# Patent

## Title
Method for dispersing aqueous based drilling fluid for drilling subterranean boreholes

## Abstract

An inhibitive water-based polymer mud system and method for using the system in drilling and in stabilizing wellbores for use in water sensitive formations as an alternative to oil-based muds or water-based muds comprising ferro-chrome lignosulfonates. The system comprises a fresh water or salt water base thinned or dispersed with a sulfonated acrylic copolymer having a hybrid/graft lignosulfonate multipolymer structure containing carboxylate and sulfonate functional groups with synthetic polymer side chains covalently linked to a base lignosulfonate material, having a molecular weight in the range of about 1,000 to about 15,000, and having a high anionic charge density.

## Background
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to controlling the rheology and/or the viscosity of water based mud systems. More particularly, the present invention relates to methods and compositions for dispersing aqueous based fluids used in well drilling and other well operations in subterranean formations, especially subterranean formations containing oil and/or gas. This invention also relates to a drilling fluid thinner and/or dispersant having improved temperature stability, dispersing properties and “solids contamination” tolerance.
2. Description of Relevant Art
A drilling fluid or mud is a specially designed fluid that is circulated through a wellbore as the wellbore is being drilled to facilitate the drilling operation. The various functions of a drilling fluid include removing drill cuttings or solids from the wellbore, cooling and lubricating the drill bit, aiding in support of the drill pipe and drill bit, and providing a hydrostatic head to maintain the integrity of the wellbore walls and prevent well blowouts. Specific drilling fluid systems are selected to optimize a drilling operation in accordance with the characteristics of a particular geological formation.
For a drilling fluid to perform its functions, it must have certain desirable physical properties. The fluid must have a viscosity that is readily pumpable and easily circulated by pumping at pressures ordinarily employed in drilling operations, without undue pressure differentials. The fluid must be sufficiently thixotropic to suspend the cuttings in the borehole when fluid circulation stops. The fluid must release cuttings from the suspension when agitating in the settling pits. It should preferably form a thin impervious filter cake on the borehole wall to prevent loss of liquid from the drilling fluid by filtration into the formations. Such a filter cake effectively seals the borehole wall to inhibit any tendencies of sloughing, heaving or cave-in of rock into the borehole. The composition of the fluid should also preferably be such that cuttings formed during drilling the borehole can be suspended, assimilated or dissolved in the fluid without affecting physical properties of the drilling fluid.
Most drilling fluids used for drilling in the oil and gas industry are water-based muds. Such muds typically comprise an aqueous base, either of fresh water or brine, and agents or additives for suspension, weight or density, oil-wetting, fluid loss or filtration control, and rheology control. Controlling the viscosity of water based muds or mud systems has traditionally been done with lignosulfonate deflocculants and/or thinners. Such low molecular weight, heavily sulfonated polymers are believed to aid in coating clay edges in the subterranean formation with a lasting or effectively permanent negative charge. Some alkaline material, such as, for example, caustic soda or potash, is typically added to achieve a pH range from about 9.5 to about 10. This pH environment is believed to aid the solubility and activation of the portion(s) of the lignosulfonate molecules that interact with the clay. These portions are believed to be the carboxylate and phenolate groups on the lignosulfonate.
Lignosulfonates are obtained from byproducts of the spent acid process used to separate cellulose from wood in the pulp industry. The pulp industry has begun to turn away from the spent acid process in recent years in favor of another process that does not have a lignosulfonate byproduct. Consequently, the drilling fluid industry has begun efforts to find a substitute for lignosulfonates in drilling fluids. Also, increasingly, there is an interest in and need for deflocculants and/or thinners that can work effectively at lower pH ranges of about 8 to about 8.5, in freshwater and saltwater based muds, and at higher temperatures ranging upwards to about 450° F., while also being environmentally compatible.
SUMMARY OF THE INVENTION
The present invention provides improved methods of drilling wellbores in subterranean formations employing water-based muds and compositions for use in such methods. As used herein, the term “drilling” or “drilling wellbores” shall be understood in the broader sense of drilling or wellbore operations, to include running casing and cementing as well as drilling, unless specifically indicated otherwise.
The drilling fluids of the invention comprise an aqueous base and a water soluble thinner/dispersant comprising an acrylic copolymer of low molecular weight (in the range of about 1,000 to about 15,000) with high anionic charge density. In one embodiment, the thinner/dispersant comprises a sulfonated polymer having a molecular weight of 5000 to 10,000. In another embodiment, the thinner/dispersant comprises a sulfonated polymer having a molecular weight of 4,000 to 8,000. The polymer chemistry for both of these embodiments is that of a hybrid/graft lignosulfonate multipolymer, containing both carboxylate and sulfonate functional groups, where synthetic polymer side chains are grown covalently off of a base lignosulfonate material.
This thinner/dispersant for use in the invention has the flexibility of utility with, and solubility in, a fresh water drilling fluid base, as well as in a salt water (brine) drilling fluid base, and is effective even at a near neutral pH of about 8.0 to about 8.5, while still being effective at a higher pH, up to about 10.5. Moreover, the thinner/dispersant may be used in solid or liquid form.
Drilling fluids of the invention provide an advantage over fluids employing prior art lignosulfonate thinners in that the fluids of the invention maintain satisfactory rheology for drilling at temperatures as high as 400° F. to 450° F. while also being useful at lower temperatures, including temperatures approaching as low as 40° F. Moreover, the thinner/dispersant used in the present invention does not contain chromium, commonly used with prior art lignosulfonate thinners, and thus the present invention is more environmentally friendly or compatible than such prior art.
Methods of the invention include a method of drilling a wellbore in a subterranean formation employing an aqueous based drilling fluid comprising the thinner/dispersant discussed above and a method of thinning or dispersing a water-based drilling fluid using such thinner/dispersant.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph comparing the yield point versus dispersant concentration of two different thinners/dispersants of the invention with a ferro-chrome, lignosulfonate thinner, in a gypsum/salt water, 22 lb/bbl AQUAGEL, containing 66 lb/bbl Rev Dust, hot rolled at 150° F., with a pH in the range of 9.2 to 10.
FIG. 2 is a graph comparing the yield point versus concentration of two different thinners/dispersants of the invention with a ferro-chrome, lignosulfonate thinner, in fresh water containing 66 lb/bbl Rev Dust and 22 lb/bbl Bentonite Slurry, hot rolled at 300° F.
FIG. 3 is a graph comparing the yield point versus pH of two different thinners/dispersants of the invention with a ferro-chrome lignosulfonate thinner in a concentration of 5 lb/bbl in fresh water containing 66 lb/bbl Rev Dust and 22 lb/bbl Bentonite Slurry, hot rolled at 300° F.
FIG. 4 is a graph comparing the gel strength versus pH of two different thinners/dispersants of the invention with a ferro-chrome lignosulfonate thinner and a chrome-free lignosulfonate thinner in a concentration of 5 lb/bbl in a fresh water drilling fluid, hot rolled at 300° F.
FIG. 5 is a bar graph correlating average molecular weight of thinners/dispersants to the yield point of bentonite slurry treated with 5 lb/bbl thinners/dispersants, hot rolled at 300° F.
FIG. 6 is a bar graph comparing the yield point of samples of a 16 ppg water-based drilling fluid having no thinner, having 5 lb/bbl (100% active) ferro-chrome lignosulfonate thinner, and having two different 5 lb/bbl (100% active) thinners/dispersants of the invention, hot rolled at 300° F.
FIG. 7 is a bar graph comparing the yield point of samples of a 14 ppg water-based drilling fluid having no thinner, having 5 lb/bbl (100% active) ferro-chrome lignosulfonate thinner, and having two different 5 lb/bbl (100% active) thinners/dispersants of the invention, hot rolled at 300° F., and hot rolled at 400° F.
FIG. 8 is a bar graph comparing the relative API filtrate of 14 lb/gal fresh water-based drilling fluid treated with either 5 lb/bbl (100% active) ferro-chrome lignosulfonate thinner or with two different 5 lb/bbl (100% active) thinners/dispersants of the invention.
FIG. 9 is a bar graph comparing the filtration control properties of a thinner/dispersant of the invention with a ferro-chrome lignosulfonate.



DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
In methods of the present invention, drilling of shales and offshore hydratable formations may be conducted with an aqueous-based drilling fluid which affords rheology control and maintains wellbore stability even though the wellbore penetrates smectites, illites, and mixed layer clays and even though the wellbore temperatures exceed about 350° F. and approach temperatures of about 400° F. or higher.
The present invention provides thinners/dispersants that impart thinning to water based drilling fluids or mud systems comparable to or better than prior art lignosulfonate deflocculants and/or thinners while effecting such thinning at lower concentration, and less caustic pH, namely about 8.0 to 8.5, than with prior art lignosulfonate deflocculants and/or thinners. Moreover, such thinners/deflocculants of or for use in the invention have the advantage of containing no transition group elements (i.e., heavy metals such as chromium, and cadmium) and are believed to be more environmentally friendly than prior art deflocculants/thinners containing such heavy metals. Further, the thinners/dispersants are effective at thinning water based muds or dispersing solid particles in water based muds at high temperatures and over a relatively broad pH range (from about 8.0 to about 10.5), and are tolerant of contaminants such as cement, anhydrite and sodium, as well as drill solids.
The thinners/dispersants of or for use in the invention comprise an acrylic copolymer of low molecular weight with high anionic charge density. In one embodiment, the thinner/dispersant comprises a sulfonated polymer having a molecular weight of 5000 to 10,000. In another embodiment, the thinner/dispersant comprises a sulfonated polymer having a molecular weight of 4,000 to 8,000. The polymer chemistry for both of these embodiments is that of a hybrid/graft lignosulfonate multipolymer, containing both carboxylate and sulfonate functional groups, where synthetic polymer side chains are grown covalently off of a base lignosulfonate material.
The thinners/dispersants for use in the invention have a high thinning efficiency and can mitigate the flocculating effect of electrolyte (salt) in water based fluids even at temperatures as high as 400° F. or higher. The thinners/dispersants effect thinning and/or deflocculation in saltwater based fluids and in fresh water based fluids and are believed useful and readily soluble in any water based mud suitable for use in drilling or well operations in a subterranean formation, particularly for the discovery and/or recovery of oil and/or gas. Such muds should not contain chromium (or other similar heavy metals) and most preferably will have a pH of about 8.0 to about 8.5, although the thinners/dispersants of or for use in the invention will provide thinning and/or deflocculation over a pH range of about 8.0 to about 10.5.
In one embodiment, the drilling fluid of the present invention comprises the above thinner or dispersant in an amount that thins the particular drilling fluid as needed for drilling. The drilling fluid maintains rheology and filtration control with a significantly lower quantity, i.e., lower concentration, of thinner/dispersant of the invention than is typically used when prior art thinners, dispersants or deflocculants are used.
In a method of the present invention of drilling a wellbore in a subterranean formation, a water based drilling fluid of the invention containing a thinner or dispersant of the invention is used. In one embodiment, the thinner or dispersant is provided with a pH environment of about 8.0 to about 8.5. In another embodiment, the pH may be as high as 10.5 or otherwise in the range of 8.0 to 10.5. In one embodiment, the drilling fluid has a brine base, and in another embodiment, the drilling fluid has a fresh water base. The subterranean formation may have a temperature as low as 40° F., as high as 400° F., or some temperature in between.
The following experiments and examples are illustrative of the advantages of the invention.
EXPERIMENTAL
Drilling fluid samples were prepared according to test procedures in API 13J, known to persons of ordinary skill in the art, and incorporated herein by reference. Generally, 350 ml drilling fluid samples were prepared and sheared on a multi-mixer for 60 minutes and then rolled in an oven at the test temperature. Bentonite slurry was mixed according to the Quality Assurance Laboratory Standard Test Procedure for Thinning Efficiency of Fe/Cr Lignosulfonates (STP 17.01.002.01), incorporated herein by reference. A Fann 35A from Fann Instruments was used for the rheology measurements. A pH meter model 420A+ from Thermo Orion was used for the pH determinations. A Zetasizer Nano Series from Malvern Instruments was used to determine the zeta potentials of the thinners/dispersants. The zeta potential of the thinners/dispersants was determined by preparing known concentrations of the thinners/dispersants in ethanolamine buffer at pH 9.4. The zeta potential was measured at 25V and 25° C. using the Zetasizer instrumentation.
Thinning efficiency of the thinners/dispersants was calculated as follows:




