Characterization of Corrosion Products in Saudi Aramcos Oil and Gas Facilities Using the X-ray Powder Diffraction Method

Authors: Dr. Syed Rehan Zaidi, Dr. Husin Sitepu and Ahmed A. Al-Shehry

ABSTRACT
Boiler tubes have occasionally failed in refineries and gas plants. The Research and Development Center (R&DC) has helped plant engineers overcome problems by identifying the nature and source of compounds leading to failure (e.g., corrosion products, formation materials and scale deposits). The boiler consists of a furnace, boiler tubes, steam drum, mud drum and boiler. The furnace provides heat to the boiler, changing water into steam. The presence of certain compounds in sample deposits from boiler tubes can indicate why they fail. The presence of vanadium and sodium compounds in the sample indicates the quality of burning fuels is poor. If large quantities (>15%) of hematite, Fe2O3, appear in the deposits, it indicates the presence of dissolved oxygen in the boiler feed water. If iron carbonate appears in the samples, it indicates the presence of dissolved carbon dioxide (CO2) in the system. If the metallic copper is present in the deposits, it indicates erosion in the boiler. In the last case, special precautions to prevent the plating out of copper during cleaning operations are required. The procedures used to identity corrosion products, formation materials and scale deposit materials will be described.

ADVANTAGES OF THE XRD TECHNIQUE

XRD is an excellent analytical technique used for the phase identification of a crystalline material in the form of a solid or powder, such as a catalyst, scale deposit, chemical, core, shell, clay mineral and cement1-10. XRD identifies compounds, whereas XRF, induced coupled plasma and atomic absorption techniques only identify elements. A sample XRD and XRF analysis is given in Table 1. The XRD method1-10 differentiates between different forms of a compound with the same chemical formula. If the sample is calcium carbonate (CaCO3) either it is calcite (scale formation materials), aragonite (scale), or vaterite. Additionally, XRD identifies the forms of a compound, such as the iron sulfides (FeS), that have different chemical formulae; e.g., pyrite (FeS2), marcasite (FeS2), mackinawite (FeS0.9), pyrrhotite (Fe7S8) and greigite (Fe3S4). It is very important to know the form of (FeS), because some of these iron sulfides are pyrophoric. Furthermore, the XRD technique can differentiate the hydration state of compounds, e.g., gypsum (CaSO4.2H2O), bassanite (CaSO4.0.5H2O) and anhydrite (CaSO4).

XRD APPLICATIONS IN SAUDI ARAMCO

The X-ray Group of the Analytical Service Division fully supports the R&DC Downstream and Strategic and Upstream research projects, on topics such as scale mitigation, oil to hydrogen, pipeline integrity, black powder and catalysts. We support the Engineering Service Agreement projects, including mineralogical determination for the Qusaiba shale in the northwest region (ERAD), analytical services support for the Operation Service Division of the EXPEC ARC, and hydrajetting impacts in the filtration system. We support the Technical Service Projects (TSPs) in facilities, such as the Weight Percentage XRF Wt% Element Wt% 60.4 Ca 0.2 28.8 Si 0.1 0.5 P 0.1 0.2 (Wt%) XRD Compound Wt% Magnetite-Fe304 44 Hematite-Fe2O3 28 Pyrite-FeS2 7 Sulfur-S 21

INTRODUCTION
The furnace, boiler tubes, steam drum, mud drum and boiler are all parts of the boiler. When the furnace provides heat to the boiler, the water changes into steam. The failure of boiler tubes has been observed in refineries and gas plants for several years. The failures occurred mainly due to corrosion erosion, deposition and scale formation. Due to the failure of boiler tubes, the refinery and gas plants were shut down, ultimately causing a financial loss. Therefore, the Research and Development Center (R&DC) provides support to plant engineers in identifying the nature and source of compounds leading to failure (e.g., corrosion products, formation materials and scale deposits), using X-ray powder diffraction (XRD) and X-ray fluorescence (XRF) techniques. The findings will help engineers to take proper action to prevent future occurrences, avoiding plant slowdowns that result in loss of production.
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Element Fe S Na Al

