Recent Developments in Urea Plant Design: Pan Orphanides

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Recent Developments in Urea Plant

Design
The paper will review the recent Urea Technology developments: a) In Urea synthesis technology for
the design of large scale single unit grass root plants, up to capacities of 4,500 MT; b) In the use of
new materials with improved corrosion resistance and mechanical strength, offering safe operation,
reduction of investment cost; c) In the revamping of conventional urea plants towards big capacity
increase and improved efficiency offering attractive investment saving; d) In the Urea Granulation;
e) For cooling – conditioning of prilled & granular urea

Pan Orphanides
ORPHANCO Greece

Introduction • Refurbishing old plants to high capacity & effi-


ciency increase by obtaining important capital


U rea plant design and construction in the
have been characterized by the following
trends in the last years:
Large single line plants- simplified layout, of a ca-
savings.

1. Recent Technology Improvements in


pacity greater than 3500 MTD Urea Synthesis
• Overcome limits in manufacturing – transportation –
erection. For plant capacity of 3500 MTD urea In Chapter 1.1 we will discuss developments in the
plants reactors 380 tons, pool condenser 300 tons Urea Synthesis focusing mainly on the break through
and strippers 230 tons are manufactured, transported opening the way to single line large capacity plants: By
and erected in a single piece. Carbamate Condenser of a new design first applied
• High reliability - on-stream factor, increased main- by Stamicarbon’s Pool Condenser in the 80s. Ten years
tainability – operability later Toyo Engineering followed by their Vertical Sub-
• High corrosion resistance – high mechanical merged Condenser and recently Casale with their Full
strength materials Condenser. The development is continuing with the
• New Casale Urea synthesis process Pool Reactor (Fig.1.1.2a-2), introduced in the late 90s
• High quality urea delivered to remote final destina- by Stamicarbon in the 1100 MTD urea plant in DSM
tions /Geleen
• New granulation process of Stamicarbon
• First Hydro granulation revamped to Stamicarbon In chapter 1.2 we will discuss New Improved ma-
concept terials.
• Advance of Urea Granulation against prilling
New Technologies in refurbishing old, or conven-
tional technology plants for high capacity increase

AMMONIA TECHNICAL MANUAL 312 2004


and/or efficiency improvement will be discussed in • simplified synthesis section
Chapter 1.3. • reactor weight reduction for large size plants >
3500 MTD
Developments in Urea Granulation will be dis- • further improvements are obtained in CO2
cussed in Chapter 1.4 and in Chapter 1.5 Developments stripping plants by combination of revamped
and Advanced features in urea cooling are given. conventional Falling Film Condenser with split
stripper gaseous effluent flow, part directly to
1. 1 High Pressure Carbamate Condenser the reactor and part only to the condenser, as it
(HPCC) is shown and explained in Fig. 1.1.3c, 1.1.3c-1
and 1.1.3c-2. This system is applied by Urea
1.1.1.Conventional HPCC with carbamate forma- Casale in a conventional CO2 stripping plant
tion on tube side, in spite of recent improvement has and allowed a substantial capacity increase,
many disadvantages: without any additional equipment, as it is
• even distribution of gas /Liquid load, in each shown and explained in Fig. 1.3.4.
individual tube is not easily achievable, result-
ing in reduced condensation efficiency The new generation HPCC will allow the design of
• short retention time, resulting in non complete single unit large capacity urea synthesis plants, as well
condensation as revamping of existing plants by de-bottlenecking up
• low heat transfer, especially for falling film to factor 2 urea synthesis section and by factor 3 Recir-
type condensers culation. Furthermore capacities up to 4500 MTD will
• due to unequal distribution of liquid and gas be feasible by re-incorporating in the new HPCC de-
flows through tubes hot spots are formed creat- sign, the 20 bar Medium Pressure Section in CO2 strip-
ing high corrosion rates, especially in kettle ping process shown in Fig. 1.1.3a. The concept of com-
type condensers. bining Pool Reactor with 20 bar Re-circulation section
is under Construction in DSM Geleen.
1.1.2. These problems have been radically solved
by Stamicarbon’s Pool Condenser of a new design first The Pool Reactor shown in Fig.1.1.2a-2 operates in
applied by in the 80s, and by a further development the condenser part with NH3/CO2 (N/C) ratio of about
uniting condenser and reactor introduced in the middle 2.3-2.6, that means on the top ridge line[1], where the
90s shown in Fig. 1.1.2a-1. The development is con- boiling temperature and kinetics are at maximum. 2.5
tinuing with the Pool Reactor (Fig.1.1.2a-2), intro- N/C ratio is close to the top ridge line at the beginning
duced in the late 90s by Stamicarbon in the 1100 MTD of urea formation>> fast urea formation up to 60% of
urea plant in DSM /Geleen. A few years ago Toyo fol- equilibrium. Then the solution is transferred in the reac-
lowed by their Vertical Submerged Condenser tor section by NH3 ejector and N/C becomes 3.1, close
(Fig.1.1.3b) and recently Casale with their Full Con- again to the top ridge line for conditions prevailing in
denser shown in Fig. 1.1.3c, Fig.1.3c-1, Fig. 1.3.c-2. the reactor part, those increasing urea formation.
With this development the following has been
achieved: Toyo’s Submerged type HPCC is applied in Si-
• more than 20 min retention time in the con- chuan Chemical Works (China): Improved ACES with
denser, resulting in important urea conversion the design capacity of 2460 MTPD is under commis-
of carbamate solution before entering the reac- sioning.
tor, allowing by this the conversion efficiency 1.1.5 Furthermore, with the application of the new
increase in the reactor, close to the equilibrium generation Carbamate Condenser in old technology,
point Total Recycle urea plants, large capacity increase up to
• heat transfer increased substantially, increasing
the Condenser capacity [1] More about stripping process principles & liquid –gas
equilibria in a NH3-CO2-H2O system can be read in the pa-
• higher steam pressure steam is generated
per of P.J.C. Kaasenbrood & Dr. H.A.G. Chermin “ Stripping
• low corrosion due to uniform distribution of Technology, Phase Equilibria & Thermodynamics”, (Pro-
liquid and gaseous phase in all tubes, and be- ceedings No. 166- December 1977, of the International Fertil-
cause hot spots non presence izer Society/London

