Technical Bulletin

Xanthan Formulated Systems

General Guidelines
Unique to xanthan biopolymers, such as KELZAN and XANVIS, is that they can be used with or without bentonite, i.e. as a secondary or primary viscosifier/suspending agent. Unlike other polymers (cellulosics, polyacrylamides, starches), xanthan develops significant viscosity at low shear rates (LSRV) to provide suspension of weight materials in high-density fluids. KELZAN XC and KELZAN XCD, or XANVIS can be used in a wide range of makeup waters, ranging from fresh water to saturated sodium chloride, in formate brines, and near-saturated calcium chloride. Following are some general guidelines to achieve optimum fluid efficiency in the field: 1. As with any polymer-based system, the use of efficient solids control equipment is recommended, including high speed, fine screen shale shakers, hydroclones, and decanting centrifuges. Overall stability is based on maintaining low-density solids in the 5% by volume range, and using the biopolymers to increase LSRV. 2. Bingham Plastic parameters, the plastic viscosity (PV), yield point (YP) will often be inverted, preferably varying between a PV:YP ratio of 1:2 to 1:3 with a PV in the 10-20 range for unweighted systems. Using KELZAN XC, XCD or XANVIS to improve carrying capacity will automatically maintain a low PV while increasing viscosity at low shear rates (5.1 sec-1), as measured with the Fann 35 and Brookfield viscometers. 3. Using the Power Law model, n values, as calculated between 3 and 300 rpm, should be maintained between 0.25 and 0.35 for optimum shear thinning characteristics and hydraulic efficiency. K values >10 dynes.secn/cm2 are recommended to assure sufficient LSRV for suspension. Hole conditions should dictate the need for increasing K. Fill on trips, settling, barite sag, and trouble making connections are all symptomatic of hole cleaning problems brought about by inadequate LSRV, and indicate the need to add KELZAN or XANVIS biopolymers. 4. In saturated brines or relatively high concentrations of salt, non-dispersible KELZAN XC or the XANVIS L slurry may be the preferred product since they will hydrate at a faster rate than KELZAN XCD under these conditions. 5. For optimum stability, pH of xanthan systems should be maintained between 8.0 and 9.0. Avoid high pH above 10.0 with soluble calcium such as in drilling cement since precipitation of the polymer can occur. Pre-treat with SAPP or bicarbonate of soda to minimize the effect. 6. Under high temperature applications above 200F, use of an oxygen scavenger will minimize thermal degradation. 7. In low pH, fresh water and low salinity brines (<10% salt) a biocide is highly recommended especially if the fluid is to be stored.

Kelco Oil Field Group

10920 W. Sam Houston Pkwy North, Ste 800

Houston, TX 77064

(713) 895-7575

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Formulation and Maintenance

Fresh Water. Depending on the application, KELZAN XC, KELZAN XCD, and XANVIS can be used independently or in conjunction with bentonite. Table 1 Fluid Formulation for Fresh-Water-Based Systems Additive KELZAN XC, XCD or XANVIS Bentonite NaOH, KOH Polyanionic Cellulose, LV Derivatized Starch Polyacrylamide Deflocculant Barite Glutaraldehyde Concentration (lb/bbl) 1.0 - 2.0 0 - 10 0.2 - 0.5 1.0 - 2.0 2.0 - 4.0 0.25 - 1.0 as needed as needed 500 - 1000 ppm Function Viscosifier Viscosifier pH Control Filtrate Control Filtrate Control Shale Inhibition Deflocculant, Dispersant Weight Material Biocide

NOTE: Fluid loss additives may be used independently or in conjunction with each other, dependent on the application.

