Title: Control of Asphaltene Deposition Laboratory Screening and Evaluation of Asphaltene Inhibitors Author: Stephan Allenson, Nalco/Exxon Energy

Chemicals, Sugar Land TX, USA ABSTRACT Introduction: Asphaltene deposition can reduce well productivity, restrict or plug flowlines/pipelines and foul production handling facilities. In a deepwater production system asphaltene deposition can greatly affect the economics of the system even to the point where development of the project becomes uneconomical. There is a great incentive to accurately determine the potential of asphaltene related production problems and to devise a program that will prevent or at least limit the amount of asphaltene deposition that will make production of the system economical. Determining if a new development has the potential for an asphaltene related production problem is a very difficult process. The tests needed to determine that potential are PVT analysis, High Temperature Gas Chromatography (HTGC), SARA Analysis, Isothermal Depressurization Study, Isobaric Depressurization Study, Flocculation Point Apparatus (FPA) Test, Asphaltene Dispersant Test (ADT) and other tests. If it is determined that a system is likely to have asphaltene deposition, then a program that prevents or limits the amount of asphaltene deposition is needed. The conventional method to combat asphaltene deposition is by remediation. Conventional remediation methods used to handle and/or operate problematic (waxy and asphaltenic) reservoir fluids include mechanical, thermal, chemical and/or a combination of the three methods (McClaflin and Whitfill, 1983; Svetgoff, 1984; Woo et al., 1984). For downhole and flow line treatment, both chemical methods such as solvent soaks with aromatic solvents and/or aromatic solvents blended with dispersants, and physical removal such as wirelining, pigging, hydroblasting, and drilling are commonly used. In deepwater production systems these approaches are extremely costly and do not prevent the problem from recurring. The remediation cost of a deepwater sub-sea tie back well and flowline begins at one million dollars and can go much higher. These costs are inclusive without factoring in lost production. Asphaltene inhibitors were developed to improve the economics of

asphaltene treatment. Asphaltene inhibitors prevent the asphaltenes from depositing into the system. The inhibitors work by stabilizing the asphaltenes, preventing their flocculation and/or deposition. This paper describes the evaluation of a Gulf of Mexico (GOM) deepwater crude oil to determine its asphaltene deposition potential. This paper further describes a systematic evaluation of asphaltene inhibitors in the crude oil at reservoir and at stock tank conditions. Discussion: Pressure compensated DST fluid samples were taken from a deepwater well in the Gulf of Mexico. This well is sub-sea tie back located in 5400 feet of water with a 10-mile tie back to the host platform. During the course of system design it was necessary to evaluate this fluid for asphaltene deposition potential. The steps used to do this evaluation are summarized as follows: (1) Assess asphaltene stability in reservoir fluids at realistic production conditions of temperature, pressure and/or composition using PVT analysis, High Temperature Gas Chromatography, SARA Analysis, Isothermal Depressurization Study and Isobaric Depressurization Study. (2) Screen various asphaltene inhibitors and optimize respective treatment concentrations using representative dead oil samples at ambient conditions (i.e. minimize cost) with the Flocculation Point Apparatus Test and Asphaltene Dispersant Test. (3) Confirm/validate (independently) the effectiveness of the selected candidate asphaltene inhibitors and respective dosage for live fluids at realistic production conditions of temperature, pressure and/or composition using the Isothermal Depressurization Study. For asphaltene stability evaluation it is important to take a representative DST sample in a pressure compensated cell in order to maintain reservoir conditions. The results of the PVT analysis and analyses on dead oil are depicted below. TABLE 1: Downhole Conditions Reservoir Pressure 7063 psia/69MPa Temperature 190F/88C B.P. 3390 psia/33MPa Depth 14,8000ft/3031M

Table 2: Measured Fluid Properties

COMPONENT CO2 N2 C1 C2 C3 I-C4 N-C4 I-C5 N-C5 C6 C7+ Molecular Weight In situ density (g/cm3) MOL% 0.15 1.15 40.91 5.67 5.37 0.79 2.39 1.19 1.3 2.29 38.78 101.7 0.8445

Table 3: SARA Analysis on Dead Oil Saturates 47.1 Aromatic 32.1 NSO 16.8 Asphaltenes 4.0 C15+ 53.2

Figure 1: Isothermal Depressurization Graph and Asphaltene Onset Point

O IL 1 @ 8 0 .6 C )

Laser Power (Arbitrary Units)

O IL 2 @ 6 8 .3 C ) A sp ha lte ne O nse t ~ 5 0.4 M P a

R ed issolu tion on set ~ 24 .4 M P a

B ub b le P o in t

10

20

30

40

50

60

70

P re ssu r e (M P a )