  
    Thinning
    ⁢
    
      
    
    ⁢
    efficiency
  
  =
  
    
      (
      
        
          (
          
            
              YP
              ⁢
              
                
              
              ⁢
              Control
              ⁢
              
                
              
              ⁢
              Mud
            
            -
            
              YP
              ⁢
              
                
              
              ⁢
              Test
              ⁢
              
                
              
              ⁢
              Mud
            
          
          )
        
        
          (
          
            
              YP
              ⁢
              
                
              
              ⁢
              Control
              ⁢
              
                
              
              ⁢
              Mud
            
            -
            
              YP
              ⁢
              
                
              
              ⁢
              QUIK
              ⁢
              
                -
              
              ⁢
              THIN
              ⁢
              
                
              
              ⁢
              ®
            
          
        
      
      )
    
    ×
    100
  




where the Control Mud, the Test Mud and the QUIK-THIN® thinner mud all had the same composition except that the Control Mud had no thinner added thereto, the Test Mud had a test thinner added thereto, and the QUIK-THIN® thinner mud had QUIK-THIN® thinner added thereto. QUIK-THIN® thinner is a ferro-chrome lignosulfonate commercially available from Halliburton Energy Services, Inc. in Houston, Tex. and Duncan, Okla., that helps to control rheological and filtration properties of water-based drilling fluids and can be used to maintain dispersed water-based drilling fluids. YP is an abbreviation for yield point.

