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Carbon dioxide removal section in ammonia plant is highly energy intensive. Many developments have been made to make it more energy efficient and environmental friendly. a-MDEA process for CO2 removal is one of the best available process to meet the specific plant conditions of high CO2 purity, minimum H2 loss, no corrosion, low energy requirement and low capital investment. At IFFCO Kalol MEA CO2 removal process was revamped to direct solution swap of a-MDEA process. Revamping of CO2 removal section was part of uprating the plant capacity for higher production. a-MDEA process have increased the CO2 absorption capacity and reduced the energy
requirement with no capital cost. 1.0 Introduction
Carbon dioxide is an undesirable constituent in the synthesis gas because it poisons the ammonia synthesis catalysts. CO2 content in the synthesis gas therefore must be reduced to 5 to 10 PPM by volume. CO2 absorption is carried out by selective absorption after the low temperature shift conversion. The CO2 removal processes are based on chemical and physical absorption of CO2 in a solvent. There are number of processes available to remove CO2 from the synthesis gas. Based on the process used, the gas absorption can be classified as Physical or Chemical absorption process.
A.M. Kunjunny Senior General Manager
M.R. Patel Senior Manager (Process)
Navin Nath Senior Engineer (Process)
leading to very low energy consumption. Contd. Mostly used solutions were monoethanolamine (MEA).3/- .0 Various CO2 removal processes CO2 removal is a significant step in ammonia production process with respect to investment and energy consumption and due to fast increasing energy costs. Salient features of different CO2 removal processes are given in table-1 : Table-1 : Salient Features of different CO2 removal systems Parameters MEA UOP-II MEA UOP IV Benfield Glycine Vetrocoke a-MDEA Straight Single Double solution stage Stage Swap 99..-2Physical absorption processes generally use an organic solvent which absorbs CO2 as a function of its partial pressure. diethanolamine(DEA) etc.000@ * Based on the actual plant data. low circulation rates and less utility costs are involved for these types of processes.5 500 6. Due to high CO2 loadings.000 9. Present day most preferred solution in alkanolamines processes is activated Methyl Diethanol Amine (a-MDEA).500 Selexol CO2 purity % CO2 slip in product gas. Commercially available Hot potassium carbonate processes are Befield process.000 29.95 99. The bulk of the solution can be regenerated by simple flashing.000 99. @ Additional refrigeration system is required for selexol process. The most commonly used physical absorption process is Selexol process where solvent used is a homologue of diethylether of polythelene-glycols. the alkanolamines process and other chemical absorption process.000* 99. which are attainable.0 100 36. As a result of this the requirement of energy has been reduced from 36000 Kcal/kg mol of CO2 removed to about 9500 Kcal/kg Mol of CO2 removed. The chemical absorption process can be classified in three main categories .000 98.5 99. ppm Energy required Kcal/kgmole of CO2 99. the CO2 removal processes are being continuously improved.the hot potassium carbonate process. Glycine Vetrocoke process and Cataract process.0 100 25. 2.4 300 16.5 500 19.000 98. Activated MDEA process for CO2 removal is a physical/chemical absorption process. It behaves as a physical absorption process at higher partial pressure of CO2 and as a chemical absorption process at low CO2 partial process.95 100 100 100 32. In Alkanolamines processes solution has an amine component.