Table 1. XRD phase identification and XRF elemental analysis of corrosion products

Rabigh refinery, Jiddah refinery and Ras Tanura refinery (RTR), Berri gas plant (BGP), Juaymah gas plant and Abqaiq gas plant, and the Consulting Services Department (CSD). In the present study, we identified the compounds of deposits formed in the boilers of refineries and gas plants by using the XRD technique, as requested by the TSP Program Director, and determined the nature, source and formation mechanism of the deposits. Once all the phases for each of the deposits in the XRD data had been identified using HighScore Plus software, then the quantitative phase analysis, i.e., weight percentage (Wt%) for each phase, was completed using the Rietveld method7-9. The findings will help refinery and gas plant employees to take proper action to prevent future occurrences.

X-rays emitted by these elements. The intensity of the rays was processed by the instruments software to determine the elemental concentrations.
XRD Data Measurements

EXPERIMENTAL PROCEDURE
Sample

The starting powders were collected from boiler tubes F-3001 in the Jiddah refinery, the RTR boiler #8 tubes, screen tubes of a boiler at the Yanbu gas plant and at boilers at the Berri gas plant. The deposits were considered to be excellent canidates for this study because these deposit materials caused the failure of the refineries and gas plants boiler tubes. The untreated deposit samples were manually ground with an agate mortar and a pestle, and homogenized. Subsequently, 5 grams of the homogenized deposit sample were further manually ground for several minutes to achieve a fine particle size. This grinding was conducted to achieve adequate intensity reproducibility7-8. The fine powder was then mounted into the XRD sample holder by back pressing.
XRF Spectra Measurements

Step-scanned patterns were measured with a PANalytical XPERT XRD diffractometer. The XRD data were measured from 4 to 90 in a 2 Bragg angle. A position sensitive detector (PSD) XCelerator was used with a scanning step time of 10 seconds, ensuring reasonable intensity counting statistics. PSD length in 2 was 2.12, with irradiated and specimen lengths of 1 mm and 10 mm, respectively. A detector step size of 0.01 was employed to provide adequate sampling of the peaks (full width at the half maximum (FWHM) approximately 0.11 to 0.34). All of the samples were spun during the data collection to improve particle counting statistics, so the intensities are not dominated by a small number of crystallites. Figure 1 shows the goniometer of the XRD instrument used in this study.
XRD Phase Identification

For the qualitative analysis (i.e., phase identification), the software package PANalytical HighScore Plus, combined with the International Center for Diffraction Data (ICDD) and powder diffraction file (PDF) database of the standard reference materials, was used. Elemental composition data obtained from the EDXRF analysis was used as additional information for the phase identification.

Quantitative Phase Analysis (QPA) Using the Rietveld Method

Quantitative Phase Analysis (QPA) of multicomponent mixtures10-14 using XRD data10 has been used worldwide to determine the Wt% for a given phase. This QPA method does not require measurement of calibration data or the use of an internal standard; however, knowing the approximate crystal structure of each phase of interest in a mixture is necessary. The use of an internal standard10 will allow the determination of total amorphous phase content in a mixture. Analysis of synthetic mixtures has yielded high-precision results, with

XRF is one of the powerful analytical tools used to determine the elemental composition of all kinds of materials. In this study, we used the SPECTRO energy dispersive X-ray fluorescence (EDXRF) spectrometry to analyze the elemental compositions of the corrosion product samples. This spectrometry simultaneously detects the element from sodium (Na) to uranium (U). The concentration range goes from the part per million level to 100%. Due to the X-ray interaction with electrons, the elements with high atomic numbers provide better accuracy than the lighter elements. Four grams of the fine powder were mixed well and homogenized with 0.9 grams of Licowax C micropowder PM binder (Hoechstwax). The homogenized mixtures were pressed at a pressure of 20 tons to form pellet samples with a diameter of 31 mm. The pellet samples were then irradiated with X-ray photons from a molybdenum X-ray tube. The energies of the X-rays emitted by the sample were measured using a silicon semiconductor and were processed by a multichannel analyzer. Subsequent processing of the data provided spectral information that identified the elements present in the sample and the intensities of the

Fig. 1. The parts of the XRD goniometer and optics.

