SPE-106610 Shafawi Removal

Mercury Removal System for Upstream Application: Experience in Treating Mercury From Raw Condensate

Muhamad Rashid Sainal, Petronas Carigali Sdn. Bhd; Azman Shafawi, Petronas Research and Scientific Services Sdn. Bhd.; and Ir. Abdul Jabar Mohamed, Petronas Carigali Sdn. Bhd.

Copyright 2007, Society of Petroleum Engineers This paper was prepared for presentation at the 2007 SPE E&P Environmental and Safety Conference held in Galveston, Texas, U.S.A., 5-7 March 2007. This paper was selected for presentation by an SPE Program Committee following review of information contained in an abstract submitted by the author(s). Contents of the paper, as presented, have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material, as presented, does not necessarily reflect any position of the Society of Petroleum Engineers, its officers, or members. Papers presented at SPE meetings are subject to publication review by Editorial Committees of the Society of Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper for commercial purposes without the written consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of where and by whom the paper was presented. Write Librarian, SPE, P.O. Box 833836, Richardson, Texas 75083-3836 U.S.A., fax 01-972-952-9435.

Abstract

This paper presents an approach undertaken by PETRONAS Carigali Sdn Bhd, an E&P subsidiary of PETRONAS in selecting, optimizing and installing a mercury removal system in one of its operations in Malaysia. It focuses on the treatment of the raw condensate stream that was noted as having much higher mercury content as compared to the gas stream. Since the experience in mercury removal in raw condensate is limited, this paper also presents the work done to mitigate the risks and improve the removal performance. The paper shares the initial performance of such system and the issues faced to sustain its long term effectiveness.

Through operation surveillance, mercury was observed to be present in the hydrocarbon delivered by PETRONAS Carigali to its downstream customers. A Mercury Removal Project was initiated in March 2005 to treat and remove the mercury from the hydrocarbon. The Project was conducted on a fast track basis. Adsorbent technology was selected following a thorough evaluation that includes carrying out performance tests in the laboratory. The project is among the first in the world to remove mercury from raw condensates. (The gas was not treated after the data established that the mercury content in the gas meets specifications).

The project was completed in stages with the first system installed in March 2006, and the second in July 2006. The results show that the units managed to remove mercury from the condensate with more than 95% efficiency. The project demonstrated that the treatment of mercury could be done upstream prior to exporting the hydrocarbon liquids. It is an approach that should not be ruled out in the gas processing value chain whether for reasons of risks mitigation or value improvement or both.

Mercury is a natural occurring element and could be present in varying concentrations and of various species in oil and gas fields. Mercury is not only hazardous to human health and the environment but could also attack equipment components that have mercury reactive materials, leading to a potential catastrophic failure to the plant.

Introduction

PETRONAS Carigali Sdn Bhd (PCSB) operates a network of gas production facilities and infrastructure onshore and offshore Terengganu, Malaysia. The main gas producing fields are notably Duyong, Resak and Angsi, which produces both crude oil and gas. The gas from Duyong and Resak are delivered to shore via dedicated pipeline systems namely the Joint Delivery System (JDS) and Resak Delivery system (RDS, landing at the Onshore Gas Terminal (OGT) in Kertih, Terengganu. Feeding into these delivery systems are also supplies from other fields such as Sotong, Malong, Anding, the PM-9 PSC fields and PM3 PSC. (The gas from Angsi field is delivered to shore via a separate pipeline system operated by others). Figure I shows the Gas Fields and the main pipeline systems.



The gas and condensate delivered through these pipeline systems are sent to the Gas Processing Plants (GPPs) which are located nearby in the vicinity. The GPPs will process the gas and condensate prior to sending the various products (sales gas, ethane, butane, stabilised condensate etc.) to the various Petrochemical Plants, Power Plants and downstream consumers.

