A Report On

INCIDENTS HAPPENED IN THE FERTILZER INDUSTRY & TECHNOLOGICAL ADVANCES

Submitted by :-

Varun Paul
(3rd year, Integrated Dual Degree (B.Tech +M.Tech))

(Department of Chemical Engineering) (INDIAN INSTITUTE OF TECHNOLOGY, ROORKEE)

Under the guidance of :-

Shri Tapas Kumar Bag (Senior Manager, Process) Shri Animesh Jha (Engineer, Process)

(INDO GULF FERTLIZERS, Jagdishpur) (An Aditya Birla Nuvo Unit)

Preface
As a part of my undergraduate program I was sent for industrial training at Indo Gulf Fertilizers, Jagdishpur for the period 21.05.2012 to 13.07.2012 . I feel highly obliged to be associated to such a reputed firm and to work under such educated and highly skilled people. This report is an insight into our experiences at the plant and what we learnt during our tenure. The report consists of two sections. The first section consists about a brief about the various units at Indo Gulf Fertilizers, Jagdishpur. To the interest of a chemical engineer, the plant consists of Ammonia Unit Urea Unit Cooling Towers De-mineralization of water

The first unit also consists our learning about the Fire and other Safety related issues and Strategies to keep cooling water clean. The second section is dedicated to the Incidents that happened in the Fertilizer Industry, their root causes, corrective actions taken and recommendations for the future. It also includes the major technological advances that have taken in the fertilizer industry in the last decade. This project was assigned to us to do a detailed study about the small glitches that lead to such huge losses and be careful while working in the industry and also to be prepared with remedial steps in case of an emergency. It was also an attempt by the firm to create a formal report on such cases for the newly joined employees so that they also get aware of such incidents and operate the plant safely and with proper understanding. I would be highly grateful if the readers provide their feedback and valuable inputs. I tried my level best to keep the report concise and easy to read. I hope this would turn out to be valuable to the firm and to the industry.

Varun Paul (Indian Institute of Technology, Roorkee)

Acknowledgement

I take this opportunity to put forward my gratitude to the people who wholeheartedly supported me throughout my task. Firstly, I thank my parents to provide me with facilities to sudy and gain knowledge from the various institutes I have been to. I also thank the faculty members of IIT Roorkee to provide me with he knowledge of chemical engineering which helped me understand the various processes at Indo Gulf. Sincere thanks to Dr. B Prasad, Associate Professor, IIT Roorkee to impart the knowledge of manufacturing of Ammonia and urea during his course on Chemical Technology. After that course, it was much easier for me to understand the functioning of these units at the above mentioned firm. Sincere thanks to Shri A.K Gupta (AVP, Production), Shri Tapas Kumar Bag (Sr. Manager, Process), Shri Vikas Kumar (Senior Engineer, Process) and Shri Animesh Jha (Engineer, Process) for their guidance throughout my tenure. I also owe a humble gratitude Shri Kailash Gupta (Secretary to AVP, Production and to Head, Engineering) for providing me with all kinds of study material necessary for detailed study. Most importantly I thank my project partner Mr. Amandeep Singh Bamrah, IIT Roorkee for his hard work and sincere effort . Without the cooperation of all the persons mentioned above it would have been really tough to work on all this.

VARUN PAUL (Indian Institute of Technology, Roorkee)

Certificate

This is to certify that the project titled Incidents Happened in the Fertilizer Industries and Technological Advances is a work by Varun Paul, student, 3rd year, Integrated Degree, Chemical Engineering (Enrolment no. 09210018). It is approved for partial fulfillment of the above stated course in chemical engineering from Indian Institute of Technology, Roorkee. The project was completed under the guidance and mentorship of the undersigned.

Shri Tapas Kumar Bag (Senior Manager, Process) (Indo Gulf Fertilizers, Jagdishpur)

Shri Animesh Jha (Engineer, Process) (Indo Gulf Fertilizers, Jagdishpur)

INTRODUCTION
Indo Gulf Fertilisers (A Unit of Aditya Birla Nuvo Ltd.), a prime fertiliser manufacturing unit is a part of Aditya Birla Group - a true Indian multi-national business conglomerate. It is situated in Jagdishpur Industrial area of Uttar Pradesh on the famous Hazira-Vijaipur-Jagdishpur (HBJ) natural gas pipeline of GAIL (India) and manufactures UREA, a nitrogenous fertilizer under the brand name of Birla shaktiman. The company was formed in 1983. To establish itself in the Northern India fertiliser market, seed marketing programme was commenced in 1987, while commercial production started in November 1988. IGF had been allotted 833.33 acres for the fertilizer plant and township by UP State Industrial development Corporation (UPSIDC). IGF fertilizer plant, township, demonstration farm and vocational training centre are situated in Jagdishpur, Chatrapathi Sahuji Maharaj district. The IGF plant is easily approachable by road and is located on Lucknow -Varanasi highway NH.56 at a distance of about 78 Km from Lucknow the capital of UP. The nearest railway station is Sindurwa on Lucknow Varanasi railway line and is about 2 kms. away from the site in the North. Nihalgarh is the railway station of Jagdishpur town & the same is situated at approximately 10 km from the site. The nearest commercial Airport Amausi (Lucknow) situated approx. 85 km away from site. The company enjoys leadership position in the Indo-Gangetic plains due to its strong brand Birla Shaktiman as well as strong distribution and customer service network. The consumers or end-users of urea fertiliser are farmers. The main products of IGF are Urea and Neem Coated Urea which is marketed under the brand name Birla Shaktiman Gold and Birla Shaktiman Krishidev respectively. Originally, Ammonia plant was designed to produce 1350 MTPD of Ammonia by Haldor Topsoe, Denmark and Urea plant was designed to produce 2 x 1100 MTPD of Urea based on Snamprogetti ammonia stripping technology.

Each section of IGF complex has been performing very well right from the inception. Considering the consistent good performance of the plant, IGF revamped existing ammonia & urea plant and current ammonia plant capacity is 1910 MTPD and urea plant capacity is 3275 MTPD. In addition to the main plants, it also has utility, auxiliary and other off site facilities such as steam generation plant, power plant, bagging plant, cooling towers, DM plant, water treatment plant, railway siding and truck loading facility, fuel and other material storages, fire fighting facilities, Quality Assurance & Environment Control cell, first aid etc.

TABLE OF CONTENTS

S no.
1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 1.10 2 3 4 5 5.1 5.2 5.3 5.4 5.5 6 6.1 6.2 6.3 6.4 6.5 7 7.1 7.2 8 9 9

Topic
Ammonia Unit Desulphursation Primary Reforming Secondary Reforming Waste Heat Boiler High Temperature Shift Convertor Low Temperature Shift Convertor Boiler Feed Water Preheater Carbon Dioxide Removal System Methanation Ammonia Synthesis Urea Unit Cooling Towers Demineralisation of Water Unit Fire Safety Fire Triangle Classification of fire Extinguishers for class A fire Extinguishers for class A and B Extinguishers for class B and C Safety from hazards Hand Protection Body Protection Head Protection Various Health Hazards PDCA Cycle Strategies to Keep Cooling Water Clean Prevention of Scale Formation Microbial Control Mishappenings and Technological Avances Appendix Bibliography

Page no.
1 1 1 1 2 2 2 2 3 3 4 6 9 10 11 11 11 11 12 12 13 13 13 13 14 14 15 15 16 17 36 41

1. Ammonia Unit
The plant commissioned in 1988. Ammonia is prepared using natural gas supplied by GAIL & RIL. The capacity of ammonia production at Indo Gulf Fertilizers, Jagdishpur is 1910 tonnes/day. The ammonia unt is built on M/s Haldor Topsoes Technology. It has the following units :-

1.1 Desulphurisation
Natural Gas from GAIL is filtered and condensate is separated out. Desired level of sulphur in natural gas is less than 0.5 ppm. Natural Gas at 39 kg/cm2 (g) is mixed with Hydrogen and heated to 390 degrees celcius. This takes place in the presence of Co-Mo catalyst. H2 + S -> H2S The gas is then passed over zinc oxide absorber to absorb H2S. This takes place at 300 to 400 degrees celcius. ZnO + H2S -> ZnS + H2O

1.2Primary Reforming
First the desulphurised natural gas is preheated to 497 degrees celcius and then sent to the primary reformer. The reformer consists of 288 tubes filled with Nickel based catalysts. The reformer operates at 33.8 kg/cm2 (g) and 781 degrees celcius. CnHm + nH2O -> n CO + (m/2 +1)H2 It is an endothermic reaction. Therefore, 576 burners are provided. Steam/Carbon = 3.3 Increase in temperature causes a decrease in hydrocarbon in the effluent. Increase in pressure reduces the conversion and increases hydrocarbons in the effluent. Carbon deposition on the catalyst may occur if catalyst poisons, for instance because of sulphur.

