snamprojectti; they are used world-wide. TOYOs process description includes ground level reactor, vertical submerged carbamate condenser (VSCC) and optimum selection of synthesis condition. Snamprojectiis Urea Technology process description includes Synthesis and High Pressure (HP) recovery, Medium Pressure (MP) purification and recovery, Low Pressure (LP) purification and recovery. The product is urea ammonium nitrate solution. Its produced via direct mixing of urea solution, and ammonium nitrate solution.

Chapter Two: Fertilizers I. History:

The process of adding substances to soil to improve its growing capacity was developed in the early days of agriculture. Ancient farmers knew that the first yields on a plot of land were much better than those of subsequent years. This caused them to move to new, uncultivated areas, which again showed the same pattern of reduced yields over time. Eventually it was discovered that plant growth on a plot of land could be improved by spreading animal manure throughout the soil. Over time, fertilizer technology became more refined. New substances that improved the growth of plants were discovered. The Egyptians are known to have added ashes from burned weeds to soil. Ancient Greek and Roman writings indicate that various animal excrements were used, depending on the type of soil or plant grown. It was also known by this time that growing leguminous plants on plots prior to growing wheat was beneficial. Other types of materials added include sea-shells, clay, vegetable waste, waste from different manufacturing processes, and other assorted trash. Organized research into fertilizer technology began in the early seventeenth century. Early scientists such as Francis Bacon and Johann Glauber describe the beneficial effects of the addition of saltpeter to soil. Glauber developed the first complete mineral fertilizer, which was a mixture of saltpeter, lime, phosphoric acid, nitrogen, and potash. As scientific chemical theories developed, the chemical needs of plants were discovered, which led to improved fertilizer compositions. Organic chemist Justus von Liebig demonstrated that plants need mineral elements such as nitrogen and phosphorous in order to grow. The chemical fertilizer industry could be said to have its beginnings with a patent issued to Sir John Lawes, which outlined a method for producing a form of phosphate that was an effective fertilizer. The synthetic fertilizer industry experienced significant growth after the First World War, when facilities that had produced ammonia and synthetic nitrates for explosives were converted to the production of nitrogen-based fertilizers.

II. Advantages and disadvantages of organic fertilizers:

Advantages: Improve biodiversity (soil life). Provide long-term productivity of soil. Prove a large depository for excess carbon dioxide. Increase the abundance of soil organisms by providing organic matter and micronutrients for organisms.

Disadvantages: Organic fertilizers may contain pathogens and other disease causing death of organisms if not properly composted.

Organic fertilizers nutrient contents are very variable and their release to available forms that the plant can use may not occur at the right plant growth stage. Organic fertilizers are comparatively too bulky to deploy the right amount of nutrients that will be beneficial to plants

III. Advantages and disadvantages of Inorganic fertilizers:

Advantages: Inorganic fertilizers are usually given as a rescue treatment to plants that are dying. They are appropriate in this situation because the nutrients needed by the plants are readily available. Inorganic fertilizers are relatively cheap. Inorganic fertilizers are easily used and prepared. Disadvantages: Inorganic fertilizers contain nutrients that have been broken down already into the most basic of its components for easy absorption by the plants. It can also be washed away easily when watering or irrigating the plants, and this is called leaching. Inorganic fertilizers contain salts and other compounds. These are not absorbed by the plants so they are left behind in the soil and build up over time. This can alter the chemistry of the soil that makes it less ideal for planting. Inorganic fertilizers application with great amount may burn the delicate plant structures such as the roots. This could affect the over-all development of the plant.

IV. Nitrogen fertilizers:

Nitrogen fertilizer is an inorganic fertilizer consisting of nitrous compounds such as ammonium nitrate. It is available in different forms: liquid, which must be injected into the ground, or dry pellets, which can be applied to the surface of the soil by hand or by machine. In some cases, industrial by-products such as pure ammonia can be used as a nitrogen fertilizer, but these should be avoided as they are toxic and pose health problems in terms of handling and exposure.

A.

Importance of nitrogen fertilizers:

Fertilizers are used to maintain the correct level of nitrogen in the soil, ensuring strong, green plants with a healthy growth rate. Nitrogen fertilizers can be used on a wide range of flora, from the household garden to commercial crops. They are currently used in one-third of the world's total crop production, including species such as maize, barley and soybean. Nitrogen fertilizers are also extensively used on commercial lawns, including a large proportion of the world's golf courses. 4

B. Advantages fertilizers:

and

disadvantages

of

nitrogen

Advantages: Nitrogen fertilizers are able to make up the deficiency when the soil has become depleted of its natural nitrogen stores. The use of nitrogen fertilizers helps to keep nutrient levels at an optimum level, protect against disease and control weeds, resulting in healthier crops and consistent quality and quantity of yields. Disadvantages: Excess nitrogen not absorbed by the plants has been shown to leach into the groundwater and nearby rivers. High levels of nitrogen in the water can create algal blooms, large growths of algae that imbalance the delicate ecosystem to the detriment of other aquatic species.

V. Organic and inorganic chemical nitrogen fertilizers types:

This type of fertilizer is divided into different groups according to the manner in which the nitrogen combines with other elements.

A.

Sodium Nitrate:

Sodium nitrates are also known as Chilean Nitrate. The nitrogen contained in sodium nitrate is refined to 16%. This means that the nitrogen is immediately available to plants and is a valuable source of nitrogen in this type of fertilizer. When one makes a soil amendment using sodium nitrates as a type of fertilizer in the garden, it is usually as a top- and side-dressing. Particularly when nursing young plants and garden vegetables. Sodium nitrate is quite useful as a type of fertilizer in an acidic soil. However, the excess use of sodium nitrate may cause de-flocculation.

B.

Ammonium Sulfate:

This fertilizer type comes in a white crystalline salt form. It is easy to handle and it stored well under dry conditions. However, during the rainy season, it sometimes forms lumps. Though this fertilizer type is soluble in water, its nitrogen is not readily lost in drainage, because the ammonium ion is retained by the soil particles. Ammonium sulfate may have an acidic effect on garden soil. Over time, the long-continued use of this type of fertilizer will increase soil acidity and thus lower the yield. The application of ammonium sulfate fertilizer can be done before sowing, at sowing time, or even as a top-dressing to the growing crop.

C.

