UREA A BRIEF HISTORY:

First synthesized in 1828 from ammonium cynate by the scientist Woehler.

HCNO +NH3 = NH4CNO (AMMONIUM CYNATE) (CYNIC ACID) NH4CNO = NH2CONH2(urea)

In 1870 ,Bassarow produced urea by dehydrating ammonium carbamate. In 1920,I.G.Farben built a plant in Germany based on ammonium carbamate process. IN 1950,the world urea production was less than 1 lakh tones & In 1960 was less than 5 lakh tones. Actual demand started in 1960s.

Why Urea used as a fertilizer?

Nitrogen

content is highest per Kg . Cheaper as compared to other fertilizers. Not a flammable or explosive substance. Not a toxic substance. Have a better flowing characterstics.

Properties of urea:
Mol.

Wt: 60.047 Melting point at 1 atm: 132.47*c Specific gravity at 20*C: 1.335 Bulk density: 672.756 kg/m3. Angle of repose: 23*

UREA SYNTHESIS REACTION

1) 2NH3+CO2=NH2COONH4+37.64Kcal/Mole
Ammonium carbamate Fast & Exothermic

2) NH2COONH4=NH2CONH2+H2O-6.32Kcal/Mole
Urea Slow & Endothermic

Reaction No.1-given above is exothermic in nature and 37.64 K.Cal of heat is produced in the formation of Amm.Carbamate. Reaction No.2 is endothermic and 6.32 K Cal. is consumed in the dehydration of Ammonium Carbamate.

Parameter effecting the synthesis reaction: Pressure Temperature NH3/CO2

Ratio H20/C02 Ratio Residence Time

1.Pressure

Higher pressure favors the urea formation. The equilibrium pressure becomes higher & higher when reactor temperature increases. Pressure has to be higher than the dissociation pressure of carbamate at reactor temperature.

2.Temperature

The rate of conversion is propersionaly increases with temperature but maximum equilibrium yield is obtain at around 195-2000c Higher leads to corrosion.

NH3/CO2 Ratio

Increase of NH3 or CO2 increases the conversion. Theoretical ratio is 2 but at conversion is only 43.5% at 170atm/1550c. When N/C ratio increase from 2 to 9 the conversion increase from 43.5% to 85.2%. When N/C ratio change from 2 to 0.5 the conversion increase from 43.5% to 46%. The soln become corrosive under CO2 rich condition. N/C ratio range from 3 to 5.

H20/C02 Ratio

Excess water disturb the urea formation. Excess water recycle reduces the reactor volume w.r.t to reactants. Too low causes clogging in the system. Optimum ratio 0.4-1.0.

Residence Time
Higher

residence time : Higher conversion. Higher residence time increase capital cost. Min RT to attain equilibrium :20 min.

VARIOUS UREA PROCESS TECHNOLOGIES

Once

Through process. Partial Recycle process. Total Recycle process . <a> Conventional process <b> Stripping process.

Disadvantage of once through/ partial recycle process:

Lower conversion efficiency. Higher energy consumption. Dependence on other fertilizers unit. Higher capital cost.

DIFFERENCE BETWEEN CONVENTIONAL AND STRIPPING PROCESS

Conventional Process:

DEFINATION-The process based on the 1st principal of decrease in pressure and increase in temperature and than have a series of decomposition stage where the Reactor discharge is treated in successively at lower pressure. PRESSURE OF REACTOR- More than 200 ata UTI----210 Ata MTC---250 Ata CPI----380-400 Ata MONTEDISON---210 Ata CONVERSION-CONVERSION HIGH WATER CARRYOVER i.e. Recycling Water carryover high about 10%,because high differential pressure. ENERGY-High energy due to high pressure and water recycling. FUTURE-Due to high energy and high cost of liner, no future.

Stripping Process ;

To reduce the partial pressure of product by swamping the system by one of the reactant which reduce the partial pressure of other reactant considerable without changing the total pressure either CO2 or NH3 or both can be used as a stripping agent. Below than 200 Ata
STAMICARBON-------------140 Ata SNAMPROGETTI-------------158Ata IDR--------------------------------180Ata ACES----------------------------175 At ACES-21-------------------------155 Ata

CONVERSION COMPARATIVELY LOW Water carryover low about 3-4% because stripping at same pressure of Reactor. Low energy due to low pressure and less recycling of water. Future bright due to introduction of submergible carbamate condenser/pool condenser, reactor LOW ENERGY,LOW COST,FUTURE BRIGHT.

Basic difference b/w different Process:

Method of feeding of reactants. Method of recovering unconverted NH3 & CO2. Mode of recovering unconverted NH3 & CO2. Method of separating Reaction Water from Urea solution.1) Vacuum concentration, 2)Crystallization route. Method of heat recovery or utilization from condensation of vapours. Mode of product finishing. 1) Prilling 2) Granulation

1)MONTEDISON TOTAL RECYCLE PROCESS ( NFL, Nangal )

It

is a Montedison total recycle process Revamped by M/S Urea casale. 1000 MTPD Plant was installed in April, 1978. Plant capacity increased to 1450 MTPD using HEC process & HET. Commercial production after revamping started on Feb 1st,2001.