1.3Secondary Reforming
Process gas at 781 degrees celcius is mixed with process air at 558 degrees celcius. The reactions take place at 33-35 kg/cm2 (g) pressure. 2H2 + O2 + 3.8N2 --> 2H2O + 3.8N2 + ht CH4 + Air --> CO2 + CO + H20 + N2 + ht The catalyst in the combustion zone is predicted to range b/w 1100 and 1200 degrees celcius. Catalyst is Nickel based. Outlet temperature and pressures are 980 degrees celcius and 33 kg/cm2 (g) respectively.

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1.4Waste Heat Boiler

The reformed gas at 980 degrees celcius is passed through tube side and cooled to 356 degrees celcius. The excess heat is used to produce process steam.

1.5High Temperature Shift Covertor

Reformed gas from W.H.B enters at 33.4 kg/cm2 and 356 degrees celcius and leaves at 32.6 kg/cm2 and 426 degrees celcius. The CO present in the gas is shifted to carbon dioxide in the presence of Fe2O3 as catalyst. Exit gas analysis from HTS Convertor is :Component Hydrogen Nitrogen CO Carbon Dioxide Argon Methane Mole % 59.67 21.33 2.8 15.59 0.26 0.35

1.6Low Temperature Shift Covertor Catalyst consists of copper, zinc and aluminium in one bed. The temperature in this section
varies from 210 to 240 degrees celcius. The gas leaves the catalyst bed at 30.6 kg/cm2 and217 degrees celcius. Exit gas analysis from LTS Convertor is :Component Mole % Hydrogen 60.68 Nitrogen 20.8 CO 0.24 Carbon Dioxide 17.69 Argon 0.25 Methane 0.34

1.7Boiler Feed water Preheater

The process gas exchanged heat with B.F.W in 2 exchangers in series and is cooled to 164 degrees celcius.

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1.8CO2 Removal Section

Absorption of carbon dioxide takes place in aqueous GV solution containing K2CO3, activator glycine, Diethanolamine and a corrosion inhibitor Venadium Pentoxide (V205). K2CO3 +H2O+ CO2 -> 2KHCO3 + ht The process gas at 29.2 kg/cm2 and 164 degrees celcius exchanges heat with GV solution and cools down to 134 degrees celcius. The process gas is further cooled to 125 degrees celcius to produce LP steam and then to 108 degrees celcius to preheat B.F.W. This gas is fed to the bottom of the absorber containing 3 packed beds . The packing inhe absorber provides surface area for transfer. Exit gas is sent for condensate separation. Exit gas analysis :Component Hydrogen Nitrogen CO Carbon Dioxide Argon Methane Mole % 73.63 25.27 0.29 0.09 0.3 0.42

The absorbed carbon dioxide in GV is stripped in the regenerator and clean GV solution is recycled back to the CO2 removal section.

1.9Methanation
CO +3H2 -> CH4 + H2O + ht CO2 + 4H2 -> CH4 + 2H20 +ht The methanation starts at a temperature of about 240 degrees celcius but in order to ensure a sufficiently low content CO and CO2, the operating inlet temperature would be 280 degrees celcius. Catalyst is nickel on ceramic base. Higher temp means better efficiency but at same time shorter life of catalyst. Exit gas analysis :Component Hydrogen Nitrogen Argon Methane Mole % 73.30 25.59 0.31 0.80

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1.10 Ammonia Synthesis

At the top of the convertor, a min temperature of 360 to 380 degrees celcius is required to ensure sufficient reaction rate. If the temperature of catalyst inlet is below 360 degrees celcius, the rate becomes too slow. On the other hand the catalyst temperature should be as low as possible to prolong the catalyst life. Optimum Pressure is 220 kg/cm2 (g). The H2/N2 of the make up gas should be 2.45 to 3.00.

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2. Urea Unit
The ammonia and Carbon Dioxide produced in the Ammonia Unit are routed to the Urea Unit for production of Urea prills to be used directly by the farmers. Since Ammonia produced is in excess, a part of it is diverted to the Ammonia Storage Tanks. The capacity of Urea production is 3275 tonnes/ day.

2.1 Reactor
The compressed CO2, NH3 from the Ammonia Unit and the unreacted reactants recycled back from the stripper are made to react and ammonium carbamate is formed. The liquid mxture containing ammonia and carbamate at 125 degrees celcius from carbamate ejector enter the reactor bottom. CO2 from the compressor discharged at 160 kg/cm2 and 105 degrees celcius enters the reactor.At optimum conditions reaction top should be 188 degrees celcius. 2NH3 + CO2 -> NH2COONH4 + 38.1 kCal/gmol NH2COONH4 -> NH2CONH2 + H20 -7.1 kCal/ gmol A small amount of air is added to the carbon dioxide at the compressor section in order to passivate the stainless steel.

2.2 Strpper
Reactor effluent enters the tube side of the stripper. The carbon dioxide content of the reactor effluent is reduced by the stripping action of ammonia as it boils out of the solution. Dilute Urea/ Carbamate solution is collected at the bottom b/w 205 and 210 degrees celcius

2.3 M. P Decomposer
Solution coming from the stripper bottom at 147 kg/cm2 and 210 degrees celcius is flashed to 17 kg/cm2 (g) in M.P Decomposer. Part of ammonia, carbon dioxide and water goes to the vapour phase. There is heat and mass tranfer between the downcoming liquid and rising vapours. The liquid takes heat from the rising gases and a part of unconverted carbamate decomposes here itself to give ammonia and CO2. Urea solution is stored in the M.P Decomposer Holder

2.4 Ammonia M.P Absorber

The carbamate solution at 85 degrees celcius after condensation goes to the absorber. Ammonia gas which is in excess in the solution separates out and rises. There are 4 bubble cap trays in the absorber. Any carbon dioxide whch goes along with ammonia is scrubbed down.

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2.5 Ammonia Condenser

Ammonia vapours from the absorber are sent to the shell side of ammonia condenser. At 165 kg/cm2 pressure, ammonia condenses with cooling water at 32 degrees celcius. The condensed liquid ammonia leaves the condenser and flows to ammonia receiver in a 6 line. The uncondensed ammonia and inerts leave from condenser and flow to the Ammonia Receiver in a 4line.

2.6 Ammonia Receiver

Liquid ammonia makeup from Ammonia Plant/ Ammonia Storage and from Ammonia Condenser is received hare. Ammonia vapours and inerts from the ammonia condenser rise in the receiver and get condensed in the packed bed.

2.7 M.P Ammonia Absorber

The uncondensed gases from the receiver containing ammonia and inerts at 35 degrees celcius are made to exchange heat and mass with cooled condensate. Gas phase leaving from top is free of ammonia.

2.8 L.P Decomposer

Urea solution from M.P Decomposer Holder at 158 degrees celcius and 16.5 kg/cm2 is further flashed at 3.5 kg/cm2. Due to rise in temperature some ammonia and carbon dioxide go into the vapor phase along with the water vapors.

2.9 1st Vacuum Concentrator

The temperature of solution drops down to 90 degrees celcius due to flashing. Th inlet concentration of 71% Urea is concentrated to outlet of 94.97% Urea.

2.10

2nd Vacuum Concentrator

It is operated at 0.03 kg/cm2. The 95% Urea solution is concentrated in a single pass rising film concentrator upto 99.7% Urea melt.

2.11

Prilling Tower

The concentrated Urea at 138 degrees celcius and 18 kg/cm2, from the Concentrators is sent to the prilling tower. At the top is a rotating basket with holes as per the required prill size. The solution is poured in the basket and cold air is blown from the bottom. As the drops of concentrated solution fall, the air removes the moisture from them to produce urea prills. The tower has an internal free falling height of 72.5 m. During the fall the droplets of Urea first solidfy and then are cooled to 60 degrees celcius.