Ammonium Nitrate:

This fertilizer type also comes in white crystalline salts. Ammonium nitrate salts contain 33 to 35% nitrogen, of which half is nitrate nitrogen and the other half is in the ammonium form. As part of the ammonium form, this type of fertilizer cannot be easily leached from the soil. This fertilizer is quick-acting, but highly hygroscopic thus making it unfit for storage. Ammonium nitrate also has an acidic effect on the soil, in addition this type of fertilizer can be explosive under certain conditions. D.

Ammonium Sulfate Nitrate:

This fertilizer type is available as a mixture of ammonium nitrate and ammonium sulfate. It is recognizable as a white crystal or as dirty-white granules. This fertilizer contains 26% nitrogen, three-fourths of it in the ammonium form and the remainder (i.e. 6.5%) as nitrate nitrogen. Ammonium sulfate nitrate is non-explosive, readily soluble in water and is very quickacting. Because this type of fertilizer keeps well, it is very useful for all crops. Though it can also render garden soil acidic, the acidifying effect is only onehalf of that of ammonium sulfate on garden soil. Application of this fertilizer type can be done before sowing, at sowing time or as a top-dressing, but it should not be applied along the seed.

E.

Ammonium Chloride:

This fertilizer type comes in a white crystalline compound, which has a good physical condition and 26% ammoniac nitrogen. It is not recommended to use this type of fertilizer on crops such as tomatoes because the chlorine may harm the crop. F.

Urea:

This type of fertilizer usually is available to the public in a white, crystalline, organic form. It is a highly concentrated nitrogen fertilizer and fairly hygroscopic. This also means that this fertilizer can be quite difficult to apply. Urea is also produced in granular or pellet forms and is coated with a nonhygroscopic inert material. It is highly soluble in water and therefore, subject to rapid leaching. It produces quick results. When applied to the soil, its nitrogen is rapidly changed into ammonia. Urea supplies nothing but nitrogen and the application of urea as fertilizer can be done at sowing time or as a topdressing, but should not be allowed to come into contact with the seed.

G.

Ammonia:

This fertilizer type is a gas that is made up of about 80% of nitrogen and comes in a liquid form as well because under the right conditions of temperature and pressure, ammonia becomes liquid (anhydrous ammonia). Another form, aqueous ammonia, results from the absorption of ammonia gas into water, in which it is soluble. Ammonia is used as a fertilizer in both forms. The anhydrous liquid form of ammonia can be applied by introducing it into irrigation water, or directly into the soil from special containers.

H.

Organic Nitrogen Fertilizers:

Organic nitrogen fertilizer is the type of fertilizer that includes plant and animal by-products. These by-products can be anything from oil cakes, to fish manure and even to dried blood. The nitrogen available in organic nitrogen fertilizer types first has to be converted before the plants can use it. This conversion occurs through bacterial action which is a slow process. The upside of this situation is that the supply of available nitrogen lasts so much longer. This type of fertilizer may contain small amounts of organic stimulants that contain other minor elements that might also be needed by the plants that are being fertilized. Furthermore, they may also contain small amounts of organic stimulants, or some of the minor elements needed by plant. Oil-cakes contain not only nitrogen but also some phosphoric and potash, besides a large quantity of organic matter. This type of fertilizer is used in conjunction with quicker-acting chemical fertilizers.

VI. Future of fertilizers:

Fertilizer research is currently focusing on reducing the harmful environmental impacts of fertilizer use and finding new, less expensive sources of fertilizers. Such things that are being investigated to make fertilizers more environmentally friendly are improved methods of application, supplying fertilizer in a form which is less susceptible to runoff, and making more concentrated mixtures. New sources of fertilizers are also being investigated. It has been found that sewage sludge contains many of the nutrients that are needed for a good fertilizer. Unfortunately, it also contains certain substances such as lead, cadmium, and mercury in concentrations which would be harmful to plants. Efforts are underway to remove the unwanted elements, making this material a viable fertilizer. Another source that is being developed is manures. The first fertilizers were manures; however, they are not utilized on a large scale because their handling has proven to be too expensive. When technology improves and costs are reduced, this material will be a viable new fertilizer.

Chapter Three: Raw Material of Urea production I. Ammonia: A. History:

The name ammonia is derived from sal ammoniacum (Oasis Ammon in Egypt, today Siwa). Sal ammoniac was known to the Ancient Egyptians. Free ammonia was prepared for the first time in 1774 by J. B. Priestley. In 1784, C. L. Berthollet recognized that ammonia was composed of the elements nitrogen and hydrogen. W. Henry, in 1809, determined the volumetric ratio of the elements as 1:3, corresponding to the chemical formula NH3. Following the discovery of the nature and value of mineral fertilization by Liebig in 1840, nitrogen compounds were used in increasing quantities as an ingredient of mineral fertilizers. At the end of the last century ammonia was recovered in coke oven plants and gas works as a by-product of the destructive distillation of coal. The produced ammonium sulfate was used as fertilizer. Another nitrogen fertilizer was calcium cyanamid. Since both sources of nitrogen were limited in quantity they did not suffice for fertilization. In 1913, the first Haber Bosch plant went on stream, representing the first commercial synthesis of ammonia from the elements. Subsequently, other ammonia plants were started up. Today ammonia is a commodity product of the chemical industry.

B.

Occurrence:

Ammonia, NH3, occurs in nature almost exclusively in the form of ammonium salts. Natural formation of ammonia is primarily by decomposition of nitrogen-containing organic materials or through volcanic activity. Ammonia and its oxidation products, which combine to form ammonium nitrate and nitrite, are produced from nitrogen and water vapor through electrical discharges in the atmosphere. Ammonia and its salts are also by-products of commercial processing (gasification, coking) of fossil fuels such as coal, lignite, and peat.

C.

Physical Properties of ammonia:

Value -77.7C 33.4C 0.771 at unspecified) Table.1 Physical Properties of ammonia

Property Melting point Boiling point Specific gravity

1bar

(temperature

D.
1. 2. 3. 4. 5.

Importance of ammonia:

In the manufacture of nitric acid. In manufacture of explosives. In manufacture of synthetic fibers and fertilizers. In refrigeration. As a chemical intermediate in the production of cyanides, amides, nitrates and dyestuffs.
Natural gas steam Combustion air Fuel Desulphurisation

Primary reformer

Air

Secondary reformer

Carbon monoxide Removal

Carbon dioxide Removal

Carbon dioxide To urea plant

Methanation

Synthesis gas compression

Ammonia synthesis

chilling

Liquid ammonia

Fig.1 Block flow diagram for ammonia production

Fig. 2 Process flow diagram for ammonia production

E.

