Paper No.

09560
Thermodynamic Analysis of Formation of Black Powder in Sales Gas Pipelines
Abdelmounam Sherik Research & Development Center, P.O. Box 62, Saudi Aramco Dhahran 31311, Saudi Arabia E-mail: Abdelmounam.sherik@aramco.com Boyd R. Davis Kingston Process Metallurgy Inc., Kingston, ON CANADA K7P 1S6 E-mail: bdavis@kpm.ca

2009

ABSTRACT The product of reactions between steel pipelines and some species in processed natural gas is a significant concern to the gas industry. The corrosion product, which is a mix of iron oxides, sulphides, and carbonates, has several impacts on pipeline operations and must be periodically removed by pigging the pipeline. The difficulty in understanding the mechanisms of formation of this material comes in large part from the non-uniform conditions, such as water dew point, H2S, CO2 and O2 concentrations, in the pipeline. This paper provides an evaluation of the application of chemical thermodynamics to the formation of this material - what is commonly known in the gas industry as black powder. Given the complex nature of the formation of black powder, it was decided to study the formation and stabilities of various iron phases, namely iron oxides, sulfides and carbonates as well as elemental sulfur in sales gas pipeline environments. Our findings show that thermodynamics can be a useful tool to indicate what can, and cannot, possibly form under dewing conditions; however, compositional analysis of the powder can assist in directing the calculations. Due to these uncertainties, the results should be used as a guide to better understand the corrosion mechanisms inside the pipeline. Keywords: black powder, computational thermodynamics, internal corrosion, Sales Gas, moisture content.

2009 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE International, Copyright Division, 1440 South creek Drive, Houston, Texas 777084. The material presented and the views expressed in this paper are solely those of the author(s) and are not necessarily endorsed by the Association. Printed in the U.S.A.

Copyright

INTRODUCTION

The product of reaction between the steel of natural gas pipelines and components in processed natural gas is a significant concern to the gas industry. This corrosion product, commonly referred to as black powder, is a mix of iron oxides, sulphides, and carbonates and causes wear in valves and must be periodically removed by pigging the pipelines1-4. Black powder samples collected from sales gas pipelines showed only the presence of iron oxides and carbonates as can be seen in Table 14 The difficulty in understanding the mechanisms for formation of this material comes from the non-uniform conditions in the pipeline. Water content and dew points, H2S and CO2 concentrations, and the presence of oxygen will all have a significant impact. Since corrosion is anticipated to have occurred due to condensed water (liquid phase), the dew points under several operating conditions were calculated to determine deleterious conditions. Furthermore, the composition and pH of aqueous phases were calculated using various assumptions. E-pH diagrams were then generated to determine what iron ion species would be predominant in the aqueous environment. Preliminary mass balances were done to support the E-pH diagram calculations to ensure that proposed mechanisms were consistent. One of the main challenges in the current thermodynamic analysis was understanding, in sales gas with oxygen ingress, the predominance of iron oxide phases (magnetite-Fe3O4, and FeOOH) in the collected black powder knowing from the literature 5-7 that FeCO3 would be the expected dominant species. This is reflective of the significant complexity of the corrosion problem resulting from changing conditions in the gas phase (such as oxygen ingress or changes in H2S, CO2 and/or H2O levels), the effect of kinetics on the reaction of pipeline steel with the solution, and the subsequent conversion of reaction products in a dry environment (for example conversion of FeCO3 to Fe3O4). An added complexity to the current analysis is that the analyzed black powder samples do not represent black powder that have formed at well defined conditions (specific location and time) in the pipeline. They instead represent samples collected from the sum of black powder products that have formed at varying locations and times along the pipeline (for example, water condensation might have occurred only at low points and for a few hours during the winter season or oxygen ingress takes place at low pressure points, etc). All this makes the possibility of correlating the results of the current thermodynamic analysis with actual field X-ray diffraction results quite a difficult task. This means that an attempt at quantitative analysis of the thermodynamics as they apply to the formation of black powder could be misleading as a result of the wide range of potential conditions and kinetic limitations on the reactions. However, thermodynamics can be a useful tool to predict what can, and cannot, possibly form under dewing conditions. The fact that there is a wide range of products (iron oxides, carbonates and elemental sulfur) sampled from the pipelines indicates that this is not a homogeneous process that is controlled by thermodynamics. In other words, if the gas phase is relatively constant, thermodynamics would predict one stable phase for each of the non-metallic components in the gas phase (i.e. S and C). The fact that there are all the above mentioned phases present means that there are regions of kinetic control in the pipeline. However, thermodynamics can be a useful tool to