A 221b/bbl Bentonite slurry, sheared in Gypsum/Salt water, was treated separately with QUIK-THIN® thinner, and two thinners/dispersants of the invention at various concentrations and then rolled at 150° F. for 16 hours for initial screening tests. Tables 1 and 2 depict the rheological properties measured with a Farm 35A for three lb/bbl and five lb/bbl treatments of the thinners/dispersants. The corresponding Thinning Efficiency (TE) was calculated from the above equation. As can be seen in Tables 1 and 2, not only did the thinners/dispersants of the invention compare well with the ferro-chrome lignosulfonate thinner, but the Thinning Efficiency of the thinners/dispersants increased with a decrease in the amount of thinner used relative to the ferro-ligno sulfonate thinner. This is particularly significant because ferro-lignosulfonates, and particularly QUICK-THIN® thinner, are leading prior art dispersants for clay particles in salt water.







TABLE 1







Thinning Efficiency of 5 lb/bbl Dispersants on Salt


Water Mud after Hot-Rolling at 150° F. for 16 hours














Thinner/
Thinner/




Ferro-Chrome
Dispersant
Dispersant



Control
Lignosulfonate
A of Invention
B of Invention















pH
7.06
9.43
9.55
9.84


600 rpm
60
45
46
57


300 rpm
50
32
30
37


 6 rpm
26
14
11
12


 3 rpm
25
13
10
11


10 s gel,
21
14
16
18


lb/100 ft2


10 m gel,
23
19
13
35


lb/100 ft2


PV, cP
10
13
16
20


YP,
40
19
14
17


lb/100 ft2


TE, %

100
114
110
















TABLE 2







Thinning Efficiency of 3 lb/bbl Dispersants on Salt


Water Mud after Hot-Rolling at 150° F. for 16 hours














Thinner/
Thinner/




Ferro-Chrome
Dispersant
Dispersant



Control
Lignosulfonate
A of Invention
B of Invention















pH
7.06
9.13
9.21
9.83


600 rpm
60
55
50
53


300 rpm
50
42
32
37


 6 rpm
27
20
19
17


 3 rpm
26
19
17
16


10 s gel,
21
20
18
19


lb/100 ft2


10 m gel,
23
55
16
25


lb/100 ft2


PV, cP
10
13
18
16


YP,
40
29
14
21


lb/100 ft2


TE, %

100
236
173









The trend of the effect of the thinners/dispersants on the yield point (YP) of the salt water bentonite slurry is shown in FIG. 1. Under the conditions tested, the two thinners/dispersants of the invention showed an optimum thinning concentration at about 3 lb/bbl. This is an indication of the effectiveness of the thinners/dispersants of the invention in preventing the reduction of the repulsive forces by the electrolytes and allowing the clay particles to be dispersed at lower concentrations of the thinners than with ferro-chrome lignosulfonates.
A similar test was performed on the bentonite slurry in fresh water. Again, the results were very satisfactory for the thinners/dispersants of the invention. In comparison to the ferro-chrome lignosulfonate, the thinners/dispersants of the invention were effective in thinning the slurry at lower concentrations. FIG. 2 shows the yield point of the thinners/dispersants at various concentrations after rolling the sample at 300° F. for 16 hours.
In order to act as good deflocculants in either fresh water or salt water, lignosulfonate thinners require some caustic soda to bring the pH of the fluid in the range of 8.5-10. At this pH level it is believed, without wishing to be limited by theory, that most of the acidic functionalities are deprotonated to increase the anionic charge density. Thus, the pH effect on the thinners/dispersants of the invention was evaluated relative to the lignosulfonate thinners.
Bentonite slurry containing 66 lb/bbl of drilled solid material in fresh water was prepared and samples were treated with 5 lb/bbl of QUIK-THIN® thinner, ENVIRO-THINTM thinner or a thinner/dispersant of the invention and then rolled for 16 hours at 300° F. Thereafter, each of the treated fluid samples was tested for yield point and gel strengths while the pH was varied. The results of the yield point and gel strength were plotted against the pH as shown in FIGS. 3 and 4. The yield point values of the samples with the thinners/dispersants of the invention were all lower than the yield point values of the samples with the lignosulfonate thinners for the pH range tested. The results show that the thinning effect of lignosulfonate is more pH dependent than the thinning effect with the thinners/dispersants of the invention.
Since the thinners adsorb on the edges of the clay particles to maintain an electric double layer and fortify the repulsive forces, the size of the double layer that results will depend on the anionic charge density of the thinner. The zeta potential will not decrease because the electrolyte tolerance capacity will increase with increase in charge density.
The zeta potentials and the electrophoretic mobility of the thinners/dispersants of the invention were measured and the results are shown in Table 3 in comparison with the ferro-chrome lignosulfonate thinner. The zeta potentials of the thinners/dispersants of the invention compared favorably with the ferro-chrome lignosulfonate thinner, which is indicative of why the thinners/dispersants performed well in the salt water bentonite slurry, and zeta potential can be correlated to charge density.