Process Steps of Ammonia Production:

The complete process of industrial ammonia production may be subdivided into the following sections: Synthesis gas production 1. Feedstock pre-treatment and gas generation 2. Carbon monoxide conversion 3. Gas purification Compression Synthesis and purge gas management The most fundamental changes over the years have occurred in synthesis gas production and gas compression. In the synthesis section itself, some progress has been made in converter design and optimization of heat recovery.

10

Table.2 feedstock distribution of world ammonia production capacity

F.

Synthesis Gas Production:

The goal is preparing a pure mixture of nitrogen and hydrogen in the stoichiometric ratio of 1: 3. The raw materials are water, air, and a carboncontaining reducing medium that, for its part, may contain hydrogen (natural gas, CH4; naphtha, CH2; petroleum, CH) and nitrogen.

G.

Feedstock Pre-treatment and Raw Gas Production:

The chemical reaction of hydrocarbons with water, oxygen, air, or any combination of these is generally referred to as gasification. It yields a gas mixture made from CO and H2 in various proportions along with carbon dioxide and where air is used, some nitrogen. Any carbon containing feedstock will undergo a reaction: CH4+H2O CO+3H2 H= 88563.678 BTU/Ibmole

Natural gas consists predominantly of methane and is therefore the most hydrogen-rich and energetically the best raw material for the steam-reforming route. To introduce nitrogen to achieve the required stoichiometric hydrogen/nitrogen ratio for ammonia synthesis, the reforming reaction is split into two sections. In the first section, the primary reformer, the reaction proceeds in indirectly heated tubes filled with nickel-containing reforming catalyst and is controlled to achieve a partial conversion only [in conventional plants 65 % based on methane feed, leaving around 14 mol % methane (dry basis) in the effluent gas]. In the following secondary reformer a refractorylined vessel filled with nickel catalyst the gas is mixed with a controlled amount of air introduced through a nozzle (burner). By combustion of a quantity of the gas the temperature is raised sufficiently (to about 1200 C) that the endothermic reforming reaction is completed with the gas adiabatically passing the catalyst layer. A concept developed by Uhde goes a step further in this direction: exchanger reforming and subsequent non-catalytic partial oxidation, which provides the 11

reaction heat, are accommodated in a single vessel. This combined auto thermal reformer (CAR) design, was operated in a demonstration unit producing 13 000 m3/h of synthesis gas.

H.

Carbon Monoxide Shift Conversion:

As ammonia synthesis needs only nitrogen and hydrogen, all carbon oxides must be removed from the raw synthesis gas of the gasification process. In the water gas shift reaction, traditionally known as carbon monoxide shift conversion, the carbon monoxide serves as reducing agent for water to yield hydrogen and carbon dioxide. In this way not only is the carbon monoxide converted to readily removable carbon dioxide but also additional hydrogen is produced: CO+H2O CO2 + H2 H= -177127.355E-1 BTU/Ibmole

I.

Gas Purification:

In further purification, carbon dioxide, residual carbon monoxide, and sulfur compounds (only present in the synthesis gas from partial oxidation) have to be removed as they are not only useless ballast but above all poisons for the ammonia synthesis catalyst. In contrast steam reforming requires removal of sulfur from the natural gas and light hydrocarbon feed stocks upstream of gasification to avoid poisoning of the sensitive reforming catalysts. This is usually performed by hydro desulfurization and adsorption of the H2S by ZnO. As this is an essential part of the steam reforming process it is treated in Section. The classical method for CO2 removal is to scrub the CO2 containing synthesis gas under pressure with a solvent capable of dissolving carbon dioxide in sufficient quantity and at sufficient rate, usually in counter current in a column equipped with trays or packing . Nowadays, various chemical and physical absorption systems are available for CO2 removal, aMEDA, Benefield, Amine Guard and selexol. Uhde has used all these processes in the past, the lowest energy consumption process is achieved by using the activated aMEDA, process .The key to these energy savings is that the solution is primarily regenerated by flashing rather than steam stripping. In addition, the process offers the following advantages: High CO2 recovery rate (<96%) and CO2 purity (<99%by volume). No need for corrosion inhibitors as the solution is not corrosive to carbon steel

12

Minimization of solution losses because aMEDA, has a low vapour pressure and does not degrade during operation .No reclaiming of the solution is required. No toxic solvents. No crystallization problems.

J.

Methanation:

Methanation is a physical-chemical process to generate Methane from a mixture of various gases out of biomass fermentation or thermo-chemical gasification. The main components are carbon monoxide and hydrogen. The following main process describes the methanation: CO+3H2 CH4 +H2O

Methanation is the reverse reaction of steam methane reforming, which converts methane into synthesis gas. Its the simplest method to reduce the concentrations of the carbon oxides well below 10 ppm and is widely used in steam reforming plants.

K.

Ammonia Synthesis:

Under the conditions practical for an industrial process ammonia formation from hydrogen and nitrogen is limited by the unfavorable position of the thermodynamic equilibrium, so that only partial conversion of the synthesis gas (25 35 %) can be attained on its passage through the catalyst. Ammonia is separated from the unreacted gas by condensation, which requires relatively low temperatures for reasonable efficiency. The unconverted gas is supplemented with fresh synthesis gas and recycled to the converter. The concentration of the inert gases (methane and argon) in the synthesis loop is controlled by withdrawing a small continuous purge gas stream. N2+3H2 2NH3 H= -397418.756E-1 BTU/Ibmole

The main feature of this unit is its high conversion rate which is achieved by a large catalyst volume. In order to minimize reactor size and cost while keeping the pressure drop low, the large catalyst volume requires: The use of small grain-size catalyst Application of the radial-flow concept in the ammonia reactor Uhdes ammonium synthesis unit is based on a three-bed reactors system, each bed with a radial flow.

13

L.

