technical

Chemical-assisted pipeline pigging cleaning operations

by Jonathan J Wylde, Clariant Oil Services, Aberdeen, UK Details have been given on the development of a successful cleaning chemical for hydrocarbon transport pipelines. Elaboration on the formulation research of the new product and laboratory testing is summarised with case histories of applications in western USA and the Gulf Coast. Hydrocarbon transportation can result in precipitation of paraffins, asphaltenes, and naphthenates that adsorb to the walls of the pipeline becoming associated with corrosion originated iron sulphides. Pigging operations alone do not always remove all these deposits due to compaction and a strong adherence to the walls of the pipeline. It therefore becomes necessary to add surfactant based chemicals to assist in the break-up and removal of these deposits. A literature review is made regarding the current practice of pipeline cleaning, including the key properties required of cleaning chemicals namely: wettability, solubilisation, emulsification, dispersion, detergency, and defoaming. One case history details how the pipeline operator had previously tried to clean a 12 inch diameter, 15 km section of pipeline with a pig. The pig was launched and became stuck along the pipeline. Application of the newly developed product was able to free the stuck pig and remove significant debris that the pig has become lodged against. Details of the pigging programme, coupled with chemical solutions for this programme, are given.

nternal pipeline deposits are a common observation. These deposits can restrict flow to the extent where shut downs and offline cleaning programmes become necessary. A plethora of solids can be found in pipelines and can come from a wide variety of sources and formation mechanisms. One method of characterisation of the solids uses the media that the pipeline carries as the classifier. It should be noted, however, that this is just a general rule and is governed by the fact that very few pipelines actually transport 100 per cent of any single phase. For example, practically all oil export pipelines transport associated water between 0.2 and 5.0 per cent by volume. This small amount of associated water can result in deposits such as mineral scales even though the dominant phase is hydrocarbon and would not be associated at all with such deposits. The general rules, however, follow: A crude transportation pipeline becomes fouled with organic scales. Crude oil contains asphaltenes, naphthenic acids, and paraffinic components, all of which during transportation can precipitate and adhere to pipeline walls [1]. A gas transportation pipeline can also form organic scale deposits, condensed from gaseous state. Mineral based scales may also form of zinc, lead, arsenic, or mercury. Furthermore, if the gas is even slightly wet and sour conditions are present, sulphide scales will form [2]. Water transportation pipelines most commonly form corrosion deposits such as iron carbonate (FeCO3), iron oxide / hydroxide (FeO, Fe2O3, FeOOH), and iron sulphide (FeS, FeS2, etc.). A key factor of iron sulphide scales is that they are oil wetting (oleophillic) and when even low concentrations of liquid hydrocarbon are present in the water then a mixture of iron scale and hydrocarbon scale results [3]. Multiphase fluid and gas transport pipelines can have a combination of all the previous deposits

described above. These deposits can often be the most compositionally complex resulting in complex removal and mitigation solutions. The most common method of cleaning pipelines is through pigging. This can be performed whilst the pipeline is either online or offline. Recently, focus has been made to chemically assisted pigging operations as it has been recognized that both inorganic and organic scales can become compacted to the walls of pipelines. The addition of chemical surfactants assists in breaking up, softening, and transportation of these adherent deposits [4].

Chemicals used to clean transportation pipelines

A literature search yielded very few results regarding compositional information of commercially available chemicals used during chemically assisted pigging operations only references pertaining to very specific deposits such as paraffins could be found [5]. A review of oil degreasing and solid removal technology yielded several parameters that can be deemed essential to efficient chemical cleaning during pigging operations [68]. The key parameters described below show the different types of surfactant properties required in an ideal cleaning product: Wetting: the action of a surfactant to reduce surface tension of a media. This reduction is achieved by molecular attraction towards a dissimilar surface. For pipeline cleaning, wetting agents help to remove hydrocarbon deposits from oil wet scale therefore allowing access to inorganic materials. Emulsification: surfactants enable the formation of a stable emulsion of two or more immiscible liquids similar to micellular solubilisation but with larger solubilised particles. During pipeline cleaning it is necessary to emulsify hydrocarbon and solid particles removed in order to prevent redeposition downstream.

