Proceedings of ETCE 2001 Engineering Technology Conference on Energy February 57, 2001, Houston, TX

ETCE2001-17085

INNOVATIVE APPROACH TO THE MERCURY CONTROL DURING NATURAL GAS PROCESSING

Zdravko Spiric
Environmental Protection Manager INA-Naftaplin, Subiceva 29, 10000 Zagreb, Croatia T: 385-1-459 22 36, F: 385-1-459 21 73, E: zdravko.spiric@ina.hr

ABSTRACT Natural gas, being produced from gas fields around the globe, along with a large number of other harmful substances (CO2, H2S, RSH, COS, etc.), often contains mercury. Mercurys potentially harmful effect on humans and on the ecological system as a whole as well as the risk regarding mercurys corrosive effects to the very sophisticated and expensive process material, equipment and catalysts is making its removal an imperative. The frequently applied procedure to remove mercury as an impurity and environment pollutant from process streams utilizes adsorption on a fixed bed consisting of sulfur impregnated activated carbon. This paper deals with data, results and more than seven years of practical field experience obtained by research of mercury removal unit efficiency during production and enhancement of natural gas at Molve, Croatia. Paper details the operating implications of handling and processing natural gas containing mercury, showing the results of the innovative approach in the process control, resulting in safety reliability and process efficiency improvements by plant modification due to change of gas flow direction. KEYWORDS: natural gas, mercury removal, sulfur impregnated activated carbon, process safety, environmental protection

INTRODUCTION Chemical and petroleum processes and pipelines pose very special risks to public safety and the environment. Whether the cause of the risk/damage is a catalyst poisoning, corrosion damage, sudden spill or the gradual contamination of a site through underground leakage, major financial losses are a constant threat. Environmental laws focused on occupational and public safety, along with "right to know" laws, have become increasingly more stringent relative to these issues. Rising public pressure and regulation prescribe minimum design, construction, operations, control and maintenance requirements for such facilities. Due to stringent environmental laws, which make activities more difficult and more expensive, all industry sectors, especially petrochemical operators have to consider removal of hazardous pollutants. Even in small amounts, mercury and its compounds have an extremely harmful effect on human health [1]. Mercury also represents a very important and complex problem in hydrocarbon exploration & production conditions (detection, protection, and removal). Moreover, mercury corrosion attack endangers dramatically process plants and facilities. Numerous reported cases all over the world (USA, Algiers, Indonesia) describe huge failures resulting with great damage and environmental catastrophes as a consequence of uncontrolled presence of mercury in gas. Therefore, prevention of mercury entering into eco-technology-system is absolutely critical. The problem of mercury content in the natural gas has to be approached and solved in an accomplished and safe way, taking into consideration three seemingly contradictory and yet compatible and equally important criteria:

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1. 2. 3.

Technological Ecological Economical

MERCURY REMOVAL Separation processes represents a practical and costeffective approach for eliminating pollution substances from petroleum and chemical processing applications. Mercury is very often removed as an impurity and environment pollutant from process fluid gas streams by adsorption on a fixed activated carbon bed [9]. The adsorbent is primarily designed to extract elemental mercury, i.e. mercury in its vapor state. Physical forces of adsorption are not always sufficient for total adsorption of a particular component, e.g. mercury. In this case, the large inner surface may serve as a carrier of the active component and/or chemical compound, i.e. to take over and distribute an optimum quantity of impregnating agent. The impregnation process increases the activated carbon capacity significantly, in order to produce a special type of sulfur impregnated activated carbon with a great adsorption capacity for mercury vapors [10]. The mercury removal process is based on principle of adsorption and of chemical reaction (chemisorption) of mercury present in natural gas using impregnated elemental sulphur in a micro-porous adsorbent. This reaction results in a stable and insoluble compound, the mercury sulfide. Several factors are influencing efficiency of mercury removal from natural gas: composition of gas as well as concentration of mercury vapor, presence of higher hydrocarbons, water and other impurities, temperature, pressure, gas flow rate, activated carbon characteristics, contact time, etc. [11,12]. It is extremely hard to design the breakthrough curve, or to accurately predict the effective capacity and expected bed life. To solve all problems a multidiscipline approach to a mercury removal problem is necessary. The purpose of this research was to define mercury removal efficiency, mercury loading and distribution profile in the activated carbon bed and variation in concentration of elemental sulfur through the bed in the real process conditions, as well as to optimize plant performance and gas flow directions trying to prolong bed life and improve process efficiency. MERCURY ADSORBER Mercury removal unit (MRU) consists of an adsorber, Fig. 1b. [13], located in the process plant, treating water washed natural gas. Beside hydrocarbons (more than 70% methane), natural gas contains CO2, H2S, and near saturated levels of water vapor. MRU contains 64 m3 commercial granular palletized sulfur impregnated activated carbon and is designed to remove mercury from an average inlet concentration of 1000 g/m3 to less than 5 g/m3 for a period of 3 years.

