Amine Degradation: Problems, Review of Research Achievements, Recovery Techniques

Majid Abedinzadegan Abdi, Ph.D., P.Eng. Head of Gas Research Division Research Institute of Petroleum Industry Pajoheshgah Blvd.,Old Qom Road, Tehran, Iran E-mail:abedinzadeganm@nioc-ripi.org

Axel Meisen, Ph.D., P.Eng. President and Vice-Chancellor of the Memorial University of New Foundland and Professor of Chemical Engineering President Office St. Johns, NF, Canada A1C 5S7 E-mail:president@mun.ca

ABSTRACT Amine solutions, which are widely used in the gas processing industry for the removal of acid gases, frequently become contaminated with amine degradation products, heat stable salts, heavy hydrocarbons and particulates. The source of impurities are discussed together with their principal effects on plant operations, i.e. reduced capacity, operational instabilities and corrosion. Amine based gas purification plants generate large volumes of spent solution which are disposed of by incineration or deep well injection. This practice is not environmentally beneficial and constitutes a loss of valuable amine since the spent solutions usually contain up to 85% of the virgin amine. A rather comprehensive review of the latest research activities on amine degradation is presented. Methods for coping with impurities are also presented with particular emphasis on the recovery techniques proposed by authors and other researchers or companies.

INTRODUCTION Most sour gas processing facilities use chemical absorption using alkanolamines (or amines in short) to separate hydrogen sulfide and carbon dioxide from the raw gas. The alkanolamines of prime significance include monoethanolamine (MEA), diethanolamine (DEA), methyldiethanolamine (MDEA), diisopropanolamine (DIPA), and diglycolamine (DGA). Normally the amine processes are cycles of absorption and desorption in order to permit the use of the absorbent. Due to the closed loop nature of these processes, non-regenerable contaminants tend to accumulate and can cause major reduction in efficiencies and operational problems. This paper focuses on contaminant issues in amine plants and the impact on the gas plant operations. NATURE OF CONTAMINANTS Contaminants in amine solutions can arise from various sources and usually exist in several different forms. Although a single contaminant may necessitate a certain plan of action, gas treating solutions rarely contain only process.
Amine Degradation Products

one or two impurities.

Instead, many different

impurities exist in varying concentrations, many of which have some adverse effect on the

Although the acid gas-amine reactions are reversible, irreversible reactions may also occur, resulting in products from which the amines are not easily recovered. This phenomenon is called degradation. Amines may be degraded through the following routes: 1. 2. 3. 4. 5. 6. 7. Thermal degradation CO2 induced degradation Degradation caused by COS and CS2 Degradation by carbon monoxide Amine loss through the formation of heat stable salts and the reaction of amines with Oxidation Sulfur and polysulfide degradation

strong acids

Extensive studies have been conducted to provide insight into alkanolamine degradation caused by the presence of carbon dioxide, carbon disulfide and carbonyl sulfide and their mixtures [1-10]. Thermal degradation of alkanolamines has also been addressed [4,5]. Previous studies have shown that the degradation rate (particularly the CO2 induced degradation) depends on the chemical structure of the amines and the plant operating conditions. The presence of oxygen in the sour gas streams or treating solutions may cause oxidative degradation and lead to the production of organic acids [11]. The presence of some anionic species and/or stronger acids (as compared with hydrogen sulfide and carbon dioxide) in the raw feed gas to amine plants, leads to the formation of amine salts from which amine is not recoverable through steam stripping process. The amine salts are called heat stable salts and both organic and inorganic salts may occur. The inorganic salts such as chloride, sulfate and phosphates typically are found in produced or cooling waters. Sulfate and thiosulfates and cyanates can also be formed by reaction between oxygen and H2S and cyanic acid and H2S, which are more prevalent in petroleum refinery gases. The issue of degradation induced by the presence of sulfur, polysulfides and carbon

monoxide is a subject that oil refiners and gas plant operators have been dealing with during the past few years. In FCC units of petroleum refineries the CO formed during the fluidized regeneration of the cracking units slips to the gas purification units. Carbon monoxide reacts very slowly with the amine and forms formyl compounds. Degradation of amines by sulfur and polysulfides in oil refineries and gas plants is also a rather new disturbing subject for plant managers. Some researchers believe that the formation of formyl compound and degradation of amine by sulfur and polysulfide may be inter-related.

