Production Enhancement

Considerations Concerning use of QT-900 and QT1000 CT for Work in Sour Wells

n 2002, there were 2 major QT-900 coiled tubing (CT) failure incidents, both of which involved contact with

PH 2 S ( psia) = % H 2 S x BHP( psia )

Example: If %H2S = 0.01% and BHP = 10,000 psia, then PH2S = 1 psia or 0.07 bars.

high H2S containing fluids and were classified as Sulfide Stress Cracking (SSC) failures. In both cases, failures were aided by presence of OD mechanical damage from gripper blocks and commingling of HCl acid with the high H2S environment downhole. OD mechanical damage causes an increase in local CT hardness which increases susceptibility of the tubing to environmental cracking (EC). And, introduction of acid downhole drastically lowers pH of the environment. It is strongly suspected that if the contacting environment had been controlled, these failures would not have occurred. Therefore, control and knowledge of the environment in which the CT operates is paramount to helping avoid unexpected CT failures in H2S wells. This paper discusses industry knowledge on this issue, describes the important environmental variables, defines zones of acceptable service and identifies chemical inhibitors which can mitigate potential H2S related environmental cracking failures.

PH 2 S ( psia ) = ppm H 2 S x 10 6 x BHP ( psia )

Example: If H2S = 100 ppm and BHP = 10,000 psia, then PH2S = 1 psia or 0.07 bars. For liquid systems, one needs to know the mole fraction H2S in the gas phase at bubble-point conditions to more accurately calculate PH2S. The in situ pH should be known by the well operator or it can be estimated from partial pressure of CO2 and H2S gases. A more accurate estimate of pH can be made if a water analysis is provided. And, of course, one must have a susceptible material before environmental cracking will occur. QT-1000 CT is much more susceptible to H2S environmental cracking than QT-900 CT due to the higher strength and hardness of QT-1000 CT. Per NACE International Standard MR0175/ISO 15156, carbon and low alloy steels are suitable for sour service when its hardness is 22 HRC or less. The Halliburton CT purchase specification D00032747 for new CT requires a hardness of 22 HRC maximum for QT-700, QT-800 and QT-900 CT and 28 HRC maximum for QT-1000 CT. During usage, however, OD surface mechanical damage may cause a local increase in hardness. There are several failure modes that can occur to CT when it is exposed to H2S containing fluids. All of these failure modes are directly related to hydrogen entry into the tubing metal structure. The source of the hydrogen for all of these cases is from the absorption and diffusion of atomic hydrogen produced on the CT steel surface by the sulfide corrosion process. Some terminology and definitions that may be used to describe various hydrogen related failures are given below.

Industry Knowledge concerning Environmental Cracking of Steels in H2S Knowledge gained by the industry through years of experience and by laboratory testing has shown that the primary variables related to environmental cracking of carbon and low alloy steels in H2S containing aqueous fluids are in situ pH of the water phase and H2S partial pressure (PH2S). Low pH (more acidic) and high PH2S values increase likelihood of environmental cracking of CT. Calculation of H2S partial pressure (PH2S) for systems with a gas phase can be made by multiplying the system total pressure by the mole fraction of H2S in the gas phase, as follows.

2 Sulfide Stress Cracking (SSC) Brittle cracking of metal involving corrosion and tensile stress (residual and/or applied) in the presence of water and H2S. Experience indicates that this is the primary failure mode of CT in H2S containing environment. Hydrogen-Induced Cracking (HIC) Planar cracking that occurs in carbon and low alloy steels when atomic hydrogen diffuses into the steel and then combines to form molecular hydrogen at trap sites. This may occur in coiled tubing if it contains centerline segregation. HIC may also be called Step-Wise Cracking (SWC). Hydrogen Embrittlement Brittle cracking or fracture of a ductile alloy during plastic deformation in an acidic or H2S containing environment. Hydrogen Blistering Internal blisters in the CT steel that is caused by the accumulation of molecular hydrogen. Experience with CT field failures indicates this is a rare problem but has been seen in laboratory tests. Stress-Oriented Hydrogen-Induced Cracking (SOHIC) Staggered small cracks formed approximately perpendicular to the principal stress (residual and/or applied) resulting in a ladder-like crack array linking (sometimes small) pre-existing HIC cracks.
Note: This mode of cracking can also be categorized as SSC caused by a combination of external stress and local strain around hydrogeninduced cracks. SOHIC is related to SSC and HIC/SWC. It has been observed in the seam weld of coiled tubing strings.