predict what can, and cannot, possibly form under the point conditions representative of actual field parameters. Due to these uncertainties, the results should be used as a guide to better understand the corrosion mechanisms inside the pipeline. SYSTEM DEFINITION System Determination Prior to any thermodynamic analysis, it is important to define the terms of the calculations. Table 2 shows sales gas compositions and measured dew points as obtained from two spot analyses each4. Table 3 shows impurity levels and properties of sales gas4. These levels were used to set the conditions for the calculations outlined in the following sections of the report. Assumption for the Analysis: There are two main assumptions made throughout this analysis. i. CH4 and N2 were removed from the calculations and replaced with Argon (Ar) so as not to impact on the reaction equilibrium. ii. The sales gas would behave as an ideal gas (ideal gas behavior). This is validated by the dew point calculations (see section below) that match exactly when the ideal gas model is used, but are not comparable when a real gas model is used. One problem with thermodynamic calculations is that reactions that normally do not occur due to kinetic barriers cannot be prevented in the calculations without the removal of some species from the calculation. An important example of this is the reaction between oxygen and methane: 2O2 + CH4 = CO2 + 2H2O (1)

At pipeline temperatures, methane is very kinetically stable with respect to other gases. The extent of this stability will be determined in future experimental work, but it is reasonable to assume that the interaction of methane and nitrogen with other gases in the pipeline will be limited. It is not possible to conduct thermodynamic calculations with methane and nitrogen in the calculation due to this kinetic barrier to reaction (however, the reaction still takes place in the thermodynamic calculations). For this reason, it was determined that CH4 and N2 needed to be removed from the calculations and replaced with Ar so as not to impact on the reaction equilibrium. Since this paper is intended to show the potential for thermodynamic calculations as they relate to black powder formation, this is one of the assumptions that must be made for this type of calculation to be done. The results of these calculations will be compared with experimental work currently underway on gas phase stability. Another example of this gas phase kinetic barrier issue is CO/CO2 equilibrium. At low (under 100oC) temperatures, CO and CO2 can exist together at any ratio despite thermodynamics stating that there would be a reaction between them to make elemental carbon. CO/CO2 gas blends in cylinders can be purchased that remain at the same ratio virtually indefinitely. Oxygen can be an important factor in sales gas pipeline corrosion. Oxygen ingress in gas lines can cause significant corrosion in small concentrations and combustion in larger

