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SPE 68911

SPE 68911 Stimulation of a Producing Horizontal Well Using Enzymes that Generate Acid In-Situ - Case

Stimulation of a Producing Horizontal Well Using Enzymes that Generate Acid In-Situ - Case History

Ralph E. Harris SPE, Cleansorb Ltd., Ian D. McKay SPE, Cleansorb Ltd., Justin M. Mbala, Chevron Oil Congo. Ltd. and Robert P. Schaaf SPE, Chevron Oil Congo Co. Ltd.

Copyright 2001, Society of Petroleum Engineers Inc.

This paper was prepared for presentation at the SPE European Formation Damage Conference held in The Hague, The Netherlands, 21–22 May 2001.

This paper was selected for presentation by an SPE Program Committee following review of information contained in an abstract submitted by the author(s). Contents of the paper, as presented, have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material, as presented, does not necessarily reflect any position of the Society of Petroleum Engineers, its officers, or members. Papers presented at SPE meetings are subject to publication review by Editorial Committees of the Society of Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper for commercial purposes without the written consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of where and by whom the paper was presented. Write Librarian, SPE, P.O. Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.


The Libwa 4 well offshore the Democratic Republic of Congo was stimulated in November 1999 using an enzyme-based process that generated acid in-situ. The results to date have been excellent. Well tests as high as 759 BOPD have been

recorded after the treatment compared to less than 100 BOPD before the treatment.


The Libwa field is located off the coast of the Democratic

Republic of Congo (formerly Zaire) West Africa. The field was discovered in June 1981 and declared commercial in 1983. Development was initiated soon after, but was deferred due to the subsequent discovery at the Lukami field. The Libwa field was put on production in January 1990.

The Libwa field was formed in response to growth-faulting. The structure is a fault block anticline plunging northwest- southeast. The faults bounding Libwa field in the Aptian to Albian age section formed in response to movement of the underlying salt. They extend upward into the lower Kinkasi, and are believed to extend downward into the underlying Loeme salt layer. Structural dip within the Libwa Upper Pinda reservoir averages about 14°. The depositional environment of the Libwa field is that of a shallow carbonate shelf, adjacent to a clastic-dominated coastline with the terrigenous material periodically supplied by the river systems of deltas, as observed in other nearby Upper Pinda fields.

The Libwa field is characterized as a low permeability (2 millidarcy) limestone with about 240 feet of oil column overlain by about 310 feet of gas cap. The oil leg is laterally continuous through the field and the gas zone is very thin at the downdip portions of the field that thickens towards the crest of the structure. Core samples indicated that there is virtually no vertical permeability and minimal natural fracturing. All of the Libwa wells currently on production required acid stimulation in order to establish economic production rates. The Libwa Upper Pinda reservoir is a saturated oil system with a large gas cap. Original oil in place is estimated to be 350 MMSTB and the original gas in place in the gas cap is estimated to be 114 BCF. PVT analysis indicated a solution gas-oil ratio of approximately 470 scf/STB at a bubble point pressure of 2540 psia. Cumulative oil recovery from the field through year 2000 is 5.2 MMSTB or only 1.5% of the original oil in place. Libwa 4 is a horizontal well that was drilled in 1990 into the low permeability (2 md) limestone of the Libwa field [Figure 1].

Figure 1. Libwa Field Schematic Oil bounds Gas cap
Figure 1. Libwa Field Schematic
Oil bounds
Gas cap



SPE 68911

Due to initial low production, Libwa 4 was acidized with 15% hydrochloric acid via jet washing with a work string immediately after the completion. A post stimulation production of 2361 BOPD declined to 800 BOPD during the first month with an increase in gas production. This may have been the result of the downward coning of gas leading to a reduction in oil production. There has been evidence that the well was suffering from the presence of residual drilling damage. Fluid production was occurring from only 150 feet of the 2306 feet open hole wellbore when a production log was run in October 1990.

Since 1990 oil production from the Libwa 4 well has declined at an annual rate of 15% to the pre-treatment rate of under 100 BOPD. The oil production decline has been accompanied by an increase in the gas-oil ratio to over 6000 SCF/bbl. The well has always produced a negligible amount of water. The well was considered to be a good candidate for a stimulation treatment.

Well Stimulation Options

Different methods of stimulation were considered to increase the production of the well. These included (a) placing 15% hydrochloric acid (HCl) throughout the well bore using coil tubing (b) pumping 15% HCl from the surface, and (c) using enzymes that generated acid in-situ. When the job was first being planned, early 1999, oil prices were at very low levels.

