Revamping of CO2 removal section in Ammonia plant at IFFCO Kalol

Abstract
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)

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-2Physical absorption processes generally use an organic solvent which absorbs CO2 as a function of its partial pressure. Due to high CO2 loadings, which are attainable, low circulation rates and less utility costs are involved for these types of processes. The most commonly used physical absorption process is Selexol process where solvent used is a homologue of diethylether of polythelene-glycols. The chemical absorption process can be classified in three main categories ;the hot potassium carbonate process, the alkanolamines process and other chemical absorption process. Commercially available Hot potassium carbonate processes are Befield process, Glycine Vetrocoke process and Cataract process. In Alkanolamines processes solution has an amine component. Mostly used solutions were monoethanolamine (MEA), diethanolamine(DEA) etc. Present day most preferred solution in alkanolamines processes is activated Methyl Diethanol Amine (a-MDEA). 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. The bulk of the solution can be regenerated by simple flashing, leading to very low energy consumption.

2.0 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, the CO2 removal processes are being continuously improved. 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. 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 99.5 99.95 99.95 100 100 100 32,000 29,000 9,500 Selexol

CO2 purity % CO2 slip in product gas, ppm Energy required Kcal/kgmole of CO2

99.0 100 36,000*

99.0 100 25,000

98.5 500 19,000

99.4 300 16,000

98.5 500 6,000@

* Based on the actual plant data. @ Additional refrigeration system is required for selexol process. Contd..3/-

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3.0 Details of CO2 Removal section at IFFCO Kalol

During the selection of Technology, Monoethanol amine (MEA) solution with sieve tray tower design were selected for CO2 removal section of ammonia plant at IFFCO Kalol. Please refer figure -1. Mononethanol amine solution is highly corrosive and problems of corrosion in CO2 removal section were experienced resulting in frequent shutdown, loss of production and higher energy consumption. To reduce the corrosion rate and for energy saving, UCAR Amine Guard -II system was installed in 1979. With the adoption of UAGII, system, it was possible to reduce the reboiler steam in the CO2 stripper reboiler by 25 t/hr. As a result of this change, frequent failures in the CO2 removal section was eliminated. Reduction in energy consumption was 0.13 Gcal/t of ammonia. This does not include the gain realized by uninterrupted running of the plant. Later while attempting to uprate the plant in 1994 from 910 tpd to 1100 tpd, CO2 removal section was also one of the bottlenecks, due to use of naphtha as part of feed stock. CO2 production was increased by 27 %. UCAR Amine guard II CO2 removal system was major limitation for plant capacity increase to 1100 tpd. 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.

Various CO2 removal processes were studied to suit our requirement and it was found that a-MDEA process is the most suitable.

3.1 Advantages of a- MDEA Process:

The main advantages of activated MDEA process as against other processes are summarized below: 1. Higher CO2 removal in activated MDEA process with same equipments and lower circulation rate. 2. Low inerts make-up in synthesis gas due to low CO2 slip. This was desired because of the existing synthesis section is designed for low inerts. Low CO2 slip with product gas has further advantages such as less consumption of H2 in methanator, higher conversion per pass in synthesis converter due to less inerts and reduction in purge gas from synthesis loop. Contd..4/-

-43. Purity of CO2 in case of activated MDEA process is 99.8 % while in case of other processes, it is about 98. 5 %. The hydrogen content in CO2 in case of activated MDEA is less. The hydrogen content in CO2 makes explosion mixture in urea plant and higher hydrogen increases the ammonia losses. Higher hydrogen also has an influence on corrosion in urea process because it contributes to hydrogen penetration and consequent destruction of oxide film. 4. Utilisation of all the existing equipments i.e. not making any changes in the system. 5. Lower energy requirement. 6. Lower MDEA make up requirement. 7. MDEA (Methyl diethanol amine) is environment friendly and biodegradable chemical. 8. MEA solution is a corrosive solution, while MDEA is non-corrosive. Hence MDEA system does not require any corrosion inhibitor. 9. Additional refrigeration system was required for Selexol process.