for 30 days at 75F (except for one test at 100 bars PH2S which was done at 100F) at high applied stress levels. The majority of tests were done using four-point bent beam specimens at 1% strain. A total of 196 individual tests were performed including 60 uniaxial, 122 fourpoint bent beam and 14 slow strain rate tests. Both as-milled and pressure-cycled tubing (at 33%, 50% and 75% NFT) was tested. Test specimens were taken from parent metal, seam weld and bias weld locations. In addition, some QT-900 CT butt welded samples were tested. The test data was used to construct No SSC and SSC zones of service on a pH-PH2S diagram (butt weld test results were excluded). A test period of 30 days was selected because this is the standard testing time to qualify materials for NACE MR0175/ISO 15156, the global standard of materials requirements for H2S service. The specimens were laboratory type specimens and therefore did not contain any surface irregularities or damage. The relatively long test period perhaps offsets the fact that the specimens did not contain surface mechanical damage, unlike used CT. Exposure time is an important factor. However, in practice, it is very difficult if not impossible to predict when a failure will or will not occur. A few limited tests were run on QT-1000 CT in the intermediate sour service domain (4.2 pH and 25 mbar PH2S) to determine time to failure. This testing showed no EC failures after 1 day exposure but after 3 days or longer, surface fissuring and SSC occurred in various locations. QT-900 CT No Inhibitor Fig. 1 below shows the No SSC Zone and SSC Zone for QT-900 CT. Basically, QT-900 CT can be operated in the mild and intermediate sour service domains without environmental control but should not be used in the severe sour service domain unless special precautions are taken to exclude H2S fluid from contact with CT and/or to use chemical inhibition (i.e., CoilGard). The area of uncertainty shown in Fig. 1 at low pH and low PH2S is an area where test specimens showed surface fissuring but no SSC or complete failures occurred. Surface fissuring is detrimental to the long-term life of the tubing but test results suggest that sudden unexpected failures may not be expected from a single exposure.

Surface Fissuring Surface fissuring is characterized by shallow longitudinal surfaces that are less than about 0.005 inches (0.13 mm) in depth and are perpendicular to the applied tensile loading. Usually cracking is initiated but then becomes blunted by the corrosion process. Laboratory Testing of QT-900 and QT-1000 CT Laboratory testing by Halliburton on QT-900 and QT1000 CT was performed to identify pH-PH2S zones where QT-900 and QT-1000 CT could be safely operated without special precautions (re: SPE 93786 and SPE 99557). All tests were performed in acidified aqueous solutions with H2S partial pressures ranging from 0.00345 to 100 bars (0.05 to 1,450 psia) and pH from 3.5 to 6.5, with and without CoilGard inhibitor. All tests were conducted

If there is significant doubt where the downhole environment resides on the pH-PH2S diagram, then environmental precautions should be taken.

QT-1000 CT No Inhibitor Fig. 2 below shows the No SSC Zone and SSC Zone for QT-1000 CT. Basically, QT-1000 CT should only be operated in the very mild sour service domain without exercising some type of environmental control (i.e., exclude H2S fluids from contacting the CT and use of CoilGard inhibitor). The area of uncertainty shown in Fig. 2 at low pH and low PH2S has same connotation as the area on the QT-900 CT graph, i.e., it is an area where test specimens showed surface fissuring but no SSC or complete failures occurred. The red dashed line represents conditions at which testing showed failures (i.e., failures occurred at the red dashed line and at conditions to the right of the red dashed line). This test data indicates that QT-1000 CT must be operated in higher pH or lower PH2S environments to avoid SSC. However, the exact line of demarcation is unknown therefore QT-1000 CT should only be used in

Fig. 1 No SSC and SSC zones for QT-900 CT, no inhibitor.

very mild sour service conditions. Also, if there is doubt where the downhole environment resides on the pH-PH2S diagram, then environmental precautions should be taken.

Example 1 - Question: What is recommendation for using QT-900 CT in oil reservoirs with 3,000 to 5,000 ppm H2S in the gas phase (GOR = 175 sm3/m3 or 983 scf/bbl) and the reservoir is producing above the bubble point. Generally, since the wells are being acidized, free H2S gas would not be expected during this phase of the operation. However, lifting operation follows acidizing so a portion of the QT-900 tubing would be contacted by free H2S gas and acid by-products from the stimulation treatment. The reservoir temperature is 90C (194F) and reservoir pressure is 4800 psi (330 bar). Answer: PH2S calculates to be 24 psia (1.65 bars) worst case which puts the reservoir environment in the Severe Sour Service domain (SSC Zone) since acid is involved. On the positive side, there is a relatively low GOR so environmental cracking is potentially reduced due to the inhibiting effect of an oil film on the pipe. On the negative side, the well is being acidized and it is known that low pH significantly increases possibility of environmental cracking if wet H2S gas is present. Recommendation would be to use SCA-130 acid inhibitor in the acid treatment fluid and swab pipe OD with CoilGard inhibitor.