PLANT DESCRIPTION

Reciprocating CO2 Compressor & H.P. Pumps Urea synthesis. Urea separation. Recovery section. Vacuum section. Prilling section. Waste water section.

UREA SYNTHESIS

Urea Reactor { Old } Volume 50m3 No. of trays 14 Type of trays High eff. Casale trays Temp. bot/top 188/198*C Pressure 220 Kg/cm2 Liner SS 316 L UG Thickness 12mm ( orignal )

UREA SYNTHESIS

UREA REACTOR { NEW } Volume 33m3 No. of trays 9 Type of trays High eff. Casale trays Temp. bot/top 188/198*C Pressure 220 Kg/cm2 Liner 2rRE69 Thickness 8mm ( orignal )

UREA SEPARATION

1st decomposition stage: Pressure-70 kg/cm2 Temperature-188*c Urea concentration-54.5% 2nd decomposition stage: Pressure-12 kg/cm2 Temperature-150*c Urea concentration-65% 3rd decomposition stage: Pressure-3 kg/cm2 Temperature-130*c Urea concentration-72% The 72% urea solution is now send to vaccum section through candle filter.

RECOVRY SECTION
Pressure Temp. Outlet

1.5 Kg/cm2 125*C 0.04% 1.0%

condition -NH3 -Urea

VACCUM SECTION

1st vaccum section: Pressure-0.3 ata Temperature-128*c Urea concentration-95% 2nd vaccum section Pressure-0.04 ata Temperature-138*c Urea concentration-99.6%

PRILLING SECTION

Tower height:104.5 mtr Free fall height: 80mtr Urea in emission: 43mg/Nm3 Scrapper: Conical Air flow:8,00,000 Nm3/hr.

MONTEDISON TOTAL RECYCLE PROCESS OVER MITSU TOATSU TOTAL RECYCLE PROCESS
Advantages:

High grade heat recovery. Energy consumption less. Water recycle is less. Disadvantages: Conversion efficiency is less

SNAM PROGETTI PROCESS (NH3 STRIPPING) , NFL Vijaipur.

To mark the development of the technology just a few milestones are indicated , very significative and very robust. 1966-Snamprogetti builds its first 70 MTPD urea plant in Gela Italy 1971-Snamprogetti builds the first industrial urea plant at Nera Montoro,Terni Italy.300 MTPD 1982-Snamprogetti completes the Worlds largest worldwide single stream urea plant project of its time at Baruch,India 1800MTPD 1983-Snamprogetti completes its time urea granulation project at pont Lisas. Trinidad/Tobago 810X2 MTPD 1990- In 1990 more than 20 urea plants were built in China alone.

2001-Snamprogetti completes Worlds largest single urea project in BAHIA BLANCA ARGENTINA 3250 MTPD. 2002-Snamprogetti achieves the remarkable figure of 100 plants based on its proprietary technology. Introduction of total Zirconium stripper in 2004. The development of further Jumbo plant design (up to 5000TPD single train urea synthesis) the largest root ammonia urea plant under implementation with an overall capacity of 5000 TPD of urea for OMAN INDIAN FERTILIZERS CO-OMIFCO,OMAN More steam production in the carbamate condenser by installing the carbamate preheater. Less steam consumption in the vacuum concentrator by installing the vacuum preconcentrator

OPERATING PARAMETER OF THE PROCESS

Reactor pressure: 160 kg/cm2 Reactor temperature: 190*c NH3/CO2 Ratio: 3.6:1 CO2 conversion:65% Stripper temp. Top/Bottom:188/206*c Pressure L/D stages:17/3.5ata Evaporation Stages:0.3/0.03 ata Reactor liner:SS316LM Stripper liner:2RE69/Ti/Zr Stripper outlet composition: NH3=34.3% ,CO2=5.8%

EFFECTS OF EXCESS AMMONIA

Avoid

corrosion. Promotes Stripping. Higher conversion Less biuret content. Flexibility in operation. Less passivation air.

UNIQUE FEATURE INTRODUCE BY SNAM PROGRETTI

The

installation of ejector. Use of centrifugal compressor. Bimetallic tubes, Design of horizontal layout. Low pressure and low temperature. Stripping at reactor pressure.