Safety Features &health aspects of ammonia:

In ammonia production three potential hazard events can be identified: fire/explosion hazard from the hydrocarbon feed system; fire/explosion hazard due to leaks in the synthesis gas purification, compression, or synthesis section (75 % hydrogen); and toxic hazard from release of liquid ammonia from the synthesis loop. In addition there is also a potential toxic hazard in handling and storing of liquid ammonia. The long history of ammonia production since 1913 has demonstrated this production technology is a very safe operation. In ammonia production, storage, and handling the main potential health hazard is the toxicity of the product itself. For this reason this section concentrates on ammonia only. Other toxic substances such as carbon monoxide or traces of nickel carbonyl (which may be formed during shut down in the methanation stage) may be only a risk in maintenance operations and need appropriate protection provisions as well as blanketing or flushing with nitrogen. As about 85-87 % of the ammonia consumption goes into the manufacture of fertilizers, it is obvious that the future of the ammonia industry is very closely bound up with future fertilizer needs and the pattern of the world supply.

II. Carbon Di-oxide: A. History:

CO2 discovered in 1750s, with temperature range (20-250C), carbon dioxide is an odorless, colorless gas; it is faintly acidic and non-flammable. Its molecular formula (O=C=O). CO2 exists commonly in the gaseous phase, exists in solid phase (at temperature below 780C), and in liquid phase. Liquid carbon dioxide exists as a dissolved form with water. CO2 is only water soluble when pressure is maintained but after pressure drops carbon dioxide gas will try to escape to air. Carbon dioxide can be found mainly in air, but also in water as a part of the carbon cycle.

B.

Carbon dioxide in the gas form:

Carbon dioxide gas is uniformly distributed over the earths surface at a concentration of about 330 ppm, as the concentration of the CO 2 is low in nature so its not practical to extract the gas from air, so its commercially obtained as a by-product from other industries such as the production of ethanol by fermentation and manufacture of ammonia. So, if we are building ammonia plant fertilizer next to urea plant fertilizer we can get both raw materials from the neighborhood plant. Also, we can get CO2 from combustion of coke or other carbon containing fuels C (coke) + O2 CO2 (g) 14

Carbon dioxide is released into our atmosphere when carbon containing fossil fuels such as oil, natural gas, and coal are burned in air. As a result of the tremendous world-wide consumption of such fossil fuels, the amount of CO 2 increased with a rising rate 1ppm/year.

C.

Carbon Dioxide in the liquid form:

in addition to being a component of the atmosphere, carbon dioxide also dissolves in water of the oceans. At room temperature, the solubility of CO2 is about 90 cm3 of CO2 per 100 ml of water. In aqueous solution, CO2 exists in many forms first is simply dissolves. CO2 (g) CO2(aq)

Then an equilibrium is established between the dissolved CO2 and carbonic acid H2CO3 CO2 (aq) +H2O (l) H2CO3 (aq)

Only about 1% of the dissolved CO2 exists as H2 CO3. Carbonic acid is weak acid which dissociates producing water and CO2.

D.

Gasification of coal:

Coal gasification can be used to produce synthesis gas, a mixture of carbon monoxide (CO) and hydrogen (H2) gas. (Coal) + O2 + H2O H2 + CO

The synthesis gas is fed into the water gas shift reaction where CO2 is evolved CO + H2O CO2 + H2

However, the process main concern is H2 but H2 will also serves in the fertilizer plant to produce ammonia from H2 and urea from the liberated CO2 .

15

E.
Property

Properties of carbon dioxide:

Value 44.01 1.53 at 21 oC 29.216 Ib/ft3 370,3E7 ppm High Pressure < 4.158 bar Temperature < -78 oC 0.29815 Ibmol/ Ib . bar 0.9 volume/volume at 20 oC Table.3 Properties of carbon dioxide

Molecular weight Specific gravity Critical density Concentration in air Stability Liquid Solid Henry constant for solubility Water solubility

F.

Environmental hazards for CO2: 1. CO2 Emissions:

Due to human activities, the amount of CO2 released into the atmosphere has been rising during the last 150 years. As a result, it has exceeded the amount sequestered in biomass, the oceans, and other sinks. Carbon dioxide concentrations are climbed in the atmosphere of about 280 ppm in 1850 to 364 ppm in 1998, mainly due to human activities during and after the industrial revolution, which began in 1850. Humans have been increasing the amount of carbon dioxide in air by burning of fossil fuels, by producing cement and by carrying out land clearing and forest combustion. About 22% of the current atmospheric CO 2 concentrations exist due to these human activities, considered that there is no change in natural amounts of carbon dioxide.

2.

Greenhouse Effect:

The troposphere is the lower part of the atmosphere, of about 10000- 15000 m thick. Within the troposphere there are gasses called greenhouse gasses. When sunlight reaches the earth, some of it, are converted to heat. Greenhouse gasses absorb some of the heat and trap it near the earth's surface, then earth is warmed up. This process, commonly known as the greenhouse effect, has been discovered many years ago and was later confirmed by means of laboratory experiments and atmospheric measurements.

16

Chapter Four: Urea Fertilizer I. History:

Urea was first discovered by a French scientist, named Hillaire Rouelle in 1773.The synthesis of urea by Wohler in 1828 by heating ammonium cyanate had a profound influence upon chemistry and upon civilization. It was the first time that a substance produced by life had been prepared in the laboratory, thus opening up the entire of the synthetic organic chemistry. For 100 years, the epoch-making compound was relatively un-important industrially and was made by the acid hydrolysis of calcium cyanamide. In 1933 Du Pont began production at Belle, W. Va., and remained the sole domestic producer until 1950 when Solvay opened their plant at South Point, Ohio.

II. Importance of urea:

12345Used in nitrogen fertilizers. Used in plastics in combination with formaldehyde and furfural. Used in adhesives. Used in coatings, textile anti shrink compounds, Ion-exchange resins. Used as an intermediate for ammonium sulfamate, sulfumic acid, and the phthalocyanine pigments.

III. Physical Properties of pure urea:

Color Odor Melting point Colorless Odorless 132.7 oC Table.4 Physical Properties of pure urea

IV. Advantages and disadvantages of Urea Fertilizer:

Advantages: Urea has the highest nitrogen content, equal to 46%. This percentage is much higher than other nitrogenous fertilizers available in the market. Urea production cost is relatively low since carbon dioxide required for its manufacture is easily obtained. Urea is not subject to fire or explosion hazards, and hence there is no risk in the storage of urea. Urea can be used for all types of crops and soils. After its assimilation by plants, urea leaves behind only carbon dioxide in the soil through the interaction of nitrifying bacteria. This carbon dioxide does not harm the soil. 17

Urea can be applied to soil as a solid, or solution, or to certain crops as a foliar spray. Urea manufacture releases few pollutants to the environment.

