Paper No. 3.

Processes and Technologies for Grass-Roots Ammonia Plants

by F. Baratto, M. Rizzi, P. Nibioli Ammonia Casale S.A. Lugano, Switzerland

Prepared for presentation at the Casale 3rd Customer Symposium Lugano, Switzerland June 6th 10th, 2011

Processes and Technologies for Grass-Roots Ammonia Plants

FOREWORD
AMMONIA CASALE S.A. is one of the oldest companies active in the field of synthetic ammonia production. It was established in Lugano (Switzerland) in 1921 for the industrial development and commercialization of Dr Luigi Casales inventions relating to the catalytic synthesis of ammonia. From the very start and throughout its history, AMMONIA CASALE has been engaged in the construction of new plants: to date over 200 Casale-designed plants have been built worldwide. The company has also acquired an unrivalled track record in revamping (retrofitting) existing plants of any type to improve their performance. More recently, AMMONIA CASALEs activities have expanded into the fields of urea and methanol production, and the company structure has evolved accordingly. Today CASALE is a group of four companies, each with a discrete focus on a principal area of the development of ammonia, urea and methanol production technologies. The distinctive strength of CASALE lies in the licensing of its technologies; most which are developed in house by teams of people with highly specialized knowledge and experience. Thanks to the tradition of innovation established by the companys founder, Dr Luigi Casale and maintained and nurtured by subsequent management teams, CASALE has always invested significantly in technology development and still does today. Nowadays, though, what was formerly a more or less empirical art married to an intuitive sense for good design has a far more systematic basis. Process design is now supported by sound insight into the chemistry of the processes, behaviour of catalysts, kinetic data, heat and mass transfer phenomena, fluid mechanics, the science of construction materials and cost analysis. The present paper will describe the standard CASALE ammonia process for grass-roots plants from natural gas and coal gasification, which is the result of a wide experience gained both with revamping and grass-roots projects. The description will go into energy saving technologies and glance at other aspects that are of primary importance for an operating plant such as safety, reliability and environmental impact. Between 1980 and 2000 Casale technology was almost always supplied for plants fed with natural gas. But in 2000 the feedstock choice began to change dramatically in favour of coal, and of the 44 synthesis loops that AMMONIA CASALE has supplied in the last 10 years, with capacities ranging from 300 MTD to 2,050 MTD, 30 were for coal-based plants. This paper describes how the design and behaviour of these plants are influenced by the peculiarity of the gas composition and other site-specific factors, and reports on the experience acquired with these synthesis loops and converters.

NATURAL GAS-BASED AMMONIA PROCESS FOR GRASS-ROOTS PLANTS

CASALE has developed, as a natural evolution of its revamping activity, new technologies for grassroots ammonia, urea and methanol plants.

F. Baratto, M. Rizzi, P. Nibioli

Processes and Technologies for Grass-Roots Ammonia Plants

The Standard ammonia process

The CASALE Standard process for natural gas-based ammonia plants is founded on the classical steam reforming route. The main process steps are, as shown in Fig.1: Desulphurization Primary and secondary reforming HT and LT shift conversion CO2 removal Methanation Syngas drying Compression Ammonia synthesis Hydrogen recovery

Fig. 1 CASALE Standard ammonia process Process description

The feed gas is desulphurized in two steps: hydrogenation and sulphur adsorption on zinc oxide. The desulphurized gas leaving the zinc oxide beds contains less than 0.1 ppm of sulphur. The gas is then mixed with process steam coming from the process condensate stripper and is heated in the mixed feed heater coil before entering the reformer catalyst tubes, where the gas and steam react in the presence of a nickel-based catalyst to form hydrogen and carbon oxides. The steam/carbon (S/C) ratio is 2.9. The fuel for the main burners is mainly natural gas, supplemented with tail gas from the hydrogen recovery unit, flash gas from the CO2 removal section and, in some cases, surplus syngas (for balancing CO2/NH3 production).