loss of production and higher energy consumption. Low inerts make-up in synthesis gas due to low CO2 slip. higher conversion per pass in synthesis converter due to less inerts and reduction in purge gas from synthesis loop. With the adoption of UAGII. Reduction in energy consumption was 0. Low CO2 slip with product gas has further advantages such as less consumption of H2 in methanator. Monoethanol amine (MEA) solution with sieve tray tower design were selected for CO2 removal section of ammonia plant at IFFCO Kalol. This was desired because of the existing synthesis section is designed for low inerts.MDEA Process: The main advantages of activated MDEA process as against other processes are summarized below: 1.1 Advantages of a. Revamp of CO2 removal section was carried out for:- • • • • Increasing CO2 removal capacity To reduce specific energy consumption To reduce corrosion rate To adopt environment friendly and biodegradable chemicals. Please refer figure -1. Later while attempting to uprate the plant in 1994 from 910 tpd to 1100 tpd.0 Details of CO2 Removal section at IFFCO Kalol During the selection of Technology. CO2 production was increased by 27 %. To reduce the corrosion rate and for energy saving. 2. system. Higher CO2 removal in activated MDEA process with same equipments and lower circulation rate. frequent failures in the CO2 removal section was eliminated. As a result of this change. Various CO2 removal processes were studied to suit our requirement and it was found that a-MDEA process is the most suitable. Mononethanol amine solution is highly corrosive and problems of corrosion in CO2 removal section were experienced resulting in frequent shutdown. This does not include the gain realized by uninterrupted running of the plant. due to use of naphtha as part of feed stock.4/- . it was possible to reduce the reboiler steam in the CO2 stripper reboiler by 25 t/hr.13 Gcal/t of ammonia. CO2 removal section was also one of the bottlenecks. UCAR Amine Guard -II system was installed in 1979.. 3. UCAR Amine guard II CO2 removal system was major limitation for plant capacity increase to 1100 tpd. Contd.-3- 3.
. 1) Straight solution swap. 5. The hydrogen content in CO2 makes explosion mixture in urea plant and higher hydrogen increases the ammonia losses. The hydrogen content in CO2 in case of activated MDEA is less. MEA solution is a corrosive solution. 2) Single stage MDEA process. 3. Purity of CO2 in case of activated MDEA process is 99. Considering the steam network of the plant and utilisation of all the existing equipments i. 7. it was decided to go for straight solution swap. Utilisation of all the existing equipments i. 8. no addition of new equipments. 3) Two stage MDEA process.2 Revamping at IFFCO Kalol After detailed study. Following three modules for revamping the existing CO2 removal section were available.-43. 4. 9. not making any changes in the system. Hence MDEA system does not require any corrosion inhibitor.8 % while in case of other processes. Lower energy requirement. 6.e. it is about 98. while MDEA is non-corrosive. Following benefits are achieved with a-MDEA (methyl diethanol amine) straight solution swap system : 1) 2) 3) 4) 5) Low energy requirement No capital cost Lower MDEA make up Environment friendly and biodegradable chemical Lower operating cost and Non corrosive chemical Contd.5/-5- . Lower MDEA make up requirement.e. MDEA (Methyl diethanol amine) is environment friendly and biodegradable chemical. Additional refrigeration system was required for Selexol process. 5 %. Higher hydrogen also has an influence on corrosion in urea process because it contributes to hydrogen penetration and consequent destruction of oxide film. it was found that BASF's activated MDEA process is most suitable to our requirement.
With a-MDEA. Additional capital cost required in this option was zero. iron in the circulating solution is remaining below 5 ppm.5% piprazine is circulated in close loop in the system. 8. CO2 loading in rich MDEA solution remains 35 to 45 Nm3/t of solution. Gcal/Kgmole of CO2 removed Solution circulation rate m3/hr CO2 slip in raw syn gas. Only requirement was replacement of MEA solution with a-MDEA solution. After change over. The energy requirement and operating parameters of both the processes are summarised in table-2. 6. 7.3.5 kg/cm2g steam requirement in steam reboiler remains at 10 to 15 t/h against earlier steam consumption of 20 to 25 t/h even though CO2 removal requirement is 27% higher. CO2 slip in the product stream is remaining below 250 ppm (v/v).2. 2. 4. While CO2 loading in lean solution remains about 5 Nm3/t of solution. it was possible to reduce the energy consumption to 26000 Kcal/kgmole of CO2 removed as against the design consumption figure of 32000 Kcal/kgmol of CO2 removed.1 Low energy requirement: With MEA system energy consumption was 36000 Kcal/kgmol of CO2 removed.2. No. 40% MDEA solution along with 6. deg C Top Bottom Energy savings Gcal/t 3. Gcal/hr Energy requirement. Table-2 : Energy requirement and Process parameters Sr.2 No Capital Cost : Direct swap of a-MDEA 05 in CO2 removal system do not require any addition of new equipments.6/- . Parameters MEA UCAR a-MDEA. 5. Contd. tpd Reboiler duty. Also time required to change over system is about 1 week which was carried out in short shut down. % Stripper Temperature.. amine guard II straight solution swap 910 1100 40 35 36000 780 <100 99 93 118 --26000 620 <250 99 84 114 0. The 3. 3.08 1. Plant load. ppm CO2 product gas purity.