amounts. A 1988 survey of 44 natural gas transmission pipeline companies in North America indicated that the gas quality specifications allowed maximum O2 concentrations ranging from 0.01mol% to 0.1mol% with typical value of 0.02 mol%6, 8. It has been shown that an oxygen content of approximately 0.01 mol % has little effect on steel corrosion in the presence of stagnant water inside sales gas transmission pipelines, while 0.1 mol % produces fairly high corrosion rates6, 8. This again points to the difficulty in making a quantitative analysis of the entire system. As a general rule of thumb, it has been recommended that operators of transmission pipelines should consider limiting maximum oxygen concentration of 10ppmv (0.001 mol%)6, 8. It is important to understand that O2 due to air ingression in the gas will in reality, not be at equilibrium with the other gases in the methane stream due to the low kinetics of methane reacting with oxygen at the operating temperatures. Oxygen cannot exist (thermodynamically) in a reducing environment such as sales gas as indicated by reaction (1), since it would react with methane. If oxygen were at equilibrium with the methane, the partial pressure of O2 would be undetectable in this reducing atmosphere, and CO2 and water concentrations would increase. (H2S would remain relatively unaffected). This means that the conditions indicated by the equilibrium gas composition (i.e. the Eh* and pH of the water or the equilibrium CO2 in the gas phase) will not reflect the true kinetically controlled situation. Therefore, any calculations or diagrams generated based on the gas phase equilibrium must be interpreted in light of the expected kinetics (i.e. that oxygen could remain in the system as a kinetically stable gas phase). Specific reactions in black powder production that are problematic with regards to the application of thermodynamics are outlined below. The ramification of the kinetic barriers is that it is difficult to accurately predict the equilibrium aqueous phase. However, by suppressing reactions in the calculations that will not occur in the pipeline, a reasonable estimate of the aqueous phase can be made. This allows for a much more useful analysis of the iron reaction products, since E-pH diagrams can be studied with the knowledge of the aqueous phase chemistry. Dew point determination In order to demonstrate the validity of the calculations, the dew points were calculated for a range of conditions and are shown in the following figures. The operating temperature and pressure range were 15-30C and 720-900 psig, respectively. Dew point calculations considered both that the balance of the sales gas was N2 and CH4 (CH4/N2 = 15.67) or Ar for purposes of the calculations. It was determined that pressure has the largest effect on dew point, more than any other variable. Calculations were performed to determine if dew point temperature change as a function of contaminant concentrations and pipeline pressure. Figure 1 shows the comparison between the results obtained a commercially available software package and the dew point calculated using the alpha moisture system (http://www.dew-point.com/calculate.html) dew point calculator. In all cases, the results are within about 2oC of each other. As expected, the impurities (H2S and CO2) had no significant effect on the dew point while pipeline pressure and [H2O] significantly affect dew point temperature. Point Calculations: Point calculations are thermodynamic calculations done to attempt to simulate the conditions in the precipitated water in the pipeline. They are most effectively used to identify reasonable ranges of pH or redox for EpH diagrams or to help better understand
Eh refers to the redox potential E of the solution, usually the Y axis on the EpH diagram (sometimes called an Eh-pH diagram).
*

reaction mechanisms. All calculations are based on one liter of gas and are in units of moles. The output from the thermodynamic model gives the equilibrium gas phase and the aqueous condensed phase. By changing the values of CO2, H2S, and O2, a range of values for pH, Eh, and aqueous species concentrations can be obtained. The concentration of aqueous species is important so that the EpH diagrams can be set to the correct values. Oxygen can be used in these calculations because methane and nitrogen have been replaced with Ar. This condition represents a sort of transient condition where O2 has ingressed into the pipeline but remains as unreacted with methane due to kinetic constraints. In this way, a grid was set up to see the impact of changing gas conditions on the Eh and pH of the solution. The results of this (low and high CO2 content) are shown in Tables 4 and 5. The water concentration was selected at a maximum value of 0.55 mg/l These point calculations indicate that CO2 will buffer the aqueous solution to a pH of about 4 typical of carbonate solutions. The addition of H2S in a reducing environment has little impact on pH. The presence of oxygen also naturally drives up the Eh value, so there is the potential for localized increases of Eh along the pipeline due to oxygen ingress. The fact that there are no pH conditions that would be above about 5 in line with the work by Sridhar et al.5 which have a range of conditions used for their test with CO2 at 10 psi and all conditions (except the one loaded with NaOH) show a pH around 5. The results mentioned above reinforce the difficulties of studying the problem in isolation of its surrounding. These relatively highly acidic pH conditions are not encountered in the pipeline. The presence of iron in the system has a dramatic effect on the actual chemistry. The pH of the system is normally found to be between 5 and 6.5 due to the reaction of CO2 with iron. When iron is introduced into the calculation, FeCO3 precipitates and the pH increases to 5 and FeOH+ is found in the aqueous solution. This is much more in line with the actual field findings. The formation of Fe3O4 is thermodynamically possible but depends on the availability of iron to the system (ratio of iron to gas phase). This could help to explain the range of compounds found in the pipeline. The progression of product formation can be studied by looking at the calculated reaction products as iron is introduced into the system. In the presence of any Fe (given an oxygen free system), FeS2 is the first iron compound to form (at around pH ~4). FeCO3 forms next if the available sulphur is exhausted which will increase the pH to above 5. However, the relative rates of these reactions are not known and are affected by the relative concentrations of the gases. It has been stated in the literature that when CO2 and H2S are both present in condensed moisture, the corrosion product that forms is a function of the partial pressure of both acid gases and temperature. Several investigators have suggested different CO2/H2S ratios, such as 200 and 500, which represent the change from predominately FeCO3 to FeS6. It should be noted that the preference of CO2 forming carbonate over H2S forming FeS (both reactants in aqueous form) is a kinetic phenomenon, and not based on thermodynamics. Thermodynamically, iron will preferentially react with S than CO2 at virtually any concentration of reactants. The fact that FeCO3 is found preferentially at high levels of CO2/H2S indicates that the kinetic reaction for S is less than that for CO2 (perhaps due to a passivating film that occurs with sulphur, or due, as mentioned above to exhaustion of S at the reaction site due to the slow dissolution of more H2S into the water (slow replenishment of S in the water).