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errors generally less than 1.0% absolute. Since this technique fits the complete diffraction pattern, it is less susceptible to primary extinction effects and minor amounts of preferred orientation6-9. Additional benefits of this technique over traditional quantitative analysis methods1-5 include: (1) The determination of precise cell parameters and approximate chemical compositions, and (2) The potential for the correction of preferred orientation6-9 and microabsorption effects15. The weight of a phase in a mixture is proportional to the product of the scale factor, as derived in a multicomponent Rietveld analysis of the powder diffraction pattern, with the mass and volume of the unit cell. If all phases are identified and crystalline, the weight fraction W of phase p is given by:

where s, Z, M and V are the Rietveld scale factor, the number of formula units per unit cell, the mass of the formula unit and the unit-cell volume (in 3), respectively. This equation is the basis of a method providing accurate phase analyses without the need for standards or for laborious experimental calibration procedures. It is noted that the Rietveld method for quantification of a mixture of 20 phases using the HighScore Plus software (with a total of 6,000 reflections) is 30,000 times more powerful than the reference intensity ratio method1-5 for the quantification of just two phases of the mixture.

to take corrective measures, preventing scale buildup and avoiding future tube failure. Table 2 shows the elemental composition obtained from the EDXRF spectrometry and the chemical compounds obtained from the XRD technique. Vanadium, sulfur and sodium are present in fuel oil. When fuel oil is burned, vanadium and sodium compounds present in the fuel in high quantities react with oxygen to form V2O5 and Na2O in the furnace, and they stick to the metal surface. The V2O5 and Na2O react on the metal surface to form a low melting point phase of the conpound, such as sodium vanadate. Under optimum conditions, they can form a liquid that fluxes the protective oxide scale, exposing the underlying metal to oxidation. Therefore, these ash deposits pose potential corrosion problems. The presence of sodium oxide and vanadium oxide in ash deposits suggests the occurrence of fuel ash corrosion. To mitigate this corrosion, fuel oils that contain low quantities of vanadium, sodium and sulfur are used. If the above option is not possible, a fuel additive treatment can be adopted to prevent the formation of a low melting point phase of the sodium vanadate complexes. Additives containing magnesium and aluminum oxide have been successful in controlling fuel ash corrosion.
Identification of Scale Removed from RTR Boiler Tubes

RESULTS AND DISCUSSIONS

Analysis of External Deposits from Boiler Tubes in the Jiddah Refinery

Scale deposits were observed in the high-pressure boiler tubes at RTR. Figure 2 shows two samples of the affected tube sections submitted to the R&DC TSP Program Director: (1) A section cutout from wall and screen, and (2) A large tube. For the tube in Fig. 2a, an analysis was required to identify the deposits. The identification of the deposits led to a procedure to chemically clean the boiler tubes without damaging them.
2a 2b

The Jiddah refinery boiler is an oil-fired boiler. A huge accumulation of ash deposit was observed on the external surface of the tubes. The engineers asked the R&DC TSP Program Director to identify the deposits to determine the source and formation mechanism, so they could use the results Weight Percentage (Wt%) XRF Elemental XRD Chemical Composition Composition V 31.5 Vanadium oxide - V2O5 70 S 5.9 Sodium vanadium oxide 15 NaV2O5 Ni 5.4 Sodium vanadium sulfate 13 hydrate - Na(SO4)2. H2O Na 4.6 Mackinawite - FeS 2 Si 1.3 Calcite - CaCO3 Trace Fe 1.2 Al 0.9 Ca 0.2 Table 2. Summary of elemental and chemical compositions of the Jiddah boiler deposits

Figs. 2a and 2b. Scale deposits accumulated in high-pressure boiler tubes at RTR.