F. Baratto, M. Rizzi, P. Nibioli

Processes and Technologies for Grass-Roots Ammonia Plants

The air supply for the reformer burners is usually heated in a combustion air preheater. The primary reformer can be supplied by most qualified licensors, based on CASALEs process specification and preliminary design. Process gas from the primary reformer is further reformed in the secondary (autothermal) reformer using CASALE patented burners. The amount of air is controlled to produce a synthesis gas mixture at the converter inlet with an H2:N2 molar ratio of exactly 3:1, allowing for additional hydrogen recycled from the hydrogen recovery unit (HRU). The effluent from the secondary reformer is cooled in the main waste heat boiler and the recovered heat is used for steam production. The gas leaving the waste heat boiler is further shifted to produce carbon dioxide and hydrogen. This conversion is accomplished in two steps, the high-temperature shift (HTS) and low-temperature shift (LTS), which are both equipped with CASALE axial-radial internals. The reacted gas leaving the LTS is cooled before entering the purification section. Process air for the secondary reformer is filtered and compressed in a two-case, four-stage machine. Where the ammonia plant is associated with a urea plant, this also provides the passivation air introduced into the urea plant in the carbon dioxide feed. There are three water-cooled intercoolers with condensate separators. All of the condensate coming from inter-stage separators is recovered as cooling water make-up. The process air from the final stage of the compressor is heated in the convection zone of the primary reformer and then fed to the secondary reformer. Carbon dioxide is removed from the process gas using high-efficiency third-party technology. The CO2 content of the gas at the outlet of the absorber is less than 300 ppm if amine-based solutions are used. The gas then flows to the methanator feed-effluent exchanger. Rich solution leaving the base of the CO2 absorber is regenerated in a stripper column with a lean/semi lean arrangement in which only a minority of the solution is regenerated to the highest standard. The gas leaving the absorber is heated to the reaction temperature for methanation in the feed/effluent exchanger. The gas exiting the methanator, now containing less than 5 ppmv of carbon oxides (as CO+CO2), is then cooled and sent to the synthesis gas compression section. The centrifugal synthesis gas compressor has two casings, low-pressure (LP) and high-pressure (HP), and four stages in all, including the synthesis loop recycle compression impeller, which is in the HP case. All stages are provided with intercoolers. The compressor is driven by an extraction/condensing steam turbine. All of the hydrogen recovered by the HRU is added to the syngas, either in the second stage of the syngas compressor or at compressor suction. The gas leaving the second stage is dried by washing with liquid ammonia. This washing is performed in the make-up gas ammonia scrubber, which uses a special AMMONIA CASALE design. The expected water and CO2 content after ammonia washing are less than 0.1 ppmv. The dried synthesis gas flows directly to the suction of the HP case and is compressed to the synthesis loop pressure. The combined make-up and recycle gas stream from the circulator is fed to the hot gas-gas exchangers. The preheated gas then enters the ammonia converter, in which it reacts over an iron-based ammonia synthesis catalyst.

F. Baratto, M. Rizzi, P. Nibioli

Processes and Technologies for Grass-Roots Ammonia Plants

The ammonia converter is typically of a well proven AMMONIA CASALE design, containing three adiabatic axial-radial beds with intermediate cooling by heat exchange in two inter-bed exchangers. At the converter outlet, the product gas is cooled and the heat removed is used for steam production. The gas next passes through the hot side of the hot gas-gas exchangers and then enters the condensation section, where ammonia is condensed in a water cooler and then in ammonia chillers. A considerable amount of ammonia is condensed in these coolers on account of the high ammonia concentration achieved in the highly efficient AMMONIA CASALE converter design. Purge gas from the synthesis loop and inert gas from the refrigerant receiver are washed with water in two separate packed columns to absorb their ammonia content. The outlet gas leaving the ammonia absorption section has a low ammonia content (less than 10 ppm) and is fed to the HRU unit, which is normally membrane-based. The ammonia refrigeration section usually comprises a four-stage compressor. Gaseous ammonia from the fourth-stage discharge is condensed and collected in a refrigerant receiver. The cold ammonia product is exported to the urea plant by a pump. In normal operation it passes through a heat recovery section inside the refrigeration section and is then delivered to the urea plant at 20C. When the urea plant is down all the ammonia produced is DELIVERED to storage at -33C.

Characterizing elements
The main characterizing elements of the CASALE process are the advanced technologies placed in the key section of the plant: CASALE high-efficiency design for the secondary reformer. CASALE axial-radial technology for the shift conversion. CASALE ejector ammonia wash system. CASALE axial-radial technology for the ammonia converter. CASALE advanced waste heat boiler design in the synthesis loop.

The CASALE high-efficiency secondary reformer design is based on the most advanced CASALE secondary reformer burner technology, which has been developed, using CASALEs deep knowledge of combustion and fluid dynamic phenomena, to achieve very high combustion efficiency with low energy consumption. The CASALE advanced secondary reformer burner has the following features: Superior mixing in the flame; Low pressure drop in both air and process streams; Homogeneous gas composition and temperature distribution at the catalyst bed entrance; Reduced flame length, avoiding catalyst impingement even at high operating loads; Low temperature of the burner surfaces exposed to the flames; Protection of the refractory lining from the hot core of the flame itself.

Thanks to the above features of the burner, the CASALE high-efficiency secondary reformer design minimizes the size of the item, guaranteeing also a high reliability with a long duration of the burner itself.