As with CO2, the calculations involving S as described are also kinetically controlled. The prediction of the formation of SO42- from thermodynamics is not what occurs in the field. Reactions of oxygen and H2S appear to be kinetically slow and the preferential reaction is as per the following reaction (2). 2 H2S + O2 = 2 H2O + 2S EpH Diagrams EpH diagrams can be used to identify regions of pH and E (redox potential, or the oxidizing or reducing environment of the solution). These diagrams are often presented in a series with varying conditions of activity of one of the species. This is because, while EpH diagrams can be constructed for metals in water, when a non-metallic element is introduced (in this case carbon or sulphur) another degree of uncertainty is added to the system. This has to be removed by setting the activity or partial pressure of a compound containing that non-metallic element. However, providing a series of diagrams with no reference to the actual system has little value in understanding the mechanism of reaction. For this reason, the point calculations that were performed in this work are useful in helping to determine reasonable concentrations of aqueous species for carbon and sulphur. As a baseline, the EpH diagram for water was constructed and is shown in Figure 2. FeOOH, the data for which was entered into the commercial software package from literature8, was not shown to appear. Conditions for its formation are not, at present clear, but it can be assumed that it forms in the presence of oxygen via the following reactions (3). 2Fe + H2O(l) + 3/2 O2 = 2 FeOOH or through conversion of reaction products reactions (4) and (5): 4FeS + 2H2O + 3O2 = 4FeOOH + 4S Fe3O4 + 3/2 H2O + 1/4 O2 = 3 FeOOH (although likely kinetically limited) (4) (5) (3) (2)

This diagram is at 15oC, although the effect of temperature is negligible over the range that is experienced by the pipelines. The region of interest is between the two dashed lines. These lines indicate the region where water is stable. It is clear that with only pure water and a basic pH, it is possible to form Fe3O4 as shown by the region in Figure 2. The progression is from elemental Fe, to FeO (or Fe(OH)2 as shown) to Fe3O4 and finally to Fe2O3 the most oxidized iron oxide. If the aqueous species were to be removed from the diagram, it would show each phase field layered on top of each other as the E(V) increases (becomes more oxidizing). Influence of CO2 on the system: With the addition of CO2, the EpH diagram changes to that shown in Figure 3 for a system with low CO2 in the gas phase (0.1 mol%). Here, because C is added to the system, there must be a species selected that has a fixed concentration. This can either be a gas (i.e. CO2) or aqueous species (i.e. HCO3 ). HCO3 was selected, and a representative value was taken from the point calculations done in the last section.