Upon investigating the mercury removal technologies available, Croatian scientists concluded that according to the best world experience, sulfur impregnated activated carbon was the best suited for achieving the mercury removal objectives at Molve natural gas processing plant [2]. MERCURY CORROSION The implication of the effects of mercury in natural gas was not reported until 1973, when a catastrophic failure of aluminium heat exchangers occurred at the Skikda liquefied natural gas plant in Algeria [3]. Investigations determined that mercury corrosion caused the failure and that the mercury likely came from an accidental source, such as test instruments used in plant and field start-up. After the Skikda failure, a study of the Groningen field in Holland revealed similar corrosion in the gas-gathering system. CO2 was initially thought to be the cause [4], but later investigations [5] pinpointed mercury, with concentrations ranging from 0,001 to as high as 180 g /m3. Phannenstiel et al. [6] state that most if not all of the mercury in natural gas is in the elemental form and that no natural gas processing plant problems are suspected to have been caused by organic or inorganic mercury compounds, and that elemental mercury is the probable cause of mercury corrosion problems. Even more, trace quantities of H2S, very often present in the natural gas, are the catalyst for the reaction of mercury with iron oxide from the pipe (vessel/reactor). Although the concentration of mercury in a given natural gas may be considered extremely low, Audeh [7] observes that its effect is cumulative as it amalgamates. Elemental mercury forms an amalgam with the surface layer of the metal it contacts. To date, the most serious problems reported by the industry owing to mercury corrosion have been the result of mercury forming an alloy with aluminium (amalgam), which is much weaker than the metal itself and is often referred to as an embrittlement. To initiate aluminium corrosion, the tightly adhering aluminum oxide layer on the surface of the aluminium must be removed. The mercury/aluminium amalgam process removes this oxide layer. Saunders et al [8] observed that brazed aluminium plate-fin heat exchangers are the predominant choice for cryogenic service. Aluminium is used due to its brazeability, excellent mechanical properties at cold temperatures, and superior heat transfer characteristics. They further state that mercury can damage the aluminium used in these exchangers and must be completely removed to no detectable levels in upstream equipment.

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MERCURY MEASUREMENTS The levels of mercury in natural gas were detected and quantified at the selected sampling points (inlet to and outlet from the adsorber bed), applying the mercury analyzer based on fluorescence detection technique (PS Analytical Sir Galahad) [14]. Sulfur content in mercury saturated activated carbon, as total sulfur, was detected by using the instrument with X-ray fluorescence spectroscopy method. As to problems related to preservation and storage of field samples containing mercury [15], it is recommended to conduct the detection and analysis of activated carbon mercury content on site, immediately upon unloading, since there is no need for special preparation prior to sample treatment by means of suitable field analytical devices. The samples are subject to significant mercury evaporation at ambient temperature and pressure. Therefore, in order to complete the investigation, we have used the standard gravimetric procedure (Escha), that covers adequately the required concentrations, resulting with reliable and reproducible data under given circumstances [16]. RESULTS AND DISCUSSION The mercury removal efficiency results obtained during this test period clearly indicate good performance of the sulfur impregnated activated carbon bed [17]. However, after two years of operation, analyses performed on activated carbon samples obtained from the mercury removal bed indicated (unexpectedly) high mercury loading, with mercury loading through very long mass transfer zone (MTZ), requiring a change-out of the activated carbon load. Following the carefully prepared unloading and replacement schedule, the level of the activated carbon withdrawn from the adsorber vessel has been investigated. The spent activated carbon was replaced by fresh load, Fig. 2. Based on sample analysis data, i.e. on results of saturation investigation, along with determination of fill-up weight and sulfur content in replaced activated carbon, it was desired and expected to establish the behavior/progress of the mass transfer front wave and efficiency of the adsorption process. The results of determination and investigation of spent activated carbon did not reveal expected efficiency as was suggested by literature data. Nevertheless, the obtained results indicated almost linear regularity of activated carbon mercury load distribution across the depth of adsorber bed, Fig. 1.a. A reduced concentration of impregnated sulfur (8 %) is evidenced at the top of the bed layer, when compared to original carbon. Namely, in the deeper shifts of adsorber bed, sulfur content rises to values typical for the fresh carbon (15