Historically since the first gas development and production in the 1980's, the gas produced from those initial fields does not require any treatment for contaminants. Offshore treatment processes were mainly confined to dehydration and water treatment systems. Though there were some contaminants such as H2S, CO2 and trace elements present, they were very minimal and required no further treatment to meet the gas supply specifications. Similarly, the onshore facilities also only consisted of mainly slugcatchers and custody transfer metering systems prior to exporting the gas and condensate to the GPPs. Nonetheless, continuous surveillance and checks were conducted as part of routine operations to ensure compliance to the quality specifications and HSE requirements (33).

However, during recent years, elemental mercury was found in vessels and piping low points of the gas production facilities. Contaminants studies and data analysis were conducted for both the RDS and JDS gas and condensate, in order to ascertain the mercury level of both streams. The results show that the mercury level in the gas stream was very minimal and far below the specification. However, the raw condensate stream contained a much higher level of mercury. A project was initiated to remove mercury from the raw condensate prior to delivering it to the GPPs and downstream consumer.

2.0 What is Mercury

2.1 Mercury in Oil and Gas industry

Knowledge of the total mercury content and of the different species present in natural gas condensate is extremely important. Mercury in most forms is highly toxic, particularly when present as the organo-mercury species which causes great environmental concern. In addition, the damage caused to industrial plants by the presence of mercury can be severe especially when unscheduled shut-downs are forced.

2.1.1 Mercury in Natural Gas Industry

Mercury occurs naturally, in trace quantities, in natural gas. Although difficult to generalise, the typical mercury concentration in natural gas/natural gas condensates is between 1 and 200 ¦Ìg m -3 (1,2,3,4). Although the concentration of mercury in natural gas and natural gas condensates may be considered to be very low, the effect is cumulative because it amalgamates. Mercury in natural gas condensate may be present in various chemical states: metallic, organic or inorganic forms, that all show unique species-dependent physical, physiological and chemical properties (1,5,6).

The implications from the presence of mercury in natural gas was not reported until 1973, when a catastrophic failure of an aluminium heat exchanger occurred at the Skikda liquefied natural gas plant in Algeria (4, 7, 8, 9).

The presence of mercury in oil and gas is recognised world- wide and has been reported for Gronigen field in Holland (8), in Indonesia (10), in Thailand (9,11,12),in Malaysia(13,14), fields in Australia (15), the Commonwealth of Independent States (9,16), Western and Southern Africa, Chile and Venezuela (17), Canada, in several states in the US (Kansas, Texas, Utah, Colorado, Oklahoma, and Wyoming) (18,19), as well as The Irish Sea, Japan and China (19).( Table 1)

2.1.2 Mercury in the Petrochemical Industry

As with the gas industry, several petrochemical companies, using natural gas liquids containing mercury, have also had some unfortunate experiences of damaging cryogenic heat exchangers at their petrochemical complex (9,20,21). Other petrochemical processes directly or indirectly utilise a catalyst with precious metals such as platinum, palladium, nickel etc. as an active surface. The presence of mercury in any stream of a petrochemical process may easily poison the catalytic process. (20, 22).

2.1.3 The Petroleum Industry and Environmental Impacts from Mercury

Mercury is a naturally occurring contaminant in geological hydrocarbons and is distributed freely throughout production, processing, transportation and consumption systems. The toxic contaminants from these activities can enter into the environmental cycle and food chains easily, through emission during processing stages or unregulated disposal of wastes or accidents. As shown in Table I, hydrocarbons from different geological locations contain mercury in microgram levels. The values shown are estimations (23) and may change from time to time, depending on geological factors and production practices.



2.2 Determination of Mercury

The determination of mercury in natural gas and gas condensates is made difficult by the very low concentrations involved, the highly volatile nature of mercury and the complexity of the sample matrix. This dictates that either a highly sensitive detector or a large sample volume or both is needed. A variety of techniques with different sensitivities are presently available for the determination of mercury. However, strict procedures including proper sampling techniques have to be followed to ensure accuracy and reproducible results. Some analytical techniques are listed in Table II