2004 313 AMMONIA TECHNICAL MANUAL


100% and substantial energy saving can be obtained as • Lower inert in reactor resulting in higher con-
shown in Fig. 1.3.3, and 1.3.5 version efficiency

Safurex for oxygen free urea synthesis?


1.2 Improved materials: Advantages of 27-
28% Cr min. Duplex steels against According to Sandvik – Stamicarbon, so far the
25/22/2 L Mn austenitic steels only Duplex-Steel quality resisting carbamate corrosion
in urea services under almost nil oxygen passivation is
It is known that balanced ferritic- austnitic content SAFUREX (28.5% min. Cr content, Ni 5.8-7.5%, Mo
Duplex steels with up to 26.5 –27.5 % Chromium and 1.2-3.6%, N 0.3-04%)
W addition made it possible to produce urea synthesis As there are All -Safurex synthesis loops under
components with high mechanical strength and high construction, it is expected that a gradual reduction
corrosion resistance in urea-carbamate solutions. program to lower oxygen values will take place. This
Nevertheless passivation by oxygen was necessary in will probably be a along term test!
order to maintain corrosion resistance, as it was the case In case oxygen content is near zero and everything
with the high austenitic steel 25/22/2. is going OK, then the equipment shown in red in
Fig.1.1.2a-1 will not be needed, resulting in important
• High mechanical strength, good weldability, savings in investment and operating costs! Stamicarbon
formability claims that savings of up to 10% in investment cost
• Comparably good corrosion resistance in urea- have been achieved.
carbamate solution Finally it is worthwhile mentioning here that a
• Slightly less passivation oxygen resulting in smaller Safurex made stripper ordered for a CO2 strip-
slightly more CO2 compressor capacity ping plant was installed as part of an urgent replace-
• Thinner pipes resulting in less weight, less ma- ment of the failed original stripper in a Snamprogetti
terial cost (2.5-3.0 times higher yield strength large urea plant two years ago. Next inspection will
than 316 Urea grade stainless steel) show if Safurex can withstand with similar, or better
• High resistance to stress corrosion cracking in corrosion resistance rate as bimetallic Zirconium tubes,
chloride containing environment operating under the conditions typical for a Snampro-
• Thermal expansion close to carbon steel getti design urea synthesis and to be a cheaper alterna-
• Duplex steel pipes for 16” HP piping needed tive to a Zr tube and entirely Zr lined stripper.
for large capacity plants
• Duplex stainless steel is easy to passivate com-
pared to austenitic one, which means duplex
steel requires less amount of dissolved oxygen
1.3 Recent efficient revamping Techniques
compared with austenitic stainless steel applied for large capacity (40-50%) &
efficiency increase
Additional properties of Special Duplex steel Sa-
furex
In Fig.1.3.0 the bottlenecks and over-designs,
which are usually available in many plants, are given.
The new Duplex steel Safurex with up to 28.5-30 %
The right time for improvements is always, when im-
Cr, developed in co-operation of Santvik and Stamicar-
portant aged equipment needs replacement: This can
bon is promising to eliminate almost entirely the use of
save up to 50% investment cost against new plant. In
passivation air:
the below given list of Figures, attached to the end of
• high Cr content, min. 28.5%, excellent corro-
the paper text, the various applied technologies are
sion resistance in pilot tests without passivation
given and their most important characteristics are com-
• Thinner tubes resulting in more stripping sur-
mented:.
face for same OD tube, due to higher yield
• Less stripper tubes, resulting in less material, Fig. 1.1.3a Adding a MP decomposition section. A
less stripper weight (-16%) concept developed by Stamicarbon, as explained in
• Almost nil passivation oxygen requirements, paragraph 1.1.3 above and shown in Fig.1.1.3a. The
resulting in more CO2 compressor capacity