%). Regarding the above assumption, we were able to find out and establish a non-uniformity of (total) sulfur content across the adsorber bed, Fig. 1.c. It was found that mercury removal efficiency is strongly related to the MRU inlet stream temperature. This finding provides some fundamental data for research into sulphur impregnated activated carbon mercury removal inefficiency caused by the loss of active species. Considering that elevated temperatures promote the chemical reaction with sulfur, forming mercury sulfide, and the possibility that mercury occurs in its vapor state increases, it is desirable to obtain the mercury removal at the highest possible temperature. Moreover, natural gas is saturated with steam, and, condensation of water within carbon pores should be prevented. This problem can also be solved by application of the corresponding temperature regime. When problems with condensation in the activated carbon bed, as well as reduction of sulfur content in activated carbon became evident, a process improvement was introduced, related to change of gas flow direction, Fig. 3. Gas was sent towards the heat exchanger E-3201A/B, and then to the adsorber V-3102 and not, as originally designed, first to the adsorber and then to the heat exchanger. Following the process enhancement, an efficient and safe operation of investigated system has been established and confirmed [18], since the most adequate removal prevented introduction of mercury into process and transportation system. CONCLUSIONS Improving plant safety/reliability, economic and environmental efficiency is a major goal of all petroleum companies. In recent years, there have been significant advances in safety standards in the industry, and the development and implementation of environmental, healthy and safety (EHS) management systems have become the norm. A key component of EHS effective management is the CONTROL - recording and analysis of EHS performance measures. The objectives of advanced EHS management and effective process control are to reduce risk: to establish safe and environmentally friendly production, to control a process units product qualities closer to specification and to maximize its throughput against operating constraints. This research is dealing with the process of mercury removal from natural gas, based on principle of adsorption and of chemisorption of mercury by means of sulphur impregnated activated carbon. In spite of remarkable advances in control systems, due to a large number of determining parameters, variability of process variables and to their interaction (composition and properties of the adsorbent, process stream,

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flow diagram) an accurate and safe control of separation process is not achievable. It is extremely hard to accurately predict the effective capacity, the breakthrough curve, or the expected adsorber bed life. The numerous restrictions make it also impossible to elaborate a reliable automatic control system for removal of mercury from natural gas. The problem lies in selection and application of suitable mathematical expression and/or equation (process modeling techniques) that would allow the numeric evaluation and description of the correlation, i.e. of the function of interdependency of all systems key properties and of the process performances. Therefore, to avoid safety/reliability problems in the process, the complex procedure and the key parameters of the system under research have to be closely and continuously monitored and analyzed following the program defined and scheduled ahead. With such a monitoring of process conditions and MRU performances, failures can be predicted and sometimes avoided by making operating changes. By defining mercury distribution profile in the activated carbon bed and variation of elemental sulfur content throughout the bed, we determined the behavior/progress of the mass transfer front wave, i.e. mass transfer zone, as well as the dynamics and efficiency of the adsorption process. The process modification step, that improves mercury removal efficiency from natural gas in real process conditions, was suggested. The MRU was re-designed to increase process safety and to meet the stringent purity requirements, less than 1,0 microgram Hg/m3 natural gas. This investigation also revealed that described methodology enables an appropriate characterization of analyzed system and insures reliable results for mercury content in natural gas, in saturated activated carbon as well as in process plant environment. One of the main advantages of this approach is that this techniques offers a direct, very accurate and reliable introspection into dynamics and efficiency of mercury removal from natural gas by means of activated carbon, exposing also the problems and restrictions that accompany this procedure. Finally, all test results clearly indicate that our innovative approach in mercury control program has been, and continues to be fully effective in the process equipment protection and at minimizing contribution of mercury in the working and living environment.