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Figure 1: EDX analysis on the inorganic portion of the pig-trash sample used to evaluate the efficacy of newly developed pipeline cleaning chemical systems. Element Fe Mn S Ca P Si Br O C Total KeV 6.403 5.898 2.307 3.691 2.013 1.740 1.480 0.523 0.277 Weight % 83.55 0.86 0.70 0.40 0.12 0.78 0.87 5.04 7.69 100 Atomic % 58.88 0.61 0.85 0.39 0.16 1.09 0.43 12.41 25.19 100

readily frees solids from the walls of the pipelines. Surfaceactive components provide emulsification and dispersion characteristics that render insoluble deposits and multi-phase liquids as a single entity enabling more efficient transport and less secondary precipitation. As a final note, it may also be commonplace to add an antifoam chemical into a finished formulation as surfactants tend to display high foaming potential when agitated. Often, glycol or specialty antifoams are incorporated to bring this under control. Although relatively well documented using straightforward organic solvents for pipeline cleaning is less efficient than the previously described specialty blends. Base solvents do not provide an effective means to transport the mixed composition slurries that would result after the organic components are dissolved this means secondary deposition is very likely. Furthermore, it is common for aggressive organic solvents (such as toluene and xylene) to be incompatible with pig bodies.

Laboratory development and testing

Overview
All testing was performed using a variety of real solid pigtrash samples obtained from pigging operations in West Texas pipelines. The testing specifically involved: Identification and characterization of samples; Solids reactivity with specialty pipeline cleaning products vs standard organic solvents; Hydrocarbon solvency; and, Arsine and H2S gas generation propensity. Of note is that the specialty pipeline cleaning formulations all contained the same highly concentrated base-surfactant cleaning components. The difference between the products is with some of the minor components in terms of odour control and chelating agents. The base organic solvents used as benchmarks for the specialty products included xylene, toluene, methanol, and acetic acid.

Table 1: Quantified elemental composition of the inorganic portion of the pig-trash sample used to evaluate the efficacy of newly developed pipeline cleaning chemical systems. Solubilisers: surfactants that can affect otherwiseinsoluble materials. When a surfactant concentration is high enough, micelle structures can form which incorporates the insoluble materials and brings them into an apparent solution. The best example of this is where it is required to recombine hydrocarbon and water. Detergency: the ability of a surfactant to remove particles from a surface. In pipeline cleaning it is a mandatory requirement to release hydrocarbons and other solids from a pipeline wall upon wetting to promote rapid release [9, 10]. Detergency is an essential component to mobilise hydrocarbon phases after wetting to remove them from the pipeline wall. Dispersion: surfactants that retain insoluble particles in suspension by preventing aggregation of particles with one another. Ideally, particles are small and this will lead to a more stable dispersion. Similar to emulsification this property of surfactants prevents redeposition of solid particles by maintaining them in suspension [11]. When these functionalities are combined to form an ideal pipeline cleaning chemical, the resultant product could become a complex blend of five to seven chemical components. The result, however, is a more purpose-driven product as a product that gives good wetting, solvency, and detergency more

Sample identification and characterisation

A typical sample had a dark brown or black colour with a sulphurous odour. Weight loss on ignition showed that over 50 per cent of the sample of organic and the residual inorganic components were analysed using energy dispersive x-ray analysis (EDX). The EDX spectrum can be found in Figure 1, with the corresponding quantified composition in Table 1. It can be seen that iron and sulphur dominate, as well as a very high phosphorous content (often associated with arsenic). Sodium and silicon were also detected which is indicative of sand, silt or clay minerals, and residual salt. The dominance of iron sulphide can lead to evolution of H2S gas and the sample showed evidence of arsenic presence which can lead to the evolution of arsine gas. During the identification experiments it was noted that, upon removal of the hydrocarbon component, it was possible to chemically mobilize the residual solids from the pipeline.

Hydrocarbon solvency tests

Simple tests were performed to determine the ability of specialty formulation 1 to render organic components soluble

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Figure 2: Neat and serial dilutions of specialty formulation 1.

