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Recent Achievements and Advances in Urea Technology


Toyo Engineering Corporation

8-1, Akanehama 2-chome, Narashino-shi, Chiba 275-0024, Japan INTRODUCTION
Since established in 1961, Toyo Engineering Corporation (TOYO), a global leading engineering contractor and urea process licensor, has licensed its technologies for over 100 urea plants including granulation units, sharing 1/4 of world urea production capacity as of January 2006. In 2000, TOYO and PT Pupuk Sriwidjaja (PUSRI) Indonesia, completed the R & D of its latest urea synthesis technology named ACES21 [1]. ACES21 is advantageous in low investment cost and low energy consumption for urea production. A major feature of this technology is that it reduces the number of equipment in the urea synthesis loop to simplify the system, which lessens construction costs with the installation of the reactor on the ground in CO2 stripping process (resultantly existing urea reactor can be re-utilized in revamp case). In addition, the operation conditions of synthesis section have been optimized under the lower operation pressure than the previous process. As a result, a remarkable reduction in energy consumption has been achieved. Another premium advantage of ACES21 is that it is flexible for various utility environment. Although in middle to large scale urea plant CO2 compressor is usually driven by steam turbine, it is sometimes required to be driven by electric motor depending on availability and cost of steam (water) vs. electricity. If CO2 compressor is driven by electric motor, excess low pressure steam usually utilized for admission to steam turbine must be exported. If no low pressure steam user is found outside the urea plant, it must be vented or condensed. Needless to say, it is waste of steam and energy. Even in case CO2 compressor is driven by electric motor, ACES21 enables the urea plant be operated without exporting low pressure steam. This process variation is also advantageous in case CO2 compressor is driven by 110 barG steam turbine because 110 barG top steam consumption can be minimized by limiting extraction steam consumption required for heating HP stripper. ACES21 has been first selected for modernizing a 1,620 mtpd conventional urea plant of Sichuan Chemical Works (Group) Ltd. (SCW) to increase production capacity to 2,460 mtpd and reduce energy consumption by 30%. The first ACES21 plant for SCW has been smoothly operated since its successful commissioning in 2004 [2]. The second but the first complete new urea plant based on ACES21 technology is for PT Pupuk Kujang Indonesia (see Photo-1). The fertilizer complex named Kujang-1B consists of 1,000 mtpd ammonia unit, 1,725 mtpd urea unit with ACES21 and associated service unit. The initial start-up of the urea plant on October 24, 2005 was very smooth and urea prills were produced only several hours after ammonia was initially fed to the plant. The performance test run conducted in January 2006 has demonstrated the important features of ACES21, i. e. low energy consumption, environment-friendliness and high operability [3]. In the same year 2006, TOYO was awarded two landmark contracts; one is an

engineering contract from MAN Ferrostaal AG (MFS) for the Chemical Fertilizer Complex planned by Methanol Holdings (Trinidad) Limited (MHTL) to produce Urea Ammonium Nitrate and Melamine, at Point Lisas Industrial Estate in Trinidad and Tobago; and the other is an license and PDP supply contract from PetroChina Tarim Petrochemical Company. The former contract is to license the ACES21 technology for a 2,100 mtpd Urea synthesis unit in Trinidad and the latter is to license TOYOs Spout-Fluid Bed granulation technology for a 2,640 mtpd granulation unit to be built in Korla, Xinjiang Autonomous Region, China. Upon completion of the first ACES21 urea plant, TOYO has started licensing technologies for so-called Jumbo Urea Plant over 3,000 mtpd capacity. Design and engineering up to 4,500 mtpd have completed and a number of proposals of 3,000 3,500 mtpd single train plants have been carried out. In early 2007, TOYO was awarded an epoch-making contract to supply license and to perform basic engineering to build a 3,250 mtpd Urea Plant in Iran. TOYOs ACES21 and Spout-Fluid Bed granulation technologies are being applied to the project. This paper reviews the latest advances in urea process technology; updated status of ACES21 process, and TOYOs approach to Jumbo Urea Plant.