Disadvantages: Urea is very soluble in water, and hygroscopic water; hygroscopic water creates a thin layer surrounding individual soil particles, which makes water unavailable to plants, and hence requires better packaging quality. Urea contains impurities more than 2%, it cannot be used as a fertilizer, since the impurities are toxic to certain crops, particularly citrus.

V. Modifications process:

of

the

Stami-carbon

CO2-stripping

Throughout the study of many technologies concerning urea production the most commonly used technology in Egypt is Stami-carbon technology, so we are focusing now on the Stami-carbon technology

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A.

The Original Stamicarbon CO2-Stripping Process:

Fig.3 block diagram for Stamicarbon CO2 stripping Urea Process In this first-generation CO2-stripping plant, the high-pressure carbamate condenser was of the vertical falling-film type. The condensed liquid carbamate is flowing down along the inside wall of the (vertical) heat exchanger tubes. Condensation of ammonia and carbon dioxide gases occurs in the high-pressure carbamate condenser at synthesis pressure. Besides condensation, also chemical formation of ammonium carbamate from ammonia and carbon dioxide takes place in this condenser. Because of the high pressure, the heat liberated from the condensation and subsequent ammonium carbamate formation is at a high temperature. This heat, therefore, can effectively be used for the production of 4.5bar steam for further use in the urea plant itself. The condensation in the high-pressure carbamate condenser is not effected completely. Remaining gases are condensed in the reactor and provide the heat required for the dehydration of carbamate. Ammonia and carbon dioxide are introduced to the reactor with a molar ratio 3:1.The operating conditions of the reactor are 190 oC and 140 bar. Therefore, maximum urea yield per pass is achieved. Ammonia and carbon dioxide are stripped off. The stripper is realized in the form of a falling-film evaporator, 19

where the urea synthesis solution flows as a falling film along the inside of the vertical heat-exchanging tubes. Heat, in the form of medium-pressure steam, is supplied to the outside of these tubes. The supply of heat at this place results in decomposition of unconverted ammonium carbamate into ammonia and carbon dioxide. Moreover, the heat supplied in this way will transfer ammonia and carbon dioxide from the liquid phase into the gaseous phase. Fresh carbon dioxide and air are supplied to the bottom of the tubes flows counter-currently to the urea solution from top to bottom. Addition of air and lowering the temperature are important to maintain a corrosion-resistant layer. To avoid the formation of explosive hydrogenoxygen mixtures in the tail gas of the plant, hydrogen is catalytically removed from the carbon dioxide feed. The carbon dioxide acts as a stripping agent, enhancing the transfer of ammonia from the liquid phase into the gaseous phase. Stripping with carbon dioxide not only recycles ammonia, but also effectively reduces the carbon dioxide content of the urea synthesis solution flowing down the heat exchanger tubes. Low ammonia and carbon dioxide concentrations in the stripped urea solution are obtained, such that the recycle from the low-pressure recirculation stage is minimized. Before the inert gases, mainly oxygen and nitrogen, are purged from the synthesis section, they are washed with carbamate solution from the low-pressure recirculation stage in the high-pressure scrubber to obtain a low ammonia concentration in the subsequently purged gas. Further washing of the off-gas is performed in a low-pressure absorber to obtain a purge gas that is practically ammonia free.

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Fig.4 Flow diagram of Stamicarbon CO2-stripping Urea Process.

1.

Main Reactions:

The commercial processes in current use are based on two reactions: CO2 + 2NH3 NH4CO2NH2 NH4CO2NH2 NH2CONH2 + H2O (1) (2) H= -67,000 BTU/Ibmole H=+18,000 BTU/Ibmole

Reaction (1) is fast and exothermic and essentially goes to completion under the reaction conditions used industrially. Reaction (2) is slower and endothermic and does not go to completion. The conversion (on a CO2 basis) is usually in the order of 50-80%. The conversion increases with increasing temperature and NH3/CO2 ratio and decreases with increasing H2O/CO2 ratio.

2.
Hydrolysis of urea: CO(NH2)2+H2O

Side reactions:

NH2COONH4

2NH3+CO2

(3)

Biuret formation from urea: 2CO(NH2)2 NH2CONHCONH2 + NH3 (4)

Formation of isocyanic acid from urea: CO(NH2)2 NH4NCO NH3+HNCO 21

(5)

All three side reactions have in common the decomposition of urea; thus, the extent to which they occur must be minimized. The hydrolysis reaction (1) is nothing but the reverse of urea formation. Whereas this reaction approaches equilibrium in the reactor, in all downstream sections of the plant the NH3 and CO2 concentrations in urea-containing solutions are such that Reaction (1) is shifted to the right. The extent to which the reaction occurs is determined by temperature (high temperatures favor hydrolysis) and reaction kinetics; in practice, this means that retention times of urea-containing solutions at high temperatures must be minimized. The biuret reaction (2) also approaches equilibrium in the urea reactor .The high NH3 concentration in the reactor shifts Reaction (2) to the left, such that only a small amount of biuret is formed in the reactor. In downstream sections of the plant, NH3 is removed from the urea solutions, thereby creating a driving force for biuret formation. The extent to which biuret is formed is determined by reaction kinetics; therefore, the practical measures to minimize biuret formation are the same as described above for the hydrolysis reaction.

B.

Urea 2000 plus: 1. Urea 2000 plus with pool condenser:

In the 1990s, Stamicarbon introduced a new synthesis concept under the name Urea 2000plus. The key difference with respect to the previous Stamicarbon processes is the application of pool condensation in the condensing step in the synthesis recycle loop.