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3. Cooling Towers
1. Cooling water is used for cooling purposes in equipments such as heat exchangers Ammonia, Urea and Utilities Plants. 2. Due to the scarcity of water it cannot be thrown away and thus has to be reused in the cooling purposes. 3. Thus, cooling towers are required where this water can be cooled every time after service. 4. Cooling Towers at Indo Gulf Fertilizers are of Induced Draft Type in which hot water is sprayed from the top and air is sucked from the sides by Induced Draft fans mounted at the top. 5. Chemical treatment is needed for preventing corrosion, scaling, fouling and microbial growth in the system. 6. Makeup water is required to compensate the water losses due to evaporation, wind and blow down. 7. The cooling towers are provided with a side filtration system. Part of the circulating water passes through pressure filters and returns to the cooling tower basin thereby reducing suspended solids. 8. Control limits for cooling towers are listed below :pH Total Hardness Chlorides Silica Turbidity Anti scaling agent 7.0 to 8.0 <500 ppm as CaCO3 <150 ppm as chlorine <160 ppm <10 ppm 100 ppm

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4. Demineralisation of water (D.M) Unit

1. Water obtained from the natural sources is not fit for use as Boiler Feed Water (B.F.W). 2. Modern high pressure boilers require water which should be of high degree of purity and conditioned with certain chemicals. 3. Dissolved salts in raw water dissociate into ions 4. Calcium, Magnesium and Sodium cations along with Bicarbonate, Sulphate and Chloride ions are present in most raw water supplies. 5. The dissolved solids of calcium and magnesium make the water hard. 6. Bicarbonates of Ca and Mg scale on boiler tubes. The scale being bad conductor causes overheating of boiler tubes resulting in tube failure. 7. Silica has a peculiar property of volatility at higher pressure and temperature. If present beyond 0.01 ppm in boiler drum water, it vaporizes and gets deposited on the blades of turbine resuling in low turbine efficiency and mechanical failures. 8. Demineralised water used in high pressure boilers should have following specifications :Total cations Total anions Silica Iron Oil Conductivity pH 0.1 ppm as Ca2+ 0.1 ppm as CO320.01 ppm Not Traceable Not Traceable 0.3 micro Siemens/cm 6.5-7.5

9. The water is demineralised by passing it through ion exchanger beds. 10. Sodium sulfite solution is dosed to neutralize the chlorine content. 11. Thereafter the water passes through strong cation exchangers where cations like Ca2+, Mg2+, Fe3+ and Na+ are removed. 12. The water is then sent to degasser for removing unstable acidity H2CO3. It breaks into water and carbon dioxide.CO2 is removed. 13. The water is now sent to anion exchangers where anions such as CL-, SO42-, SiO22- are removed. 14. Then sent to mixed bed units for removal of any left out salt. 15. In the ion exchangers, ion Exchange resins are used for deionization which contains mobile ions of a solid in a net like structure which are exchanged for the ions of like charge in the solution.

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5. Fire Safety
5.1 Fire Triangle:
The fire triangle or combustion triangle is a simple model understanding the ingredients necessary for most fires.

5.2 Classification of fire : Class A Fire : Fire in ordinary materials (Paper, wood, cloth). The quenching and cooling effects of water or of solutions containing large percentage of water are important in extinguishing these fires. Class B Fire : Fires in flammable liquids as gasoline, oil, grease etc. A blanketing or smothering action is of primary importance on fires of this class. Class C Fire : Fires in flammable gases such as hydrogen, LPG, natural gas etc. Class D Fire : \ Fires involving combustible metals.. Class E Fire : Fires involving electrical appliances.

5.3 Extinguishers for class A only : The soda and acid extinguishers contain a solution of bicarbonate or soda in water in the outer shell and a bottle of sulphuric acid in the neck of the extinguisher. When the plunger is struck, it breaks the bottle of acid which then combines with bicarbonate solution and CO2 is produced.

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5.4 Extinguishers for class A & B : The foam type extinguisher which contains a solution of water, bicarbonate/soda and a foam making ingredient in the outer cylinder. In the inner cylinder a solution of aluminium sulfate is kept sealed.

5.5 Extinguishers for class B & C : Carbon Dioxide extinguisher : It contains liquid CO2. It has a horn like nozzle through which the gas escapes when a valve is opened which smothers the fire by exclusion of air. Dry Chemical Powder extinguisher : They have a small cartridge of carbon dioxide or nitrogen to expel the dry chemical filled inside the extinguisher.

6. Safety from hazards

The most common hazards are : Handling corrosive fluids such as acidic, caustic potash, caustic soda etc. without protection. Dissolving solids without protection. Welding or examining equipments such as furnaces without protection.

6.1 Hand Protection :

1. 2. 3. 4. Canvas Gloves For most light work. Leather Gloves For rough or abrasive material. Rubber/PVC Gloves Corrosive chemical hazards. Electrical Rubber Gloves Against electric shocks. Tested to a potential of 15000 volts.

6.2 Body Protection :

In industrial environment exposure to fire, extreme heat, molten metal, corrosive chemicals, cold temperature etc. are the hazards often encountered and are known as Job Exposure. 1. Leather Aprons/Suits Against heat and splashes of hot metal. Also protects against ultraviolet and infrared radiations. 2. Asbestos Aprons Same as leather and used by workers in hot steam lines or cold atmosphere. 3. PVC/Rubber Suits Against acids/alkali and other corrosive chemicals.

6.3 Head Protection :

Safety helmets protect not only from impacts but from flying particles as well as from electric shocks.

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6.4 The different hazards from various chemicals are listed below :-

CHEMIICAL
Ammonia Carbon Monoxide

PHYSICAL STATE
Colorless gas with a pungent odor Colorless, Tasteless

FIRE HAZARDS
Ignitable Flammable gas, forms explosive mixture with air Non-Flammable

HEALTH HAZARDS
Severe irritation to skin, eyes and respiratory passage. Toxic, extremely hazardous to health, may cause death in case of exposure in high conc. Low toxic but large quantity may cause death by suffocation. Non toxic but causes suffocation. Non-toxic but may causes asphyxiation by exclusion of oxygen It is asphyxiant.

Carbon Dioxide

Colorless

Hydrogen

Colorless, Odorless

Nitrogen

Colorless, Tasteless

Highly flammable and forms explosive mixture with air. Non-Flammable

Natural Gas

Colorless, Tasteless

MEA

Clear colorless liquid with ammonia like odor.

Highly explosive when mixed with air/oxygen even at lower concentrations Amine vapor can ignite

Venadium Pentoxide

Yellow to red crystalline solid

Non-Flammable

May cause severe irritation with corneal injury which may result in permanent impairment of vision. Extremely toxic. May be fatal if swallowed. May cause blindness, bloody nose or coughing of blood.

6.5 Key Elements of Health and Safety Management PDCA Cycle 1. PLAN Establish goals and hence break down into subgoals. Develop detailed action plans, identifying who is responsible for what. 2. DO Management should use all communication channels to inform all employees about the goals and the action plans, including clarification of the authority. 3. CHECK Most activities in the plan are carried out at the operational level. Every month managers check whether the activities outlined have been completed and do the results support the goals. 4. ACT If the results do not support the goals, the causes must be identified and corrective actions must be taken.

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7. Strategies To Keep Cooling Water Clean

1. Cooling Towers are critical components in Chemical Process Industries. 2. Concentration of contaminants in the makeup water results in scale formation and biological fouling. 3. Unless prevented, it can lead o loss in cooling efficiency and in extreme cases can even lead to unit shutdown. 4. If the water used in an open circulating system has not been properly treated to remove unwanted constituents, the dissolved species will become progressively concentrated. As the solubility limits exceed for calcium carbonate, calcium sulfate and calcium silicate, scale will form.

7.1 Prevention of scale formation Name

Sulfuric acid injection combined with Cr04- feed

Advantages

Disadvantages
Chromate is toxic.