Note that the carbonate phase, FeCO3, is covered by the aqueous FeOH+ and Fe2+ fields. This only indicates the ionic concentration in the system, since the diagram is set to the typical 10-6 concentration for the sum of ionic species (if the total of all ionic species is at least 10-6, the predominant ionic species will be shown on the plot). To see the solid phases, the ionic species can be suppressed in the output, giving a result as shown in Figure 4. This plot without aqueous species shown clearly demonstrates that FeCO3 is the significant phase in the E and pH range that is of interest. This supports the point calculations showing that FeOH+ is present with CO2 and has an influence on the pH of the system. Often, EpH diagrams are shown with the aqueous phase boundaries as dotted lines over the top of the solid phases. The concentration of aqueous species over a phase field gives an indication of the drive for corrosion, since corrosion will occur with greater intensity if the dissolved Fe ions are able to build to a high concentration before equilibrium is reached. For ease of discussion in this section, the concentration of aqueous species will be set at 0.001 so that the solid phase fields may be seen with the aqueous species. It is evident that Fe3O4 forms at pH values above about 6.5 but that the phase field overlaps the FeCO3 for a given pH, depending on the Eh of the system. This could explain why both FeCO3 and Fe3O4 are found in the black powder since a pH of 6.5 or greater is found in laboratory tests at Saudi Aramco and it is reasonable that the Eh could change depending on the availability of oxygen. Influence of H2S on the system: The effect of H2S on the pipeline is highly dependent on the atmosphere in the pipeline and kinetics as mentioned, oxygen does not react kinetically with H2S to create sulphates. This means that EpH diagrams can vary widely as to the fields of stability depending on the situation in the system. A simple EpH diagram using the pH2S as the basis for the calculation yields the diagram in Figure 5. This shows Fe3O4 in between FeS and FeS2. The Fe3O4 field is very narrow (and is only visible as a thicker line) but at lower H2S concentrations it is more predominate. This demonstrates that there is the likelihood for FeS and FeS2 to form depending on the redox potential. Since oxygen ingression will affect the redox potential significantly, and oxygen ingression is a relatively non-uniform event (sometimes minor, sometimes major) it is likely that both FeS and FeS2 will be found in a range of concentrations with one another. Both the case of CO2 and H2S demonstrate why a variety of solid material is found in black powder. Oxygen ingress can widely vary the Eh of the system and favor the formation of one compound over another. The nature of the ingress ranging in concentration and location leads to this non-uniform residue and complicates the overall analysis of its formation.

CONCLUSIONS It is clear from this analysis that internal corrosion of pipelines and black powder formation in sales gas pipelines is a complex process that is not thermodynamically controlled however, thermodynamics can assist with our understanding of the underlying chemical processes. The fact that there is a wide range of products (iron oxides, iron carbonates and elemental sulfur) sampled from the pipelines indicates that this is not a homogeneous process that may not be

controlled by thermodynamics. These products are mainly due to: (1) intermittent ingress of oxygen resulting from process upsets and (2) the cyclical wet-dry conditions resulting from process upsets and seasonal temperature changes. This makes the attempt to correlate the iron phases obtained at well defined thermodynamic conditions to the composition of the black powder that has formed in the pipelines at varying conditions (thermodynamic and kinetic controlled regions) a complex task. However, thermodynamics can be a useful tool to predict what can, and cannot, possibly form using well defined conditions (the point conditions provided by Saudi Aramco).

REFERENCES 1. A.M. Sherik, S.R. Zaidi, E.V. Tuzan and J. Perez, Black Powder in Gas Transmission Systems, Corrosion NACE 2008, pp. 2. R.M, Baldwin, Black Powder in the Gas Industry-Sources, Characteristics and Treatment, GMRC, Report No.TA97-4, May 1998 3. A. M, Sherik, Black Powder in Sales Gas Transmission Pipelines, Saudi Aramco Journal of Technology, Fall issue, 2007, pp.2-10 4. A. M. Sherik, Effects of Simulated Pipeline Processes on Black Powder Formation in Sales Gas Pipelines, Report No. DR-002/05-COR, April 2007 5. N. Sridhar, D. S. Dunn, A. M. Anderko, M. M. Lencka and H. U. Schutt, Effects of Water and Gas Compositions on the Internal Corrosion of Gas Pipelines-Modeling and Experimental Studies, Corrosion, Vol.57, No.3, 2001, pp221-235 6. B. Kermani, J. Martin, and K. Esaklul, Materials Design Strategy: Effects of H2S/CO2 Corrosion on Materials Selection, Corrosion NACEXPO2006, Paper No.06121, pp1-18 7. F. F. Lyle, Carbon Dioxide/Hydrogen Sulfide Corrosion Under Wet Low-Flow Gas Pipeline Conditions in the Presence of Bicarbonate, Chloride and oxygen, PRCI Final Report PR15-9313. 8. J. Majzlan, K.-D. Grevel, and A. Navrotsky, Thermodynamics of Fe oxides: Part II. Enthalpies of formation and relative stability of goethite (-FeOOH), lepidocrocite (FeOOH), and maghemite (-Fe2O3), American Minerologist, 88, 855-859, 2003