Non-volatile Contaminants and Suspended Solids

Non-volatile contaminants arise from diverse sources such as gas wells or make up water. Another common types of non-volatile contaminants are particulates, which may be carried into the amine solution by the raw feed gas. Iron sulfide is very common and undesirable, usually because of its potential to stabilize foams or enhance foaming tendencies. Solid contaminants of any type can decrease the efficiency of the absorber and stripper by plugging contactor trays, contactor packings and process piping. The exact situation has been occurring at the Kangan gas plant and has troubled the plant capacity increase programs. One solution is to use filter cartridges with very small pore sizes inside the inlet separators to catch the very fine particles whose average diameters are sometimes smaller than 5 microns. However, some particles can pass through the most efficient filter cartridges.
Hydrocarbons
At the high pressure and low temperature prevailing in the absorption tower, heavy hydrocarbons and even some lower boiling constituents of the feed gas are dissolved in the amine solutions [12]. Most of the low boiling hydrocarbons are flashed off in the flash drum or are removed in the stripping tower. However, the heavy hydrocarbons tend to stay in solution and pose another form of contamination in amine solutions.

Other Contaminants

In addition to the aforementioned impurities, other contaminants may exist in the amine solutions such as anti-foaming agents, sealants, lubricants and corrosion inhibitors. Despite their low concentration in amine solutions, they may accumulate over time and affect the overall solution efficiency and plant performance.

ANALYSIS OF CONTAMINATED SOLUTIONS In order to understand the behavior of contaminated amines, the impurities and their concentrations must be known. A summary of the relevant analytical techniques has been given by Meisen et al. [13]. The nature and concentrations of impurities may differ from plant to plant and depend on the specific circumstances under which the plant is working. Table 1 shows the analysis for a typical DEA solution. The concentration of individual compounds shown in the table may vary within 10-25% range. The solution pH is about 10.

IMPACT OF CONTAMINANTS As the amine solutions become contaminated, they lose their effectiveness and cause operational problems, which can lead to plant shutdowns. impurities, the following problems may arise.
Reduction in Solution Capacity and Gas Plant Performance

Depending on the type of

As the level of contaminants increases and the amine content of the solution is reduced due to degradation, the solution capacity to absorb acid gases decreases. To compensate for this effect, the absorbent circulation can be increased. However, the increased circulation affects other parts of the process such as the heat duty of the exchangers and the hydrodynamics of the absorber. Alternatively, operators may have to reduce the raw gas flow to meet product gas specifications. If operators do not compensate for the presence of contaminants, there is a danger of overloading the amine solutions with acid gases. Excessive amine loading (e.g. rich amine>0.4 mole acid gas/mole of amine, for a 25-30 wt.% DEA solution) can lead to unacceptably high corrosion rates, particularly in areas where there are rapid changes in pressure, temperature and/or velocity [14]. High contaminants levels usually increase the viscosity of amine solutions which reduces the mass transfer rates in the absorber and stripper. The higher viscosity also increases the foaming tendency in the solutions. This problem is discussed in the next paragraphs of this article.

Foaming and Fouling

The presence of particulate matter, which exacerbates foaming, may lead to severe fouling in heat exchanger and accumulation on the contactor and stripping tower internals. Furthermore, hydrocarbon contaminants cause changes in interfacial tension which may stabilize amine foams. This can, in extreme cases, cause significant pressure drops across the contactor and amine entrainment. Foaming also reduces the mass transfer efficiency in the contactors and increases the acid gas content of the treated gas leaving the contactors. Activated carbon filtration is often used to contain hydrocarbon contamination, but heavy hydrocarbons are difficult to remove (especially when the pore size of the carbon is too small to capture the molecules). Mechanical filtration can be used to deal with coarse fines. However some fines are so small that conventional filtration media cannot capture them. Leaving such fine particulates in solution can lead to fouling of heat transfer surfaces, which in turn lowers, their efficiencies.
Corrosion

Several types of corrosion can result from contaminated amine solutions. In the case of increased circulation rates, erosion corrosion may occur which is physical wearing away of metals by the abrasive action of either suspended solids or extremely high fluid velocities in restricted areas. Fouling which causes solid deposition or scaling may result crevice corrosion [14]. Concentration cells can be set up beneath the deposit or scale leading to high localized corrosion rates. Some degradation products such as ethylenediamined are suspected to be very corrosive due to the formation of iron complexes. Chlorides entering the plant via poor inlet filtration or cooling water exchanger leaks can accelerate pitting corrosion in stagnant areas [14]. High levels of heat stable salts contribute significantly to the corrosion rates found in amine units. Corrosion rates are a function of the type and quantity of amine salt(s) present [15]. REMEDIATION OF AMINE SOLUTION CONTAMINATION When concentration of contaminants in amine solutions becomes excessive, there are basically four types of remediation action: (i) Partially purging the contaminated solution and

replacing it with fresh amine; (ii) replacing the entire inventory of contaminated solution; (iii) injecting caustic to free the amine bound up as heat stable salts and some CO2-induced degradation products; and (iv) reclaiming the solutions.
Solution Purge