MDEA solution is a non toxic. Solution was circulated for 15 hrs. hence solution losses are quite low. all the equipments of CO2 removal section was thoroughly cleaned with DM water. Following problems were faced during the lining up of a-MDEA system :- 4.5 Lower operating cost With a-MDEA straight solution swap.4 Environment friendly and biodegradable chemical IFFCO Kalol plant is situated in a land locked area. System was again filled with DM water and 4 % K2C03 solution and the temperature in the system was maintained to 70 deg C by lining up steam in the reboilers.1 Foaming problem During change over for about one month the activated carbon bed filter was not taken in line and foaming tendency was not observed.2. Exchangers were hydrojetted from shell and tube sides. environment friendly and non corrosive solvent. 3. easily biodegradable. 4. resulted in higher requirement of anti foamer. MEA solution was posing an environmental and pollution problem. MDEA was charged and concentration was slowly increased to 40 %. The solution has long term shelf life and high chemical and thermal stability. Contd.-6- 3. However with MEA system make-up quantity used to be 35 to 40 t per year.3 Lower MDEA Makeup: Activated MDEA has a low vapour pressure.0 Change over from MEA to a-MDEA system : For smooth change over. Average makeup requirement of the solvent is 10-12 t per year. operating cost of CO2 removal section is lower than the MEA UCAR amine guard system. Then solution was drained. when activated carbon bed filter was taken in line foaming severity increased. Total operating cost of a-MDEA system is much lower than the MEA system. 3. System was again filled with DM water. during the second month of operation. This in turn saves the costly inhibitors and operating cost of the system. MDEA is non corrosive solution hence it became possible to isolate the corrosion inhibition system of UCAR amine guard.2.2.. However.7/- .
the size of the distributor pipe in both the CO2 strippers was increased from 10 inches to 12 inches.4% (V/V) from 0. a-MDEA system was the excellent choice for revamping the CO2 removal section. Due to thermosyphon breaking steam flow used to vary from 4000 kg/hr to 10000 kg/hr. operating reliability and low maintenance of a. After changing over to a-MDEA system.2 kg/cm2g steam. foaming tendency reduced. Size of the distributor was increased to take care the higher vapour generation in the MDEA system. Even after increasing the size of the distributor pipe. carbon filter inlet and carbon filter outlet was cleaned and found that lot of antifoamer is being removed in the filters. system is working extremely well. 4. Mechanical filters provided at absorber liquid outlet.3 Thermosyphon breaking in steam reboiler of strippers There are two steam reboilers. 5. IFFCO Kalol is satisfied with the operating performance. Activated carbon bed was isolated. Inlet flow control valves and down stream piping will also be modified. 4. . Steam flow variations are controlled by throttling the steam line manual valve. Antifoamer consumption remained very high. there is failure of the inlet distributor and its supporting system. due to low energy requirement.-7- Also this increased higher reflux ratio. Hydrogen concentration reached as high as 1. higher concentration of MDEA in reflux and higher hydrogen concentration in product CO2. Each boiler was originally designed for condensing the 31700 kg/hr 3. Lower steam requirement has reduced the natural circulation in the reboilers. steam flow has come down to about 7500 kg/hr in each reboiler.MDEA system.0 Conclusion Activated MDEA process is most suitable in the plants which are using MEA CO2 removal process. With time the system has become stable. Operation of the system is excellent and smooth even at uprated plant load with least energy requirement.8 % V/V.2 to 1. Higher dosing of anti foamer agent did not reduce the foaming tendency.2 Stripper inlet distributor failure During the change over. This breaks the thermosyphon phenomena of the reboilers. To overcome this problem it is proposed to increase the distributor pipe size to 14 inches.
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