Fig. 2 No SSC and SSC zones for QT-1000 CT, no inhibitor.

Example 2 - Question: Contractual obligations has created a situation in the region where we have to perform a coiled tubing job in a well that has a BHT of 275 F and the well is producing 2000 ppm H2S. The only string available is a new string of 1 QT-1000 CT. This job is critical enough that if we have to, we can junk the CT

4 string after the one and only job. Question is, do you think we can do this one job without developing sulfide stress cracks in the coiled tubing? Answer: Although only the ppm H2S and temperature is given, PH2S is very likely to be in the SSC Zone of Fig. 2. For example, if pressure was only 1000 psia (69 bars) the PH2S would be 2 psia (0.14 bars). This would mean that the environment was in the SSC Zone up to pH of ~6 (near the red dashed line). Therefore, it is recommended in this case that precautions be taken to exclude H2S fluids from contacting the CT and use CoilGard inhibitor in treating fluids as well as coating the tubing OD. It is likely that new QT-1000 CT will survive the job after taking appropriate environmental precautions. The effect of the relatively high temperature of 275F only means that the environmental cracking susceptibility of QT-1000 CT is lessened downhole but as the CT is POOH, the metal temperature will drop which makes the tubing more susceptible to SSC as it is plastically deformed over the gooseneck and reel. However, if the tubing has avoided being hydrogenated downhole, then no environmental cracking will occur. CoilGard Inhibitor CoilGard inhibitor is a tool that can be used to help prevent SSC. CoilGard inhibitor can be applied by swabbing neat onto the pipe OD and/or be added to the treating fluids. For use in treating fluids, the recommended concentration is 0.2 vol%. Precautions are being taken in some locations to prevent environmental QT-900 and QT-1000 CT with CoilGard Inhibitor As shown in Fig. 3 below, when CoilGard inhibitor was present at 0.2 vol% concentration in the H2S containing test fluids, no SSC or other type of environmental cracking occurred in any of the QT-900 or QT-1000 CT test specimens up to 100 bars PH2S. The most severe environment tested was performed on QT-1000 CT at 100 bars PH2S and 3.5 pH at 100F. Environments containing a PH2S greater than 100 bars (1,450 psia) may also be suitable when using CoilGard inhibitor but have not been tested. cracking failures by routine use of CoilGard inhibitor. The tubing OD is coated with CoilGard inhibitor using an injector sub below the stripper as it is run in the well and, in addition, the inhibitor is mixed with the treating fluids. CoilGard inhibitor replaces Crack-Chek 97M inhibitor. CoilGard inhibitor is similar to Crack-Chek 97M inhibitor but the cost of manufacture has been significantly reduced. It should be noted that CoilGard inhibitor is not environmentally suitable for use in the North Sea. For acid systems, a different H2S inhibitor, SCA-130, must be utilized. CoilGard inhibitor is not an acid inhibitor.
Fig. 3 No SSC and SSC zones for QT-900 and QT-1000 CT with 0.2 Vol% CoilGard inhibitor.

5 Conclusions and Recommendations 1. QT-900 CT may be used without environmental precautions in the mild or intermediate sour service No SSC Zones shown in Fig. 1. Environmental precautions (excluding contact with H2S and/or using CoilGard) should be taken when the downhole environment falls into the severe sour service SSC Zone shown in Fig. 1. 2. QT-1000 CT should be used without environmental precautions only in very mild sour service conditions as indicated in Fig. 2. Generally, due to its higher hardness and strength, environmental precautions (excluding contact with H2S and/or using CoilGard inhibitor) are recommended for QT-1000 CT in sour wells. 3. Fatigue cycling up to 50% utilization did not appear to increase H2S susceptibility of CT and there was no significant increase in H2S susceptibility of QT-900 CT after 75% fatigue utilization. Therefore, considering the safety factors incorporated into Cerberus software, no special precautions need to be taken for used CT except to note that heavily damaged pipe may be more susceptible to cracking. The tests run were long-term (30 days) with no damaged surfaces. Future tests are planned on used CT with various forms of surface damage. 4. If there is significant doubt where the downhole environment resides on the pH-PH2S diagram, then environmental precautions should be taken to increase reliability of CT in sour wells. 5. CoilGard inhibitor has been shown to be extremely effective during static laboratory tests. However, some questions remain to be answered such as what fluid velocity will strip CoilGard inhibitor off the pipe surface. 6. CT containing butt welds should not be used in sour wells since there is potential for higher weld zone hardness and variable weld quality. However, exceptions to this rule may be possible under very controlled conditions.