Contaminated solution purge and make up with fresh amine reduces the impurity levels, but obviously not a very effective technique given the high cost of lost amine. A short term improvement results, but further contaminant build-up makes this procedure generally cost prohibitive in the long term. This procedure is therefore best suited to reduce operational difficulties for a short time while their root causes are identified and remedied. The disposal of purged solution is another problem. Alkanolamines are not readily biodegradable, and they cannot be easily processed in municipal waste water systems and therefore pose a threat to the environment.
Solution Replacement

Complete replacement of the contaminated amine eliminates the contamination problem. Amine gas plants work trouble-free with fresh solutions. Problems start when the level of contamination starts to increase. The high cost of amine replacement and the increasingly high disposal costs of contaminated amine make this option not so desirable. It should be noted that most spent amine solutions typically contain over 80% of the original active amine. The current disposal practices of deep well injection and incineration are both environmentally and economically unattractive.

Caustic Addition

The addition of strong bases such as NaOH, KOH and K2CO3 converts heat stable amine salts to the corresponding sodium or potassium salts, thereby returning the amines to their active form. The addition of strong alkali also reverses some of the degradation reactions leading to the release of amine from the degradation products. However, alkali addition introduces another impurity into the system, which raises the solution viscosity, corrosivity and scaling potential. This is especially true for sodium salts, which have low solubilities and, when they precipitate on heat transfer surfaces, not only reduce heat transfer but may also liberate acids thereby causing additional corrosion.
Solution Reclamation

The previous three techniques are useful, but do not address the contamination problems on a long-term basis. Reclaiming the amine from the contaminated solutions is a more permanent and environmentally friendly technique, which ensures high solution purity necessary for optimal plant operation. It may also be the most cost-effective approach. SOLUTION PURIFICATION METHODS Purification techniques of alkanolamine solutions fall into three major categories: treatment with adsorbers, reversal of degradation reactions and distillation. Distillation can , in turn, be subdivided into atmospheric, vacuum and steam stripping. method follows:
Adsorption and Ion Exchange

A brief description of each

Activated carbon is widely used to remove contaminants present in amine solutions. Typically, vertical beds of granular activated carbon are incorporated into the lean amine section, to remove contaminants such as suspended solids and foam-inducing compounds such as dissolved hydrocarbons.

Various authors from activated carbon producer companies have claimed that activated carbon can also remove DEA degradation compounds from amine solutions [16]. However, laboratory tests [5,17] as well as industrial tests [18] suggest that activated carbon cannot remove significant quantities of major degradation products. Since the sites for adsorbing degradation products are also active for adsorbing the parent amine (i.e., the compounds are all from the same family of amine compounds), and since the degradation products are always accompanied by relatively large parent amine concentrations, fast saturation of activated carbon beds is inevitable. The disposal of the spent activated carbon particles impregnated with degradation compounds and amine itself is a difficult task to perform in an environmentally friendly manner. Several ion exchange processes have been developed to remove ions and heat stable salts that cause corrosion and poor plant performance [19]. In such processes, the basic processing scheme consists of a cation resin bed for sodium removal, and an anion resin bed for the removal of anions. Although the processes may be effective in reducing the ion content of amine solutions, there is no published work which shows their ability to remove amine degradation products. Ion Exchange resins also adsorb amines, thereby potentially contributing to amine losses.
Reversal of Degradation Reactions

The principle of reversing the degradation reactions to regenerate amines is very attractive because amine recovery is potentially greater than that achievable by any other techniques. In practice, strong bases such as sodium and potassium hydroxides have been found to be able to regenerate DEA from some degradation products and heat stable salts. Chakma [20] conducted investigations aimed at the recovery of DEA from CO2-induced degradation products. It was found that some of degradation reactions are completely reversed while some others could not be affected. Therefore the success of caustic addition is limited to the reversal of some degradation products and heat stable salts. A further problem is the need to control salt accumulation.