Fig.1 shows a typical process flow sheet for ACES21 urea plant and Fig. 2 shows a schematic flow sheet of ACES21 synthesis section consisting of a reactor, a stripper and a carbamate condenser. Liquid ammonia is fed to the reactor via HP Carbamate Ejector which provides the driving force for circulation in the synthesis loop instead of gravity for the original ACES Process. Most of the carbon dioxide 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 as a raw material and to passivate the reactor. The reactor is operated at N/C ratio of 3.7, 182 - 184C and 152 barG. The CO2 conversion to urea is as high as 63 - 64% at the exit of the reactor. Carbamate solution from the carbamate condenser is fed to the reactor after being pumped by the HP ejector that is motivated by high pressure liquid ammonia. 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. Stripped urea solution is sent to MP decomposition stage to be purified further. The stripped off gas from the stripper is fed to Vertical Submerged Carbamate Condenser (VSCC), operated at N/C ratio of 2.8 - 3.0, 180 - 182C and 152 barG. Ammonia and CO2 gas condenses to form ammonium carbamate and subsequently urea is formed by dehydration of the carbamate in the shell side. Reaction heat of carbamate formation is recovered to generate 5 barG steam in the tube side. Packed bed is provided at the top of VSCC to absorb uncondensed ammonia and CO2 gas into recycle carbamate solution from MP absorption stage. Inert gas from the top of the packed bed is sent to MP absorption stage.






PROCESS FEATURES Low Elevation and Compact Layout

In CO2 stripping technology, the reactor, the largest and the heaviest vessel 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. TOYO and PUSRI have jointly developed ACES21 process aiming at installing the reactor on the ground level, maintaining advantages of CO2 stripping technology. The two stage synthesis concept in combination of VSCC and the reactor is employed to enable the reactor 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 VSCC be installed on fairly low elevation. As shown in Photo-1, HP equipment in the synthesis section is laid-out quite compactly in low elevation. The highest level in the synthesis section, that is VSCC top, is only 30 to 35m.

Vertical Submerged Carbamate Condenser (VSCC)

Fig. 3 illustrates a configuration of the Vertical Submerged Carbamate Condenser (VSCC) which functions to: (1) condense NH3 and CO2 gas mixture from the stripper to form ammonium carbamate in the shell side; (2) synthesize urea by dehydration of ammonium carbamate in the shell side; (3) remove the reaction heat of ammonium carbamate formation by generating 5 barG steam in boiler tubes. Advantages of the vertical submerged configuration of carbamate condenser are: (1) High gas velocity, appropriate gas hold up and sufficient liquid depth in the bubble column promote mass and heat transfer; (2) An appropriate number of baffle plates distributes gas bubbles in the column effectively without pressure loss; (3) A vertical design inevitably requires smaller plot area.

VSCC is categorized into a kind of bubble column reactor with boiler tubes. VSCC consists of the condensation-reaction section in the main cylindrical shell and the scrubbing section with packed bed in the top. The condensation-reaction section is equipped with a U-tube bundle and baffle plates. A down flow pipe connects the scrubbing section and the condensation-reaction section so as to feed carbamate solution from the scrubbing section to the bottom chamber of the VSCC by gravity. Mixed gas from the stripper is introduced and distributed into the bottom compartment as small bubbles via a gas sparger. Carbamate solution is introduced to the bottom compartment of the condensation-reaction section from the scrubbing section via the down-pipe as absorbent. From the bottom to the top of the condensation-reaction section, the mixed gas bubbles rise through the bundle of boiler tubes and partially condense, contacting with urea-carbamate solution. The condensation (carbamate formation) heat is removed by the boiler tubes in which saturated boiler water is circulated by a circulation pump. The shell side volume is sufficient to promote dehydration of ammonium carbamate to form urea at the conversion rate of 40 to 50%. Fig. 4 shows a result of a computational fluid dynamic (CFD) analysis for gas bubbles and solution in a compartment of VSCC. The rising bubbles in the central tube bundle area agitates the urea-carbamate solution to circulate between the space among bristled boiler tubes and the surrounding open annular space near the interior wall, giving high mass transfer between the gas bubbles and the absorbent urea-carbamate solution and high heat transfer between the carbamate solution and the boiler tubes. The bubbles enter the compartment through holes provided among the tube holes on the lower baffle plate, then rise in the space among the tubes and finally gather beneath the upper baffle plate to be re-distributed evenly as the form of small bubbles while passing through the holes on the baffle plate. Urea-carbamate solution enters a compartment from an opening provided on each baffle plate, then circulates, being agitated by the rising bubbles and exits to the next compartment through the next opening provided on the next baffle plate. Such carbamate formation heat removal - urea formation process cycle taking place in a compartment between two baffle plates repeats compartment-by-compartment from bottom to top, achieving high CO2 conversion to urea at the exit of VSCC