F. Baratto, M. Rizzi, P. Nibioli

Processes and Technologies for Grass-Roots Ammonia Plants

CASALE Axial-Radial Technology is used for the design of both the shift converters and the ammonia converter. In an axial-radial catalyst bed (see Fig. 2) most (about 90%) of the gas passes through the catalyst bed in a radial direction, resulting in very low pressure drop. The balance passes down through a top layer of catalyst in an axial direction, thus eliminating the need for a top cover on the catalyst bed. Mechanically the bed is very simple, being made only of the two vertical perforated walls and of one bottom closure plate. The absence of a top cover greatly simplifies and facilitates the construction of the converter internals. The essential advantages of the axial-radial catalyst bed concept are the same wherever in the ammonia plant it is applied, namely: Low pressure drop; High efficiency thanks to the use of small-size catalyst.

Fig. 2 Axial-radial bed

Fig. 2 Axial-radial catalyst bed

High efficiency and low pressure drop are important features to minimize equipment size and energy consumption.

Fig. 3 HT and LT shift converters at Iranian plant

The use of CASALE axial-radial technology in both HT and LT shift converters guarantees, in addition to the above mentioned features, the following advantages: Low average CO outlet concentration. High reliability and longer catalyst life thanks to higher resistance to poison and water carry over. Longer catalyst life thanks to the fact that the pressure drop across the unit remains stable all along the catalyst life.

F. Baratto, M. Rizzi, P. Nibioli

Processes and Technologies for Grass-Roots Ammonia Plants

Before entering the synthesis loop, the syngas is dried using the CASALE Ejector ammonia wash system, which is uses liquid ammonia to dry the syngas. CASALE ejector ammonia wash system consists of a specially designed ejector, which guarantees a perfect contact between the liquid ammonia and the syngas, followed by a separator, and is, therefore, very simple and efficient, completely removing water and CO2 from the syngas. The main advantages of this system are the following: The energy consumption of the refrigeration compressor is minimized, as the syngas can be sent straight to the ammonia converter The energy consumption of the circulator is also Fig. 4 Ejector ammonia wash minimized because of the very low suction system temperature. The ammonia synthesis converter is also based on the CASALE axial-radial technology. This technology is combined, in the CASALE axial-radial ammonia converter, with a three-bed configuration, with two interchangers, to attain very high thermodynamic efficiency and catalyst volume utilization. The conversion per pass is, therefore, maximized, minimizing the energy consumption of the loop and the size of the loop equipment. Another important feature in the design of the ammonia synthesis loop is the CASALE advanced design for the waste heat boiler/HP BFW preheater that is downstream the converter. The CASALE waste heat boiler is a U-tube exchanger with the boiler feed water on the tube side and the process gas shell side. The pressure shell is kept cooled by the outlet colder gas flow. The only ferritic parts in contact with the hot gas are the tubes, which are cooled by the BFW. With this special design it is possible to avoid any risk of nitriding. All the above mentioned characterizing elements used in the CASALE Standard ammonia process have been used in many applications proving their efficiency, reliability and long operating life. Performance Thanks to the characterizing elements explained in the previous sections, the CASALE Standard ammonia process has very outstanding performance. Steam : carbon ratio (referred to NG stream only): 2.9 : 1 CO slip from LTS: less than 0.3% vol. (dry base) CO2 from absorber: less than 300 ppm vol.

Fig. 5 CASALE synthesis converter

F. Baratto, M. Rizzi, P. Nibioli

Processes and Technologies for Grass-Roots Ammonia Plants

Ammonia loop pressure: 140-160 bar Ammonia conversion per pass: ~20%

In addition, total energy consumption (evaluated as feed + fuel + steam import from package boiler steam export to urea) is very low: ~ 6.7 Gcal/MT of produced ammonia

On account of its very high efficiency, the size of equipment needed for a given capacity, and therefore the investment cost, is lower for the CASALE Standard ammonia process than for other processes.

Recent developments
Some additional elements can be added to the standard ammonia process to further reduce the energy consumption of the plant: The use of gas turbine exhaust as reformer combustion air (Fig. 6); Low-temperature heat recovery (Fig. 7); Cryogenic hydrogen recovery.

Fig. 6 Turbine exhaust as process air

F. Baratto, M. Rizzi, P. Nibioli

Processes and Technologies for Grass-Roots Ammonia Plants

The gas turbine is used to drive the process air compressor. It is thermally more efficient than a steam turbine, while using its exhaust as preheated combustion air makes use of heat which would otherwise be dispersed into the atmosphere or used in a less profitable way. Furthermore, it delivers its exhaust at sufficient pressure to obviate the need for a forced-draught fan for the combustion air. Using the gas turbine option renders the combustion air preheater at the end of the convection section unnecessary, providing the opportunity for additional heat recovery from flue gas at relatively high temperature. Therefore, this system is perfectly coupled with Casale lowtemperature heat recovery, the object being to recover as much heat as possible from the flue gas without compromising the safe operation of the flue gas stack. That is achieved by recovering heat at very low temperature with the use of liquid ammonia.