Fig. 3. XRD histogram of deposits from boiler tubes at RTR (inside screen tube) along with the reference patterns of identified phases.

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Compounds Magnetite-Fe304 Hematite-Fe2O3 Hydroxylapatite Ca5(PO4)3(OH) Magnesium phosphate hydroxide Mg2(PO4)OH Anhydrite - CaSO4 Talc - Mg3Si4O10(OH)2

Weight Percentage (Wt%) Screen Side Large Large Tube Wall Tube Tube Inside Inside Inside Outside 41 46 60 47 34 28 14 12 13 13 11 -

12 -

13 -

15 -

13 8

Fig. 6. XRD histogram of deposits from boiler tubes at RTR (outside large tube) along with the reference patterns of identified phases.

Table 3. Summary of chemical compositions of deposits from boiler tubes at RTR

Compound Magnetite - Fe3O4 Hematite - Fe2O3 Copper - Cu

Weight Percentage (Wt%) 39 35 26

Table 4. Summary of results of deposits from a boiler at Yanbu gas plant

Fig. 4. XRD histogram of deposits from boiler tubes at RTR (inside wall tube) along with the reference patterns of identified phases.

Fig. 7. XRD histogram of deposits from a boiler at Yanbu gas plant along with the reference patterns of identified phases.

The deposits were removed from the boiler tube and submitted by the CSD to R&DC to support failure analysis work. The XRD results, Table 4 and Fig. 7, showed a high percentage of hematite and metallic copper, which indicates the presence of dissolved oxygen in the boiler feed water and also erosion in the boiler tubes.
Fig. 5. XRD histogram of deposits from boiler tubes at RTR (inside large tube) along with the reference patterns of identified phases.

Identification of Scale Deposits Removed from BGP

The XRD results, Table 3 and Figs. 3 to 6, showed that the scale deposits scraped from the insides of the tubes mainly consisted of iron oxide corrosion products with calcium phosphate hydroxide (apatite) and magnesium phosphate hydroxide. The deposits removed from the outside of the large tube consisted of calcium sulfate and iron oxide corrosion products. Additionally, the high percentage of hematite might indicate the presence of dissolved oxygen in the boiler water.
Identification of Deposits from Screen Tubes of a Boiler at Yanbu Gas Plant

Scale deposits were observed in a high-pressure boiler at the Yanbu gas plant. The boiler tube failed due to these deposits.

An unknown material produced with a sulfur product was found in a condenser at a plant in the BGP sulfur recovery unit. The plant engineers concern was that the unknown material might be from the super claus catalyst (alumina and silica). If this was the case, it meant that the mesh holding the catalyst has a pinhole, causing a catalyst leak, which would require total plant shutdown and catalyst removal to repair or replace the mesh. The XRD results, Table 5 and Figs. 8 to 10, showed no alumina or silica, as expected by the BGP engineers. It meant that the mesh holding the catalyst is good. Ammonium hydrogen sulfate can be formed in the boiler feed water due to treatment with the chemical compound, which contains ammonia. The formation of ammonium hydrogen sulfate can be avoided by increasing the furnace temperature to burn the ammonia.
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Compounds Ammonium hydrogen sulfate - (NH4)3H(SO4)2 Sulfur - S

Weight Percentage (Wt%) Plant Plant Plant Deposit as White Yellow Received Part Part 84.8 15.2 100 92.2 7.8

oil is not good; if hematite is present in the boiler deposits, it means that the boiler feed water contains dissolved oxygen; and if the metallic copper is present in the deposits, it indicates erosion in the boiler tubes. Special precautions must then be taken to prevent the plating out of copper during cleaning operations.

ACKNOWLEDGMENTS
The authors would like to thank the management of Saudi Aramco for permission to publish the results in this article. Awad M. Al-Mofleh, Yazeed Al-Dukhayyil and Abdulelah AlNaser are acknowledged for their encouragement and support for this study. Thanks are also due to Fahad Al-Khaldi for his help in preparing the XRF samples.