tube bundle area

open annular space

upper baffle plate

lower baffle plate



and efficient heat recovery in VSCC. The urea-carbamate solution leaving the top compartment on the top baffle plate is extracted through a down-pipe to be fed to the HP ejector. Mixed gas containing uncondensed ammonia and CO2 entrained by inert is introduced to the scrubbing part where the most of NH3 and CO2 is absorbed adiabatically into carbamate solution recycled from the downstream middle pressure stage while contacting counter-currently in a packed bed. The mixed gas which is rich with inert after scrubbing is sent to middle pressure stage for further treatment. Sufficient annular space is available between the U-tube bundle and the interior wall of the shell so that inspection and maintenance personnel can work and walk through. Tube thickness is precisely measured for full length of all the U-tubes from channel side by eddy current technique.

Optimized Synthesis Conditions

Fig. 5 shows CO2 conversion and equilibrium pressure vs. N/C. In ACES21 Process, the N/C ratio in VSCC differs from that in the reactor. VSCC is operated at N/C ratio of 2.8 3.0 where the equilibrium vapor pressure of urea-carbamate solution gives the lowest. This optimum N/C selection allows VSCC be operated at relatively high temperature (180 182 C) and low pressure (152 barG), rendering efficient heat transfer between the shell and the tube and higher reaction rate of ammonium carbamate dehydration to form urea as high as 45% conversion from CO2. The reactor N/C ratio is selected at 3.7 to maximize CO2 conversion with appropriate excess pressure to that of equilibrium. As inert gas fed to the reactor is only 1/5 of that of conventional CO2 stripping process, vapor fraction in the reactor decreases drastically and the reactor volume is fully utilized for urea synthesis reaction which takes place only in the liquid phase. Resultantly, high CO2 conversion of 63 - 64% is achieved in the reactor at relatively low temperature and pressure, i.e. 182 - 184 C and 152 barG. The higher CO2 conversion at lower synthesis pressure requires less decomposition heat in HP stripper and less energy for CO2 compression and liquid ammonia and carbamate solution pumping.
80 200




180 160 140 120 100





40 2 2.5 3





Unique Heat Integration Concept

The unique heat integration between the HP stage and MP/LP stages further reduces energy requirement (see Fig. 6). MP steam is supplied to HP stripper in synthesis section to decompose and separate excess NH3 and carbamate. The stripped NH3 and CO2 gas mixture is sent to the VSCC to form ammonium carbamate solution. The reaction heat (condensation heat) in VSCC is recovered by generating LP steam. The generated LP steam is utilized in medium pressure decomposition stage, in the low pressure decomposition stage and evaporation stage. The heat of ammonium carbamate formation in MP stage is also utilized to evaporate water in evaporation section. This multiple heat integration concept, originally invented and developed by TOYO, realizes the most energy efficient urea process.