LITERATURE 1. Agency for Toxic Substances and Disease Registry (ATSDR)., Toxicological profile for mercury. Atlanta, GA: U.S. Department of Health and Human Services, Public Health Service, 1994. Spiric Z. and Vadunec J.: Protection of Process Plant and Environment against Mercury during Natural Gas Production, 12-th International Congress of Chemical and Process Engineering - CHISA 96, Prague 1996. Kinney, G.T.: Skikda LNG Plant Solving Troubles, Oil&Gas J. Sept, 15, 1975 Leeper J.E.: Processing/ (A study of) Mercury Corrosion in (Mixes-Refrigerant) Liquefied Natural Gas Plants, Q. Can. Gas Process. Assoc. Meet. (Calgary 9/10/80) Energy Process., Vol.73, N.3, Jan.Feb. 1981. 46-51, Situmorang M.S. and Muchlis M.: Mercury Problems in the Arun LNG Plant. 8th Int. Gas Union-Int. Inst. Refrig.-Inst.Gas Tecnol., Jt. Int. LNG Congress, Los Angeles, paper 1 II-6., 1986, Phannenstiel L.L., McKinley C. and Sorensen J.S.: Mercury in Natural gas, Paper PAP76-T-12 presented at the American gas Assn. Operation section Transmission Conference, Las Vegas, May 3-5, 1976. Audeh C.A.. Hoffman B.E. and Kirker G.W.: Process for the production of natural gas condensate having a reduced amount of mercury from a mercurycontaining natural gas well stream, Patent: United States; US 5209913 A, Application: US 343693 890427, PP.: 7 pp., 1996. Saunders J.B., Pahade R.F. and Delnicki W.V.: Cryogenic Nitrogen rejection, Proc. ASME Annual Energy- Sources Technology Conf. Hydrocarbon Process Symposium, Dallas, pp. 43-49, Feb.15-18, 1987. Ruthven DM (1984) Principles of Adsorption and Adsorption Processes, Wiley, New York Hutchins RA (1979) Activated Carbon Systems for Separations of Liquids, in Scweitzer PA (Ed.), Handbook of Separation Techniques for Chemical Engineers, McGraw-Hill, New York pp. 1-415 Biscan D.A. and McNamara J.D.: Mercury Detection and Removal: Field Experience in the USA and Abroad, Proceedings 14-th Int. Conf. LNG., pp. 8-17, April 7-14, 1980. Bourke M.J. and Mazzoni A.F.: The roles of activated carbon in gas conditioning, Proc. Laurance Reid Gas Cond. Conf., PP.: 137-58, 1989. Spiric Z (1996) Mercury Removal from natural gas with sulfur impregnated activated carbon - our experience, 4-th International Conference on Mercury as a Global Pollutant, Hamburg Spiric Z. and Stockwell P.B., Ambient Air Mercury measurements during Natural Gas Production,

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American Environmental Laboratory Vol. 10, No. 5., 16-20 (1998) Bloom NS (1992) Considerations in sampling for and analysis of mercury at uncharacterized spill sites, in Charlton DS and Harju JA, eds., Workshop on Mercury Contamination at Natural Gas Industry Sites: Chicago, GRI-92/0214 Spiric Z. and Hraste M, (1998) Mercury saturation profile across the sulphur impregnated activated carbon bed, In Ebinghaus R, Turner RR, Lacerda D, Vasiliev O. and Salomons W. (eds), Mercury Contaminated Sites: Characterization, Risk Assessment and Remediation, 409-417, Springer Environmental Science, Springer Verlag Heidelberg, Spiric Z, Dragas M, Vadunec J, Mashyanov NR and Ozerova N. (1999) Investigation of mercury content in Podravina gas fields and environment, 6th International Petroleum Environmental Conference, November 1619, Houston, USA Horvat M, Jeran Z, Spiric Z, Jacimovic R and Miklavcic V.: Mercury and other elements in lichens at INA-Naftaplin gas treatment plant, Molve, Croatia, Journal of Environmental Monitoring, 2000, volume 2, issue 2, 139-144.

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15

Hg Saturation (%) 10

0 0 0,5 1 1,5 Depth (m) 2 2,5 3 3,5 4 4,5 5 Depth (m) 0 0,5 1 1,5 2 2,5 3 3,5 4 4,5 5

15

S Concentration (%) 13 11

a
o

c
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Figure 1 Hg saturation and the S content profile

m 0.5 1

Hg (% ) 8 .1

m 0.1 1

Hg (% ) 2 1 .49

m 0.1 0.5 1

Hg (% ) 2 1 .5 0 .2 0

1 .2

a 14.04.1993.

b 02.06.1994.

c 11.09.1995.

d 06.06.1996.

F ig u r e 2 . M T Z A D S O R B E R R E W I E V
zasicenje V-3102 xar 27 09 96

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41o C 52 bar

to aMDEA process

E-3201A/B
water from P-3606A/B from V-3102
55o C 52 bar

BEFORE
aMDEA in

52 bar

feed gas (inlet manifold)

48o C 52 bar

E-3201A/B V-3102
aMDEA out

V-3101

T-3101

F-3101 P-3101A/B

gas to aMDEA process

Figure 3. Process modification by change of gas flow direction

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