There are some patent disclosures of research work on catalytic reversal of amine degradation reactions using hydrogen, catalysts and heat to crack degradation products [21]. It has been claimed that the amine degradation products can be converted to the original amine by hydrotreating reactions. No mechanism has been explained to show how amine degradation reactions are reversed and what role hydrogen may play in reversing the degradation reactions. The high cost of hydrogen production is believed to be a major draw back for this process if the million gallons of amine inventory in a gas plant wants to be treated by hydrogen and high pressure and temperature of the process. It should also be noted that amines are rapidly thermally degraded at the high operating temperatures of the process.
Distillation

Distillation method can be divided into the following types: Atmospheric Distillation: This method is suitable for MEA solutions because MEA is stable at its normal boiling point. Although it is generally accepted that DEA cannot be regenerated at atmospheric pressure without decomposition, there are some atmospheric distillation processes which have been used to reclaim DEA [22,23]. For processes purifying DEA at atmospheric pressure, no indication was given of the volume of waste generated, the concentration of amine in the waste stream, the separation efficiency, and the purity of the product. Steam (or Inert Gas) Stripping: Atmospheric reclaiming of amine solutions, involving the injection of steam or hot carbon dioxide into the reclaiming still, has been reported [22,23]. Under the conditions in the still, when CO2 was used as stripping gas, a fraction of DEA was converted to a higher boiling compound, which was suspected to be TEA. However, the degradation studies conducted by Kennard and Meisen [5] suggest that the compound is more likely to be one of DEA degradation products. When steam is used for stripping, the result is a diluted product, which may be re-concentrated by water evaporation. consideration. The energy requirement to remove additional water is another cost, which must be taken into

10

Vacuum Distillation: Solution containing higher amines (like DEA) cannot be purified by application of the above methods. The high normal boiling point of these amines suggests the use of vacuum distillation. All types of contaminants (e.g., amine degradation products, iron sulfide and particulates, salts, heavy hydrocarbons and solids, etc.) can be separated by distilling the used amine solutions as they all have very high boiling points and remain in the distillation residue. A Canadian company (Canadian Chemical Reclaiming Ltd. Or CCRL) recently developed a process, which incorporates caustic treatment and single stage vacuum distillation to reclaim degraded amine solutions including DEA [24]. In spite of operating under vacuum and proprietary heating system of the CCRL process, there is the possibility that part of DEA fed to the CCRL process may be further degraded and that the reclaimed solution may contain unacceptable levels of one of amine degradation products having close boiling point to that of the amines. The recovery efficiency of the CCRL process is reported to be between 80-90% as some of the DEA is left in the residue product to enhance heat transfer and carry solid materials in suspension form. It has been proposed to enhance the capabilities of the CCRL process by replacing the single flash separator with a distillation column and using an inert liquid to reduce the possibility of amine further degradation [25]. It has been claimed that the proposed process can achieve almost completed recovery of DEA. Other Technics Using electrodialysis technology has also been suggested to clean amine solvents [26]. In this process, anionic and cationic ion exchange membranes are arranged in a stack. When a current (DC) is impressed across it, and with correct sequencing of amine and water flow between the membranes, salts are transferred from the amine to the water. It has been claimed that the process yields a water stream that is essentially a 5 wt.% salt solution and a regenerated amine stream. Again due to the nature of the process, only ionic species could be removed and other types of contaminants including amine degradation products and hydrocarbons remain unaffected in the used solutions.

11

COCLUSION Contaminants found in industrial amine solutions present, if their build-up is unchecked, major operational difficulties such as corrosion, foaming, solid deposition, losses of valuable amine and environmental problems. Gas plants run with fresh solutions hardly ever have any problems. Problems start when the contaminants start to build up in the solutions. It is strongly recommended that gas plant managers and operators take a good care of their solutions and try to keep them clean. Amine degradation is an on going research area as there are many unknowns to be discovered. Recovery techniques are being developed to improve recovery efficiencies and reduce environmental impacts and operating problems of the reclaiming units.

REFRENCES 1. 2. 3. 4. 5. 6. 7. 8. Polderman L.D. and Steele A.B., Why Diethanolamine Breaks Down in Gas Treating Choy E. J., Degradation of DEA Treating Solutions, M.A.Sc. Thesis, University of Kim C.J. and Sartori G., Kinetics and Mechanism of Diethanolmaine Degradation in Kennard M.L. and Meisen A., Mechanism and Kinetics of Diethanolamine Meisen A. and Kennard M.L. DEA Degradation Mechanism, Hyd. Proc., 61(10), 105Chakma A. and Meisen A., Degradation of Aqueous DEA solutions in a Heat Transfer Dawodu O.F. and Meisen A., Degradation of Amine Blends by Carbon Dioxide, Proc. Dawodu O. F., and Meisen A., The Effects of Operating Conditions on COS-induced

Service, Oil and Gas J., 54(5), 206-214 (1956) British Columbia, BC. (1978) aqueous Solutions Containing Carbon Dioxide, Int. J. Chem. Kinetics, 16, 1257-66 (1984) Degradation, Ind. Eng. Chem. Fund., 24(2), 129-140(1985) 8(1987) Tube, Can. J. Chem. Eng., 65, 264-273(1987) The 42nd CSChE Conference, Toronto, Ontario, Oct. 18-22(1992) degradation of Aqueous Diethanolamine Solutions, Gas Separation and Purification, 6(3), 115(1992)

12

9.