AMMONIA TECHNICAL MANUAL 314 2004


concept of combining Pool Reactor with 20 bar Re- 1.4 Urea Granulation Developments
circulation section is under construction in DSM -
Geleen / The Netherlands 1.4.1 Most important features:
• Melt water content from 1.0 to 6%: merits –
Fig. 1.3.1 Adding a parallel stripper to CO2 strip- demerits: finally Hydro granulation by 95%
ping plant: Stamicarbon CO2 Stripping Revamping by urea melt represents an overall optimum in
Parallel Stripper of 25% additional stripping surface terms of investment –operating cost and prod-
was successfully applied in a 2000 MTD design capac- uct quality
ity urea plant in Saskferco Canada. 40- 50% capacity • Dispersion of melt to fine droplets, or to melt
increase has been obtained. For this revamping a rela- film: to evaporate humidity from 95% melt it is
tively large reactor volume was available and the exist- apparently necessary to atomize it to fine drop-
ing conventional HPCC has been stretched to the lets. The consequence is dust formation and
maximum of its potential. In order to obtain this high aerosols in the granulator and necessity to in-
capacity boost HETs have been provided and passiva- crease formaldehyde content, to act as crystal-
tion air has been replaced by oxygen-enriched air. lization retarder and keep dust formation under
control.
Fig. 1.3.2 Adding an HP condenser & decomposer • Water evaporation effect on cooling, on granu-
and a small 160 bar reactor to a conventional TR plant: lator size, on final water content in product,
Urea Casale HEC process for large capacity increase. and on spraying energy: the penalty of high
concentration melt is the need for higher fluidi-
Fig. 1.3.2a Adding a 240 bar small reactor, HP con- zation-cooling air flow, the bigger size of
denser & decomposer to a conventional stripping plant: granulator- scrubber
Urea Casale HEC process • High content Crystallization Retarder (Formal-
dehyde) needed to allow fine droplets to stick
Fig. 1.3.3 Adding a pool condenser and a CO2 on seeds: the main advantage of the Stamicar-
stripper to conventional TR plant: Stamicarbon in Petro bon process requiring almost 50 % less For-
China Ningxia Petrochemical Company a Pool Con- maldehyde to achieve good quality granules.
denser for a 2610 MTPD final capacity Urea Revamp • Avoid entrapment of dust on seeds by too high
fluid air temperature and too low formaldehyde
Fig. 1.3.4 Revamping a falling film vertical HPCC content, if melt is dispersed to fine droplets
to a submerged thermosyphon type Full Condenser by • Developments to achieve grain classification
Casale, First Reference in the 1100 MTD Styrol urea inside or at granulator out-let granulator not yet
plant in Gorlovka –Ukraine where Capacity was in- applied industrially (Hydro, Casale, Bayer pat-
creased to 1500 MTD ents) for urea granulation.
1.4.2 Established Urea Granulation Technologies:
Fig. 1.3.5 Adding a Toyo VSCC and a CO2 stripper
for a retrofitting of conventional TR plant, increasing More and more urea granulation plants are built in
its capacity to 2460 MTD the last years, with capacities of more than 3500 MTD.
This trend is expected to accelerate in the year to come.
Fig. 1.3.6 Adding an HP decomposer to decompose In the listed below Figures, attached at the end of the
recycled carbamate >>Reactor operates at high conver- paper, the most important characteristics of the various
sion due to low H/C ratio: Casale VRS concept for re- Granulation Technologies are given:
vamping stripping urea plants. This concept has been Hydro Agri (Figs.1.4.2a-1/2)
applied in the Agrium’s Carseland, Alberta, Canada and Toyo (Fig.1.4.2b-1)
plant capacity has been increased from 1920 to 2350 New Stamicarbon FBG Process (Fig. 1.4.2c-1)
MTD in 1997
Hydro Agri, Toyo are well-established Urea Granu-
Fig. 1.3.7 Use enriched in Oxygen Air for passiva- lation technologies with many plant references and
tion, (for small capacity increase, when applied alone). large number of technical literature. In the attached
Figures only the main characteristics of these processes