Figure 4: Solvency tests during chemical development after 1 hour contact time with test fluids. From left to right: methanol, toluene, xylene, specialty formulation 2, specialty formulation 2 50 per cent, specialty formulation 3, specialty formulation 3 50 per cent, specialty formulation 4, specialty formulation 4 50 per cent.

Figure 3: Neat and serial dilutions of specialty formulation 1 tested on crude oil dispersion and detergency. and transportable. The same behaviour was exhibited by all the specialty formulations as they all had the same surfactant components with the same dissolution, emulsification, and dispersion properties. Figure 2 shows the dilution of specialty formulation 1 in water to activities of 50, 25, 15, 10, 5, and 1 per cent. To test efficacy, 10 parts of the dilution was added to 1 part crude oil. This represented a worst case test for the oil and grease expected to be encountered in an offline pipeline. Figure 3 shows the results of this test, in which dispersion and detergency were the key parameters observed. It can be seen from Figure 3 that the 15 and 10 per cent concentration tests resulted in a single phase and the crude oil was removed from the surface of the test vessel. This test determined that a single wash of a 10 per cent concentration of the various specialty formulations was appropriate for an applied concentration in the field.

Figure 5: Solvency tests during chemical development after 12 hours contact time with test fluids. From left to right: methanol, toluene, xylene, specialty formulation 2, specialty formulation 2 50 per cent, specialty formulation 3, specialty formulation 3 50 per cent, specialty formulation 4, specialty formulation 4 50 per cent.

Figure 6: Solvency tests during chemical development after removal from the test fluids. From left to right: methanol, toluene, xylene, specialty formulation 2, specialty formulation 2 50 per cent, specialty formulation 3, specialty formulation 3 50 per cent, specialty formulation 4, specialty formulation 4 50 per cent. Photographs of the tests taken after 1 hour and 12 hours contact time were taken and are shown in figures 4 and 5, respectively. Figure 6 shows a photograph of the residual left over at the end of the test after the liquid component was removed. The organic content of the pig trash was removed using a 50 per cent dilution of specialty formulations 2 and 3. The ball of pig trash was broken down into a transportable slurry composed of discrete granular particles. Weight loss indicated that all the specialty products had similar dissolution properties that were comparable to methanol. Interestingly, toluene and xylene displayed no dissolution efficacy whatsoever.

Pipeline cleaning efficacy tests

A range of solvents were ranked using a rolled ball solvency test [12] and were tested alongside the specialty formulations. This test determined the efficacy each chemical displayed with respect to dissolution and dispersion of the pig trash solid samples. Pea-sized balls of pig trash were accurately weighed and placed in to the glass test jars. Equal volume of the test chemicals were added and visual observations made over 12 hours. A post-test analysis of the appearance was performed and then the residual solvent removed and the samples reweighed to determine solubility. The chemicals tested were as follows: Xxlene Toluene Methanol Glacial acetic acid 1 per cent Glacial acetic acid 25 per cent Specialty formulation 1 water soluble / oil miscible Specialty formulation 2 water soluble / oil miscible with chelant Specialty formulation 3 oil soluble / water miscible with odour control Specialty formulation 4 oil soluble / water miscible with odour control and chelant.

Arsine and hydrogen sulphide gas generation

The unique challenge for the testing protocol required an evaluation of the arsine (AsH3) gas and hydrogen sulphide (H2S) gas evolved. The evolution of these toxic gases during pipeline cleaning has been documented in the literature [13]. It is possible for pipeline cleaning chemicals to evolve these gases especially when pH is low. This poses a health hazard, thus any chemical treatment needs address this issue while still maintaining high efficiency at removing deposits within the pipeline to assist the pigging operation. Specialty formulation 3 was used in this test as it was the highest performance product in previous tests. It was benchmarked against a 1 and 25 per cent active acetic acid solution. The pig trash was tested with a 2 hour contact time and the evolved gas tested for arsine and H2S and the residual liquid left in the test vessels was

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Test Fluid Acetic acid 1% Acetic acid 25% Specialty formulation 3 50% pH 2.93 2.24 7.20 Soluble arsenic (ppb) 75 100 0 ASH3 (ppm) >2.0 >2.0 0.1 H2S (ppm)

>2000 >2000 0

Table 2: Results of tests determining the evolution of AsH3 and H2S gas during fluid contact with pipeline scale and residual aqueous arsenic in the test fluids.