Fig. 7 Low-temperature heat recovery

A stream of HP liquid ammonia from the loop separator is heated to about 200C in the last coil of the primary reformer flue gas duct. The ammonia is then expanded to about 18 bar a in a machine coupled with the refrigerant ammonia compressor or an electricity generator. The ammonia is then condensed at the expander outlet with cooling water. This results in a stack temperature of 135C, which is far enough above the dewpoint to allow for safe plant operation. The low-temperature heat recovery system can produce about 75 KWh/MT of NH3. Cryogenic purge recovery is aimed at further enhancing the recovery of hydrogen and nitrogen from the standard hydrogen recovery units. It should be noted that cryogenic separation is more selectivity towards hydrogen but has virtually no impact on system pressure. That allows the recovery of about 95% (mol/mol) of hydrogen and 60% (mol/mol) of nitrogen in the purge stream without a significant pressure drop. The recovered hydrogen can be reintroduced to the synthesis loop at the circulator suction. Given the fact that synthesis gas is the key element in the ammonia loop energy cost, it is evident that recovering hydrogen as efficiently as possible leads to the greatest benefits in terms of overall loop performance, higher conversions per pass, lower circulating flow rates and thus lower overall consumptions.

F. Baratto, M. Rizzi, P. Nibioli

Processes and Technologies for Grass-Roots Ammonia Plants

Through the introduction of these three improvements, the energy consumption of the plant can be lowered to below 6.5 Gcal/MT or about 6.6 Gcal/MT in case it is desired to balance NH3 and CO2 for urea production.

Projects and industrial experience

CASALE has completed and is also currently working on several projects that incorporate the technologies described in the previous sections. The CASALE Standard ammonia process is currently operating in a 2,050-MTD plant in Iran operated by Razi Petrochemical Company. The new plant, which has been designed by CASALE and built by the Iranian contractor Pidec, has been in operation since the beginning of 2008. A second 2,050-MTD ammonia plant in Iran, for Shiraz Petrochemical Company, is at an advanced stage of construction. And recently, CASALE has been awarded three more contracts for the design of three new 2,050-MTD ammonia plants in various locations in Iran.

Fig. 8 Pictures from CASALE Razi III plant

CASALEs typical scope of supply for grass-roots ammonia projects from natural gas consists of the basic engineering design of the entire plant; detail design and material supply is limited to the proprietary items. But CASALE reviews the entire detail engineering work (performed by others) to check for compliance with the basic engineering package and assists with commissioning and start-up activities, including catalyst reduction, through to parameter optimization and test runs. During this period CASALE personnel also provide training to the clients staff operators.

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Processes and Technologies for Grass-Roots Ammonia Plants

COAL-BASED AMMONIA PROCESS FOR GRASS-ROOTS PLANTS

Nowadays most of the world output of ammonia is produced from natural gas feedstock. But in recent years a new trend has been established towards the exploitation of different types of feedstock, like coal and petroleum coke, where they are abundant and less expensive than natural gas. China led this revolution, constructing and commissioning a number of ammonia plants based on coal gasification which account for almost 33% of world ammonia production. Chinese ammonia production is, in fact, mainly based on coal: the output of coal based ammonia accounts for 75% of total domestic production. The utilization of these solid feedstocks requires different technological approaches, not only in the preparation of the synthesis gas but also in its use to produce ammonia, mainly because of the composition of the synthesis gas obtained from gasification, which is practically free of components that are inert under the conditions in the ammonia synthesis loop. Thanks to its advanced technologies in ammonia plants, CASALE was able successfully to enter the Chinese market and has become a major player.

CASALE technical involvements in Chinese projects

CASALE is generally involved in Chinese projects as licensor and technology provider, supplying its proprietary equipment for ammonia and methanol projects in the front end section or in the back end section or both. As a world leader in the design of converters, CASALE has designed and supplied the perfect technologies for the sour CO shift sections in seven coal-based ammonia and methanol plants. As a consequence of the success of its well-known three-bed, two-interchanger ammonia synthesis converter, in 30 Chinese ammonia projects CASALE has provided license, basic design engineering package (BDEP) or process design package (PDP) of the synthesis section, refrigeration section and, in some cases, ammonia cryogenic storage section, the proprietary internals of reactor and site services.
CO 2 & H 2 S

COAL

GASIFIER

CO SHIFT

AGR

N2 WASH

SYNLOOP

ASU

AMMONIA

REFRIGERATION SECTION

AMMONIA

STORAGE

Fig. 9 Coal-based ammonia plant block flow diagram

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Processes and Technologies for Grass-Roots Ammonia Plants