Figure 2: FPA of Dead Oil

F P A T e s t o f G O M O il
1 .4 1 6 .5 9 6 1 .2

Voltage of transmittance (V)

0 .8

0 .6

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0 0 5 10 15 20 25

V o l u m e o f Is o - o c t a n e ( m L )

SDS Isothermal Depressurization Test (Figure 1) indicates that the asphaltene onset pressure point is approximately 4000 psia, which is about 650 psia above the bubble point. The asphaltene onset point is the pressure at which asphaltenes phase out of the oil and start to agglomerate, forming particles large enough to prevent transmittance of the light through the SDS cell. Generally, the higher that onset point pressure is above the bubble point, the more unstable the asphaltenes are in the crude. The SDS Isothermal Depressurization Test also measures the amount of asphaltene particles that can be filtered out. At the end of the Isothermal Depressurization Test the oil was filtered at 3000 psia through a 0.2m filter. The filtrate was washed with warm n-pentane. The extracted solids weighed 360 mg. The solids were then analyzed and they were determined to be 90% asphaltenes. The amount of asphaltenes extracted from the oil was 0.62% of the mass of the oil tested. This amount was considered to be significant. The FPA (Figure 2) test also indicated that the asphaltenes in the oil were unstable. The FPA gave a flocculation point value of 16 mL. Oils with a flocculation point value of 20mL or less are generally considered unstable. The SARA analysis (Table 3), which also indicates asphaltene stability, was inconclusive. Overall, the tests indicated that the oil contained unstable asphaltenes and asphaltene deposition problems were likely. Because of the possibility of asphaltene deposition in this system, asphaltene inhibitors were evaluated

on this oil. The ADT test was used to screen the chemical inhibitors. The best inhibitor was ratio tested using the ADT test. The results of the ratio test are listed below in table 4. Table 4: ADT Asphaltene Inhibitor Ratio Test
Asphaltene Inhibitor (ppm) 0 ppm (untreated) 100 250 500 750 1000 ppt mls 1 0.9 0.7 0.2 0.05 0.05 %T 31 31 24 17 13 13

The ADT test showed that it would take between 250 to 500 ppm of the asphaltene inhibitor to stabilize the asphaltenes enough to prevent deposition. These results were further validated on the FPA test (Figure 3). Figure 3: FPA Test With Asphaltene Inhibitor
F P A T e s t G O M O il T r e a te d w ith 4 0 0 p p m in h ib ito r
1 0 .9

Voltage of Transmittance

0 .8 0 .7 0 .6 0 .5 0 .4 0 .3 0 .2 0 .1 0 0 5 10 15 20 25 30

V o lu m e o f is o - o c t a n e ( m L )

The FPA results showed that with 400 ppm of the asphaltene inhibitor, there was no flocculation point indicating that the asphaltenes in the oil were completely stabilized. Isothermal Depressurization testing was repeated using 500 ppm of asphaltene inhibitor. The onset point was not significantly affected by the addition of the inhibitor. The amount of asphaltene recovered through filtration however was reduced from 360 mg to 24 mg. The filtered asphaltenes were considered negligible.

Conclusion: A systematic experimental program was developed to critically assess and control the potential for asphaltene deposition from reservoir fluids. By following the methodology, the GOM crude oil was successfully evaluated for its tendency to precipitate and deposit asphaltenes under typical production conditions. An asphaltene inhibitor that stabilizes the asphaltenes was also successfully evaluated. References: Allen, T. O. and Roberts, A. P. 1989. Production Operations: Well Completions, Workover, and Stimulation (second edition), Oil & Gas Consultants International., Inc. Chap 2, pp 11-19. de Boer, R.B., Leerlooyer, K., Eigner, M.R.P. and van Bergen, A.R.D. 1995. SPE Production and Facilities. 2:55. Fuhr, B.J., Cathrea, C., Coates, L., Kalra, H., Majeed, A.I., 1991. Fuel. 70:1293. Hammami, A., Chang-Yen, D., Nighswander, J. A., and Stange, E. 1995. Fuel Sci. Tech. Inter. 13 (9):1167. Hammami A. and Raines, M. A. 1999. SPE Journal, 4:1. Hammami, A., Phelps, C. H., Monger-McClure, T. and Little, T. M. 2000. Energy & Fuels. 14 (1):14-18. McClaflin, G. G. and Whitfill, D. L. SPE 12204 Presented at the 58th Annual Technical Conference and Exhibition of the Society of Petroleum Engineers in San Francisco CA, October 5-8, 1983. Svetgoff, J. 1984. Oil & Gas J. (Feb 27):79. Woo, G. T., Garbis, S. J., Gray, T. C. SPE 13126 Presented at the 59th Annual Fall Technical Conference, Dallas TX, September 16-19, 1984.