2004 315 AMMONIA TECHNICAL MANUAL


are given for comparison to the new Stamicarbon Urea eliminating caking problems in bulk storage.
Granulation. This can be achieved by the use of an improved
prilling device, in connection with a simplified
Stamicarbon Urea Granulation Technology is, to BFC, as described in Fig. 1.5.1 & 2
date, in industrial operation in only two relatively • In case that due to screens disoperation, or
small-capacity (280 and 650 MTD) revamped plants. In granulation upset conditions, a dusty product is
2004 three plants of 2000 MTD each are in design fed to the FBC, most of the fines and all the
phase and will be in operation in 2006, all three in dust would have blown to the scrubber, block-
Egypt. In Fig. 1.4.2c-1 the main features of the Granu- ing its operation. For the same as above case
lator are given and in Fig. 1.4.2c –2 a Delta operating with BFC, if proper provisions, described in
and investment cost comparison between Stamicarbon Fig. 1.5.3 / 4, are taken to avoid condensation,
and Hydro Granulation process in given. the operation could continue without any
blockage.
Single line granulation units up to 4500 MTD and
above should be possible without restrictions imposed As shown in Fig. 1.5.4, urea with 0.20 - 0.25%
by design, or manufacturing /erection. Possibly, in or- Formaldehyde content behaves differently as freshly
der to reduce equipment size and layout requirements it granulated urea with 0.55%-0.60% F, in terms of mois-
will be preferable to combine air fluidization –cooling ture absorption, due to extra hygroscopicity of Urea -
in the granulator with indirect water-cooling and /or re- formaldehyde pre-condensate in the molten liquor solu-
place conventional voluminous Fluid Bed Coolers tion phase being in equilibrium with solid crystalline
(FBC) with Bulk Flow Coolers (BFC). phase and due to the extra surface activity in the porous
structure of granular urea with high F content. That
means Granular urea from the new Stamicarbon Granu-
1.5 Advanced features for urea cooling lation process, with only 0.25% F, could be cooled in
the final, as well as in the primary cooler more effi-
For the cooling of urea (prilled or granular), as well
ciently by the use of BFC, in terms of investment and
as for other nitrogenous fertilizer grades, the most com-
operating cost.
mon method of cooling is by a Fluidized Bed Cooler
(FBC), where the method of cooling by Bulk Flow
Cooler (BFC) has found a relatively restricted ap-
plication only, although cooling by FBC has some im-
portant disadvantages:

• High investment cost: FBC, Scrubber, blowers,


air chiller, large ductwork, important civil
works- instrumentation
• High operating cost: about 1.8 MW are re-
quired for a 2000 MTD nitrogen fertilizer
granulation plant for cooling by FBC, against
200 kW for cooling by BFC
• Extended lay-out required to accommodate vo-
luminous equipment and duct work
• Complex Design in which many vendors are
usually involved
• Interference with process by recycling ammo-
nia –process condensates. If treated process
condensates containing formaldehyde are used
as boiler water in HP boilers, risk of corrosion
is imminent.
• For prilled urea, the use of FBC for dedusting,
allows only partial urea cooling, not entirely

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