TABLE 3







Zeta Potential Measurement












Zeta





Potential
Electrophoretic



Test Material
(mV)
Mobility (um*cm/vs)







Thinner/Dispersant
19
−2



A of Invention



Thinner/Dispersant
18
−2



B of Invention



Ferro-Chrome
20
−2



Lignosulfonate










The lignosulfonate that results from spent sulfite liquor contains polymers having different degrees of sulfonation and varying molecular weights ranging from 1,000 to 20,000. It is much easier to control the molecular weight of a synthetic polymer, such as the thinner/dispersant of the invention. To investigate the effect of molecular weight on the efficiency of thinners/dispersants of the invention, four more thinners/dispersants substantially similar in structure and function to Thinner/Dispersant A of the invention (and to Thinner/Dispersant B of the invention, which itself is substantially similar in structure and function to Thinner/Dispersant A), except in molecular weight, were prepared, added to bentonite slurry, and yield point measured. The molecular weight of each polymer sample was measured in the Zetasizer (using an aqueous solution of each thinner/dispersant). FIG. 5 shows the correlation of the average weight of these polymers and the yield point of the bentonite slurry, treated with 5 lb/bbl of each polymer, and rolled for 16 hours at 300° F. This data shows that the deflocculating power of the thinners/dispersants has a direct relationship with the molecular weight of the thinners/dispersants. The yield point of the slurry increased with increasing molecular weight of the thinners/dispersants, for these examples. The decrease in the thinning effect with increasing molecular weight is due to decrease in the charge density if the molecular weight is increased without increasing the corresponding anionic moieties.
Evaluations of thinning efficiencies of thinners/dispersants as discussed above is not enough to determine whether the thinner/dispersant will be an efficient and effective thinner when used in a drilling fluid or that the drilling fluid will be effective with such thinner. Thus, various laboratory water-based drilling fluid (mud) samples were mixed and used to evaluate the efficiency of the thinners/dispersants of the invention in use in drilling fluids and the overall effectiveness of the drilling fluids with these thinners/dispersants.
One laboratory barrel of each mud sample was mixed on the Hamilton Beach Multi-mixer for 60 minutes according to the formulations contained in the corresponding Tables 4-9 below. The thinners (in liquid form) were added to the mud samples at a 100% active level relative to the thinners (in solid form). The samples were pressurized in the mud cells and rolled for 16 hours at the temperatures indicated in the tables for each mud. In addition to QUIK-THIN® thinner, a ferro-chrome lignosulfonate, the following trademarked products are used in the Tables below: ALDACIDE® G biocide; AQUAGEL® viscosifier, a finely ground, premium-grade Wyoming sodium bentonite which meets the American Petroleum Institute (API) Specification 13A, section 9 requirement; AQUAGEL GOLD SEAL® viscosifier, a 200 mesh, dry-powdered, premium, high-yielding Wyoming sodium bentonite containing no polymer additives or chemical treatments of any kind; BARAZAN® D PLUS viscosifier, a premium quality, powdered Xanthan gum polymer; BAROID® weighting material, a ground Barite that meets API Specification 13A section 7 requirement; ENVIRO-THINTM thinner, a modified iron lignosulfonate that contains no chrome or other heavy metals; and FILTER-CHEKTM filtration control agent. All of these trademarked products are available from Halliburton Energy Services, Inc. in Houston, Tex. and Duncan, Okla.