Figure 8: EDX spectra of the two pig trash samples from case history 1: A (top) = first stage sample, B (bottom) = second stage sample. Figure 7: Photographs of pig trash and pigs after removal at the southern end of the pipeline described in case history 1. tested for aqueous arsenic. The results of this test work are shown in Table 2. As expected, it can be seen that as the pH of the solutions decreased, the more arsine and H2S gas was generated and more residual arsenic was left in the test fluids. The gas evolved using both concentrations of acetic acid totally saturated the gas tubes and the actual gas concentrations were likely to be much higher than the minimum values stated. High phosphorous detected via EDX in the pig-trash samples are indicative of a high arsenic concentration. This also supports the field observations of high arsine gas generation when the slightly acidic commercially available pipeline-cleaning chemical was used. The most significant observation was that no was significant arsine or H2S gas was generated when using the specialty formulation 3 at a 50 per cent dilution in water. No soluble arsenic was detected either when the specialty formulation 3 was used indicating that dispersion, not dissolution, was occurring in the tests.

Case histories
Case history 1
Specialty formulation 1 was deployed to clean a natural gas transport pipeline in Texas. This was deployed by working in partnership with the integrity service division of a local pipeline pigging company, The 12 inch diameter, 15 km long section of this East Texas pipeline had previously been cleaned with a series of brush and seal pigs. One of the pigs became lodged in the pipeline resulting in minimal fluid flow. A decision was made to use a chemically assisted treatment in an attempt to dislodge the stuck pig. A total of 168 gallons (636 litres) of specialty formulation 1 was pumped neat followed by 1,680 gallons (6,360 litres) of clean water. The product was pushed with a pig towards the lodged pig. The lodged pig was moved to the south then the flow was reversed and both pigs arrived at the northern junction and were removed from the pipeline. The water from the line contained large amounts of iron and hydrocarbons. When the two pigs arrived at the trap, a large amount of solids were recovered from the pipeline (Figure 7) and a small sample was obtained for analysis.

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Element S Ca Mn Fe Cl Na Si Total C Total A Element Na S Ca Fe Si Total Si Total 1.740 KeV 1.041 2.307 3.691 6.403 1.740 Weight % 1.95 44.29 0.96 52.27 0.53 100 0.24 100 Atomic % 3.47 56.50 0.98 38.29 0.77 100 0.42 100 0.277 KeV 2.307 3.691 5.898 6.403 2.622 1.041 1.740 Weight % 14.88 1.21 1.13 80.75 0.78 1.03 0.24 100 7.69 100 Atomic % 22.79 1.48 1.01 71.03 1.08 2.20 0.42 100 25.19 100 Figure 10: EDX spectrum of the pig trash sample after ashing. The second stage of the treatment was a 6 per cent concentration treatment consisting of 250 gallons (945 litres) of specialty formulation 1 pumped in neat followed by 5,040 gallons (19,080 litres) of clean water into the southern end of the pipeline. A pig pushed the product the entire 15 km length of the line to northern trap. The water from the line contained large amounts of dispersed solids and hydrocarbons. This was followed by the arrival of the pig bringing even more solids. A further sample was obtained for a deposit analysis. The pig-trash samples were analyzed via EDX. Summaries have been plotted in Figure 8 and the quantified compositions in Table 3. The analyses showed a dominance of iron sulphide with an associated 25 to 35 per cent organic material. This process yielded the following conclusions: Large volumes of soluble hydrocarbons were dissolved and removed. Removal of the hydrocarbons resulted in solids mobilization. Iron sulphide scale is very oil wet and can often be combined with 25 per cent wall thickness (wt) or greater organic material, therefore successfully removing the oil, grease, and wax will help to mobilise the iron scale [3].