Flexibility in Various Utility Environment

ACES21 is quite flexible for various utility environment. Although in middle to large scale urea plant CO2 compressor is usually driven by steam turbine, it is sometimes required to be driven by electric motor depending on availability and cost of steam (water) vs. electricity. If CO2 compressor is required to be driven by electric motor, excess low pressure steam usually utilized for admission to steam turbine must be exported. In such situation, if no low pressure steam user is found outside the urea plant, it must be vented or condensed. Needless to say, it is waste of steam and energy. Even in case CO2 compressor is driven by electric motor, ACES21 enables the urea plant be operated without exporting low pressure steam. High CO2 conversion in urea synthesis reactor, moderate stripping in HP stripper by adjusting steam pressure and efficient integration with 16.5 barG stage into the process minimize middle pressure (lower than 20 barG) steam consumption in HP stripper without sacrificing overall process efficiency. In such case, middle pressure steam consumption decreases to 0.58 metric ton per ton of urea product. This process flexibility is also advantageous in case CO2 compressor is driven by 110 barG steam turbine. Top steam flow for steam turbine for CO2 compressor must be more

than extraction steam required by the urea plant, mainly by HP stripper. In other words, if extraction steam quantity required for maximizing stripping efficiency in HP stripper is more than 0.7 mt/mt, top steam consumption may increase unnecessarily to 0.75 mt/mt or more so as to supply sufficient steam to HP stripper. In ACES21, as aforementioned, moderate stripping in HP stripper integrated with MP decomposition stage reduces MP steam consumption to 0.58 mt/mt, enabling full utilization of 110 bar steam energy and significant reduction of overall steam consumption including CO2 compressor to 0.69 mt/mt. Table I summarizes utilities consumption for the following four cases: (1) all rotating machines are driven by electric motor, LP steam is exported; (2) all rotating machines are driven by electric motor, steam system is self-balanced (no export); (3) CO2 compressor is driven by 42 barG steam turbine; (4) CO2 compressor is driven by 110 barG steam turbine.

Table I Typical Consumption Figures of ACES21 Urea Plant

Unit Electric Motor Driven Steam Turbine Driven

Steam Import 22 bar x 300 C 42 bar x 380 C 110 bar x 510 C Steam Export 5 bar, Saturated Cooling Water (T=10C) Electricity Process Granulation kWh kWh m3 ton ton ton ton

Steam Export

Self Balance

42 bar Steam

110 bar Steam


0.58 0.80 0.69

0.24 52 105 24 52 105 24 81 21 24 75 21 24

Notes: 1) unit: per metric ton of final granular urea product 2) including CO2 compression


At 21:15 on October 24, 2005, a brand-new urea plant located in Cikampek, West Jawa, Indonesia has produced urea prills only several hours after receiving liquid ammonia to its synthesis loop for the first time. The 1,725 mtpd urea plant has been designed and constructed by TOYO based on ACES21 technology as its second application in the world, following the urea plant revamp project for Sichuan Chemical Works China. On

January 17, 2006, as soon as conditions became ready, the fourteen days performance test run commenced together with ammonia plant. The performance test has been successfully completed and the ammonia-urea complex has been handed over to PT Pupuk Kujang, an Indonesian state-owned fertilizer company. Table II outlines the profile of the second ACES21 urea project called Kujang-1B.

Table II Kujang-1B Project Profile

Plant Capacity: Location: Ammonia Process: Urea Process: Project Scope: ammonia 1,000 mtpd / urea 1,725 mtpd Cikampek, West Java, Indonesia KBR conventional TOYOs ACES21 with prilled product turn-key lump sum in cooperation with Rekayasa and IKPT as J/V partner

Technological Features of Kujang-1B

TOYO considers the latest urea plant should be designed to meet recent increasing demand for safety, health and environment. The Kujang-1B urea plant embodies the latest technological advances, enhancing reliability, safety and environment protection feature in addition to its high energy efficiency originally given by ACES21. Table III shows technological features of the Kujang-1B urea plant.