The equipment and materials required to do a 15% HCl acid placement via coil tubing is expensive. The tripod well jackets used in the offshore Democratic Republic of Congo are relatively small. Additionally the waters are rough having a strong current and constant swells. In order to use a coil tubing unit, a jack-up work barge is required to support the unit and place the coil tubing well head on the well. Being in West Africa, to get the equipment and materials to do this coil tubing job would be expensive. Coupled with the then low oil prices, the economics of this type of job would be marginal at best.

Pumping 15% HCl acid from the surface was another option. The equipment required and costs would be much less than a coil tubing job. A vessel that had pumps and tanks would be needed for the job. For this particular well, the problem with this method would be limited coverage of the exposed formation. The horizontal section of the well is 2306 feet long. The HCl acid is highly reactive and will react immediately with the first carbonate rock that it encounters. Thus, only a small section of the well bore would actually get treated. A more disturbing possibility, though, is that the HCl might penetrate into a fracture network and open a channel to the gas cap. Increasing gas production would be detrimental. The well already had a high gas-oil ratio and any increase in gas production could inhibit oil production. Since gas is not

currently marketed in the Congo, there would only be negative economic consequences if this channeling were to occur. The chosen alternative was to use a process in which enzymes produce acid in-situ.

Enzyme-Generated Acid Process The process used to treat well Libwa 4 was first described in SPE paper 30123 1 . The process uses an enzyme (a biological catalyst) to produce organic acid at a controlled rate in-situ. SPE 30123 referred to the process as Biologically Generated Acid. However, in order to adequately differentiate the process from previous less efficient acid production methods based on bacteria we would like to propose that the term Enzyme Generated Acidbe adopted in preference.

The basis of the process is that a suitable enzyme (one with activity as an ester hydrolyzing enzyme) is mixed with an aqueous solution of suitable esters (the acid precursor). The fluid is then introduced into the wellbore. The enzyme hydrolyses the ester to produce acetic acid (Figure 2). Hydrolysis occurs over a period, normally between 24 and 72 hours. The treatment fluid is neutral to slightly acidic when placed so is much lower reactivity than conventional acids.

Figure 2. Basis of the Enzyme Generated Acid Process




Hydrolysis of ester

With the enzyme-based acid treatment, the majority of the acid (typically >95%) is produced after placement of the fluid downhole giving better zonal coverage of horizontal wellbores. Problems such as worm holing associated with the use of reactive acids such as HCl are avoided. As the acid is produced from the precursor, it reacts with acid-reactive material present in the wellbore or formation. This means that there is never a high concentration of unreacted acid present in the fluid, but over the period of treatment sufficient acid is delivered to have a substantive acidizing effect.

SPE 30123 presented laboratory data that demonstrated that Enzyme Generated Acid could be used to remove drilling damage caused by water based drilling mud. The authors speculated that the process could also be used to remove drilling damage caused by oil based drilling mud if a suitable surfactant was incorporated into the treatment fluid formulation. It has subsequently been established that this is indeed the case.

Treatment Objectives

The objectives of the enzyme-based acid treatment were to remove residual damage (oil based mud filter cake containing carbonate arising from drilling), reduce draw down along the whole of the wellbore, minimize gas coning, and increase oil

SPE 68911



production. An important consideration in any stimulation treatment at the Libwa field is to minimize any increase in gas production due to the current high gas-oil ratio.

For this reason a near well bore stimulation using Enzyme Generated Acid was chosen to avoid significant penetration of acid into fracture networks and thereby prevent gas production being inadvertently increased.

Treatment Execution

The Enzyme Generated Acid formulation selected for the treatment was one which had been shown to be effective for

the removal of oil based drilling fluid damage and which generates about 5% w/v acetic acid in-situ. The acid precursor was supplied in 55-gallon drums and the enzymes in 25-liter jerry cans. The treatment was performed by the Falcon Tidestimulation vessel. The boat was ideally set-up for the treatment of offshore wells. It was equipped with mixing tanks and pumps that allowed for the efficient mixing of the components of the treatment. The sequence of operations is summarized in Figure 3.

Figure 3. Sequence of Operations in Enzyme Generated Acid Treatment

Mix acid precursor into seawater

Mix enzyme into acid precursor solution

Pump complete treatment fluid downhole


Shut in well for 48 hours to allow enzyme to produce acid in-situ

Return well to production

All tanks and lines were thoroughly cleaned before the treatment. The acid precursor was mixed into seawater. The acid precursor needs a reasonable degree of agitation to dissolve it in water. Dissolution was achieved using paddle blenders and re-circulation of the mixed fluid through hoses.









seawater the enzyme (a stabilized aqueous solution) was also mixed into the fluid. It took only about 2 hours to mix all of the chemicals. A volume of fluid of 208 barrels (33 m 3 ) was

prepared. This was 30% higher than that required to completely fill the openhole wellbore.

