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Jan van der Werf, Jo Eijkenboom, Alex Scheerder, Stamicarbon bv, The Netherlands A. Reza Foolad, Shiraz Petrochemical Company, I.R. Iran
ABSTRACT Shiraz Petrochemical Company (SPC) operates a Stamicarbon CO2 stripping urea plant since 1983 with a design plant capacity of 1500 mtpd near Shiraz in I.R. Iran. Early 2003 SPC installed the first Safurex® stripper in the world after experience was gained with Safurex® high efficiency trays in the urea reactor. As the high pressure carbamate condenser was made of BC.05 stainless steel, SPC offered the first opportunity to reduce the oxygen content in the CO2 from normally 0.6 vol.-% to 0.3 vol.-%. Stamicarbon and SPC agreed to perform a low oxygen test. The only reason to add oxygen is to passivate the stainless steels in the HP synthesis section in contact with the process medium. Having a Safurex® HP Stripper and BC.05 HPCC less oxygen is needed for passivation. Lowering the oxygen level in a urea plant leads to an improvement of the safety level. The ultimate goal is to operate an urea plant oxygen free, which is intrinsically safe. A pre-requisite is that all equipment must be in Safurex®. Lowering the oxygen level also leads to numerous other benefits such as lower energy consumption and lower investment figures. The low oxygen test at SPC is a milestone to realize an oxygen free and thus intrinsically safe urea plant. This paper presents the results of the low oxygen test at SPC both from process as well as from corrosion point of view. The low oxygen test demonstrated no increase in corrosion in the HP synthesis section. Process benefits were evident; increased reactor conversion, lower steam consumption in HP Stripper and lower ammonia emission. There are no limitations for the SPC plant to run the plant at 0.3 vol.-% oxygen. Based on this result, Stamicarbon specifies an oxygen content of 0.3 vol.-% in the CO2 feedstock in a Stamicarbon stripping plant when following pre-requisites are met: • HP Stripper in Safurex® material quality • HPCC / HP Poolcondenser in BC.05 material quality
LIST OF CONTENTS
1. 2. 3. 4. 5. 6. 7.
Introduction Low Oxygen Test Procedure Risk analysis Process consequences Corrosion consequences Process safety Conclusions
1. Introduction In the high pressure synthesis section (140 bar) of a Stamicarbon CO2 stripping urea plant, the prevailing process conditions are highly corrosive. Carbamate is the corrosive component. To protect the carbon steel pressure vessels these are lined or overlay welded with austenitic stainless steel at process side. Materials such as a 316L Urea Grade (Stamicarbon designation: BC.01) and X1CrNiMoN25-22-2 (Stamicarbon designation: BC.05) are used. Application of these stainless steels is only possible when oxygen is supplied to the synthesis. Stamicarbon recommends 0.6 vol % oxygen. Not withstanding this, still one has to account for passive corrosion rates varying between 0.05 to 0.1 mm/year, which is acceptable (corrosion allowance). However, a shortage on oxygen supply to the synthesis can result in a catastrophic increase in corrosion rates (> 30 mm/ year). Besides the risk for active corrosion, the presence of oxygen in the synthesis is not beneficial from process and safety point of view. Operating a Stamicarbon urea plant without oxygen therefore gives great technological benefits. The process scheme can be simplified by the deletion of several equipment items such as, amongst others, the HP scrubber and the 4 bar absorber. Besides a lower investment figure and longer lifetime also a lower energy consumption figure as well as higher plant output will be realized. Furthermore a urea plant without oxygen will be intrinsically safe. The requirement for an oxygen free urea plant is that all materials in the synthesis section, which are exposed to the process, are Safurex®. Safurex® is a duplex stainless steel (Stamicarbon designation: BE.06) which has excellent corrosion resistance under urea synthesis conditions without the need for passivating air (oxygen). When the alloy protection of the HP Carbamate Condenser is made from BC.05 material and the HP Stripper is made in Safurex®, one can already reduce the oxygen content that is needed for passivation. Stamicarbon expects that in this case the oxygen concentration can be reduced to 0.3 vol.-% instead of the typical 0.6 vol.-%. Shiraz Petrochemical Company is the first urea plant, which meets these requirements: The HP Carbamate Condenser is made in BC.05 material and the new HP Stripper is made in Safurex®. In the period of July 31 till September 18 2005, SPC in presence of Stamicarbon reduced the oxygen content to 0.3 vol.-%.