Technical aspects of coal-based ammonia projects

Sour CO-shift technology: CASALE axial-radial converters
The ammonia process requires maximum conversion of carbon monoxide and steam to carbon dioxide and hydrogen, for maximum ammonia production at a given syngas capacity. That is generally achieved by carrying out the shift conversion reaction in multiple reactors, (two or three), with intermediate cooling. Staging is also required because of the high CO content, which entails a large temperature rise across the converter, especially the first bed. Addition of nitrogen in the stoichiometric amount occurs in the downstream nitrogen wash unit. It is clear that the best design of the CO-shift section (and converters) is of great importance for the efficiency and reliability of the ammonia plant, bearing in mind that it features more converters in series. Especially in large plants, it is desirable to be able to guarantee a low pressure drop in the shift section over the entire life of the catalyst so as to minimize the power consumption of the downstream syngas compressor. Also, the shift converter design must be mechanically robust and adequate to the challenging reaction environment. The CASALE design for shift converters successfully provides these and other advantageous features, through the application of the renowned axial-radial concept (see Fig. 2). In the axial-radial concept, gas is distributed through the perforated walls of the catalyst canister, which ensures a low pressure drop that remains stable with time as the catalyst ages or deteriorates, as it is unaffected by any caking of the catalyst top layer that might result from entrained water droplets. Hence, by ensuring a higher suction pressure to the compressor through the catalyst life, it achieves a higher production rate. Since the pressure drop is unaffected by the catalyst, there is never any need to change of the catalyst prematurely: the catalyst working life can easily reach and exceed four years, even in the case of the first sour shift converter, which is the one operating in the most severe conditions. Low pressure drop is, in fact, the major feature of the CASALE axial-radial concept, allowing the converter to be designed with a much slimmer pressure vessel than an axial design would require and, consequently, a thinner pressure vessel wall. This results in significant capital cost saving, especially with respect to the first shift converter. On account of the high operating temperature, an axial bed must be designed either with a SS cartridge and an annulus for flushing the pressure vessel, or with a refractory-lined vessel. Instead, the axial-radial bed with inward flow, keeps the hot gas at the centre of the converter, away from the vessel wall, so that only the outlet nozzle is exposed to high temperatures, allowing much easier, cheaper and robust construction. The advanced design of the CASALE sour shift started to be successful in Chinese coal-based plants with the Tianji project in 2005; these sour shift reactors were inspected during catalyst replacement in June 2009 and no cleaning and/or repairing works were necessary on the internals. The proven and reliable CASALE design with its attractive cost-saving and process performance has been persuading further clients to select CASALE sour shift technology.

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Processes and Technologies for Grass-Roots Ammonia Plants

Client
RONGXIN CHEMICAL CO., LTD. Erdos City, Inner Mongolia P.R. of China LUAN XINJIANG YILI COAL CHEMICAL INDUSTRY CO., LTD. P.R. of China JIUTAI ENERGY CO. LTD. P.R. of China TIANJI COAL INDUSTRY GROUP CHEMICAL CO. Lucheng City, Shanxi Province, P.R. of China

CASALE Scope of Work

One sour shift converter for new methanol plant, CASALE axial-radial Two sour shift converters for new ammonia plant, CASALE axial-radial One sour shift converter for new methanol plant, CASALE axial-radial Two revamped sour shift converters and one new sour shift converter for ammonia plant, CASALE axial-radial

Capacity [MTD]
3,000

Status
Start-up 2013

1,000 3,000

Start-up 2011 In operation since 2010 In operation since 2005

1,500

Table 1 - CASALE Chinese sour shift converter reference list Ammonia synthesis loop design
The synthesis gas composition from coal gasification is characterized by the low inert content. Typically the argon and methane concentration in the make-up gas to the synthesis loop does not exceed 50 ppm by volume, while the hydrogen and nitrogen concentrations are about 75% and 25% respectively. The synthesis loop therefore has to be designed to take maximum advantage of this favourable gas composition.

Fig. 10 Ammonia synthesis loop process flow diagram

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Processes and Technologies for Grass-Roots Ammonia Plants