Fig.5 process flow diagram for Stamicarbon Urea 2000plus Process with pool condenser 22

Pool condensation is a technology where in a condensing operation; the liquid phase is the continuous phase, whereas the gases to be condensed are present as bubbles, rising through the liquid phase. As compared to the technique of falling-film condensation pool condensation offers some considerable advantages: for pool condensation in any application in the process industry: 1- The turbulence that is introduced into the liquid phase by the rising bubbles enhances the heat transfer from the liquid phase to the cooling surfaces. 2- The contact area between the gaseous phase and the liquid phase in pool condensation is considerably larger than in falling-film condensation. This advantage is specific for urea production since the liquid phase now is the continuous phase, in pool condensation the residence time of the liquid phase in the condenser is considerably longer. As the formation of urea from ammonia and carbon dioxide basically goes through two steps: first the chemical reaction to form ammonium carbamate from ammonia and carbon dioxide which is fast and exothermic. The second step is the formation of urea and water as a result of dehydration of ammonium carbamate which is slow and endothermic. The urea and water formed during the dehydration in the pool condenser have a higher boiling temperature than ammonia and ammonium carbamate. This leads to a higher net boiling temperature of the liquid mixture in the condensation step which also gives rise to a higher temperature difference between the process side and the cooling side. This increase in temperature difference can advantageously been applied for further reduction in investment (smaller heat-exchanging area required).

2.

Urea 2000 plus with pool reactor:

In a first variant of the Urea 2000plus technology, the pool condenser simply replaced the falling-film condenser provided the technological advantage of improving heat transfer in the condensing part of the urea synthesis. In a later variant of this process, the pool condenser and the urea reactor were combined into one single high-pressure vessel, called the pool reactor (Fig.6) By this combination of high-pressure equipment items, the available temperature difference over the condenser has increased by combining carbamate condensation and urea reaction in one vessel, a further investment reduction could be realized, especially for small- and medium-size production plants.

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Fig.6 Process flow diagram for Stamicarbon Urea 2000plus process with pool reactor.

In the pool-reactor concept, a further simplification of the process was realized by deletion of the heat-exchanging part of the high-pressure scrubber. The heat-exchange step was replaced by a process step where cooling of the reactor off-gases takes place through their direct contact with the relatively cold fresh ammonia .The synthesis section of the Urea 2000plus plant is completed with a single low-pressure recirculation stage. These subsequent process steps are similar to the ones in the original Stamicarbon CO2-stripping process.

C.

The Avancore process:

The Avancore urea process was introduced by Stamicarbon in 2009. It comprises a new urea synthesis concept that incorporates the benefits of Stamicarbon's earlier proven innovations. The Avancore Urea process material of construction is Safurex, and includes a low-elevation layout of the synthesis section. The excellent corrosion resistant properties of the Safurex material in an oxygen-free carbamate environment eliminate the need of using passivation air in the urea processes. Because of the absence of oxygen in the synthesis section, hydrogen or any other combustibles present in the feed no longer poses any risk of explosion for the urea plant. The ammonia emissions are also kept to a minimum because of the absence of passivation air. In the Avancore process, Stamicarbon has introduced a low-level arrangement of the synthesis section, where the reactor is located on ground level, which allows less investment and easier maintenance. The concept still makes use of a gravity flow in the synthesis recycle loop (Fig.7). However, the low-level arrangement of the reactor necessitates another heat source for the 24

endothermic dehydration reaction taking place in the reactor because the pool condenser off-gas cannot flow into this low-level reactor any more. Most of the urea formation, however, already takes place in the pool condenser and, therefore, only a minor amount of CO2 supplied to the reactor is sufficient to close the heat balance around it.

Fig.7 Process flow diagram for Avancore urea process All Stamicarbon CO2 stripping processes have some common features: The use of carbon dioxide as stripping agent in the high-pressure stripper. The use of gravity flow to maintain the main recycles flow in the high-pressure loop. The use of an azeotropic N/C ratio (3:1) in the reactor. The achievement of high degree conversion of both feed stocks (NH 3 and CO2) within the synthesis loop. As a result, only one small lowpressure carbamate recycle loop is required.

25

VI. Corrosion:
Urea synthesis solutions are very corrosive. Generally, ammonium carbamate is considered the aggressive component. This follows from the observation that carbamate-containing product streams are corrosive whereas pure urea solutions are not. The corrosiveness of the synthesis solution has forced urea manufacturers to set very strict demands on the quality and composition of construction materials. Awareness of the important factors in material selection, equipment manufacture and inspection, technological design and proper operations of the plant, together with periodic inspections and nondestructive testing are the key factors for safe operation for many years.

A.

Role of Oxygen Content:

Since the liquid phase in urea synthesis behaves as an electrolyte, it causes electrochemical nature corrosion. Stainless steel in a corrosive medium owes its corrosion resistance to the presence of a protective oxide layer on the metal. As long as this layer is intact, the metal corrodes at a very low rate. Passive corrosion rates of austenitic urea-grade stainless steels are generally between <0.01 and (max.) 0.10 mm/day. Upon removal of the oxide layer, activation corrosion set in unless the medium contains sufficient oxygen or oxidation agent to build a new layer. Active corrosion rates can reach values of 50 mm/day. Stainless steel exposed to carbamate containing. Solutions involved in urea synthesis can be kept in a passivity (non-corroding) state by a given quantity of oxygen. If the oxygen content drops below this limit, corrosion starts after some time its onset depending on process conditions and the quality of the passive layer. Hence, introduction of oxygen and maintenance of sufficiently high oxygen content in the various process streams are prerequisites to preventing corrosion of the equipment. From the point of view of corrosion prevention, the condensation of NH 3 CO2 H2O gas mixtures to carbamate solutions deserves great attention. This is necessary because not withstanding the presence of oxygen in the gas phase an oxygen-deficient corrosive condensate is initially formed on condensation. In this condensate the oxygen is absorbed only slowly. This accounts for the severe corrosion sometimes observed in cold spots inside gas lines. The trouble can be remedied by adequate isolation and tracing of the lines. When condensation constitutes an essential process step for example, in high-pressure and low-pressure carbamate condensers special technological measures must be taken. These measures can involve ensuring that an oxygen rich liquid phase is introduced into the condenser, while appropriate liquid gas distribution devices ensure that no dry spots exist on condensing surfaces. Not only condensing but also stagnant conditions are dangerous, especially where narrow crevices are present, into which hardly any oxygen can penetrate and oxygen depletion may occur.

26

B.