2. Low Oxygen Test procedure SPC operated the urea plant already at 0.45 vol.-% oxygen before the low oxygen test started. In order to judge the effect of lower oxygen content, base line readings were taken from July 31 till August 6: - Nickel content in the end product to monitor any increase in corrosion. - Essential process parameters to evaluate the effects on process conditions. Amongst others: temperature in top of Urea reactor and steam consumption in HP Stripper. On August 7 the oxygen was reduced to 0.3 vol.-% and the plant operated at this low oxygen level till September 9 and was stopped for a planned turnaround. Due to mechanical problems in the compressor the CO2 was kept constant (compressor speed and capacity did not change after reducing the oxygen content). In the TA a corrosion inspection was done in the HP synthesis section. First the base line of the Nickel content in the end product at higher oxygen content (0.45 vol.-%) was established: 0.2 ppm. In case of active overall corrosion the Nickel content will increase significantly by a factor 5 and thus readily detectable. After monitoring the Nickel content for 6 days, the oxygen content was reduced to 0.3 vol.-%. The Nickel content did not change during the test, see figure 1. The Nickel content of about 0.2 ppm is constant throughout the test.
[Ni] content end product (ppm)
0.35 0.50 0.3 oxygen content (vol % ) 0.40 0.25 [Ni] content (ppm )
Low Oxygen test
oxygen (vol %) [Ni] content (ppm)
24 /8 12 /8 31 /7 16 /8 20 /8 28 /8 4/ 8 8/ 8 1/ 9 5/ 9 9/ 9
Figure 1: Nickel content in end product (0.2 ppm). No change during Low Oxygen Test
3. Risk analysis As the proposed low oxygen test (0.3 vol%) is for the first time executed in a Stamicarbon CO2 stripping urea plant, the execution of a risk analysis before starting the test seems appropriate. 3.1. Risk analysis for Safurex® The risk to operate Safurex® with an oxygen content of 0.3 vol% can be qualified as non existing based on the following facts: 3.1.1. Zero oxygen tests on laboratory scale Stamicarbon did perform numerous corrosion tests at nearly zero oxygen levels in laboratory.
SAFUREX® 25.22.2 183ºC 183ºC 75 days 75 days 0,05 mm / yr > 30 mm / yr
mm / yr
Figure 2: Stamicarbon laboratory tests in oxygen free carbamate
From Figure 2 one can conclude that Safurex® can withstand very low oxygen contents contrary to the normal austenitic stainless steels. 3.1.2. Flange face leakage of SPC's Safurex® stripper Another evidence and experience was gained by incidence. In October 2003 as well as September 2005 a flange face leak occurred in the Safurex® stripper. Such a leak occurs in case the gasket in heavily damaged. Such an occurrence normally results in heavy corrosion of the gasket serrated ring (BC.03 material quality) and flange faces (BC.05 material quality) due to crevice corrosion (oxygen depletion in the crevice), see figure 3. In SPC's case the severeness of the corrosion could only be observed by the damage of the BC.03 serrated ring, see figure 4a. However the flange faces were intact, see
figure 4b and after cleaning and gasket replacement the operation could directly restart again. Not even machining was needed.