Removal of bicarbonate ions. Minimizing CaCO3 potential. Chromate establishes a protective surface that resembles stainless steel. Non Chromate methods at Operation at alkaline pH helps to mildly alkaline pH reduce corrosion. Treatment of makeup Hydrogen ions convert the with sulfuric acid bicarbonate to CO2 and prevent CaCO3 formation.

Phosphates, either ortho phosphates or phosphate complexes

Phosphonate treatment with a supplemental polymer

Phosphate will react with iron i.e ferrous ions produced at the anodic sites to form a protective layer while calcium phosphate precipitates in the local alkaline environment at the cathode. Phosphonates attach to deposits as they are forming and disrupt crystal growth and lattice strength.

Higher Ph increases scale formation. Acid can lead to corrosion. It introduces sulfate ions which can lead to formation of calcium sulfate. Even small upsets can cause severe calcium phosphate fouling.

Azole (Tolytriazole and Benzotriazole)

Overfeed can cause calcium phosphonate deposition. Decomposition of phosphonates reduce the effectiveness and increase the potential for calcium phosphate deposition. In systems having copper alloy tubes. Tolytriazole is most subject to Nitrogen in the triazoles bonds with decomposition by oxidizing the copper to form a plate like biocides. molecular layer at the metal surface.

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7.2 Microbial control

1. Unless properly controlled, through the use of biocides, bacteria will grow in condensers and cooling water fill, fungi will flourish on and in cooling tower wood and algae will grow on wetted tower components. 2. A big problem with bacterial growth is that once they settle, they secrete a polysaccharide layer for self protection. This film will accumulate silt from the water, growing even thicker and reducing the heat transfer. 3. Fungi will attack cooling tower wood in an irreversible manner leading to structural failure. 4. Algae will also foul cooling tower spray decks potentially leading to reduced performance.

Oxidizing Biocides
Chlorine

Advantages
Reacts with water to form HOCl which is a killing agent.

Disadvantages
If pH>7.5, killing efficiency declines. Presence of ammonia or amines also effects its potency because of formation of NH2Cl. The major disadvantage is that industrial bleach contains small amounts of NaOH, which when injected into the system, raises the Ph.

Liquid Bleach (NaOCl)

Bromine (Chlorine Oxidizer + Bromine salt (NaBr))

Chlorine Dioxide

The chemistry produces HOBr, which has similar killing powers as HOCl and also functions more effectively at alkaline pH. Also it does not react irreversibly with ammonia or amines. Its killing power is not affected by pH.

It is unstable and must be generated on site by reacting sodium chlorite (NaClO2 ) with chlorine.

Non-Oxidizing Biocides
2-2 dibromo-3-nitropropionamide

Advantages
Fast acting and degrades quickly to non hazardous compounds. Effective against bacteria and fungi. Active over a wide range of pH. Effective against all organisms depending upon the functional groups. Wide pH range

Disadvantages
Expensive and degrades at pH >9. Not effective against fungi and algae Degraded by oxidizing biocides

Isothiozoline

Quaternary amines

Can cause foaming.

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8. INCIDENTS HAPPENED IN THE FERTILIZER INDUSTRY Causes Corrective actions

Recommendations

& TECHNOLOGICAL ADVANCES OVER THE LAST DECADE

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Ammonia emission reduction in Urea Granulation Plants

Problem : 1. Free ammonia concentration in the incoming urea solution to urea granulation plant : Free NH3 from evaporation (500-600 ppm wt) NH3 added through biuret formation (90 ppm wt) Total free NH3 at inlet granulator (590-690 ppm wt) 2. From a 3500 MTPD plant, the released quantity of Ammonia amounts to 100 kg/hr. 3. Ammonia can be converted to hexamethylene tetramine by reaction with formaldehyde. The drawback is low conversion: 25% to 40%. 4. Acid Scrubbing is also an option to form diluted ammonium salt. The drawback is the possibility of formation of urea nitrate, which is an explosive or formation of ammonium sulfate which has to be treated or disposed off. Actions : 1. Ammonia Convert Technology. Ammonia emissions reduced by 80%. System is easy and reliable No waste stream Overall economics is feasible 2. In granulaton plant, in addition to a dust scrubber, an acidic scrubber stage has to be installed downstream of dust scrubber to allow a dust free gas. 3. NH3 is absorbed in the acidic solution and converted to ammonium sulfate. 4. Urea dust is washed out in the dust scrubber. 5. Ammonium sulfate solution is added to the dust recycle flow and sent for evaporation, consisting of a single evaporator and a single vacuum stage. 6. To avoid entrainment of sulfur or sulfuric acid in the urea synthesis plant, the vacuum section and process condensate are separated from it. Benefits : 1. The environment benefits from drastically reduced ammonia emissions. 2. The producer can comply with the most stringent regulations and thus reduce the production cost. 3. The consumer gets a nitrogen fertilizer with the nitrogen content of 46 wt% (min) and has added value due to traces of sulfur.

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Synloop Superheat Issues

Firm : PT Kaltim Pacifik Amoniak, Indonesia

Incident : Investigation identified following damages :1. Cracking at the heat affected zone of closing weld at the outer surface of the bottom hemispherical head located just above the manhole. 2. Pressure test indicated cracking of the tube to tube sheet welds leading to leakage. 3. Delamination of cladding of the tube sheet. 4. Nitriding of 321 stainless steel tubes. Causes : 1. 2. 3. 4. Inadequate weld heat treatment. Hydrogen and nitriding attack. The temperature on the inside is much higher than the outside Nozzles were located next to the weld which might have acted as huge heat sinks and caused nonuniform heating and cooling. 5. When condensed water is formed and then evaporates, a concentration of chemicals can occur in the bottom of the crevices formed. 6. When fillet welds are applied, delamination can also be a major problem. Actions or Design Improvements : 1. 2. 3. 4. 5. Stainless steel (SS 347) fillet welds for tube to tube sheet welds. Stainless steel overlay (SS309 + SS347) on the tube sheet instead of Inconel 600. The bottom channel was heat treated in the furnace as one piece after finishing all the welding. A drain was installed on the bottom head so that any tube to tube weld leakage could be detected. The operating procedure was also revised to ensure no water build up on the process side.

Recommendations : 1. High residual stress was the main cause of damage so no closing weld shall be located at the bottom of the vessel. 2. It must be ensured that then heat input is sufficient to bring the thermal mass of tube sheet to the dew point of the start up steam. 3. SS 321 will be affected by nitriding.

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Nickel Carbonyl
Properties : 1. High vapour density relative to air means vapours can gather n low spots. 2. Its vapour pressure means that it is possible to condensate liquid Ni(CO)4 in cold spots. 3. The fact that nickel carbonyl is denser than water means that it is possible to trap liquid spill under water. Sources of Nickel in an ammonia plant : 1. 2. 3. 4. 5. Pre reforming catalyst Methanation catalyst Primary reforming catalyst Secondary reforming catalyst Hydrodesulphurisation catalyst 50% (w/w) 30% (w/w) 20% (w/w) 10% (w/w) 5% (w/w)

Incident : 1. Partial shutdown of the plant lasted longer than anticipated and the methanator cooled down to 25 degrees celcius. 2. As a result several personnel were exposed to nickel carbonyl. 3. It was established that a gas containing a high concentration of CO leaked into the methanator. Detection and Measurement : 1. Chemiluminescence monitor. 2. Gas Chromatography. Neither of the above two is normally immediately available. 3. Drager tubes (0.1 to 1 ppm). 4. Chemical analysis Nickel Carbonyl can be oxidized to Ni2+ in solution with Br or Cl. 5. Infrared Spectroscopy Nickel Carbonyl has a strong band at 2058 cm-1. Medical issues : 1. It can be absorbed through the skin and can affect the eyes, may be carcinogen. 2. Initial symptoms (12 to 36 hr) headache, dizziness, nausea. 3. Delayed symptoms chest pain, shortness of breath, dry cough, weakness and bluish color of lips. Disposal of Ni(CO)4 : 1. Decomposition to solid nickel can be achieved bypassing nitrogen containing entrained nickel carbonyl through steel tubes provided with wire wool and heated to 240 to 250 degrees celcius. 2. Decomposition to nickel powder requires higher temp of 400 degrees celcius. 3. Incineration to nickel oxide.