Salt Water Systems

This category of fluids includes systems formulated with seawater, potassium, sodium or calcium chloride, formates, bromides, and low concentrations of potassium salts such as acetate. Fluids containing dissolved electrolytes are typically inhibitive systems used to minimize shale hydration and to provide formation protection in payzone applications. KELZAN XC, XCD, and XANVIS are natural choices for offshore drilling since Kelcos product specifications are based on viscosity development in ASTM seawater. Seawater base fluids represent the largest group in this category of salt water systems. Seawater. KELZAN XC and KELZAN XCD are generally used as the primary viscosifier, with a concentration ranging from 1.0 to 2.0 lb/bbl. Since most offshore locations include large sections of plastic or gumbo type shales, commercial bentonite is seldom used. In some cases, where drill-water is available, bentonite can be pre-hydrated and added to the system as a supplementary viscosifier. A typical seawater system can be formulated with the following materials:

Table 2 Typical Seawater System Formulation Additive KELZAN XC or XCD Pre-hydrated bentonite (optional) Polyanionic Cellulose, L.V. Polyacrylamides, etc* KCl (optional) Derivatized Starch (optional) Low Molecular Weight Acrylates and Lignosulfonates NaOH, KOH Barite Glutaraldehyde Concentration (lb/bbl) 1.0 5.0 1.0 1.0 1.5 7.0 2.0 1.5 Function Primary Viscosifier Secondary Viscosifier Filtrate Control Shale Inhibition Additional Inhibition Filtrate Control Deflocculants pH Control (8.0 - 9.0) Weight Material Biocide

10.0 - 25.0 2.0 - 4.0 1.5 - 4.0 0.25 - 0.50 As needed 500-1000 ppm

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*Various additives, including glycols, polymeric blends, resins, and salts have been developed for shale inhibition. While most are compatible with xanthan and other anionic polymers, pilot testing is highly recommended if cationic inhibitors are used. For optimum stability, xanthan should be pre-hydrated in the seawater/salt makeup fluid prior to adding cationic shale inhibitors.
Brines (NaCl, KCl, CaCl2, NaBr). This category includes systems used as drill-in fluids in horizontal drilling and workover completion operations where maximum formation protection is required. Systems are typically formulated as bentonite-free fluids with a minimum number of additives, which can be broken or dissolved using oxidizers and/or acids to provide maximum return permeability. XANVIS and XANVIS L are the preferred viscosifiers for these applications. Key to obtaining maximum viscosity development and minimizing formation damage due to microgels, is polymer mixing and handling procedures. In general, biopolymer hydration depends on: Mixing time and shear pH Salinity Temperature

Monovalent Salts. XANVIS and XANVIS L can be added directly to sodium or potassium base brines up to saturation without special mixing procedures to obtain full viscosity development. For optimum temperature stability in these bentonite free systems, pH should be maintained in the 8.0 - 9.0 range to minimize acid hydrolysis of the polymer. NaOH, KOH, and MgO can all be used for pH control. Typical drill-in fluid formulations are provided in Table 3. If temperature exceeds 200F, use of an antioxidant will help minimize thermal degradation of the biopolymer. Thermal stability to 300F+ is possible with saturated sodium chloride systems formulated with KELZAN XC, KELZAN XCD or XANVIS (Figure 1). Even higher temperatures (to >350F) can be tolerated using formates.

Table 3 Drill-in Fluid Formulations using Monovalent Salts Additive XANVIS Salt (NaCl, KCl, NaBr) Sodium Sulfite Derivatized Starch (optional) MgO NaOH, KOH Calcium Carbonate (optional) Glutaraldehyde Concentration (lb/bbl) 1.5 - 2.5 Up to saturated 0.20 - 0.3 2.0 - 3.0 0.5 - 1.0 0.3 - 0.5 As needed. 500 - 1000 ppm Function Primary Viscosifier Inhibition, Density Antioxidant Filtration Control pH Control in CaCl2 pH Control in K or Na systems Bridging Agent Biocide

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1000

80o F 300o F
100 Viscosity, cP

10

10 Shear Rate, sec

100
-1

1000

Figure 1. XANVIS, 2.2 lb/bbl in Saturated NaCl Brine + 1.0 lb/bbl MgO; Viscosity Profile at 80o and 300oF

Divalent Salts. Systems used in this category are the calcium chloride and calcium bromide brines. Because xanthan will not readily hydrate in saturated, divalent salt brines, special mixing procedures are required. For optimum viscosity development, less than saturated brine is recommended. For example, begin with a 10.5 to 11.0 lb/gal calcium chloride brine, and include the following procedures: Use XANVIS L or KELZAN XC Use a mechanical shear device Add polymer through a hopper for good dispersion Adjust pH with magnesium oxide (1.0 lb/bbl) while shearing

Due to the relatively harsh environment, hydration time will be longer when viscosifying calcium base brines as opposed to sodium or potassium base systems. Once the 11.0 lb/gal brine is viscosified, additional salt can be added.
NOTE: For overall fluid stability, the maximum brine density recommended is 11.2 - 11.3 lb/gal.