Because the make-up gas normally has a minimum inert content, there is no loop purge and the flash gas from the medium-pressure separator is recycled back to the suction of the syngas compressor so as to minimize make-up gas consumption. The overall low inert content at the ammonia reactor inlet makes it possible to achieve high production rates with low recycle ratios and low catalyst volumes. The synthesis loop is quite simple and not significantly different from the loop designed for natural gas feedstock. It comprises the ammonia synthesis converter, the hot gas-gas exchanger preheating the reacting gas entering the converter, the heat recovery section, the water cooler, the cold gas-gas heat exchanger, the two chillers, the high-pressure separator (needed to separate the liquid ammonia from the unreacted gas), the medium-pressure separator (useful for recovering dissolved gas in the liquid ammonia), and the syngas and circulating compressor. According to the overall plant steam system specific optimization, the heat recovery section can comprehend a steam superheater, a waste heat boiler and a boiler feed water preheater or, as alternative, only the waste heat boiler and the BFW preheater, or in unusual cases, only the BFW pre-heater. The amount of heat recovered is generally greater than 0.6 Gcal / MT NH3. CASALE designs normally incorporate a direct connection between the ammonia converter and the downstream exchanger, which is shown in Fig. 11. (CASALE has references for each of the alternatives described above.) This feature of CASALEs layout avoids the need for stainless steel piping which would be exposed to a combination of high pressure and high operating temperature (above 440C) that is conducive to nitriding attack. This makes a major contribution to the reliability and safety of the system.

Fig. 11 Direct connection between converter and waste heat boiler in a Chinese plant

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Processes and Technologies for Grass-Roots Ammonia Plants

CASALE usually supplies, as proprietary equipment, the heat exchanger directly connected to the converter, which can be a steam superheater, a waste heat boiler or a boiler feed water preheater, according to the particular disposition of the plant. However, CASALE is open to meet clients need to minimize investment costs and can alternatively provide a reliable design which can be procured directly by the client and manufactured in Chinese workshops. The steam superheater is typically a horizontal exchanger (TEMA type DFU). Exchanger tubes are fabricated in Inconel alloy, and the syngas inlet chamber should be overlaid in the same material to avoid nitriding due to the high metal temperature. Generally the waste heat boiler is an NKU special type, horizontally arranged, with process gas flowing tube side. The exchanger can be coupled with the converter outlet if no steam superheater is present. Insulated ferrules in nickel alloy material protect inlet tubes, keeping the hot-end tube wall temperature inside the tube sheet below 370C to avoid nitriding. All the parts in contact with process gas are in low-alloy steel to ensure a higher reliability and a longer lifetime. Parts in contact with medium-pressure steam are in carbon steel as minimum requirement. In case no superheater and waste heat boiler are installed, the BFW preheater is directly connected to the converter outlet. The exchanger is NEU type with hot gas shell side and BFW tube side. The HP shell will be in low-alloy steel and are therefore operated at lower temperature. The tubes are U type in low-alloy steel, too.

Fig. 12 Refrigeration section process flow diagram

Generally the ammonia plant refrigeration section is designed by CASALE as a "closed-loop" scheme (as shown in Fig. 12), strictly dedicated to the ammonia chillers. However, CASALE is fully prepared to customize the refrigeration section in order to meet the specific client requirements about cold duties, export or inert specification in the liquid ammonia. This could extend, in cases where there is a stringent specification about inerts content in the ammonia product, to adopting an open loop scheme.

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Ammonia converter design

The CASALE technology for this section of the plant relies on the ammonia synthesis converter with three adiabatic beds and two interchangers. The three catalytic beds have axial-radial flow, to minimize the pressure drop. The CASALE design for the ammonia synthesis converter has already proven its performance and reliability, on the grounds of the following key concepts: the axial-radial flow in the catalyst beds ensures optimal distribution of the gas in the catalyst, avoiding any hot spots, and full utilization of the catalyst; the temperatures in each of the beds is controlled independently, to keep the converter optimized under any operating conditions; the materials of construction used for the internals, i.e. SS 321 and Inconel 600, are chosen for their resistance to nitriding and hydrogen attack; all the internal parts are connected with sliding joints, allowing unrestricted differential thermal expansions, and are free from leakages due to material aging; the pressure vessel is flushed with cool gas, ensuring that it is not subject to embrittlement due to nitriding, which may lead, in the long run, to cracking; the converter effluent is directly conveyed to the downstream exchanger, which is lipsealed to the converter, thus eliminating the hot converter outlet pipe, and allowing the use of safer horizontal exchangers.

Altogether, the ammonia synthesis loop for coal-based plants is not significantly different from that used in reforming plants, except for the better overall performance (lower recycle rate, no purge, higher specific heat recovery).
Syngas Quality Specific production Converter outlet pressure Converter P Converter NH3 Converter Tout MTD/m3cat bar g bar % mol C SR ~ 15 160 <3 ~ 15 430 CG ~ 20 140 <3 ~ 18 430-450

SR: Steam reforming, CG: Coal gasification

Table 2 - Typical performances 2,000 MTD ammonia loop

Projects and industrial experience

There are ten coal-based Casale ammonia loops already in operation in China: their capacity ranges from 500 MTD to 1,000 MTD. The first of them has been in operation since 1999, while the last was put in operation during November 2009. Many others with a capacity ranging from 1,000 to 2,000 MTD are under construction (see Table 3).