B Table 3: Quantified elemental composition of the EDX analysis from case history 1: A = first stage sample, B = second stage sample. Note: C and O were not included in this quantification. Weight % Magnetite (Fe3O4) Amorphous 1 10 > 50

Case history 2
Three parallel gas pipelines in South Louisiana required an oil soluble product with odour control to chemically assist a pigging campaign. The pipelines were comprised of a 24 inch line and two 30 inch lines, all of which were 102 km long. A cleaning programme was required prior to an intelligent pigging run as the lines has been in service for 32 years and not undergone any offline pigging. Clearly, cleanliness and cleaning efficacy were a high priority. Aromatic solvent was used to dilute specialty formulation 3 to 10 per cent activity and this mixture was pumped into the pipelines and pushed with a series of brush pigs at a planned 17.6 kph. For each pipeline 500 gallon (1,890 litres) of mixture was used. A significant amount of unexpected oil, grease, and solids were removed from the system. A sample of the pig trash was analyzed using weight loss, EDX, and x-ray diffraction (XRD). Figure 9 shows a photograph of the pig trash as it appeared in the trap. The thermal weight loss showed an organic content of 55.4 per cent and this appeared to be heavy-end hydrocarbons such as paraffins and asphaltenes. The XRD analysis can be seen in Table 4 and this shows the inorganic

Table 4: XRD analysis results on the inorganic component of pig trash in case history 2.

Figure 9: Photograph of the pig trash sample from case history 2.

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Element C O Na Al Si S Ca Mn Fe Ba Total KeV 0.277 0.523 1.041 1.487 1.740 2.307 3.691 5.898 6.403 4.465 Weight % 0.00 15.46 1.03 0.38 2.42 3.61 1.09 0.43 74.92 0.66 Atomic % 0.00 37.08 1.72 0.54 3.31 4.32 1.04 0.30 51.50 0.19

100

100

Table 5: Tabulated EDX results showing quantified elemental composition for the pig trash recovered in case history 2. Arsenic (mg/l) Pig trash from case history 2 36.3 Mercury (mg/l) 11.4

Table 6: ICP analysis on the pig trash sample from case history 2. portion to be poorly crystalline. The presence of magnetite (Fe3O4) suggests corrosion was occurring. EDX analysis has been summarized in Figure 10 and Table 5, and this shows the inorganic portion was largely composed of iron and oxygen. As well as magnetite (identified by XRD), there could also be other iron oxides (FeO, Fe2O3) and iron oxyhydroxide (FeOOH). Other detected minor elements included silicon (siliceous material in the form of sand, silt or clay), sulphur (suggesting iron sulphide minerals), and manganese (supports a corrosion origin for the solids). Both arsenic and mercury were detected in an acid digestion of the sample followed by inductively coupled plasma mass spectrometry (ICP-MS). This has been summarised in Table 6 and showed the pig trash had the potential to generate arsine gas. This however did not occur due to the use of specialty formulation 3 to assist with cleaning instead of previously more acidic products. The overall cleaning operation of the pipelines ensured success of the intelligent pig run and maximized value to the overall operation.

Case history 3
This final case history concerns a 10 inch diameter US West Coast offshore in-field pipeline. This is a carbon steel pipeline 28 km in length which was required to be brought back into service after being mothballed for several years. There was a legislative requirement to determine the pipelines integrity and therefore its ability to transport multi-phase production of 8,000 bbl/d of fluid (60 per cent water cut and 14 API oil). Existing deposits in the pipeline had already been determined through intelligent pigging prior to mothballing: the cleaning campaign needed therefore to be aggressive, and hence a chemically assisted pigging strategy was devised. The cleaning campaign was applied in three stages:

Figure 11: Photographs of the brush pig after removal during run 2 in case history 3. P reflush using 300 gallons (1,140 litres) of specialty formulation 1 injected neat, followed by 5,400 gallons (20,440 litres) of treated seawater. Cleaning run 1 using 3,000 gallons (11,360 litres) of aromatic solvent, followed by 1,000 gallons (3780 litres) of specialty formulation 1 injected neat, followed by 9,000 gallons (34,070 litres) of treated seawater.

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The specialty formulations described here are recommended for use in any offline cleaning application and have particular applicability prior to intelligent pigging campaigns.

This article was first presented at the Pipeline Pigging and Integrity Management (PPIM) conference held in Houston in February, 2011, and organised by Tiratsoo Technical (a division of Great Southern Press) and Clarion Technical Conferences.