Table III Technological Features of Kujang-1B Urea Plant

CO2 Compression Liqiud Ammonia Feed Carbamate Solution Feed Urea Reactor HP Stripper HP Condenser centrifugal compressor driven by extraction-admission-condensing steam turbine centrifugal pump driven by condensing steam turbine Ditto operating conditions: N/C = 3.7 mol/mol, 152 barG type : bubble column with baffle plates Type : falling film with CO2 stripping material : swirler = DP28W, tube = DP12 operating conditions: N/C = 2.9 mol/mol, 152 barG type : vertical submerged (VSCC) material : tube = 25Cr22Ni2Mo vacuum evaporation + prilling (acoustic nozzle) hydrolyzer & stripper for BFW use continuous monitoring with nitrogen gas purge circuit continuous urea analysis by TOYO-MCI proprietary analyzer

Finishing Waste Water Treatment Liner Leak Detection BFW Quality Monitoring

Leak Detection System for HP Equipment Liner Plates

In urea plant, anti-corrosive liner plates are usually applied to high pressure static equipment exposed to urea-carbamate solution. It could be told even correct material selection, elaborate fabrication and careful maintenance do not eliminate risks of liner leakage which might damage the pressure holding shell made of carbon steel as learned from past experiences. Therefore it is essential to prevent the equipment damage and to minimize shut-down period once leakage happens. Conventionally, weep holes connecting the space between the liner and the pressure holding shell to outside of the shell (atmosphere) are usually provided to detect leakage from liner plates. The vent holes are sometimes connected to bottles containing ammonia-sensitive reagent by tubing so as to detect leakage more easily and quickly. However the system may take longer time to detect very minute leakage and the tubing is susceptible to plugging due to crystallization of urea or ammonium carbamate. Although some urea plants have already applied liner leak detection system with continuous gas circulation or purging between liner and pressure holding shell to improve the reliability and response time, such urea plants are still minority. The Kujang-1B urea plant applies continuous nitrogen gas purge circuit to detect liner leakage for urea reactor, HP stripper and HP condenser (VSCC). The continuous nitrogen gas purge circuit is featured by: Accurate and reliable in detecting liner leakage. Quick response Easy identification of leakage location Nitrogen gas is circulated in the loop by a gas circulator. Flow meter is provided to the gas inlet tubing to each segment of liner plate or group of liner plates so as to control and distribute the purge gas flow rate appropriately. Nitrogen gas is made up to the circuit to maintain the system pressure. A water sealed breather protects the liner plates from overpressure. Ammonia detector detects ammonia in nitrogen gas circuit at as low as ppm levels. The signal from the ammonia detector is connected to central control room so that plant operators find occurrence of liner leakage quickly. The on-line leak detection system for HP Equipment liner has been successfully operated in Kujang-1B urea plant since October 2005.

Continuous On-line Analysis of Urea in Treated Process Condensate

Water (process condensate) is the largest byproduct of urea production process, which amounts stoichiometrically 0.3 mt/mt-urea and industrially as high as 0.5 mt/mt-urea, and the treatment of process condensate containing ammonia and urea has been the challenges since urea production process was industrialized. In former times, the process condensate was treated by steam stripping and hydrolysis to the level of 50 100 ppm for being utilized as cooling tower make-up or disposed outside of urea battery limit. Recently, deep urea hydrolysis and steam stripping technology reducing urea and


ammonia content to lower than 1 ppm in treated process condensate has been developed, enabling its use for make-up for boiler feed water (BFW). In case the treated process condensate is utilized for BFW make-up, urea content must be strictly controlled because urea can not be removed in ion-exchange resin bed. In case urea is contained excessively in BFW, it is hydrolyzed in boiler to form carbon dioxide which lowers pH and resultantly excessive corrosion in boiler may happen. As conductivity meter does not show the level of urea content (urea does not become electrolytes in aqueous solution), urea in treated process condensate must be periodically analyzed in laboratory where a few hours are required to obtain urea analysis result. To eliminate the risk of corrosion in boiler due to low pH by excessive urea in BFW, urea in treated condensate should be analyzed continuously and real-time. TOYO and Mitsui Chemicals Inc. (MCI) have developed proprietary on-line urea analyzer for process condensate, which analyzes urea continuously and real-time in the range from 1 ppm to 300 ppm. As the TOYO-MCI on-line urea analyzer is simply configured and does not require any chemicals and reagents, its initial and running cost is rather low. Figs. 7 and 8 show an example of its application and schematics of the analyzer. The TOYO-MCI on-line urea analyzers have been running in MCI Osaka Factory (Japan) and Kujang-1B since 2001 and 2005 respectively.