An analyser for the determination of mercury in naphtha has now been developed ie the NIC mercury analyzer (27), Leco, Gallahard with precon system etc,. an atomization/oxidation, traping/amalgamation and Cold Vapour Atomic Detection principle is applied in this method. It has also been reported that a rapid determination of total mercury in natural gas condensates using vaporization/trap at elevated temperature on gold amasil then thermally desorbed and detected by Cold Vapour Atomic Fluorescence, gives satisfactory and consistent results.(28)

2.3 Mercury speciation in natural gas Condensate

The determination of different mercury compounds, or 'speciation', in gas condensates is of interest not only because of the ecotoxicological aspect but also because of the interest in those problems associated with the processing, utilisation and movement of gas condensate which contains mercury (6). At present, it is not well known which chemical forms of mercury are present in natural gases and gas condensates and, in addition, methods for the determination of total mercury concentrations must be regarded to be of unproven reliability because of a lack of adequate standard reference materials and poor accuracy (5).

In recent years, many methods have been developed for the speciation of mercury in various types of samples. However, there has been limited success with complex organic liquid matrices due to the analytical challenges those samples offer. The first attempt at speciation of mercury in gas condensates (semi-quantitative determination) was performed using HPLC coupled with CVAAS (6). Various mercury species in an aqueous system were separated by reversed phase HPLC using gradient elution to investigate the preliminary condition required.

The determination of mercury species in gas condensates by on-line amalgamation traps (gold/platinum wires) for the collection of mercury species separated by capillary GC for detection by MIP-AES was able to remove the carbon background emission and allowed the determination of dimethyl mercury in condensate. (25).

It also reported that speciation of mercury in condensate was achieved by using GC-ICP-MS (29) and GC-Pyrolyser-AFS (30). Several species of mercury i.e. elemental mercury, mercury (II) chloride, DMM, methyl ethyl mercury (MEM) and DEM were identified. However no organo-mercury halide species were detected in the majority of samples analysed.

3.0 Mercury Data Surveillance and Analysis

A detailed data analysis was conducted based on the reports and operational surveillance conducted by PCSB and PETRONAS Research and Scientific Services (PRSS) from year 2001 to 2005. Based on these analyses, the following was concluded:-

• The mercury present in the gas streams for both RDS and JDS are significantly below the gas sales specification limits.
• Condensates have higher mercury content than gas. Under normal operations, mercury loading ( kg / day ) to GPP in untreated condensate is 3 to 9 X higher than that of gas.
• There is no specific trending (increasing or decreasing with time) observed for both mercury in gas and condensate.
• The condensate and gas stream from OGT are delivered separately to GPP. At GPP, they are commingled again in common inlet separators. As a result of this commingling, it is highly likely that the migration of mercury from the condensate stream occurs to the gas stream resulting in increased mercury content in the processed gas stream (34).

Based on the available data, it was recommended and agreed to treat the condensate stream only for the time being. However, continuous surveillance will be conducted for both the gas and condensate streams to ensure conformance to specifications.

4.0 Project Definition

A project called, "Mercury Removal Project 1 (MRP1) was initiated in 2005 to remove mercury from the raw condensate. Two locations were considered for the project, ie offshore platform or onshore gas terminal. The followings highlighted the considerations for both locations:-

Offshore Platform

• Potentially 8 - 12 vessels including pretreatment units need to be installed per platform. This will impose significant space and weight requirements on each platform
• Structural modifications and extension need to be conducted to accommodate the units
• Possibility of constructing new platforms or extensions to accommodate the units. Though this is possible, it will have a significant impact on the schedule and cost
• More than one platform or location

Onshore Gas Terminal

• Availability of space for current units and further future expansion
• Eliminate the immediate need for individual Mercury Removal Unit on each offshore platform
• Faster project completion
• Lower overall costs due to logistics during project and operation
• Avoid prolonged production shutdown leading to gas supply interuption

Based on the above, it was decided that the Mercury Removal System will be installed at the Onshore Gas Terminal.

4.1 Project Risks and Challenges

There were 2 major challenges identified during the project definition.