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Fig. 13 Chinese ammonia plant in operation

Client Inner Mongolia Nailun Group Guizhou Kaiyang Chemical Co. Guizhou Kaiyang Chemical Co. Jinjiang Chemical Co. Shaanxi Popular Jurassic Yanchang Petrochemical Group Hulumbeier New Gold Chem. Co. Shilien Chem Ind Jiangsu Co. Goudian Chifeng Chemical Co, Yankuang Xinjiang Coal Chem. Co. Luan Xinjiang Yili Coal Chem. Ind. Co. Henan Jinkai Chemical Group Heilongjiang Longmei Donghua Co. Anhui Liuguo Chem Co. CNSG Anhui Hong Sifang Co. Anyang Zhongying Fertilizer Co. Wulagai Xilinhe Coal Chemical Co. Wujian Jinniu Coal Capacity (MTD) 1,000 1,500 1,000 1,350 1,000 1,000 1,632 1,350 1,000 1,000 1,000 2 x 2,000 1,000 1,000 1,000 1,425 1,632 1,000 Scope of Supply Licence, BEP of synloop & ammonia converter cartridge Licence, BEP of synloop & ammonia converter cartridge & WHB Licence, BEP of synloop & ammonia converter cartridge & SSH Licence, BEP of synloop & ammonia converter cartridge & SSH Licence, BEP of synloop & ammonia converter cartridge, WHB & SSH Licence, BEP of synloop & ammonia converter cartridge & SSH Licence, BEP of synloop & ammonia converter cartridge & BFW preheater Licence, BEP of synloop & ammonia converter cartridge Licence, BEP of synloop & ammonia converter cartridge & WHB Licence, BEP of synloop & ammonia converter cartridge & WHB Licence, BEP of synloop & ammonia converter cartridge & WHB Two set of Sour Shift Converters Licence, BEP of synloop & ammonia converter cartridge Licence, BEP of synloop & ammonia converter cartridge & BFW preheater Licence, BEP of synloop & ammonia converter cartridge, WHB & SSH Licence, BEP of synloop & ammonia converter cartridge Licence, BEP of synloop & ammonia converter cartridge & WHB Licence, BEP of synloop & ammonia converter cartridge Licence, BEP of synloop & ammonia converter cartridge

Table 3 - New ammonia loops under construction in the PRC

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Processes and Technologies for Grass-Roots Ammonia Plants

In all Chinese projects CASALE works in collaboration with local design institutes, typically playing the role of detail design contractors of the project. Usually the procurement activities, the construction, pre-commissioning, commissioning and start-up are directly performed by the client. Design institutes are involved in the project from the very preliminary phases so that the design basis is agreed upon during contract negotiation. Typically CASALES involvement the ammonia projects extends to basic or process design of the synthesis loop, the refrigeration section and, sometimes, the cryogenic storage section. The detail design and material supply is limited to the proprietary internals of the synthesis converter, and, quite often, for ammonia projects, CASALE supplies the heat exchanger directly connected to the converter (steam superheater, waste heat boiler or boiler feed water preheater, as the case may be) and / or other critical heat exchangers of the loop. BDEP and PDP are provided by CASALE in double language (English/Chinese) and according to the relevant Sinopec standard. After BEDP or PDP delivery, a design review meeting is held with the participation of the client and design institute specialists, in which CASALE gives detailed explanations and the client reviews and comments on all the basic design documents, as necessary for the assessment of the documentation, allowing the design institute to proceed with the detailed engineering development. Typically the client and design institute participate in this meeting with a delegation of about 10 people, including project managers and specialists from all the major engineering disciplines, such as process, mechanical, piping, instrumentation, electrical, etc. Detail engineering design is then developed by the design institute and CASALE reviews this work to check compliance with the process design requirements. Also this phase is very important for smooth development of the project and it ends with a detail design review meeting in the offices of the design institute. Typical project duration, from contract signature to detail design review meeting, is 12 months, with a basic design review after 5 months from kick-off meeting. The collaboration between CASALE and the client does not end with the design phase but it continues in the field. In fact, one of the features of CASALE converter internals is their modularity and their assembly on field with the same technique developed by CASALE for in-situ retrofit. The installation is performed by the client, under the supervision of CASALE field engineers. The first catalyst loading is also performed under CASALE supervision. CASALE assistance continues with commissioning and start-up activities, including catalyst reduction. During this period CASALE personnel also provide training to the clients staff operators. CASALEs last formal commitments on site are parameter optimization and test runs. However, from experience with the Chinese projects, CASALE has learnt once more how important assistance on site is for a successful project. Therefore, CASALE maintains close co-operation with the client and provides full assistance in troubleshooting, even after the test-run period is over.

CASALE AMMONIA PROCESS: BEYOND ENERGY SAVING . . .

Although energy consumption is the key focus in designing grass-roots ammonia plants, certain other considerations are essential for satisfactory operation of the plant itself.