Table 5. Summary of chemical compositions of deposits from BGP

REFERENCES
1. Chung, F.H.: Quantitative Interpretation of X-ray Diffraction Patterns of Mixtures I. Matrix-flushing Method for Quantitative Multicomponent Analysis, Journal of Applied Crystallography, Vol. 7, 1974a, pp. 519-525. 2. Chung, F.H.: Quantitative Interpretation of X-ray Diffraction Patterns of Mixtures II. Adiabatic Principle of X-ray Diffraction Analysis of Mixtures, Journal of Applied Crystallography, Vol. 7, 1974b, pp. 526-531. 3. Chung, F.H.: Quantitative Interpretation of X-ray Diffraction Patterns of Mixtures III. Simultaneous Determination of a Set of Reference Intensities, Journal of Applied Crystallography, Vol. 8, 1975, pp. 17-19.
Fig. 9. XRD histogram of deposits (white part) from BGP along with the reference patterns of identified phases.

Fig. 8. XRD histogram of the as-received deposits from BGP along with the reference patterns of identified phases.

4. Klug, H.P. and Alexander, L.E.: X-Ray Diffraction Procedures for Polycrystalline and Amorphous Materials, 2nd edition, New York: John Wiley & Sons Inc., 1974. 5. Jenkins, R. and Snyder, R.L.: Introduction to X-ray Powder Diffractometry, New York: John Wiley & Sons Inc., 1996. 6. Sitepu, H., Sherik, A.M., Zaidi, S.R. and Shen, S.: Comparative Evaluation of Cobalt and Copper Tubes using X-ray Diffraction Data for Black Powder in Sales Gas Transport System, paper 10100, presented at the 13th Middle East Corrosion Conference, Manama, Bahrain, February 14-17, 2010.

Fig. 10. XRD histogram of deposits (yellow part) from BGP along with the reference patterns of identified phases.

7. OConnor, B.H., Li, D.Y. and Sitepu, H.: Strategies for Preferred Orientation Corrections in X-ray Powder Diffraction Using Line Intensity Ratios, Advances in X-ray Analysis, Vol. 34, 1991, pp. 409-415. 8. Sitepu, H., OConnor, B.H. and Li, D.Y.: Comparative Evaluation of the March and Generalized Spherical Harmonic Preferred Orientation Models Using X-ray Diffraction Data for Molybdite and Calcite Powders, Journal of Applied Crystallography, Vol. 38, 2005, pp. 158-167. 9. Sitepu, H.: Texture and Structural Refinement of Neutron Diffraction Data of Molybdite (MoO3) and Calcite

CONCLUSIONS
XRD is an excellent tool to determine the nature, source and formation mechanism of deposits formed by the processes in the various units of refineries and gas plants. The XRD results can guide the engineers at the affected refinery and gas plant to overcome the problems by devising the right corrective procedures. For example, if sodium and vanadium compounds appear in the samples (ash deposits) examined, it indicates the fuel
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(CaCO3) Powders and Ni50.7Ti49.30 Alloy, Powder Diffraction Journal, Vol. 24, No. 4, 2009, pp. 315-326. 10. Bish, D.L. and Howard, S.A.: Quantitative Phase Analysis Using the Rietveld Method, Journal of Applied Crystallography, Vol. 21, Part 2, April 1988, pp. 86-91. 11. Madsen, I.C., Scarlett, N.V.Y., Cranswick, L.M.D. and Lwin, T.: Outcomes of the International Union of Crystallography Commission on Powder Diffraction Round Robin on Quantitative Phase Analysis: Samples 1a to 1h, Journal of Applied Crystallography, Vol. 34, 2001, pp. 409-426. 12. Scarlett, N.V.Y., Madsen, J.C., Cranswick, L.M.D., et al.: Outcomes of the International Union of Crystallography Commission on Powder Diffraction Round Robin on Quantitative Phase Analysis: Samples 2, 3, 4, Synthetic Bauxite, Natural Granodiorite and Pharmaceuticals, Journal of Applied Crystallography, Vol. 35, 2002, pp. 383-400. 13. Hill, R.J. and Howard, C.J.: Quantitative Phase Analysis from Neutron Powder Diffraction Data Using the Rietveld Method, Journal of Applied Crystallography, Vol. 20, 1987, pp. 467-474. 14. OConnor, B.H. and Raven, M.D.: Application of the Rietveld Refinement Procedure in Assaying Powdered Mixtures, Powder Diffraction Journal, Vol. 3, No. 4, 1988, pp. 2-6. 15. Hermann, H. and Ermrich, M.: Microabsorption of X-ray Intensity in Randomly Packed Powder Specimens, Acta Crystallographica Section A, Vol. A43, No. 3, 1987, pp. 401-405.