1. There was no Process Licensor with a track record in removing mercury from raw and untreated condensate. The short-listed / selected Vendors only have proven experience in removing mercury in clean "refinery-grade" condensate. Hence MRP1 will be the 'pilot' project for both PETRONAS and the vendor.
2. Long lead time for the vessel plate and big size valves could jeopardize the early completion of the project. Vendor indicated about 32 to 34 weeks ex- work for the delivery of the plate and about 24 to 32 weeks for valves with actuators (35).

4.2 Project Risk Management

The following initiatives were taken to mitigate and address the project risks and challenges:-

• After a thorough technology selection process, a performance testing of the absorbents with the actual condensates were conducted. This gave some indication on the performance of the absorbent in 'lab' condition.
• The MRU would be installed in 2 phases, ie the JDS system and the RDS system. This would allow for the monitoring of actual performance of JDS MRU, and for any improvements to be made, if required, to the RDS MRU later.
• Provide tie - in provision for future additional MRU installation, if required.
• Conduct sourcing and source inspection for the long lead items, ie vessel plate and big sized valves (35).

4.3 Technology Selection and Design Considerations

There are many types of technology, proven and unproven, currently available. Listed below are some of the available technologies.

1. Adsorbent
2. Cyclonic
3. Chemical
4. Microbes & other emerging technologies (36)

The selection of the technology for the project was done as per the following criteria and considerations.

• Proven and reliable technology
  • The technology selected must be proven and reliable on other types of process applications.
• Process effectiveness and efficiency
  • The removal agent must be highly active towards all forms of Hg, preferably bonding irreversibly to the agent.
  • The removal agent must also remain active, ie the active surface must be resistant to blinding by components in the stream treated.
  • The system should also be flexible on demanding feedstock properties.
  • Lower resident time preferred. This will have an impact on the sizing of the vessels.
  • Stable and robust (physically and chemically).
• Ability to integrate with existing facilities
  • Minimal modification to the existing facilities.
• Used commercially
  • Removal agent should be inexpensive and easy
  to get.
• Meeting the design basis.
  • Ability of the technology to meet the design
  basis.
• Time Constraint
  • Ability for the technology and the facilities to be

4.4 Adsorbent Performance Test and Lab Analysis

Mercury removal systems for both gas and processed liquid hydrocarbon streams are commercially available. However, removal systems for raw natural gas condensates have not been sufficiently tested under real plant conditions. The removal of mercury from raw natural gas condensates is different to that from natural gas because it is in the liquid phase and the types of mercury present in the condensate may be of a different species. At present, few technologies are said to be effective in the total removal of mercury from liquid hydrocarbon feeds. There are several manufacturers, but most of the products are not well tested for mercury removal from actual 'raw' condensates. An example of such removal systems includes the sulphide-containing ion exchange resin material (20) comprising the two-stage sulphide-containing alumina process (1, 31, 32), sulphur-containing molecular sieve, sulphur-containing activated carbon and ionic salt - containing activated carbon. In view of this, the performance test using the real sample to confirm the performance of the adsorbent becomes very important.

4.4.1 The Performance Evaluation of Removal Adsorbent

The laboratory scale assessment of short-listed mercury removal adsorbent systems, in removing mercury, particularly alkyl mercury species ie DMM and DEM from actual samples from OGT is very important in deciding the most suitable system for the raw gas condensate.

The picture of the laboratory scale pilot plant used in the study is shown in Figure II.



4.4.2 Determination of Total and Mercury Species in Samples

The determination of the total mercury content in the inlet and outlet samples was carried out using the vaporisation and trapping technique (28) and that of the mercury species in the samples was carried out using gas chromatography coupled with pyrolysis-AFS respectively (30). The set-up of the analytical instruments are shown in Figures III and IV respectively.



4.4.3 Findings

The two shortlisted adsorbents (A and B) were subjected to 'raw' condensate feedstock, and the adsorbents were able to lower the Hg concentration in the sample. It is very important that the free water is removed since it will interfere with the adsorption process. Water was also identified to contain Hg compound especially non-reactive inorganic mercury.