TABLE 4







16.0 lb/gal Freshwater Mud Formulation with 35


lb/bbl Rev Dust Mud Formulations and Properties











Sample Mark
A
B
C
D











Freshwater, bbl
0.687


AQUAGEL
4


GOLD SEAL ®


viscosifier, lb


AQUAGEL ®
4


viscosifier, lb


FILTER-CHEK TM
3


filtration


control agent, lb


Rev Dust, lb
35


BAROID ® weighting
385


material, lb


ALDACIDE ®
0.2


G biocide, lb


Dry caustic soda, lb
0.35











Thinner/Dispersant A of
—
5
—
—


Invention, lb


Thinner/Dispersant B of
—
—
5
—


Invention, lb


QUIK-THIN ®
—
—
—
5


thinner, lb


12.5N Liquid caustic
—
0.7
1.3
0.6


soda, total ml


Rolled @300° F., hr
16
16
16
16


Stirred, min
15
15
15
15








Temperature, ° F.
120











Plastic viscosity, cP
27
27
27
24


Yield point, lb/100 ft2
61
−4
−5
20


10 Sec gel, lb/100 ft2
65
1
1
17


10 Min gel, lb/100 ft2
215
2
1
65


pH before rolling/
9.06/8.21
9.55/8.45
9.54/8.47
9.55/7.96


pH after rolling







Fann 35 dial readings











600 rpm
115
48
49
68


300 rpm
88
21
22
44


200 rpm
75
17
17
35


100 rpm
65
8
8
76


 6 rpm
56
1
1
16


 3 rpm
55
1
1
15


pH adjusted to

9.60
9.40
9.33


Plastic viscosity, cP

27
29
28


Yield point, lb/100 ft2

−3
−3
11


10 Sec gel, lb/100 ft2

2
1
13


10 Min gel, lb/100 ft2

3
2
72







Fann 35 dial readings











600 rpm

51
55
68


300 rpm

24
26
39


200 rpm

18
18
29


100 rpm

9
10
18


 6 rpm

2
1
8


 3 rpm

1
1
7
















TABLE 5







14.0 lb/gal Freshwater Mud Formulation with 60 lb/bbl


Rev Dust Mud Formulations and Properties at 300° F.











Sample Mark
A
B
C
D











Freshwater, bbl
0.743


AQUAGEL
8


GOLD SEAL ®


viscosifier, lb


AQUAGEL ®
8


viscosifier, lb


FILTER-CHEK TM
3.0


filtration


control agent, lb


Rev Dust, lb
60


BAROID ® weighting
249


agent, lb


ALDACIDE ®
0.2


G biocide, lb


Dry caustic soda, lb
0.35











Thinner/Dispersant A of
—
5
—
—


Invention, lb


Thinner/Dispersant B of
—
—
5
—


Invention, lb


QUIK-THIN ®
—
—
—
5


thinner, lb


12.5N Liquid caustic
—
0.7
1.3
0.6


soda, total ml


Rolled @300° F., hr
16
16
16
16


Stirred, min
15
15
15
15








Temperature, ° F.
120











Plastic viscosity, cP
32
56
45
43


Yield point, lb/100 ft2
111
7
9
102


10 Sec gel, lb/100 ft2
98
9
3
65


10 Min gel, lb/100 ft2
—
25
25
118


pH before rolling/
9.06/7.98
9.55/8.43
9.44/8.68
9.85/8.16


pH after rolling







Fann 35 dial readings











600 rpm
175
119
99
188


300 rpm
143
63
54
145


200 rpm
132
43
35
123


100 rpm
123
23
18
100


 6 rpm
115
4
2
74


 3 rpm
112
3
1
70


pH adjusted to
—
9.55
9.46
9.31


Plastic viscosity, cP
—
84
56
56


Yield point, lb/100 ft2
—
20
6
75


10 Sec gel, lb/100 ft2
—
35
3
65


10 Min gel, lb/100 ft2
—
—
43
114


API, mL/30 min
—
2.8
3.5
6.3







Fann 35 dial readings











600 rpm
—
188
118
187


300 rpm
—
104
62
131


200 rpm
—
73
42
119


100 rpm
—
40
23
85


 6 rpm
—
6
3
57


 3 rpm
—
4
2
55
















TABLE 6







14.0 lb/gal Freshwater Mud Formulation with 60 lb/bbl


Rev Dust Mud Formulations and Properties at 400° F.