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Processes and Technologies for Grass-Roots Ammonia Plants

These are: Safety Reliability Environment

It is axiomatic that a plant with serious issues in any of these areas cannot properly fulfil its availability, energy-efficiency and economic targets.

Safety and reliability

Safety in the design of petrochemical process plants primarily relies on the application of various codes of practice or design, which are based on the wide experience and knowledge of professional experts and specialists in the industry. Such application is backed up by the experience of local plant managers, engineers and operators, who have direct experience in the relevant plant operation. Process plant safety and reliability have to be given special consideration right from the start and at every subsequent step in the life of the project, covering all plant equipment, units, instrumentation, process control, emergency shut-down systems and safety relief systems. Nor does their importance diminish with the start-up of the plant; it continues over the plants entire operating life, particularly when it comes to determining maintenance practices to keep any equipment, process units, instrumentation, process control, emergency shut-down systems and safety relief system in good order and avoid any possible degradation of their reliability which might compromise the safe operation of the entire plant. The following important steps need to be followed during the design and engineering of a new grass-roots plant. Definition of the most appropriate flow scheme and operational parameters of each equipment item or unit, according to the state of the art of the available proven technology. Definition of the most appropriate design condition and material selection for all equipment / units of the whole plant. Analysis and definition of the required instrumentation for monitoring and also controlling operation within the defined operational parameters of the plant. Analysis and definition of the required instrumentation and emergency shut-down system for preventing operation outside the defined operational parameters that may offset the reliability and safety operation of any equipment, units or plant sections. Analysis and definition of a safety relief system that is able to manage any possible overpressure that may be caused by plant maloperation, utility failure or failure of process control and emergency interlock systems. HAZOP study. SIL analysis. Selection of the most appropriate equipment suppliers, particular of critical items, to assure not only the best performance but also the most proven design from a reliability and safety point of view.

Ammonia plants incorporate a certain number of critical items. Such critical items are of the greatest importance for the performance, safety and reliability of the plant. AMMONIA CASALE directly supplies a certain number of proprietary items and can also supply the critical equipment that characterize and define its ammonia plants in the world.

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Processes and Technologies for Grass-Roots Ammonia Plants

The ammonia synthesis converter and downstream heat exchanger are key items in ammonia plants. Their reliability is essential, as a plant cannot run without them. In addition, the ammonia synthesis converter is the reactor with the longest run between catalyst changes (10-15 years). Ammonia catalyst, once reduced, should not come in contact with oxygen since it is highly pyrophoric. Therefore, converters should operate between catalyst changes without repairs or inspections. To achieve this result without any impact on the safety and reliability of plants, several aspects have to be considered, as converters are subject to different metallurgical deterioration phenomena.
Physical Protection (Relief Devices) Safety Instrumented System (Interlock System) Critical Alarms, Operator Intervention Basic Process Control Process

Fig. 14 Plant layer of protection

Since the detrimental effects of the environment on materials increases with temperature, the latter needs to be kept as low as possible. The CASALE philosophy is to select a suitable material and generally keep the materials at the lowest possible temperature by using a suitable thermal insulation and/or gas flush. This concept helps improve the intrinsic safety of high-pressure parts.

Environmental impact
The CASALE ammonia process has been designed in such a way as to minimize environmental impact. The only liquid wastes are boiler blow-down and condensate from the air compressor interstage coolers. The boiler blow down, after flashing and cooling, is used as cooling water make-up for the cooling water loop. The same applies to the air compressor interstage condensate, which is returned to the cooling water return header. The only gaseous waste is the flue gas from the primary reformer, which contains about 110 mg/Nm3 of NOx. The guaranteed figure of NOx is less than the one required by the European Community for new plants (140 mg/Nm3 calculated at 3% oxygen excess).

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Processes and Technologies for Grass-Roots Ammonia Plants

CONCLUSIONS
CASALE is able to license the technology for entire ammonia plants and to give support to the EPC contractor for the best success of the plant. This technology is based on the use of all CASALE proprietary items, ensuring the most cost-effective and efficient plant design.

Fig. 15 ANHUI HUAINAN coal-based ammonia plant

Through the continuous development of its technologies, CASALE has been able to develop innovative processes for grass-roots ammonia plants for both natural gas and coal feedstock. Producing ammonia from coal gasification requires tailor-made solutions that can differ significantly from those so far utilized in the more common gas-based plants, to take full advantage of the peculiarities of the synthesis gas generated with this process. CASALE has acquired valuable experience in coal gasification projects thanks principally to the Chinese experience and the fruitful and close collaboration with Chinese clients and design institutes. With its advanced technology along with proven experience and knowledge, CASALE is ready to respond to the future market demand for challenging projects which require excellent know-how and advanced processes.

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