The stimulation vessel was equipped with high pressure Coflexive hose that attached the boat's pumps to the well head. The plan for pumping was to keep pressures well below

formation fracture pressure. The initial rate was 3 barrels per minute. After pumping at this rate for 30 minutes, the surface tubing pressures were so low, 50 psi, that the pumping rate was increased to 5 barrels per minute. The surface tubing pressure only increased to 150 psi at this higher rate. The pressures did not get any higher and started to decrease towards the end of the job. The final surface tubing pressure during pumping was 120 psi. After pumping the treatment fluid downhole the tubing was displaced with potassium chloride then diesel. All pressures were well under the calculated maximum allowable surface pressure of 2500 psi.

The entire treatment including the mixing of the chemicals took only 8 hours. The actual pumping time for the 8750 gallons of treatment fluid, 2722 gallons of 2% potassium chloride, and 2722 gallons of diesel was less than 1.5 hours.

The well was shut in for 48 hours after the treatment to allow for the acid to be generated and react with the formation. After the shut-in period, the well was put back on production. Initially the well did not produce any fluid. The well is a flowing well with no artificial lift mechanism. In order to get the well to produce required "rocking" the well. Gas from adjacent wells on the jacket was used to pressure up the tubing.

The gas and the release of pressure to the flow line helped lift

the oil and the residual fluid from the stimulation. After 2 to 3

hours of "rocking" the well, the fluid started to flow. The well has continued to flow without problem since then.

Post Treatment Response

Libwa 4 experienced a large and sustained increase in oil

production after the stimulation. Well tests as high as 759

BOPD have been recorded after the treatment compared to less than 100 BOPD before the treatment. The increase in oil

production has also been accompanied by a corresponding

increase in gas production, however the gas-oil ratio came

down by approximately 40%. The production tests taken

before and after the stimulation are listed in Table 1. The values in italics are post treatment values.


The presence of near wellbore damage can significantly reduce the production rate of a well. Damage can include filter cake

and filtrate damage which arise during drilling, or production related damage such as scaling,

After completion of Libwa 4 the well was immediately acidized with 15% hydrochloric acid via jet washing with a work string due to its initial low productivity. However, after this treatment a production log indicated that fluid was only being produced from 150 feet of the 2306 feet of the open hole wellbore. This strongly suggested the continued presence of near wellbore damage even after application of the HCl through spotting with a work string, which is generally



SPE 68911

Table 1. Production Test Results






Tot. Gas

Gas Inj.




TP psi

Tbg. Chk.




  • 20 20




  • 39500 39659


  • 790 48/64




  • 66 66




  • 10697 10740


  • 706 48/64







  • 816 2385


  • 2385 310


  • 2923 48/64







  • 505 1849




  • 1849 270

  • 3661 48/64








  • 440 1362


  • 1362 240


  • 3095 48/64







  • 312 1729


  • 1729 265


  • 5542 48/64


Results in italics are post treatment values.


considered to be a better method of placing HCl than

number of approaches to retardingacid to slow the rate of reaction of acid with acid soluble material including carbonate

bullheading. The damage present in Libwa 4 was probably a consequence of incomplete clean up of drilling fluid damage.

An important reason for choosing to produce through horizontal wells is to reduce the draw down of the well relative to vertical wells and so minimize the coning of gas or water, which can substantially reduce oil production. A reduced draw down can only be achieved if drilling fluid damage is effectively removed from the whole of the length of the wellbore. If damage is substantively removed from only part of the horizontal wellbore, it is more likely that coning will occur. The increase in GOR during the lifetime of Libwa 4, before

The effective removal of near wellbore damage along most

rock, scale or carbonate components of filter cakes have been developed by the oil industry 1 . In practice these methods can be problematic when applied in the field.

The Enzyme Generated Acid process produces acid in-situ and is an example of a highly retarded acid system in which most of the acid is produced after placement of the fluid downhole. Use of this enzyme based process offered the likelihood of obtaining excellent zonal coverage along all or most of the 2306 ft of openhole wellbore even when placed without the use of coiled tubing.

treatment with Enzyme Generated Acid, suggests that gas coning was taking place and that this was worsening with time.

or preferably all of the length of the open hole is therefore a prerequisite to obtaining the maximum benefit from the drilling of horizontal wells and is generally viewed as highly desirable.