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Rupture of primary reformer mixed feed coil header

Firm : Trinigen 1 ammonia unit in Trinidad

Incident : 1. 10th September 2010, motor operated process isolation valve upstream of HTS closed unintentionally. 2. The outlet pressure of the primary reformer increased from 455psig to 540 psig. 3. About 1 min later, the LP syngas compressor tripped due to high vibrations. 4. The fuel ramp sequence which was intended to automatically reduce firing of primary reformer in the loss of process gas also did not activate. 5. In the process to open the manual vent valve, a load noise was heard and the reformer pressure decreased rapidly, indicating that rupture of mixed feed coil took place. Damage : 1. Material damage was limited to the damage of inlet header of mixed feed coil. 2. The temperature leading to failure was 1287 degrees Fahrenheit as it was designed for 1100 degrees Farenheit. 3. The collateral damage to other equipments, pipings In the area caused by flying debris was minor. Causes : 1. Water ingress to electrical junction of the actuator of isolation valve due to incorrectly installed gasket. 2. An alarm indicating the closure was not provided. 3. Trinigen1 does not have an automatic process vent valve on the pressure gas line upstream the HTS to vent the process gas to flare system. Recommendations : 1. Up gradation of existing trip system by implementing on automatic pressure control vent valve to maintain a healthy gas flow. 2. A process isolation valve should generally feature a process vent valve upstream which automatically opens in case of closure of isolation valve. 3. It is strongly recommended to perform a creep analysis of crucial areas as a part of standard process design review.

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Problems in Synthesis Compressor Train

Firm : Indo Gulf Fertilizers, Jagdishpur

April 2007 Revamp to1910 MTPD : 1. There are two synthesis gas convertors which were operating in parallel were put in series. A new waste heat boiler was installed in the downstream of second convertor. 2. Differential pressure between balancing drum and suction of 3 rd barrel rose much higher than recommended. It rose to 15-16 kg/cm2 while normal should have been 2-3 kg/cm2. 3. 1st barrel and its end gas seal, balance drum seal were found severely corroded. April 2009 Turnaround : 1. Modified rotor having new design balance drum installed in 3 rd barrel (4th stage compression and recirculation). 2. Vibrations in 2nd barrel (3rd stage compression) started to increase. April 2010 Turnaround : Compressor was dismantled and following was observed 1. End seals of first and second barrel were severely damaged due to corrosion. Seals were made of aluminium. 2. End seals of third barrel were made of stainless steel and were in good health. 3. Thinning was observed in the impellers of first barrel. 4. Antisurge valve, balance valve and bypass valve were found passing heavily. Causes : 1. Ammonia concentration in barrels have been much higher due to heavy passing of antisuge valve leading to mixing of synthesis gas having higher ammonia content with synthesis gas to the 1 st barrel (1st and 2nd stage compression). 2. Higher carryovers of moisture from inter stage separators (water entrainment in gas). 3. Since ammonia was present in the barrels and seal material containing about 9% Cu, moisture along with ammonia might be causing corrosion of all seals. Remedial Actions : 1. Replacement of seals with SS material. Replacement with SS was a temporary solution. The firm started exploring a suitable material which does not have copper/copper alloys. 2. Implementation of molecular sieve driers at the inlet of synthesis gas compressor.

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Recycle Hydrogen Interconnection Line Failure

Firm : IFFCO Phulpur

Interconnection : 1. The recycle hydrogen header of both the ammonia plants were connected using a 4, schedule 40 pipeline. 2. It is used during start up start up of the ammonia plants at the time of introduction of the steam and hydrogen in the primary reformer. 3. This line also proves to be very useful when the back end of either ammonia plant trips. Incident : 1. On 4th Sept, 2010, fire was observed in Ammonia 1 cooling tower are, turbo generator and the boilers of power plant tripped. 2. Since the fire was in the form of a continuous flame, it was evident that the fire was because of gas leak. Damage : 1. 2. 3. 4. The fire affected the recycle H2 interconnection 2-3 m in length from the fire point on either side. Ammonia 1 CW pump turbine collapsed. Structural support beams nearby the source of fire deformed. About 266 electrical, instrument power and control cables were melted.

Causes : 1. The area in the vicinity of cooling tower is humid and the insulated piping of interconnection is not always in use. Ingression of humid air in cool pipes lead to condensation and corrosion. Corrective actions : 1. The interconnection pipeline was replaced by 4, schedule 120 i.e 11.113 mm thick pipeline. 2. A hydro test of the complete H2 pipeline was carried out at a pressure of 95 kg/cm2. Recommendations : 1. Visual inspection every six months. 2. Since the area near the cooling towers is more to corrosion due to moisture, painting of critical pipelines is recommended every year. 3. Hydro test of the pipeline is to be strictly carried out every alternate year 4. Since the interconnection recycle hydrogen line remains cool for most of the time, insulation may not be required.

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GV Absorber Shell Leak in Ammonia Plant

Firm : IIFCO Aonla

Incident : 1. On 3rd September 2010, loud noise suddenly started coming from the bottom of the skirt portion of GV Absorber with mist emanating from the nozzle holes in the vessel skirt. 2. The mist was analyzed with an explosive gas detector and it was confirmed to be process gas leakage. It was apparent that the shell was leaking. Shut down was initiated. Damage : 1. Potassium Carbonate solid deposits were noticed between the skirt and the pressure shell. 2. The Bed Limiting support beam bracket of bed#5 was found broken and badly corroded. 3. There were many notches and vertical canals of varying depth of 5-15mm over the entire circumference of shell at bed#5. Causes : 1. The GV solution at the bottom i.e near bed#5 has highest CO2 and is most corrosive. 2. During annual turnarounds, some bed limiter strips and segments were found broken and replaced. Broken bed limiter segments could have caused packing ring movement with liquid eddies and lead to scraping of passsivation layer formed by Venadium Pentoxide. 3. Recommended operating level was71% on the level controller but, since the commissioning of the plant, the absorber bottom level controller was operated with a set point of 50% i.e bed#5 was operating without any submergence in the GV solution. Corrective Actions : 1. The normal operating set point was increased to 75% on the level controller. 2. Dynamic passivation i.e circulation of CV at near normal flowrates without the introdeuction of process gas was carried out for 96 hrs, thereby forming a passivation film to form inside the GV towers. Recommendations : 1. It is not a normal practice to remove trays or unload packed beds. But, this should be considered, particularly in high vulnerable areas. 2. Regular shell thickness monitoring programs for such towers may be established to preclude unexpected equipment failures.

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Self Supported Flare Stack Vibrations in Ammonia Plant

Firm : Qatar Fertilizer Company, Qatar

Incident : 1. Some temperature upsets were observed in the top of the rectifying section of ammonia stripper. 2. The Ammonia recovery system was stripped on 17.02.2007 due to high water content in NH3 sent to storage. 3. Due to this shut down, HP purge gas from ammonia synthesis loop and flash gases from the refrigeration loop were diverted o the flare. 4. 0n 19.02.2007 the flare stack was observed swinging and shaking from the control room. Reason : 1. It was probably the partial blocking of the gas flow path due to mixing of CO2 and ammonia rich gases in the stack forming carbonates/bicarbonates. Remedial Actions : 1. All the gases earlier diverted to the flare stack were sent to the primary reformer as fuel 2. The block in the bottom 2 drain was cut with the help of mechanical rods, pressure jets and steam hoses. 3. The taps of level gauges were connected to steam hoses to heat the sludge material. 4. Both the drains of ammonia vent were opened for the removal of solid deposits. 5. The flare stack pressure reduced to 0 kPa. 6. The LTS outlet process gas vent was opened to 12% for half an hour to completely deissolve the deposits. tHis further reduced the pressure to -2 kPa. Recommendations : 1. The CO2 rich gas from CO2 removal to be sent to primary reformer as fuel. 2. The flare stack bottom separator should be checked at least once a day. 3. Flare bottom drain and its bypass line, flare bottom level gauge taps and ammonia header drains to be checked in routine. 4. Complete inspection of the flare internals including nozzles, welds and bolts to be planned in every major shut down.