Role of Temperature:

Temperature is the most important technological factor in the behavior of the steels employed in urea synthesis. An increase in temperature increases active corrosion, but more important, above a critical temperature it causes spontaneous activation of passive steel. The higher-alloyed austenitic stain Urea 11 less steel (e.g., containing 25 wt% chromium (Cr), 22 wt% nickel(Ni), and 2wt%molybdenum(Mo)) appear to be much less sensitive to this critical temperature than 316L types of steel. Sometimes, the NH 3: CO2 ratio in synthesis solutions is also claimed to have an influence on the corrosion rate of steels under urea synthesis conditions. Experiments have showed that under practical conditions this influence is not measurable because the steel retains passivity. Spontaneous activation did not occur. Only with electrochemical activation could 316L types of steel be activated at intermediate NH3:CO2 ratios. At low and high ratios, 316L stainless steel could not be activated. The higher-alloyed steel type 25wt% Cr, 22 wt %Ni, 2wt%Mo showed stable passivity, irrespective of the NH3: CO2 ratio, even when activated electrochemically. Of course, these results depend on the specific temperature and oxygen content during the experiments.

C.

Material Selection:

Corrosion resistance is not the only factor determining the choice of construction materials. Other factors such as mechanical properties, workability, and weld-ability, as well as economic considerations such as price, availability, and delivery time, also deserve attention. Stainless steels that have found wide use are the austenitic grades 316L and 317 L. Like all Cr-containing stainless steels, 316L and 317 L are not resistant to the action of sulfides. Hence it is imperative in plants using the 316L and 317 L grades in combination with CO2 derived from sulfur-containing gas, to purify this gas or the CO2 thoroughly. In stripping processes, the process conditions in the high-pressure stripper are most severe with respect to corrosion. In the Stami-carbon CO2-stripping process, a higher-alloyed, but still fully austenitic stainless steel was chosen as construction material for the stripper tubes. This choice ensures better corrosion resistance than 316L or 317 L types of material but still maintains the advantages of workability, weldability, reparability, and the cheaper price of stainless steel-type materials.

27

Chapter Five: Other technologies for urea production I. Technology for urea production (TOYO): A. History:
Since its establishment in 1961, Toyo engineering corporation has been a leader in the urea industry. TOYO has designed engineered, constructed and commissioned over 100 urea plants based on the TOYO urea process including its urea synthesis technologies and urea granulation technologies. TOYO has established the ACES21 process (advanced process for cost and energy saving urea production). Which achieves energy saving and plant cost reduction without sacrificing high performance and high efficiency of the urea plant. ACES21is advanced technology to realize low investment cost and low energy consumption for urea production .A major feature of this technology is that it reduces the number of components in the urea synthesis loop to simplify the system. This lessens construction costs with the installation of the reactor on the ground in the CO2 stripping process.

B.

Process description:

ACES21 process synthesis section consists of a reactor, a stripper and a carbamate condenser. Liquid ammonia is fed to the reactor via the HP carbamate Ejector which provides the driving force for circulation in synthesis loop instead of the gravity system of the original ACES. The reactor is operated at an N/C (NH3 to CO2) ratio of 3.7, 182 C and 152 bar. The CO2 conversion to urea is high as 63% at the exit of the reactor. Urea synthesis solution leaving the reactor is fed to the stripper where unconverted carbamate is thermally decomposed and excess ammonia and CO2 are efficiently separated by CO2 stripping .the stripped off gas from the stripper is fed to the vertical submerged carbamate condenser (VSCC),operated at an N/C ratio of 3.0, 180C and 152 bar . Ammonia and CO2 Gases condense to form ammonium carbamate and subsequently urea is formed by dehydration of the carbamate in shell side. Reaction heat of carbmate formation is recovered to generate 5bar steam in the tube side. A packed bed is provided at the top of the VSCC to absorb uncondensed ammonia and CO2 gases into a recycle carbamate solution from the MP (medium pressure) absorption stage. Inert gas from the top of the packed bed is sent to the MP absorption stage.

1.

Ground Level Reactor:

The two-stage synthesis concept employing a VSCC and an HP ejector enables the HP equipment in the synthesis section to be laid-out very compactly in low elevation. The highest level (the VSCC top) is about 30 to 35 m (Depending on the plants capacity and configuration). This is 28

significantly lower than even the traditional solution recycle process in which the reactor is installed on the ground.

2.

Vertical Submerged Carbamate Condenser:

The Vertical Submerged Carbamate Condenser (VSCC) functions to condense NH3 and CO2 gas from the stripper to form ammonium carbamate and synthesize urea by dehydration of ammonium carbamate. In the shell side, and to remove the reaction heat of ammonium carbamate. Formation by generating 5 bar steam in boiler tubes. The advantages of the vertical submerged configuration of the carbamate condenser are summarized as follows: - High gas velocity, appropriate gas hold up and sufficient liquid depth in the bubble column promote mass and heat transfer. - An appropriate number of baffle plates distribute gas bubbles in the column effectively without pressure loss. - A vertical design allows a smaller plot area.

3.

Optimum Selection of Synthesis Condition:

In the ACES21 Process, the VSCC is operated at an N/C ratio of 3.0 which allows relatively high temperature operation of the VSCC, rendering efficient heat transfer between the shell and the tube and higher reaction rate of ammonium carbamate dehydration to form urea. The reactor N/C ratio is selected at around 3.7 to maximize CO2 conversion with appropriate excess pressure. Resultantly, a high CO2 conversion of 63% is achieved in the reactor at relatively low temperature and pressure, i.e. 182 C and 152 bar. .

Fig.8 process flow diagram for TOYO urea Process

29

C.

TOYOS Process Performance:

Typical Content 46.4 wt% 0.8 wt% 0.2 wt% NH3 (100%) 0.563 ton,CO2 (100%) 0.731 ton

:OYOs Activities and Services Product Quality Nitrogen (N) Content Biuret Content Water Raw Material

Table.5 TOYOS Process Performance

II. Snamprogetti Urea Technology: A. Process description:

1. Synthesis and High Pressure (HP) recovery. 2. Medium Pressure (MP) purification and recovery. 3. Low Pressure (LP) purification and recovery.

1.