Performance Test Result

Table IV shows the results of performance test of Kuajng-1B urea plant conducted January 2006. As shown in Table IV, the plant has shown excellent performances. It should be noted that the steam consumption in urea plant including steam turbine for CO2 compressor, steam turbines for ammonia feed pump and carbamate feed pump is only 1.035 mt/mt. If ammonia and carbamate pumps were driven by electric motor, the steam consumption could have been reduced to 0.92 mt/mt.




Table IV Performance Test Result of Kujang-1B ACES21 Urea Plant

Production: Consumption - Ammonia: - Carbon Dioxide: - Steam (1) : - Cooling Water (1) (2): - Electric Power (3) : Treated Effluent - Ammonia: - Urea: Emission - Urea from Prilling Tower: 1747.2 mt/d 0.568 0.738 1.035 85.1 18.7 0.36 0.15 41.7 mt/mt mt/mt mt/mt m3/mt kWh/mt ppm ppm mg/Nm3

Notes: (1) 41.2 barG, 380 C steam including steam turbines for CO2 compressor, ammonia pump and carbamate pump. (2) at temperature rise 10.1 C (3) including power for urea dust scrubber of Prilling Tower


Nowadays urea plant capacity has been enlarging to 3,200 - 3,500 mtpd in single train. As urea plant capacity gets larger, ACES21 becomes more advantageous because fewer and smaller HP equipment are laid out in low elevation, greatly improving equipment manufacturability, transportability, constructability, operability and maintainability for the Jumbo Urea Plant. TOYO has already completed the design up to


4,500 mtpd urea plant based on ACES21 and Spout-fluid Bed Granulation; and Major HP equipment and machinery manufacturers have committed HP equipment and machinery for 4,500 mtpd ACES21 urea plant can be manufactured. Fig. 9 shows a 3-D model view of a 3,250 mtpd ACES21 Urea Synthesis Unit combined with Spout-fluid Bed Granulation Unit. As shown in Fig. 9, the HP equipment are laid out quite compactly in low elevation with the highest level of 35 m (VSCC top). In January 2007, TOYO has been awarded a contract to supply license and basic engineering to build a 3,250 mtpd urea plant in Iran based on ACES21 and Spout-Fluid Bed Granulation Technology. This project is epoch-making regarding the following aspects: the first ACES21 + Spout-Fluid Bed urea granulation plant in Middle East the largest single train Jumbo Urea Plant ever engineered by TOYO, where state-of-the-art urea technologies will be incorporated and demonstrated


The second ACES21 urea project has completed successfully in close collaboration among TOYO, PT Pupuk Kujang, PT Rekayasa Industri, PT IKPT and PT Pupuk Sriwidjaja (PUSRI, the co-licensor of ACES21), proving its advantages in energy efficiency, operability and environmental conservation. Those achievements in urea technology would lead to economical and safe urea production with minimum environmental impact, i.e. the high energy efficiency contributes to global warming prevention; on-line leak detection system for HP equipment liner enhances reliability and safety; and on-line urea analyzer for treated process condensate enhances total


utilization of process condensate for BFW without discharge. The first ACES21 urea project of 2,460 mtpd in China was indeed a challenge for TOYO. Its success has laid the technological foundation for the significant 3,250 mtpd Jumbo Urea Project in Iran. The Jumbo Plant is expected to be on stream in 2010. TOYO, as urea technology provider, continues improving its urea technology for the sustainable growth of fertilizer industry with cleaner environment.

1. 2. 3. Y. Kojima, H. Morikawa, E. Sakata, Development of ACES21 Urea Process, Nitrogen 2000, Vienna, Austria Y. Kojima, T. Yanagawa, ACES21 demonstrated in a world scale urea plant in China, Nitrogen 2005, Bucharest, Romania Y. Kojima, The Latest Advances in Urea Process Technology (ACES 21TM), 19th AFA International Technical Conference, Doha, Qatar

ACES21 is a registered trademark of Toyo Engineering Corporation in Japan (Registered Number 4309123)