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Catalyst Catastrophes
Introduction : 1. Catalyst in ammonia plant are working at very fierce conditions b/w 200 and 900 degrees celcius and pressures from 435 to 2900 psig. 2. When the catalysts are exposed to abnormal, non standard or transient conditions, there is more danger that undesirable side reactions may occur. Incident 1 (Problems with design basis) : 1. The original design was specified as natural gas feed with total sulphur level of 8.5 ppmv. 2. This required HDS section with small catalyst volume of 8m3. 3. The total sulphur level in actual was a little higher at 10ppmv that too Dimethyl Sulphide which is more difficult to break than H2S. 4. For such sulphur levels, catalyst volume of 21m3 is required. Lesson from Incident 1: 1. Accurate definition of actual operation parameters is critical. Incident 2 (HDS Catalyst damage during start up of a new charge) : 1. Turnaround led to replacement of HDS catalyst and also downstream H2S absorbent. 2. On restart, primary reformer immediately showed signs of sulphur poisoning as 3-4 ppmv sulphur mostly DMS was slipping through the new catalyst. 3. The plant was operated continuously which lead to sulphiding of active nickel of primary reformer. Causes for Incident 2: 1. It transpired that the new charge had been inadvertently heated to a temperature in excess of 500 degrees celcius. This caused damage due to thermal sintering. 2. In addition hydrogen rich gas was introduced as the HDS catalyst was cooling at 450 degrees celcius. At this temperature and hydrogen level, the active Ni and Mo phases in the catalyst will rapidly reduce to a lower oxidation state.

Lesson from Incident : 1. HDS Catalysts must be kept within the advised temperature range during commissioning and proper attention must be paid to the advised procedure for commissioning.

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Explosion of H2 in a pipeline for Carbon Dioxide

Firm : Porsgrunn, Norway

Introduction : 1. The separated carbon dioxide from ammonia synthesis gas is sent for release in 2 steps by depressurization. 2. The CO2 is then sent for liquefaction and distribution. 3. This CO2 mainly contains 2-3% hydrogen. 4. A trip system has been installed in order to shut down the transfer if the hydrogen exceeds 8%. Incident : 1. After a shut down in the firm, the hydrogen analyzers exceeded 10%. 2. Signal from only one of the analyzers was sent to the trip system. 3. Consequently the ESDV (Emergency Shutdown Valve) did not close allowing hydrogen enriched gas to enter the pipeline. 4. The gas flow was estimated to be 1000-3000 m3/h with gas containing up to 75% hydrogen. 5. Hydrogen s extremely combustible. Mixtures containing more than 4% hydrogen and 25% hydrogen will easily ignite Causes : 1. The investigation team concluded that the damaged line must have been filled with a mixture containing more than 10-15% air and 40% H2. Corrective Actions : 1. The trip system was modified from two out of two to two out of three analyzers (one for low CO2, two for high H2. 2. Separate sampling lines with block valves have been installed for each analyzer in order to eliminate common mode failure. 3. The trip limit has been changed from 8 to 6%. Recommendations : 1. Vital trip systems must be separated other systems. 2. Process knowledge must not be limited to normal operation or design operation but includes understanding of possible deviations, especially during startups and shutdowns.

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Low Temperature Methanation

Firm : Yara International ASA, Netherlands

Introduction : 1. A new methanation catalyst charge was installed to operate at a lower temperature 210-20 degrees celcius, significantly lower than the normal operating temperature of 290-310 degrees celcius. 2. The first aim was operation of the inlet/outlet heat exchanger well below Nelson Curve Limit to avoid hydrogen cracking. 3. The second aim was improved plant efficiency due to HP steam savings . Incident: 1. The analyses of gas leaving the methanator revealed the presence of higher hydrocarbons (ethane, propane, butane, pentane). Causes: 1. The formation of higher hydrocarbons can only be explained by occurrence of Fischer Tropsch reaction. 2. Though Nickel has a selectivity for mrthanation but some authors report formation of higher hydrocarbons at temperature below 280 degrees celcius. 3. Results at different inlet/outlet conditions:Inlet/oulet (oC) 215/241 225/253 235/262 245/272 255/282 Corrective Actions : 1. Brown and Root Process which consists of molecular sieves and a cold box after the methanator. 2. Butane and pentane are absorbed in the molecular sieves while ethane and propane are liquefied in the cold box. C2H6 (ppm) 8.4 6.7 6.7 6.3 3.7 C3H8(ppm) <1 <1 <1 <1 <1 60 40 30 23 18 C4H10(ppm) 11 9 6 5 5 C5H12(ppm)

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Replacement of 22 year old secondary reformer

Firm : Gulf Petrochemicals Industries Co.

Incident : 1. During the shutdown of 2005 an inspection of secondary reformer lining was done at the dome area and the area above the catalyst bed. 2. The mortar joints and the brick shapes had eroded strongly due to the hot process gas. 3. The hot face of the bricks was glazy caused by the advanced operation time and hot process gas. 4. The expansion gaps at the expansion joints were found to have increased and might not close completely during the operation. 5. Due to the joint conditions, a potential risk of gas bypassing could not be excluded. Silica based refractory MERIT It has good insulating property. DEMERIT Hydrogen reacts with solid silica to form SiO gas. If condensation of this gas takes place, fouling at the downstream heat exchangers could be a typical result.

Corrective Actions : 1. Replacement of the whole refractory during turnaround. The coast of this option was low than calling a shutdown for 50 days and going for repairs. 2. I n the new design the internal ring burner was removed and instead a ring shaped air header was provided outside which allowed injection of inlet air at high velocity at an angle. This creates a vortex and helps in better mixing of the gas. 3. The height was increased to have sufficient residence time. 4. Silica free lining in the new refractory. 5. The new lining is made up of bubble alumina. The insulating properties are not as good as silica, thus water jacket is designed for a skin temperature of 260 degrees celcius.

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Explosion of Auxiliary Boiler

Firm : Petrokemija dd Kutina, Fertilizer Company, Croatia

Introduction : 1. The auxiliary boiler is the heart of steam generation system, it generates steam at 328 degrees celcius and 126 bar. 2. The circulation through coils is thermosiphon. Incident : 1. On May 2002, the ammonia plant was being started up after a 4 day shutdown. 2. While the auxiliary boiler pilot was being lit, suddenly an explosion happened. 3. The walls of the auxiliary boiler and parts of the convection suction walls were damaged. Damage : 1. 2. 3. 4. The flue gas duct which joins the auxiliary boiler and superheater flew apart Roof panels were blown out. All the auxiliary boiler insulation was blown. The baffles in the duct from the auxiliary boiler and super heater were damaged.

Recommendations : 1. The firing system should comply with the European Standard EN 12952. 2. Fuel supply line should have two safety shut off valves. The safety trip valves should have a built in device to test leaking valves. 3. It is necessary to monitor if the air is in excess for firing by measuring the air flow and pressure. Separate equipment for regulation and control of air/fuel ratio should be provided. 4. The igniters should be provided with equipment that ensures lighting of the burners in a safe time. 5. Burner Management System which receives signal from control and safety devices and sends control commands, controls the startup sequence, supervises the burner operaton and causes controlled shutdown if necessary.

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Skimming of LTS Catalyst

Firm : Engro Chemicals Pakistan Limited Incident : 1. In March 2002, during routine monitoring of the plant pressure profile, higher pressure drop (9 psi) was observed across the LTS Convertor against a normal pressure of 5 psi. 2. Further it was revealed that this pressure drop was increasing at a rate of 1.3 to 2 psi/month. 3. Overall heat transfer coefficient of the Waste Heat Boiler located upstream of LTSS also decreased. Causes : 1. High Temperature Shift Convertor strainer was damaged. 2. High Temperature Shift Convertor Catalyst was being carried over to downstream circuit, it increased in increase with the mass flow. 3. HTSC Catalyst dust was fouling the tube side of Waste Heat Boiler. 4. HTSC dust was being deposited on the LTSC Catalyst bed causing additional pressure drop. Remedial Actions : 1. Steam/Gas ratio was reduced from 2.8 to 2.6. It reduced the mass flow of gas passing through HTSC and hence the dust carryover reduced. 2. The four year old catalyst of HTSC was replaced. 3. The bottom strainer of HTSC was inspected and a gap of 0.1 in between the bottom plate of strainer and HTSC Vessel was welded. 4. To remove pressure drop, top 1 ft layer of the LTSC Catalyst was skimmed off in N2 environment.