Since the crystallization point of 11.4 - 11.6 lb/gal calcium chloride brines is relatively high (27 - 44oF), gelation of a xanthan viscosified brine in this density range can occur, especially, if temperatures drop below 85oF. If this occurs, heating and applying additional shear will result in a more homogenous fluid. For this reason pilot testing with the proposed brine is highly recommended since composition and impurities will vary from one supplier to another. A fluid formulation, using 1.5 lb/bbl XANVIS in an 11.0 lb/gal calcium chloride brine weighted to 12.0 lb/gal, with calcium carbonate is provided in Table 4. Data illustrates properties before and after hot rolling at 150oF. Magnesium oxide improves temperature stability of calcium chloride viscosified brines, when used in the >275oF ranges (Figure 2). As density of the calcium chloride brine increases, improved thermal stability is obtained. This feature is a result of the increase in transition temperature of xanthan gum under high salinity conditions, Figure 3. Do not adjust the pH of calcium chloride brines with sodium or potassium hydroxide.

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Table 4 XANVIS (1.5 lb/bbl) in 11.0 lb/gal CaCl2 Brine Weighted to 12.0 lb/gal with 90 lb/bbl Calcium Carbonate, Before and After Aging@150oF Before Aging Temp., oF Fann 35, f1.0 600 rpm 300 rpm PV, cP YP, lb/100 ft Gels, 10sec/10min. Brookfield LV cP@0.12 sec-1 cP@0.06 sec
-1 2

After Aging 75oF 75 49 26 23 6.5/9

75oF 85 57 28 29 8/11

10,000 15,600

1000

INITIAL, 85F WITH MgO@280F

100 Viscosity, cP

280F, w/o MgO

10

10

100 Shear Rate, sec

-1

1000

Figure 2. Effect of MgO on Thermal Stability of 2.0 lb/bbl XANVIS in 11.0 lb/gal CaCl2 + Na2SO3

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150

125

11.3+ lb/gal
Viscosity, cP at 100 sec
-1

100

75

10 lb/gal

11 lb/gal

50

25

100

150

200

250

300

250

200

150

100

Temperature, F
Figure 3. Improved Thermal Stability with Increased Brine Density 2.25 lb/bbl XANVIS in CaCl2 Brines +1.0 lb/bbl MgO; Fann Model 50C@100 sec-1

Table 5 Typical Rheological Properties of XANVIS in Various Makeup Fluids, 78oF Viscosity, cP PV Seawater 1.5 lb/bbl 2.0 lb/bbl 4.5 7.0 17.5 24.0 0.2 0.19 32.0 49.0 890 1,300 28,000 59,000 YP n K 5.1 sec-1 0.0636 sec-1

Saturated NaCl 1.5 lb/bbl 2.0 lb/bbl 9 11 19 27 0.26 0.24 28.0 43.0 840 1,280 33,000 62,000

CaCl2, 11.0 ppg 1.5 lb/bbl 2.0 lb/bbl 16 20 19 26 0.42 0.41 13.0 18.5 500 700 9,000 19,000

n and K between 3 and 300 rpm; K in dynes - secn/cm2 or Poise

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Drill-in fluid design is built around the concept of minimizing formation damage, therefore, keeping fluid/filtrate invasion to a minimum is a key objective. To accomplish this, several practices can be implemented: Minimize fluid invasion by increasing LSRV of the system Particle bridging on the wellbore and/or near-wellbore region Filtrate/fluid chemistry to suppress hydration of in-situ clays When using filter cake building materials and bridging agents, such as calcium carbonate, selection should be made based on the type of completion and whether or not pre-packed screens or slotted liners will be used. Proper sizing is important to avoid plugging-off completion equipment. In general, preference should be made toward an easily removable cake to allow maximum flow from the exposed payzone. Acid washes or oxidizers can be applied to enhance removal of bridging materials and to break the viscosity contributed by xanthan. XANVIS formulated fluids can be engineered to provide a high degree of flexibility in terms of minimizing fluid invasion. In most cases, developing LSRV in the 25,000+cP range (as measured at 0.3 rpm, Brookfield LV series viscometer, No. 2 cylindrical spindle) at 100 - 120F can assist in controlling fluid invasion.