Figure 3: Flange faces after a leakage of the man way gasket in case of a BC.05 and Safurex® flange face. In the picture left the heavily corroded flange face (BC.05) is shown due to crevice corrosion. On the right hand side a Safurex® flange face is presented having no corrosion at all after a gasket leak
Not corroded Corroded BC.05 flange face
Figure 4a: (Sept. 2005): heavily corroded BC.03 gasket ring
Figure 4b: no corrosion of Safurex® flange face
Not corroded Safurex flange face
BC.03 serrated gasket ring
Not corroded Safurex flange face
3.1.3. Experiences in NH3 stripping plant No corrosion occurred in a plant test of Safurex® parts in a NH3 stripping plant at 0.25 to 0.30 vol% oxygen levels and elevated temperatures around 200 oC.
3.2. Risk analysis for Austenitic Stainless Steels 3.2.1. Conventional Urea plants Evidence that the oxygen content can be reduced safely to 0.3 vol.-% is the fact that in the old day’s conventional urea plants operated at oxygen levels of 0.3 vol.-%. The synthesis section of the conventional plants consisted of a reactor and mixer in BC.01 quality. Process conditions were even more severe from corrosion point of view: 190 °C and 200 bar. 3.2.2. HP carbamate condenser in BC.05 At SPC the HP carbamate condenser is made from BC.05. After the HP stripper the HP carbamate condenser is the most critical when reducing the oxygen content. In general corrosion is more critical at higher temperatures and low oxygen contents.
Figure 5: Temperature and partial oxygen content in the synthesis section
HP CC HP Scrubber Stripper
HP Carbamate Condenser
Figure 5 shows the temperature (red line) and partial oxygen content in the CO2 stream through the HP synthesis section. In the top of the Stripper the highest temperatures in combination with the lowest partial oxygen content prevails, indicating the worse corrosion conditions. In SPC the original stripper is replaced by a Safurex® stripper, making it no longer sensitive to corrosion anymore even at low partial oxygen pressures. Milder corrosion conditions prevail in the other equipment. The top of the HPCC is the second worse location in the synthesis form corrosion point of view. In SPC the original BC.01 HP carbamate condenser is replaced by a new HP carbamate condenser made from BC.05, a more corrosion resistant material quality. This means that also the HP carbamate condenser allows for a lower oxygen level for passivation.
4. Process consequences The reduction of the oxygen content first of all leads to more urea capacity as the air added in the CO2 compressor feed can now be replaced by CO2. Some 2% additional CO2 in this way is sent to the synthesis section at constant speed of the CO2 compressor. The reduction of the oxygen content resulted in • Increase in reactor top temperature (see figure 6) resulting in an increase in reactor conversion • This leads to a lower steam consumption in HP Stripper, see figure 7 These results are obtained at a synthesis pressure of 140 – 142 Bar.
Figure 6: Increase in reactor top temperature
Reactor Top Temperature (Deg C)
0.60 185 184.5 0.50 184 183.5 183 0.30 182.5 182 0.20 181.5 181 180.5 180
24 /8 16 /8 12 /8 20 /8 28 /8 4/ 8 8/ 8 1/ 9 5/ 9 9/ 9
Oxygen content (Vol % )
Low Oxygen Test
oxygen (vol %) Temperature (Deg C)
Tem perature (Deg C)
Figure 7: Reduction of steam consumption in HP Stripper
Steam Consumption Stripper (Tons/hr)
0.60 59 58 0.50 57 56
Oxygen content (vol %)
0.40 55 0.30 54 53 0.20 52
Low Oxygen test
oxygen (vol %) Steam (Tons/hr)
51 50 49
16 /8 20 /8 24 /8 28 /8 31 /7 12 /8 1/ 9 5/ 9 4/ 8 8/ 8 9/ 9
Reduced steam consumption per ton of end product of 40 kg was obtained.
4.1. Emission figures When less air is introduced in the HP synthesis the ammonia emission from the 4 bar absorber is reduced. In the SPC plant the throughput of the vent valve position of the 4 bar absorber was reduced from 50 % to 30 %.