Synthesis and High Pressure (HP) recovery:

In addition to the HP machinery required to feed ammonia and carbon dioxide and to recycle ammonium carbamate solution, this section includes; the reactor where urea is formed; the stripper necessary to strip out as vapors, from the urea solution leaving the reactor, a large amount of ammonia and carbon dioxide not converted to urea in the reactor; the carbamate condenser that condenses these vapors; the ejector that recycles the ammonium carbamate solution to the reactor. In this equipment the pressures are of a similar level, 150 bar, while the temperatures of the outlet solutions are 188, 205 and 155oC for the reactor, the stripper and the carbamate condenser, respectively. In the Snamprogetti technology, the urea reactors is characterized by a high ammonia-carbon dioxide ratio (NH3/CO2) (3.2 3.4) and a low water carbon dioxide ratio (0.4 0.6 molar). Inside the reactor a matching number of trays of a very simple design are installed to improve the conversion. Under these conditions 62-64% (conversion) of the total CO2 entering the reactor is converted to urea. The total carbon dioxide conversion in the HP section (or loop) is 85-90%.

30

2. Medium Pressure (MP) purification and recovery:

The purpose of this section is to partially strip out the reactants, ammonia and carbon dioxide from the urea solution and, after their condensation in water, to recycle the obtained solution to the reactor, together with the ammonia and carbon dioxide aqueous solution resulting from the downstream sections of the plant. The ammonia excess is separated in this section and recycled to the reactor separately. A distillation column is provided for this purpose. The operating pressure is 17 barg. A particular feature is included in this section. Ammonia and carbon dioxide are partially condensed in the shell of a preheater within the vacuum section, thus recovering some energy in the form of 200kg of steam per ton of urea, with an investment cost that, even in existing plants, has a pay-back time of less than two years. Another particular characteristic of the MP section is the washing of the inerts (CO, H2 and CH4) contained mainly in the carbon dioxide and the passivation air. The quantity of passivation air in the Snamprogetti technology is very small (one third compared with other technologies). It is therefore easy to recover ammonia from the inerts without the risk of explosion mainly due to H2/O2 mixtures. No hydrogen removal from carbon dioxide is required. Upon special requests, different washing systems have been designed by Snamprogetti and have already been installed in industrial plants. To completely reduce the ammonia contained in the inerts, in completely safe conditions with regard to explosions. It should be emphasized that the presence of the MP section provides great plant flexibility, which can be operated over a wide range of NH 3/CO2 ratios, with excess ammonia present in the urea stream from the stripper being recovered and condensed by the MP section.

3. Low recovery:

Pressure

(LP)

purification

and

Further stripping of ammonia and carbon dioxide is made in the LP section, operating at 3.5 bar g. The vapors, containing ammonia and carbon dioxide, are condensed and recycled to the reactor via the MP section. The urea solution leaving the LP section is about 70% and contains small quantities of ammonia and carbon dioxide.

31

Fig.9 Block flow diagram for snamprojectti Urea Process

UREA,

Fig.10 Process flow diagram for snamprojectti Urea Process

32

Chapter six: Urea-Ammonium Nitrate (UAN) I. Overview of UAN Process Technology:

Ammonium nitrate (AN) and urea are used as feed stocks in the production of urea-ammonium nitrate (UAN) liquid fertilizers. Most UAN solutions typically contain 28, 30 or 32% nitrogen but other customized concentrations (including additional nutrients) are produced. Plant capacities for the production of UAN solutions range between 200 and 2,000 ton/day . Most of the large scale production units are located on complexes where either urea or ammonium nitrate or both are produced. In some of the European UAN plants, ammonium nitrate is being synthesized directly from nitric acid and ammonia. In some cases carbamate solution from the urea reactor outlet is being used as feedstock for the production of UAN. In those plants the UAN technology is an integral part of the fertilizer complex. UAN from scrubbing systems, urea from sieving machines, etc. are fed to a central UAN system, where quality adjustments can be done. The addition of corrosion inhibitors or the use of corrosion resistant coatings allows carbon steel to be used for storage and transportation equipment for the solutions.

II. physical properties of Urea ammonium nitrate solution:

Property Nitrogen content Ph Density Salt-out temperature Value 28-32% by weight 7 to 7.5 80-82 Ib/ft3
18 to 2C depending on the N content and at its lowest when the Urea N/Ammonium Nitrate N ratio is about 1:1.

Table.6 physical properties of Urea ammonium nitrate solution

III. Description of Production Processes:

The Continuous and batch type processes are used and in both processes concentrated urea and ammonium nitrate solutions are measured, mixed and then cooled. Block diagrams for UAN production are shown in (Figures 1 2). In the continuous process the ingredients of the UAN solution are continuously fed to and mixed in a series of appropriately sized static mixers. Raw material ow as well as nished product ow, pH and density are continuously measured and adjusted. The nished product is cooled and transferred to a storage tank for distribution. In the batch process the raw materials are sequentially fed to a mixing vessel tted with an agitator and mounted on load-cells. The dissolving of the solid raw material(s) can be 33

enhanced by recirculation and heat exchange as required. The pH of the UAN product is adjusted prior to the addition of the corrosion inhibitor. A partial recycle CO2stripping urea process is also suitable for UAN solution production. Unconverted NH3and CO2 coming from the stripped urea solution, together with the gases from the water treatment unit, are transferred for conversion into UAN solutions. But nitrogen and the application of Urea as fertilizer can be done at sowing time or as a topdressing, but should not be allowed to come into contact with the seed.

Fig.11 Block flow diagram for UAN process

Fig.12 Block diagram for a partial recycle CO2 stripping urea process for UAN production 34

References:
1234Fertilizer manufacture, M.E.Pozin, 1990, MIR Publishers. Ullman chemical encyclopaedia 4th edition. Rao, N. S. Bio fertilizers in Agriculture & Forestry.IBH, 1993. Lowrison, George. Fertilizer Technology. John Wiley and Sons, 1989. 5- http://www.landscape-and-garden.com. 6- Uhde Engineering Egypt co. S.A.E (UEE). Company contacts: Internet: www.uhde-engineering-egypt.com E-mail: info.uee@thyssenkrupp.com 7- MOPCO ( Misr fertilizers production Company). Company contacts: Internet: www.mopco-eg.com 8- Published document for Helwan fertilizers company December 2011 http://www.chemicals-technology.com/projects/helwanfertiliserco/ 9- Published document for The urea technology Snamprojectti company www.saipem.it 10. Published document for ACES21 urea process by TOYO engineering corporation http://www.toyo-eng.co

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