Treatment of Libwa 4 with Enzyme Generated Acid was successful and resulted in a significant and sustained increase in production and reduced the GOR by 40%. The treatment objectives of increasing oil production without increasing the GOR were therefore achieved. The volume of Enzyme Generated Acid used to treat Libwa 4 was only sufficient to treat the near wellbore region. This indicates that the damage

The decrease in GOR following the treatment with Enzyme

Acid treatments are commonly used in attempts to treat near wellbore damage including drilling fluid damage following drilling. Acid treatments are also used to stimulate production after the well has been on production for several months or years, to remove residual drilling fluid damage or scale.

was indeed near wellbore and that the Enzyme Generated Acid effectively removed the damage.

Generated Acid suggests that gas coning was reduced by the treatment. This result would be expected if the treatment removed near wellbore damage from all or at least part of the open hole interval leading to reduced draw down.

Hydrochloric acid (HCl) is one of the acids most commonly used to treat formation damage. In wells with relatively short producing intervals HCl used in conjunction with diversion techniques and coiled tubing is generally effective. However, the difficulty of applying HCl in long horizontal producing intervals to uniformly remove drilling damage has been identified as a very serious problem. Poor uniformity of treatment (poor zonal coverage) may result in disappointing well productivity.

The poor uniformity of treatment during conventional acid treatments is largely a consequence of the rapid reaction rate of HCl with carbonate rock or scale, which prevents its uniform

Samples of the produced water taken as the well returned to production were analyzed for soluble calcium content. Elevated concentrations of calcium, above that present in the formation water and seawater were observed. This is consistent with dissolution of calcium carbonate downhole by the acid produced in-situ by the process. Insufficient samples were taken to be able to estimate the total amount of calcium carbonate dissolved during treatment of Libwa 4 but typically a peak of elevated calcium is observed in a volume of produced water 2 to 3 times the volume of treatment fluid used. In addition to achieving a successful stimulation of Libwa

placement along a wellbore or deep into the formation. A


additional benefits arise from the use of Enzyme Generated

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Acid. These benefits include operational, health, safety and environmental benefits. Handling and mixing of the chemicals is straightforward and requires only simple equipment. The chemicals are low hazard. Handling of the individual components does not pose any excessive safety problem. The mixed treatment fluid is initially non-reactive so does not pose the safety hazards that strong acids do. Due to the slow rate of acid production, there is no need for high rate, high pressure pumping such as is often used in placing conventional acids. All materials have low environmental impact. The non-reactive nature of the unmixed chemicals along with the slow rate of production of acid allows for adequate dispersion before any damage may occur e.g. in the event of an accidental spillage or leak. These additional benefits are important when treating wells, especially those in remote or challenging locations.

In the Libwa 4 treatment, the Enzyme Generated Acid process was used to stimulate a mature producing horizontal well. The process may also be used to remove near wellbore damage from newly drilled horizontal and other wells. When treating such wells the drill string and mud pumps may conveniently be used to place the fluid, rather than bullheading or using coiled tubing. There is generally no requirement to pull pumps or other downhole equipment due to the low corrosivity of the treatment fluid. In addition, there is no need to include corrosion inhibitors in the formulation.

Enzyme Generated Acid may also be used to stimulate production by increasing the permeability of a carbonate formation to a depth of several feet around the wellbore. In a long well such as Libwa 4 the volumes required would be substantial. Increasing the matrix permeability alone will not stimulate a well to the same extent as can be achieved by the effective removal of near wellbore damage. In the case of Libwa 4 a relatively low volume of treatment fluid was used,

as the principle objectives were to remove near wellbore damage without stimulating gas production. Use of a larger volume of treatment fluid has the potential to deliver further production increases due to deep matrix stimulation.


Libwa 4 probably suffered from residual drilling damage and gas coning even after treatment with HCl by jet washing with a work string.

Treatment with Enzyme Generated Acid allowed the efficient delivery of acid to the openhole section and led to a significant and sustained increase in production and a decrease in the GOR














environmentally acceptable.


The assistance of William G. Crouch (previously of Chevron Oil Congo Ltd. and now with Chevron Nigeria Ltd.) in the planning and execution of the treatment is gratefully acknowledged.


  • 1. Almond, S. et al.: Utilization of Biologically Generated Acid for Drilling Fluid Damage Removal and Uniform Acid Placement Across Long Formation Intervals, paper SPE 30123 pp 465-478 in Proceedings of the European Formation Damage Control Conference, 15-16 May 1995, The Hague, The Netherlands.