5. Corrosion consequences The Nickel content during the low oxygen test did not change, indicating that there is no increase of corrosion. During the turnaround of the SPC plant, this observation was confirmed in the corrosion inspection of the HP equipment. The SPC plant was also inspected by Stamicarbon in 2000. The findings during this inspection can thus be compared. Based on the inspection in 2000 and 2005 the condition of the HP equipment is excellent taking into account the on-stream time of the equipment. 5.1. HP Stripper (Safurex®) The Safurex® stripper, installed in 2002 has an effective on-stream time of 1097 days (3 years). The average corrosion rate measured in the heat exchanger tubes of 0.05 mm/y was far better than the corrosion rate of the former BC.05 stripper; 0.09 mm/y. The lining and overlay welding in both top and bottom channels showed no corrosion. This was confirmed by UT thickness measurements. 5.2. HPCC (BC.05) The HPCC was replaced in 1996 and has an effective on-stream time of 1956 days (5,4 years). The corrosion rate of the heat exchanger tubes in the HPCC did not change before and after the low oxygen test. During the inspection in 2000 as well in 2005 the corrosion rate in the heat exchanger tubes nears to zero. Also the liners and overlay welding in top and bottom channels showed no corrosion, as was confirmed by UT thickness measurements. This is a normal corrosion behavior for BC.05 carbamate condenser in Stamicarbon stripping plants. 5.3. HP Reactor (BC.01) The HP reactor is still original, having a total effective on-stream time of 5277 days (14.5 years). Typical in the top of the reactor the highest corrosion will take place. Based on UT measurements a corrosion rate in the top part is 0.06 mm/y and also the corrosion rate did not change due to the low oxygen test. A corrosion rate of 0.06 mm/y is low; normally a corrosion rate of 0.1 mm/y is found. 5.4. HP Scrubber (BC.01) The HP Scrubber is still the original, except for the tube bundle, which was replaced in 1999. Effective on-stream time of the heat exchanger tubes mounts up to 1744 days (4.8 years). The corrosion rate measured in the tubes is 0.02 mm/y. This was also measured in 2000. Again there is no change in corrosion rate observed before and after the low oxygen test. 5.5. HP Piping (BC.01) At random UT wall thickness measurements on all HP pipelines showed no significant corrosion from process side.
6. Process safety The vapor stream in the synthesis with the highest risk with respect to flammability is the HP purge stream from the HP scrubber (highest hydrogen and oxygen concentration under high pressure and temperature). When reducing the oxygen content in the synthesis section, the composition of the HP purge stream will change (less oxygen), but also the total purge stream will reduce (ammonia purge will be lower). Both effects will result in a situation (at 0.3 vol % oxygen) in which the composition of the HP purge stream is moved away from the explosion limits of the O2 – H2 – NH3 mixture at the given circumstances. Thus the risk for explosions is reduced.
7. Conclusions The low oxygen test showed that the SPC plant can run safely with 0.3 vol.-% oxygen in the CO2 feedstock without any risk for higher corrosion rates in the synthesis section. Process benefits were clearly demonstrated; the reactor conversion increases, steam consumption in the HP Stripper reduces and ammonia losses decreases. There became more room to increase the compressor capacity for higher plant production. The SPC compressor speed however was limited for mechanical reasons. Finally the plant runs safer at lower oxygen levels, since the composition of the HP purge system moves away from the explosion limits. The ultimate goal is to have zero oxygen for an intrinsically safe plant. This can only be realized by having all equipment in the synthesis section in Safurex®. However for existing urea plants Stamicarbon decided to set the oxygen content in the CO2 feedstock at 0.3 vol.-% when following pre-requisites are met: • HP Stripper in Safurex® (BE.06) • HPCC / HP Poolcondenser in BC.05 material quality Thus, all urea plants having a Safurex® stripper and a BC.05 HP carbamate condenser or Poolcondenser have the possibility to increase the safety level and benefit from process advantages by lowering the oxygen content to 0.3 vol.%.
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