SNAM PROGETTI PROCESS

ADVANTAGES: -Low operating pressure & temperature. -Only a single decomposition stage. -Low capital cost. DISADVANTEAGES: -More corrosion problem. -Conversion efficiency is low

THE IMPROVED ACES (ACES-21) PROCESS

In CO2 stripping technology, the reactor, the largest and the heaviest vessel in urea in urea plant , is normally installed at 20-22 meter level so as to feed urea synthesis solution to the stripper by gravity. If the reactor is installed on the ground level, civil and erection cost can be greatly reduced . TEC and PT pupak Sriwidjaja (PUSARI,Indonesia) have jointly improved the existing ACES process aiming at installing the reactor on the ground level, maintaining advantages of ACES process concepts based on proven CO2 stripping technology. The two stage synthesis concept of combination of VERTICAL SUBMERGED CARBAMATE CONDENSER(VSCC) and the reactor is employed to enable the reactor to be installed on the ground level and to simplify the synthesis loop. The forced circulation of the synthesis loop driven by HP Carbamate ejector also makes the CSCC be installed on fairly low elevation. (*) ACES: Advanced process for Cost and Energy Saving urea production

DESCRIPTION OF ACES (ACES-21) SYNTHESIS SECTION

Figure shows the improved ACES (ACES-21) process synthesis section consisting of a reactor , a stripper and a carbamate condenser. An HP Carbamate ejector provides the driving force for circulation in the synthesis loop instead of gravity for the original ACES. Liquid ammonia is fed into the reactor via the HP ejector. Most of the CO2 with small amount of passivation air is fed to the stripper as a stripping medium and a raw material for urea synthesis and the rest is fed to the reactor . The REACTOR is operated at---N/C RATIO 3.7 PRESSURE 155 Kg/cm2 TEMPERATUR 182O C CONVERSION 63% and the VSCC is operated at-----N/C RATIO 3.0 PRESSURE 155Kg/cm2 ,TEMP1800C

VERTICAL SUBMERGED CARBAMATE CONDENSER (VSCC)

The vertical carbamate condenser (VSCC) function to: Condense NH3 & CO2 gas from the stripper to form Ammonium Carbamate in the shell side. Synthesize urea by dehydration of Ammonium Carbamate formation by generating 5 Kg.cm2 steam in the boiler tube. ADVANTAGES OF THE VSCC High gas velocity,apprpriate gas hold up and sufficient liquid depth in the bubble column promote mass and heat transfer, resulting in 30% reduction of heat transfer area from original ACES Carbamate Condenser. The appropriate number of baffle plate distribute gas bubbles in the column effectively without pressure loss. A vertical design invertible requires smaller plot area.

ACES-21

VSCC

Stamicarbon MEGA Urea Plant

Stamicarbon, the leading Urea process licensor, now ready to offer their latest developed Mammoth single train Urea plant up to a plant capacity 4500 TPD. The technology is based on Pool reactor/Condenser. Plant is equipped with medium pressure recycle stage without a separate Ammonia loop with the advantage of low water concentration in recycle carbamate resulting in high conversion and lower steam consumption. Investment cost involved for MEGA capacity concept is 70Investment 7075% as compared with standard 2000 TPD Urea Plant. High pressure steam consumption is considerably less in MEGA Urea plants.

This new Urea process is an improved CO2 stripping technology, comprising application of pool condenser, pool reactor and a number of other significant improvements. Results of these improvements are mainly lower investment costs now required for the CO2 stripping synthesis section and generally a better reliability of the HP synthesis. Investment for the other downstream parts of the urea plant are by the new technology not affected. The lowest possible consumption figures, better operation flexibility and lower operating costs are characteristic for this new technology as well. Stamicarbon improvements of the previous CO2 stripping technology can be realised in two ways. The first one, suitable for the debottlenecking of the old urea plants especially, is application of the HP pool condenser.

Pool condensation is characterised by additional reaction volume, higher operating temperature, lower pressure drop, less cooling area, non sensitive behaviour to deviations of NH3/CO2 ratios and by the absence of inverse response phenomena . The application of the HP pool reactor established a totally new concept for the whole HP synthesis. The arrangement of the HP pool reactor greatly simplified the original HP synthesis loop.

Besides the same advantages as for the HP pool condenser further features concerning investment costs as well as technology arise. Basis for lower investment is the omission of costly HP vessel, HP ejector, far less HP ping in the synthesis section and lower steel and concrete structure. Pool reactor is installed in a horizontal position and in such a way the height of the plants has been immensely reduced. The baffles in the reactor prevent backmixing, so affording the nearest approach to equilibrium in the urea reaction and, consequently, the highest conversion and most economical downstream equipment sizing.

MAIN DIFFERENCE B/W UREA MANUFACTURING TECHNOLOGYS

Technology

Temp. *C 188 182 198 190

Pressur Ratio CO2 e NH3/CO2 conversi Kg/m2 on 155 140 155 220 175 3.6:1 2.9:1 3.1:1 2.9:1 2.9:1 65% 60% 63% 58% 68%

SNAMPRAGTI ACES21 MONTIDESION ACES

STAMICARBON 183

Conclusion
1) With the improvement in technology, the specific energy consumption vis cost of production has reduced considerably over last two decade. 2) Although, the conventional technologies are being improved continuously, but thrust should be given for improvement of unconventional technologies which promises use of renewable sources of energy and are environment friendly. 3) To improve these technologies, industry and educational institutions should join hands for the brighter future.