Dr. Husin Sitepu joined Saudi Aramcos Research and Development Center (R&DC), Analytical Services Division, in 2008. Currently, he is contributing to several research projects under both the Downstream and Strategic and Upstream R&DC programs, in providing crystallographic information on developed materials including nano-materials and catalysts. Before joining Saudi Aramco, Husin worked at NIST Center for Neutron Research in Gaithersburg, MD; Virginia Tech University in Blacksburg, VA; Ruhr University Bochum Universitt in Bochum, Germany; the Institute LaueLangevin, Neutrons for Science, in Grenoble, France; the University of British Columbia in Vancouver, Canada; and the Curtin University of Technology in Perth, Australia. He has authored and coauthored 32 papers in several peer-reviewed journals, including the International Union of Crystallographys Journal of Applied Crystallography. Husin has extensive experience in Rietveld refinement of polycrystalline structures using X-ray, synchrotron and neutron powder diffraction data. He received his Postgraduate Diploma, M.S. and Ph.D. degrees in Physics from the Curtin University of Technology, Perth, Western Australia, in 1989, 1991 and 1998, respectively. Husin is a member of the International Center for Diffraction Data (ICDD), the International Union of Crystallography (IUCr), and the Neutron Scattering Society of America (NSSA). Ahmed A. Al-Shehry has worked at Saudi Aramco since 1981. He started his career working in the Chemistry Analysis Unit of the Laboratory Department. He now works in the Elemental Analytical Unit, part of the Analytical Services Division of R&DC. Ahmed is a Senior Digital System Technician and an expert in several analytical techniques, including atomic absorption spectromery (AAS), which is an analytical procedure for the qualitative and quantitative determination of chemical elements employing the absorption of optical radiation (light) by free atoms in the gaseous state; flame atomic absorption spectrometry, which is a very common technique for detecting metals and metalloids in environmental samples; inductively coupled plasma optical emission spectrometry (ICP-OES), which is an analytical technique used for the detection of trace metals; and XRD and XRF used to determine the chemical compositions of corrosion products, carbonate rocks, cements and catalysts. He has successfully conducted a series of Technical Service Projects (TSPs) to support refineries and gas plants. Also, Ahmed has contributed to the Downstream and Strategic, and Upstream R&DC programs by providing chemical compositions of scale mitigation and catalysts projects.

BIOGRAPHIES
Dr. Syed Rehan Zaidi has been with Saudi Aramco since 1992. His specialized area of research is the mineralogical characterization of geological samples (clay and bulk rock) by using the XRD technique. Syed is also responsible for the XRD method development and research work. He is also familiar with the other analytical techniques, such as: XRF, SEM, FTIR, TGA, DSC and ICP instruments. Syed received his B.S. (Honors) and M.S. degrees in Chemistry from Aligarh Muslim University, Aligarh, India, in 1977 and 1980, respectively. In 1986, he received his Ph.D. degree in Inorganic Chemistry from Aligarh Muslim University, Aligarh, India. Syed has published more than 20 papers in peer review journals. He is a member of the American Chemical Society (ACS) and the Society of Petroleum Engineers (SPE).

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