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Loading of catalysts in Steam Reforming using the Spiral Load Method

Introduction : 1. The Topsoe Spiral Load Method has been proved an excellent alternative to the existing loading methods not only with regard to loading quality but also to loading speeds. Why dense/uniform loading : 1. If the catalyst is not loaded uniformly, then the flow distribution will deviate resulting in a variation n the tube wall temperature. 2. If densely packed then there s no risk of setting to an extent that the upper part of the tubes do not contain catalyst and become hot. Design : 1. Equipment consists of a no. of equally sized tube section with spiral shaped guide elements placed along the inner walls. The tube sections can be assembled and inserted in the reformer tubes to form one long loading tube. 2. When the catalyst is loaded, the velocity of the ccatalyst particles is reduced as the particles travel downwards in a helical movement. 3. At the end of the bottom loading tube a steel wire is attached. At predetermined positions, small copper (tellurites) pieces are securely fixed on the wire. These serve a dual function in carrying the loading tubes and fixing their position to give the desired falling distance of the catalyst. 4. If the loading rate is high the catalyst will pack densely and uniformly. 5. In order to control the amount of catalyst, the catalyst is fed to the tubes using a special vibrating funnel system called loader. Comparison : 1. The effective loading time with Spiral Load was found to be half the time used when loading with Socks Load. 2. The standard deviation in the pressure drops was approximately half when using Spiral Load indicating more uniform loading.

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Cooling Water System for reliable Ammonia Plant Operation

Firm : India Ammonia Plant, Tata Chemicals Limited, Babrala

Problem : 1. Microbiologically Induced Corrosion are aggravated by minor process leaks. 2. The process gases in an ammonia plant leaking into cooling water contains nutrients such as ammonia, nitrogen, hydrogen and methane whish lead to proliferation of harmful bacteria. 3. Presence of phosphate, nitrates and organic matter in the cooling water stimulate the growth. 4. Despite very good microbial control in circulation water, biofilms are formed in the coolers and minor leaks of hydrogen reduce the Oxygen Reduction Potential which results in profuse growth of microbial biofilms. Recommendations : 1. Cooling Water should be kept on the tube side to avoid problems of low velocity. 2. The tube metallurgy may have to be SS or duplex to reduce the adherence of biofilms. 3. Minor process leaks in coolers leads trapped gases in the dead zones of end covers causing slime and growth of biomass. Proper vent nipples should be provided for flushing the dead ends. 4. The local biocide dosing in exchangers shall avoid biofilm formation inside the tube and avoid pitting. 5. The Cooling Water circuit should not be kept stagnant. Wet shutdowns with stagnant water create an ideal environment for the growth of bacteria. 6. Plate heat exchangers must be used as they have good flow turbulence to reduce biofouling. 7. Instead of a single cooling tower, the system can be split into different towers so that different corrosion and microbial treatment programs can be followed. 8. Side stream filters should have should have minimum hold up volumes to avoid the dead zones as they become breeding grounds for bacteria. 9. Open self cleaning gravity filters are better than the closed pressure sand filters as the clean up is simple and biocide can be dosed any time after visual inspecton. 10. Make use of plastic material in the tower construction as lumber supports growth of algae, fungi and bacteria. 11. Locate the cooling towers as per wind flow to ensure that process emissions do not enter the cooling towers.

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Natural Gas Preheater Fire

Firm : Kribhco Ltd, Surat

Incident : 1. On 9th May, 1998, fire at thee bottom of the preheater and black smoke from the stack was observed. 2. A small fire inside the preheater blazed for 50 mins due to the crossing of ammonia battery limit valve. Damage : 1. 2. 3. 4. In the radiant section, vertical tubes were bent. Tubes and fins in the convection section were severely damaged. The support plate in the convection section had partially melted. Because of the rupture of one tube in the radiant section, the surrounding refractory in the radiant section had fallen down. 5. There was additional damage to the aluminium sheets of insulation of cobalt molybdate catalyst bed vessel, control valves of the fuel system and the cable trays. Causes : 1. Back firing of burners due to blocking of the burner tips. 2. There was no appreciable rise in the temperature controller and the reason was that the flow through the coil was low and the sensor was located far away from the furnace outlet. 3. The fuel to the preheater was not cut off immediately. 4. The valve was releasing slightly despite the complete closure. 5. Dislocation of the radiant tube assembly from the top support and tilted tube coming closer to the flame was guessed. 6. Direct impingement of burner flame on the tube due to the partial blockage of tube was also anticipated. 7. Prolonged over heating of the tubes due to considerably low flow. Remedial Actions : 1. 2. 3. 4. A trip control system was installed to maintain minimum flow to avoid overheating of the coil. Quick closing motor operated on the HP and LP gas line. Burner cleaning is scheduled in each turnaround to ensure stable flame conditions. Routine inspection of furnace of preheater to check proper geometry, impingement of flame, hot spots etc. 5. Circular holes have been provided to ensure smooth expansion and these holes have been insulated.

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Improvement in the Reformer Performance by switching over to a highly active Reforming Catalyst
Introduction : 1. The Toyo Engineering Corporation developed a highly active steam reforming catalyst, named G90EW-ISOP catalyst for hydrogen and syngas production light to moderate level hydrocarbon level natural gas. Activity : 1. Ni/Al2O3 with alkali or MgO is a constitution of conventional reforming catalyst. Pore structures of all these become similar due to the sintering of supports under operations at high temperature i.e between 500 and 800 degrees celcius. These have large diffusional resistance. 2. On the other hand the ISOP catalyst prepared by thermally stable components has bimodal pore structure comprising of mesopore or micropore as well as macropore structure. 3. The effectiveness factor of ISOP is high without any sacrifice of nickel dispersion. 4. The macropore reduces the pore diffusional resistance, thus, increasing the effective diffusivity
000 0000 000 00 000000 00000 000000 00000 000000 0000 00000 00000000

Macropore

Mesopore

Coke Resistance : 1. The amount of carbon deposited on the ISOP Catalyst is reported to be 1/3 of the amount deposited on the conventional catalyst for the same operation. 2. It is anticipated due to lower coke precursor on well dispersed nickel since coking reaction is competitive to the steam reforming. Benefits : 1. ISOP has 3-4 times higher activity. 2. Higher activity makes an approach to the equilibrium smaller, which requires lower temperature at the outlet. 3. Lower temperature means less fuel usage and thus it achieves 1.6% to 2% fuel savings. 4. Using Larsen-Miller Diagram it can also be shown that lower temperature results in extension of tube life. 5. The skin temperature decrease makes thinner tubes applicable and no. of tubes reduce which results in large cost reduction

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9. Appendix I. Dry Chemical Powder used in Extinguishers

Monoammonium phosphate : also known as "tri-class", "multipurpose" or "ABC" dry chemical, used on class A, B, and C fires. It receives its class A rating from the agent's ability to melt and flow at 177 C (350 F) to smother the fire. More corrosive than other dry chemical agents. Pale yellow in color.

Sodium bicarbonate : "regular" or "ordinary" used on class B and C fires, was the first of the dry chemical agents developed. In the heat of a fire, it releases a cloud of carbon dioxide that smothers the fire. That is, the gas drives oxygen away from the fire, thus stopping the chemical reaction. This agent is not generally effective on class A fires because the agent is expended and the cloud of gas dissipates quickly, and if the fuel is still sufficiently hot, the fire starts up again. While liquid and gas fires don't usually store much heat in their fuel source, solid fires do. Sodium bicarbonate was very common in commercial kitchens before the advent of wet chemical agents, but now is falling out of favor, as it is much less effective than wet chemical agents for class K fires, less effective than Purple-K for class B fires, and is ineffective on class A fires. White or blue in color.

Potassium bicarbonate (aka Purple-K) : used on class B and C fires. About two times as effective on class B fires as sodium bicarbonate, it is the preferred dry chemical agent of the oil and gas industry. The only dry chemical agent certified for use in ARFF by the NFPA. Violet in color.