References
Figure 12: Removal of intelligent pig after it was run note cleanliness. Cleaning run 2 was the most aggressive stage and used 1,000 gallons of aromatic solvent followed by 2,500 gallons (9460 litres) of neat specialty formulation 1 followed by 22,500 gallons (85,170 litres) of treated seawater. The final stage was never planned to be as aggressive as it was. This was optimised in response to observations during the campaign. Massive deposits were removed during the preflush and during the first cleaning run the entire 30 foot trap was filled with trash. A further 20 foot of material had to be removed before the pig could be retrieved. Following the final cleaning stage, smaller volumes of trash were recovered. Had chemical cleaning not been performed before running the intelligent pig, the information gathered would have not given the information necessary to satisfy the legislative requirements. Photographs of a typical pig after removal from the pipeline can be seen in Figure 12 along with a photo of the intelligent pig after it had completed its run in Figure 13. 1. H .A.Craddock, E.Campbell, K.Sowerby, M.Johnson, S.McGregor, and G.McGee, 2007. The application of wax dissolver in the enhancement of export line cleaning. SPE 105049. Int. Symp. on Oilfield Chemistry, Houston, TX, 28 Feb 2 Mar. 2. H.A.Nasr-El-Din, A.Y.Al-Humaidan, S.K.Mohamed, and A.M.Al-Salman, 2001. Iron sulphide formation in water supply wells with gas lift. SPE 65028. Int. Symp. on Oilfield Chemistry, Houston, TX, 13 16 Feb. 3. J.J.Wylde and W.A.Duthie, 2008. Root cause failure analysis, removal and mitigation of iron sulphide scale deposition in the BP Bruce produced water reinjection plant. Paper 08350. NACE, New Orleans, LA. 4. 4. J.Cordell and H.Vanzant, 2003. Pipeline pigging handbook. Clarion Technical Publishers. 5. G.Poole, G.Brock, S.Szymczak, and G.Casey, 2008. Successful pipeline clean out lessons learned from cleaning paraffin blockage from a deepwater pipeline. SPE 115658. SPE ATCE, Denver CO, 21 24 Sept. 6. L.O.S.Buzelin and de C.B.Campos Lima, 2008. Innovative methodology for cleaning pipes key to environmental protection. SPE Int. Conf. on HS&E, Nice, France, 15 17 April. 7. P.H.Javora, G.Baccigalopi, J.Sanford, C.Cordeddu, Q.Qu, G.Poole, and B.Franklin, 2008. Effective high-density wellbore cleaning fluids: brine-based and solids-free. SPE 99158. SPE Drilling and Completions, 23 (1), 48 54. 8. S.N.Bordalo and R.C.Oliveira, 2007. Experimental study of oil/water flow with paraffin precipitation in subsea pipelines. SPE 110810. SPE ATCE, Anaheim CA, 11 14 Nov. 9. L.Thompson, 1994. The role of oil detachment mechanisms in determining optimum detergency conditions. J. Colloid Interface Sci., 163, 61. 10. K.R.Lange, 1994. Detergents and cleaners: a handbook for formulators. Hanser, Munich. 11. F.E.Friedli, 2001. Detergency of specialty surfactants. Marcel Dekker, New York. 12. Clariant Oil Services, 2008. Procedure QPI 106 (Rev 2). Wax / asphaltene dissolver tests. In-house test procedure. 13. D.O.Trahan, 2008. Arsenic compounds in natural gas pipeline operations. Pipeline & Gas Journal, March.

Conclusions and lessons learned

The experimental conclusions are as follows: Specialty engineered chemical pipeline cleaning chemicals blended from surfactants in a synergistic way to address specific cleaning mechanisms display higher efficacy than commodity based solvent systems. The best pipeline cleaning chemicals address the following five key parameters: wetting, solubilization, emulsification, dispersion, and detergency. Laboratory evaluation of actual pig-trash samples allow for a more tailored solution and therefore more effective chemical cleaning product development. The lessons learned from the case histories are: The specialty pipeline cleaning chemicals showed high efficacy of treatment. Solids removal was more efficient than previous treatments that did not use chemical-cleaning chemicals to assist pigging. Arsine and hydrogen sulphide gas generation can be controlled using specialty cleaning formulations.

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