3.2 Revamping at IFFCO Kalol

After detailed study, it was found that BASF's activated MDEA process is most suitable to our requirement. Following three modules for revamping the existing CO2 removal section were available. 1) Straight solution swap. 2) Single stage MDEA process. 3) Two stage MDEA process. Considering the steam network of the plant and utilisation of all the existing equipments i.e. no addition of new equipments, it was decided to go for straight solution swap. 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

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3.2.1 Low energy requirement:

With MEA system energy consumption was 36000 Kcal/kgmol of CO2 removed. With a-MDEA, 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. The energy requirement and operating parameters of both the processes are summarised in table-2. The 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. 40% MDEA solution along with 6.5% piprazine is circulated in close loop in the system. CO2 loading in rich MDEA solution remains 35 to 45 Nm3/t of solution. While CO2 loading in lean solution remains about 5 Nm3/t of solution. After change over, iron in the circulating solution is remaining below 5 ppm. CO2 slip in the product stream is remaining below 250 ppm (v/v). Table-2 : Energy requirement and Process parameters Sr. No. Parameters MEA UCAR a-MDEA, amine guard II straight solution swap 910 1100 40 35 36000 780 <100 99 93 118 --26000 620 <250 99 84 114 0.08

1. 2. 3. 4. 5. 6. 7.

8.

Plant load, tpd Reboiler duty, Gcal/hr Energy requirement, Gcal/Kgmole of CO2 removed Solution circulation rate m3/hr CO2 slip in raw syn gas, ppm CO2 product gas purity, % Stripper Temperature, deg C Top Bottom Energy savings Gcal/t

3.2.2 No Capital Cost :

Direct swap of a-MDEA 05 in CO2 removal system do not require any addition of new equipments. Additional capital cost required in this option was zero. Only requirement was replacement of MEA solution with a-MDEA solution. Also time required to change over system is about 1 week which was carried out in short shut down. Contd..6/-

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3.2.3 Lower MDEA Makeup:

Activated MDEA has a low vapour pressure, hence solution losses are quite low. Average makeup requirement of the solvent is 10-12 t per year. However with MEA system make-up quantity used to be 35 to 40 t per year. The solution has long term shelf life and high chemical and thermal stability.

3.2.4 Environment friendly and biodegradable chemical

IFFCO Kalol plant is situated in a land locked area. MEA solution was posing an environmental and pollution problem. MDEA solution is a non toxic, easily biodegradable, environment friendly and non corrosive solvent.

3.2.5 Lower operating cost

With a-MDEA straight solution swap, operating cost of CO2 removal section is lower than the MEA UCAR amine guard system. MDEA is non corrosive solution hence it became possible to isolate the corrosion inhibition system of UCAR amine guard. This in turn saves the costly inhibitors and operating cost of the system. Total operating cost of a-MDEA system is much lower than the MEA system.

4.0 Change over from MEA to a-MDEA system :

For smooth change over, all the equipments of CO2 removal section was thoroughly cleaned with DM water. Exchangers were hydrojetted from shell and tube sides. 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. Solution was circulated for 15 hrs. Then solution was drained. System was again filled with DM water. MDEA was charged and concentration was slowly increased to 40 %. Following problems were faced during the lining up of a-MDEA system :-

4.1 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. However, during the second month of operation, when activated carbon bed filter was taken in line foaming severity increased, resulted in higher requirement of anti foamer.

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Also this increased higher reflux ratio, higher concentration of MDEA in reflux and higher hydrogen concentration in product CO2. Hydrogen concentration reached as high as 1.2 to 1.4% (V/V) from 0.8 % V/V. Higher dosing of anti foamer agent did not reduce the foaming tendency. Antifoamer consumption remained very high. Mechanical filters provided at absorber liquid outlet, carbon filter inlet and carbon filter outlet was cleaned and found that lot of antifoamer is being removed in the filters. Activated carbon bed was isolated, foaming tendency reduced. With time the system has become stable, system is working extremely well.

4.2 Stripper inlet distributor failure

During the change over, the size of the distributor pipe in both the CO2 strippers was increased from 10 inches to 12 inches. 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, there is failure of the inlet distributor and its supporting system. To overcome this problem it is proposed to increase the distributor pipe size to 14 inches. Inlet flow control valves and down stream piping will also be modified.

4.3 Thermosyphon breaking in steam reboiler of strippers

There are two steam reboilers. Each boiler was originally designed for condensing the 31700 kg/hr 3.2 kg/cm2g steam. After changing over to a-MDEA system, due to low energy requirement, steam flow has come down to about 7500 kg/hr in each reboiler. Lower steam requirement has reduced the natural circulation in the reboilers. This breaks the thermosyphon phenomena of the reboilers. Due to thermosyphon breaking steam flow used to vary from 4000 kg/hr to 10000 kg/hr. Steam flow variations are controlled by throttling the steam line manual valve.

5.0 Conclusion
Activated MDEA process is most suitable in the plants which are using MEA CO2 removal process. IFFCO Kalol is satisfied with the operating performance, operating reliability and low maintenance of a- MDEA system. a-MDEA system was the excellent choice for revamping the CO2 removal section. Operation of the system is excellent and smooth even at uprated plant load with least energy requirement.