Formation permeability will dictate optimum value(s) for minimizing depth of invasion. In addition, a combination of sized particulates, including drilled solids from the payzone, can assist in the bridging of pores in the near-wellbore region. Key is to minimize fines migration or forming of a deep, internal filter cake. In so doing, cleanup operations will be held to a minimum, and permeability impairment will be localized to the near-wellbore region. In the salt inhibited systems, KELZAN XC, XCD or XANVIS are the viscosifiers of choice. Any need to increase viscosity, suspension properties and cuttings carrying capacity should be accomplished by adding these biopolymers, as opposed to cellulosics, attapulgite or bentonite. This will help retain the shear thinning features of the system by not adversely affecting high shear rate viscosity. In saturated salt systems, aeration/foaming can be a problem, especially if hopper discharges are not submerged, or there is an excessive use of mudguns. A pre-hydration tank is recommended so that maintenance treatments can be added to a separate tank, where foaming can be controlled, then the pre-mix can be incorporated into the active system. When initially viscosifying a brine with KELZAN XC, KELZAN XCD or XANVIS , adding a defoamer prior to the biopolymer has provided positive results in the field. Table 5 provides typical rheological properties for XANVIS in various salt environments.

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Table 6 Diagnostic Chart for KELZAN or XANVIS Formulated Systems PROBLEM Viscosity loss SYMPTOMS Reduction in yield point, 3 rpm reading or Brookfield LSRV. POTENTIAL CAUSE / TREATMENT 1. Biodegradation if fresh water system, and low pH add biocide; pre-treat makeup water with 3% bleach (1 gal per 50 bbl). Maintain 9.0+pH. 2. High temperature (>200F) with a low MBT, fresh water system. Add 02 scavenger; control pH at 8.5 - 9.5; add BIOZAN or change over to a K or NaCl system (2 - 3% salt). 3. Cement contamination. If pH increased above 10.5 with soluble calcium. Add SAPP/ Bicarb to reduce Ca below 200 ppm, then add KELZAN, XANVIS or BIOZAN. 4. Certain cationic additives, i.e. quaternary amines, corrosion/scale inhibitors may be incompatible with xanthan; can cause precipitation of the polymer. Pre-hydrate biopolymer, add 3% salt, then add cationic additive - pilot test. High viscosity Progressive gels; high PV 1. Solids contamination. Check MBT, total LDS, solids control equipment. Dilute, evaluate mechanical equipment, add deflocculant. Control LDS 5% by volume. 2. Cross-linking. Can occur in xanthan solutions, e.g. gravel packing, if soluble iron is present; add citric acid (0.25 - 0.5 lb/bbl) to chelate iron. Increase in filtrate High API or HTHP fluid loss, drop in viscosity. Low YP, 3 rpm and Brookfield LSRV Bacteria problem if starch in use; oxidation due to high temperature. Add biocide, oxygen scavenger, change out filtrate control additive. Insufficient mixing time; high salinity; cold water temperature. Increase shear, buffer pH with NaOH, KOH, MgO to 8.0 - 9.0 dependent on makeup fluid (in calcium brines use MgO).

No viscosity development

KELZAN , XANVIS , and BIOZAN are registered trademarks of CP Kelco U.S., Inc. and may be registered or applied for in other countries. 2001 CP Kelco U.S., Inc. The information contained herein is, to our best knowledge, true and accurate, but all recommendations or suggestions are made without guarantee, since we can neither anticipate nor control the different conditions under which this information and our products are used. It is our policy, to assist our customers and to help in the solution of particular problems, which may arise in connection with application of our products. Rev. 09/05