Sample Mark
A
B
C
D











Freshwater, bbl
0.743


AQUAGEL
8


GOLD SEAL ®


viscosifier, lb


AQUAGEL ®
8


viscosifier, lb


FILTER-CHEK TM
3.0


filtration


control agent, lb


Rev Dust, lb
60


BAROID ® weighting
249


agent, lb


ALDACIDE ®
0.2


G biocide, lb


Dry caustic soda, lb
0.35











Thinner/Disperant A of
—
5
—
—


Invention, lb


Thinner/Dispersant B of
—
—
5
—


Invention, lb


QUICK-THIN ®
—
—
—
5


thinner, lb


12.5N Liquid caustic
—
0.7
1.3
0.6


soda, total ml


Rolled @400° F., hr
16
16
16
16


Stirred, min
15
15
15
15








Temperature, ° F.
120











Plastic viscosity, cP
48
66
66
44


Yield point, lb/100 ft2
164
15
7
99


10 Sec gel, lb/100 ft2
122
4
4
—


10 Min gel, lb/100 ft2
154
84
63
—


pH before rolling/
9.02/7.05
9.55/8.43
9.54/8.36
9.55/8.06


pH after rolling







Fann 35 dial readings











600 rpm
260
147
139
187


300 rpm
212
81
73
143


200 rpm
188
54
48
117


100 rpm
182
29
24
105


 6 rpm
141
3
3
85


 3 rpm
140
2
2
84


pH adjusted to

9.41
9.35
9.33


Plastic viscosity, cP

71
85
76


Yield point, lb/100 ft2

5
8
93


10 Sec gel, lb/100 ft2

4
4
113


10 Min gel, lb/100 ft2

73
53
262







Fann 35 dial readings











600 rpm

147
178
245


300 rpm

76
93
169


200 rpm

50
65
145


100 rpm

26
33
127


 6 rpm

3
3
117


 3 rpm

2
2
115
















TABLE 7







13.0 lb/gal Freshwater Mud Formulation with 35


lb/bbl Rev Dust Mud Formulations and Properties











Sample Mark
A
B
C
D











Freshwater, bbl
0.791


AQUAGEL ®
8


viscosifier, lb


BARAZAN ® D PLUS
0.25


viscosifier


FILTER-CHEK TM
3


filtration


control agent, lb


Rev Dust, lb
35


BAROID ® weighting
219


agent, lb


ALDACIDE ®
0.2


biocide G, lb


Dry caustic soda, lb
0.35











Thinner/Dispersant A of
3
—
—
—


Invention, lb


Thinner/Dispersant B of
—
3
—
—


Invention, lb


QUIK-THIN ®
—
—
3
—


thinner, lb


ENVIRO-THIN TM



3


thinner, lb


12.5N Liquid caustic
1.3
1.2
1.3
1.4


soda, total ml


Rolled @300° F., hr
16
16
16
16


Stirred, min
15
15
15
15








Temperature, ° F.
120











Plastic viscosity, cP
18
19
19
19


Yield point, lb/100 ft2
4
5
10
12


10 Sec gel, lb/100 ft2
2
3
4
8


10 Min gel, lb/100 ft2
4
4
10
30


pH before rolling/
9.60/7.08
9.55/7.29
9.54/8.30
9.55/7.91


pH after rolling







Fann 35 dial readings











600 rpm
40
43
48
50


300 rpm
22
24
29
31


200 rpm
17
19
23
25


100 rpm
10
11
15
17


 6 rpm
2
3
5
8


 3 rpm
1
4
4
7
















TABLE 8







14.0 lb/gal Freshwater Mud Formulation with 60


lb/bbl Rev Dust Mud Formulations and Properties










Sample Mark
A
B
C











Freshwater, bbl
0.743


AQUAGEL
8


GOLD SEAL ®


viscosifier, lb


AQUAGEL ®
8


viscosifier, lb


FILTER-CHEK TM
1.5


filtration


control agent, lb


Rev Dust, lb
60


BAROID ® weighting
249


agent, lb


ALDACIDE ®
0.2


G biocide, lb


Dry caustic soda, lb
0.35










Thinner/Dispersant A of
2.5
—
—


Invention, lb


Thinner/Dispersant B of

2.5
—


Invention, lb


QUIK-THIN ®

—
2.5


thinner, lb


12.5N Liquid caustic
0.9
1.3
0.6


soda, total ml


Rolled @300° F., hr
16
16
16


Stirred, min
10
10
10


Plastic viscosity, cP
56
71
49


Yield point, lb/100 ft2
12
10
105


10 Sec gel, lb/100 ft2
4
4
125


10 Min gel, lb/100 ft2
71
65
250


API, mL
6.8
3.3
9.0


HPHT, mL @500 psi
19
16
26


pH before rolling/
7.61/9.88
7.40/10.0
8.16/9.35


pH after rolling







Fann 35 Reading










600 rpm
124
152
203


300 rpm
68
81
154


200 rpm
46
59
138


100 rpm
25
32
130


 6 rpm
4
5
112


 3 rpm
3
4
109
















TABLE 9







14.0 lb/gal Freshwater Mud Formulation with 60


lb/bbl Rev Dust Mud Formulations and Properties











Sample Mark
A
B















Freshwater, bbl
0.743
0.743



AQUAGEL
8
8



GOLD SEAL ®



viscosifier, lb



AQUAGEL ®
8
8



viscosifier, lb



FILTER-CHEK TM
1.5
3



filtration



control agent, lb



Rev Dust, lb
60
60



BAROID weighting
249
249



agent, ® lb



ALDACIDE ®
0.2
0.2



biocide G, lb



Dry caustic soda, lb
0.35
0.35



Thinner/Dispersant B of
2.5
—



Invention, lb



QUIK-THIN ®
—
5



thinner, lb



12.5N Liquid caustic
0.9