Potassium bicarbonate & Urea Complex (aka Monnex/Powerex) : used on Class B and C fires. More effective than all other powders due to its ability to decrepitate (where the powder breaks up into smaller particles) in the flame zone creating a larger surface area for free radical inhibition. Grey in color.

Potassium Chloride, or Super-K: dry chemical was developed in an effort to create a high efficiency, protein-foam compatible dry chemical. Developed in the 60s, prior to Purple-K, it was never as popular as other agents since, being a salt, it was quite corrosive. For B and C fires, white in color.

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II. Drager Tubes for detection of gases

1. The basis of any direct reading Drager-Tube is the chemical reaction of the measured substance with the chemicals of the filling preparation. Since this reaction leads to a discoloration, the Drager-Tubes can also be called colorimetric chemical sensors. The substance conversion in the Drager-Tube is proportional to the mass of the reacting gas. 2. When a this indication is not practical, the alternative is a Drager-Tube with the indication based on interpretation of color intensity according to a given reference standard or set of standards. 3. The Drager-Tube user has many options available when using Drager-Tubes.Some examples are provided below. 4. One of the classic Drager-Tube reactions is the conversion of iodine pentoxide under acidic conditions to iodine by reaction with carbon monoxide. While it is basically a class selective reaction for the measurement of easily oxidizable substances, the selectivity can be increased by suitable prelayers. 5. Since chlorinated hydrocarbons are not indicated by direct colorimetric reaction, an oxidative cleavage of the molecule is necessary as a first step. This reaction is either done with potassium permanganate or chromium (VI) compounds, which forms elementary chlorine. The chlorine then reacts with the reagent preparation in the indicating layer to produce the colorimetric reaction product. 6. The oxidation reaction of C=C double bonds with potassium permanganate is the basic reaction of the Drager-Tubes for the measurement of olefins (i.e. alkenes). 7. The limits of the gas detection method must be considered when attempting to conduct an analytical determination

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III. Chemiluminescence
1. Chemiluminescence (sometimes "chemoluminescence") is the emission of light (luminescence), as the result of a chemical reaction. There may also be limited emission of heat. Given reactants A and B, with an excited intermediate , 2. [A] + [B] [] [Products] + light 3. The decay of this excited state[] to a lower energy level causes light emission. In theory, one photon of light should be given off for each molecule of reactant. This is equivalent to Avogadro's number of photons per mole of reactant. 4. In a chemical reaction, reactants collide to form a transition state, the enthalpic maximum in a reaction coordinate diagram, which proceeds to the product. Normally, reactants form products of lesser chemical energy. The difference in energy between reactants and products, represented as , is turned into heat, physically realized as excitations in the vibrational state of the normal modes of the product. Since vibrational energy is generally much greater than the thermal agitation, it is rapidly dispersed into the solvent through solvent molecules' rotation and translation. This is how exothermic reactions make their solutions hotter. 5. In a chemiluminescent reaction, the direct product of a reaction is delivered in an excited electronic state, which then decays into an electronic ground state through either fluorescence or phosphorescence, depending on the spin state of the electronic excited state formed. This is possible because chemical bond formation can occur on a timescale faster than electronic transitions, and therefore can result in discrete products in excited electronic states.

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IV. Types of Stainless Steel

1. Type 102austenitic general purpose stainless steel working for furniture 2. 200 Seriesaustenitic chromium-nickel-manganese alloys a. Type 201austenitic that is hardenable through cold working b. Type 202austenitic general purpose stainless steel 3. 300 Seriesaustenitic chromium-nickel alloys a. Type 301highly ductile, for formed products. Also hardens rapidly during mechanical working. Good weldability. Better wear resistance and fatigue strength than 304. b. Type 302same corrosion resistance as 304, with slightly higher strength due to additional carbon. c. Type 303free machining version of 304 via addition of sulfur and phosphorus. Also referred to as "A1" in accordance with ISO 3506.[6] d. Type 304the most common grade; the classic 18/8 stainless steel. Outside of the US it is commonly known as "A2 stainless steel", in accordance with ISO 3506 (not to be confused with A2 tool steel).[6] e. Type 304Lsame as the 304 grade but lower carbon content to increase weldability. Is slightly weaker than 304. f. Type 304LNsame as 304L, but also nitrogen is added to obtain a much higher yield and tensile strength than 304L. g. Type 308used as the filler metal when welding 304. h. Type 309better temperature resistance than 304, also sometimes used as filler metal when welding dissimilar steels, along with inconel. i. Type 316the second most common grade (after 304); for food and surgical stainless steel uses; alloy addition of molybdenum prevents specific forms of corrosion. It is also known as marine grade stainless steel due to its increased resistance to chloride corrosion compared to type 304. 316 is often used for building nuclear reprocessing plants. 316L is an extra low carbon grade of 316, generally used in stainless steel watches and marine applications, as well exclusively in the fabrication of reactor pressure vessels for boiling water reactors, due to its high resistance to corrosion. Also referred to as "A4" in accordance with ISO 3506.[6] 316Ti includes titanium for heat resistance, therefore it is used in flexible chimney liners. j. Type 321similar to 304 but lower risk of weld decay due to addition of titanium. See also 347 with addition of niobium for desensitization during welding. 4. 400 Seriesferritic and martensitic chromium alloys a. Type 405ferritic for welding applications b. Type 408heat-resistant; poor corrosion resistance; 11% chromium, 8% nickel. c. Type 409cheapest type; used for automobile exhausts; ferritic (iron/chromium only). d. Type 410martensitic (high-strength iron/chromium). Wear-resistant, but less corrosionresistant. e. Type 416easy to machine due to additional sulfur f. Type 420Cutlery Grade martensitic; similar to the Brearley's original rustless steel. Excellent polishability. g. Type 430decorative, e.g., for automotive trim; ferritic. Good formability, but with reduced temperature and corrosion resistance. h. Type 439ferritic grade, a higher grade version of 409 used for catalytic converter exhaust sections. Increased chromium for improved high temperature corrosion/oxidation resistance.

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5. 500 Seriesheat-resisting chromium alloys 6. 600 Seriesmartensitic precipitation hardening alloys a. 601 through 604: Martensitic low-alloy steels. b. 610 through 613: Martensitic secondary hardening steels. c. 614 through 619: Martensitic chromium steels. d. 630 through 635: Semiaustenitic and martensitic precipitation-hardening stainless steels. i. Type 630 is most common PH stainless, better known as 17-4; 17% chromium, 4% nickel. e. 650 through 653: Austenitic steels strengthened by hot/cold work. f. 660 through 665: Austenitic superalloys; all grades except alloy 661 are strengthened by second-phase precipitation. 7. Type 2205the most widely used duplex (ferritic/austenitic) stainless steel grade. It has both excellent corrosion resistance and high strength. 8. Type 2304lean duplex stainless steel. Similar to 2205 for strength but with lower pitting corrosion resistance due to low Molybdenum\

V. Phosphonates and Azoles

1. Phosphonates or phosphonic acids are organic compounds containing C-PO(OH)2 or C-PO(OR)2 groups (where R=alkyl, aryl)

2. An azole is a class of five-membered nitrogen heterocyclic ring compounds containing at least one other non-carbon atom of either nitrogen, sulfur, or oxygen. The parent compounds are aromatic and have two double bonds The numbering of ring atoms in azoles starts with the heteroatom that is not part of a double bond, and then proceeds towards the other heteroatom.

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10. Bibliography
The references for this report are listed below : Ammonia Training Manual, Indo Gulf Fertilizers , Jagdsihpur Urea Training Manual, Indo Gulf Fertilizers , Jagdishpur Ammonia Technology Manual, Indo Gulf Fertilizers , Jagdishpur Urea Technology Manual, Indo Gulf Fertilizers , Jagdishpur Utilities Training Manual, Indo Gulf Fertilizers , Jagdishpur Buecker B, CPI water and steam chemistry, Chemical Engineering, Vol. 115, No. 2, February 2008, pp 30-34 Buecker B, Steam Genaration, Thermodynamcs 101, Power Engineering, Vol. 112, No.11, November 2008, pp 106-114 AiChE Technical Manual, Ammonia Safety and other related issues, Vol. 40, Vol. 41, Vol. 44, Vol. 49, Vol. 50, Vol 52. Safety Handbook, International Fertilizer Industry Association

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