Table 1 Composition of black powder as determined by XRD technique. Main Compound Magnetite-Fe3O4 -FeOOH -FeOOH Iron Sulphides Siderite-FeCO3 Elemental sulfur Approximate average wt% 60 Trace amounts (<2) 25 Not detected 10 5

Table 2 Sales gas hydrocarbon composition and dew points

CH4 78.81 85.34 C2H6 8.12 7.26 C3H8 3.01 0.79 iC4 (IsoButane) 0.48 0.17 nC4 (normal butane) 0.83 0.30 iC5 (Isopentane) 0.20 0.10 nC5 (normal pentane) 0.16 0.09 C6 (Hexanes plus) 0.03 0.04 N2 7.38 5.78 Dew point C @130psi -19 0.0 Calculated water content 0.12mg/l 0.55mg/l

Table 3 Composition and properties of sales gas used in the current work Composition and properties of Sales Gas H2S CO2 O2 moisture (H2O) in gas Ambient Temperature Pipeline pressure Levels 2.0 and 6.0ppm 0.1, 0.5 and 1.6 mol% 0.01, 0.02 and 0.05 mol% 0.12mg/L gas and 0.55mg/L gas 15 to 30C 720 and 900psi

Table 4 Impact of changing gas concentrations on the aqueous phase (CO2 = 0.1 mol%, H2O = 0.55 mg/l, P = 720 psi, T = 15oC) O2 concentration (mol%) 0 0.01 0.05
Eh (V) 0.562 0.944 0.954

H2S Concentration (ppm) 2

pH 4.546 4.546 4.546 Eh (V) -0.003 1.216 1.227 pH 4.283 -0.205 -0.205 Eh (V) -0.003 1.237 1.248

6
pH 4.244 -0.558 -0.558

Table 5 Impact of changing gas concentrations on the aqueous phase (CO2 = 1.6 mol%, H2O = 0.55 mg/l, P = 720 psi, T = 15oC) O2 concentration (mol%) 0 0.01 0.05
Eh (V) 0.596 0.979 0.989

H2S Concentration (ppm) 2

pH 3.944 3.944 3.944 Eh (V) 0.024 1.231 1.227 pH 3.893 -0.204 -0.204 Eh (V) 0.022 1.252 1.248

6
pH 3.882 -0.558 -0.558

35 30 25

Dew Point ( C)

20 15 10 5 0 0.0 0.1 0.2 0.3 0.4 0.5 0.6

Fact 900 psi Fact 720 psi Internet 900 psi Internet 720 psi

Water Concentration (mg/L)

Figure 1 Calculated dew points as a function of pipeline pressure and two different software packages assuming ideal gas with Ar substituting N2 and CH4

10

1.8 1.6 1.4 1.2 1.0 0.8 0.6 Fe3+

T = 15oC a(ions) = 10-6

E(V)

0.4 0.2 0.0 -0.2 -0.4 -0.6 -0.8 -1.0 -1.2 0 2 4 6 Fe2+

Fe2O3(s)

FeOH

Fe3O4(s) Fe(OH)2(s)

Fe(s) 8 10

12

14

pH
Figure 2 E-pH diagram for Fe in water

11

1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6 -0.8 -1.0 -1.2 0 2 4 6 8 10 Fe(s)
FeOH +

Fe3+

T = 15oC a(ions) = 10-6

E(V)

Fe2O3(s) Fe2+

Fe3O4(s)

12

14

pH
Figure 3 E-pH diagram for Fe-C in water for low CO2 in gas phase

12

1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6 -0.8 -1.0 -1.2 0 2 4 6 8 10 Fe(s) FeCO3(s)

T = 15oC [HCO3-] = 10-5 no ions shown

E(V)

Fe2O3(s)

Fe3O4(s)

12

14

pH

Figure 4 E-pH diagram for Fe-C in water for low CO2 in gas phase (no ionic species shown)

13

1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6 -0.8 -1.0 -1.2 0 2 4 6 8 10 Fe2+
+ FeOH

T = 15oC pH2S = 10-8 a(ions) = 10

-6

E(V)

FeS2(s) Fe3O4(s)

FeS(s) Fe(s)

12

14

pH

Figure 5 E-pH diagram for Fe-S in water for pH2S = 10-8

14