Dawodu O. F., and Meisen A., Mechanism and Kinetics of COS-induced

Diethanolamine Degradation, Ind. Eng. Chem. Res., 33(3),480(1994) 10. Dawodu O.F., and Meisen A. Degradation of Aqueous Diethanolamine Solutions by Carbon Disulfide, Ibid, 10(1),1,(1996) 11. Kohl A.L. and Reisenfeld F.C., Gas Purification, 5th Ed., Gulf Publishing Co., Huoston, Texas, 1996 12. Jou F.Y., Carroll J.J., Mather A.E. and Otto F.D., Phase Equilibria in the System nButane-Water-Methyldiethanolamine, Fluid Phase Equilibria, 116(1/2),407-13(1996) 13. Meisen A., Abedinzadegan M., Abry R.G., and Millard M.G., Degraded Amine Solutions; Nature, Problems and Distillative Reclamation, Proc. 45th Annual Laurance Reid Gas Conditioning Conference, Norman, Oklahoma, 168-189(1996) 14. DuPart M.S., Bacon T.R., and Edwards D.J., Understanding Corrosion in Alkanolamine Gas Treating Plants; Parts 1&2, Hydroc. Proc., 72(4),75-80(1993) 15. Rooney P.C., DuPart M.S., and Bacon T.R., Effect of Heat Stable Salts on Solution Corrosivity of MDEA-Based Alkanolamine Plants, Part ii, Proc. 45th Annual Laurance Reid Gas Conditioning Conference, Norman, Oklahoma, 154- 168(1996) 16. Bright R.L. and Leister D.A., Gas Treaters Need Clean Amines, Hyd. Proc., 66(12), 47-8(1987) 17. Chakma A. and Meisen A., Activated Carbon Adsorption of Diethanolamine, MethylDiethanolamine and Their Degradation Products, Carbon, 27(4), 573-84(1989) 18. Islam M.R. and Chakma A.,Simulation of Activated Carbon Adsorbers Used in Gas Plants, Gas Separation and Purification, 4, 103-8(1990) 19. Keller A.E., Kammiller R.M., Veatch F.C., Cummings A.C., Heat Stable Salts Removal From Amines by HSSX Process Using Ion Exchange, Proc. 41st Annual Laurance Reid Gas Conditioning Conference, Norman, Oklahoma, 61-92(1992) 20. Chakma A.,Studies on DEA and MDEA Degradation, Ph.D. thesis, University of British Columbia, Vancouver, BC (1987) 21. US patents: 5,846,503 (1998); 5,137,702 (1992) 22. Thompson J., Reclaim Gas Treating Solvent, Hyd. Proc., 64(4),75-8(1985) 23. Ball T. and Veldman R., Improve Gas Treating, Chem. Eng. Prog., 87(1),67-72(1991) 24. Dawodu O.F., Meisen A., and Beaseley T., Reclamation of Spent Amine Solutions, Proc. Of the AICHE Spring National Meeting, Houston, TX (March 28-April 1, 1993)

13

25. Abedinzadegan Abdi M. and Meisen A., A Novel Process for Diethanolamine Recovery from Partially Degraded Solutions; Parts 1 and 2, Ind. Eng. Chem. Res. 38(8), 30963114(1999) 26. Price J. and Burns D., Clean Amine Solvents economically and on line, Hyd. Proc., 74(8), 140-1(1995)

APPENDIX Table 1: Typical composition of a contaminated DEA solution obtained from a gas treating plant in Western Canada

Compound Name Water Active Amines: Diethanolamine(DEA) Triethanolamine(TEA) Triethylenediamine (THEED) Hydroxyethyl Piperazine (BHEP) Residual Amine (Heat Stable Salts) Hydroxyethylimidazolidone Oxazolidone (HEOD) Ethylene Glycol Other contaminants including suspended solids

Wt.% 68.6 18.6 0.5 4.2 2.9 2.2 0.2 0.2 0.1 2.8

14