From both sets of trials (doped and undoped with DMM), adsorbent A indicated better performance in removing mercury from the 'raw' condensate. Adsorbent A was recommended to be selected for the Mercury removal system for raw condensate.

The above results indicated that speciation of the mercury content is important in evaluating the efficiency of an adsorbent system. The performance of an adsorbent was dependent upon the type of adsorbent, the mercury species and other impurities present in the feed stream. The determination of total mercury only in feed and product samples in the system will provide information on the performance of the adsorbent but will not give all the necessary information for an unbiased evaluation to be made of the performance of an adsorbent.

The percentage of removal efficiency of adsorbents for the experiment is summarised in Figures V & VI and the example of chromatogram for the species analysis is shown in Figure VII.




5.0 Project Execution

5.1 Project Execution Plan

The PCSB gas fields and gas infrastructures supply a significant amount to Peninsular Malaysia's gas demand. It is imperative to ensure that this project does not disrupt the continuous gas supply to consumers. The main objective and driver for the Projects are HSE and Schedule. A normal schedule for a project of this size is about 24 months from inception. With a commencement date of January 2005, the current forecasted project completion date would be December 2006. However, due to the criticality of the subject matter, the PCSB Management had requested the Project team to complete the first unit by the end of the 1st Quarter, 2006 (expedited by 9 months) (33). In order to meet this, a different approach was taken by the project.

1. Contracting Strategy Maximum parallel engineering, procurement and construction can be best realized through EPCC contracting where the interfacing and coordination works among the various contractors/parties can be minimized. It also provided a single point direction in the management of those works thereby enabling earlier commencement of site works. An EPCC Contract was executed consisting of the technology subject expert (PRSS and the technology provider), the detailed design consultant and the construction, installation and commissioning contractor.
2. Material Sourcing The project completion date is dictated, to some extent by the critical path. The critical path for the Project is the supply of the Mercury Removal unit. In order to expedite the schedule, the pre procurement and sourcing processes were conducted by the project team prior to the award of the EPCC contract to the EPCC Consortium

5.2 Project Development

The Mercury Removal Project I (MRP I) development was carried out in two phases:-

Project Definition (EPCC Pre Award Works)

• Data Analysis
• Technology Selection
• Lab Adsorbent Performance Test
• Front End Engineering Design (FEED)
• Basic Design of the Mercury Removal System

Phase 1 - Installation of MRU for JDS

• Commenced the engineering, fabrication and installation of JDS MRU
• Commenced on the engineering and pre-fabrication of RDS MRU
• Monitoring Period
  Conducted a 6-month monitoring period after the completion of the Phase JDS MRU. This enabled data gathering on the MRU performance for lessons learnt and improvement on the RDS MRU.

Phase 2 - Installation of MRU for RDS

• The detailed designs were revisited taking into consideration of the lessons learnt from the JDS MRU.
• Installation of the RDS MRU
• Monitoring Period for the RDS MRU.

6.0 Performance Monitoring

The Mercury Removal Unit for the JDS and RDS were installed on 31st March 2006 and 30th July 2006, ahead of the planned schedule. Performance Monitoring Period was conducted for both of the systems to ascertain the system performance. The Mercury Removal Unit for both of the system managed to successfully remove mercury from the raw condensate to below the sales gas specifications and the project target, with more than 95% efficiency (37). Figures VIII and IX show the mercury removal performance for both the JDS and RDS Mercury Removal System.







7.0 Conclusion

The mercury removal from raw condensate project shows how the PETRONAS Group had adopted an integrated approach to effectively address mercury in its gas supply thus ensuring that not only does its products conform or even exceed specifications, but demonstrates the Group's commitment to sustainable development and good environment management through technology application.

Mercury mapping, speciation study and adsorbent performance analysis are key activities and capabilities that ensure the right technology was narrowed down and selected. Being among the first mercury removal projects for raw condensate application, this project provides the baseline experience in the development of skill and capability in the area of mercury mitigation for PETRONAS group and the E&P Industry.

8.0 Acknowledgement

We would like to thank PETRONAS and PCSB Management for their support and approval for us to publish this paper.

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