0.6



soda, total ml



Rolled @300° F., hr
16
16



Stirred, min
60
60



Plastic viscosity, cP
48
37



Yield point, lb/100 ft2
10
52



10 Sec gel, lb/100 ft2
3
53



10 Min gel, lb/100 ft2
48
146



API, mL
7
8



HPHT, mL, 200° F. @500 psi
26
26



pH before rolling/
7.3/9.3
8.2/9.3



pH after rolling







Fann 35 Reading











600 rpm
106
126



300 rpm
58
89



200 rpm
40
79



100 rpm
22
56



 6 rpm
3
40



 3 rpm
2
38










FIG. 6 depicts the yield point of the 16 lb/gal mud samples treated with 5 lb/bbl of a thinner/dispersant of the invention in comparison with a ferro-chrome lignosulfonate thinner at 300° F. The thinning effect of all of the thinners varied with pH but the thinners/dispersants of the invention reduced the yield point lower than the ferro-chrome lignosulfonate thinner (see Table 4).
The thinning efficiency of the thinners/dispersants was evaluated on a 14 lb/gal mud having 10% drill solids (Rev Dust) and a high concentration of bentonite. All mud samples were treated with a 5 lb/bbl thinner/dispersant at 100% active level. The mud samples were rolled at 300° F. and 400° F. for 16 hours. The yield point values of the mud samples are shown in FIG. 7 (see also Tables 5 and 6). The yield point of the mud containing the lignosulfonate thinner decreased compared to the untreated base mud, but the yield point values of the mud samples with the thinners/dispersants of the invention were much lower than the yield point values of the mud containing the lignosulfonate thinner. The increase in temperature to 400° F. resulted in significant increase in the yield point values of the lignosulfonate mud samples while the yield point values of muds with the thinners/dispersants of the invention minimally increased. This observation demonstrates the advantages of the present invention at high temperatures above 350° F.
The effect of thinners/dispersants of the invention on the filtration control of the fluid systems was also evaluated and compared to the effect of lignosulfonate thinners on such systems. Four 14 lb/gal and 13 lb/gal mud samples were made and treated with 5 lb/bbl of the thinners, and rolled at 300° F. for 16 hours. The pH of the fluids was adjusted with 50% sodium hydroxide solution to 9.3-9.8. The results obtained from the API filtration testing are depicted in FIG. 8 for the sample's filtrate after 30 minutes. The thinners/dispersants of the invention had filtrate values about 50% lower than the ferro-chrome lignosulfonate thinner (see Tables 7 and 8). This observation demonstrates another advantage of the present invention.
Further tests were conducted to determine the lowest amount of Thinner/Dispersant B of the Invention that would give filtration control results comparable to the ferro-chrome lignosulfonate thinner. A 14 lb/gal mud was mixed and treated with different concentrations of Thinner/Dispersant B and the ferro-chrome lignosulfonate thinner, rolled at 300° F., and tested for both API and HPHT (high pressure high temperature) filtration control. At half of the concentration of the ferro-chrome lignosulfonate thinner, the Thinner/Dispersant B of the Invention would produce the same amount of thinning effect as the ferro-chrome lignosulfonate. Further, only 50% of the Thinner/Dispersant B of the invention was needed to produce the same amount of filtrate—provide the same or comparable filtration control, as the ferro-chrome lignosulfonate. These comparative filtration results are depicted in FIG. 9 and Table 9.
The above tests demonstrate that thinner/dispersants of the present invention lower the viscosity and gel strength of thick aqueous-based drilling fluids as well as or better than the best lignosulfonate thinners and such drilling fluids of the present invention have high deflocculating power and are more salt tolerant and stable at high temperatures than comparable fluids thinned with lignosulfonate thinners.
As indicated above, the advantages of the methods of the invention may be obtained by employing a drilling fluid of the invention, including the thinner/deflocculant of the invention, in drilling operations. The drilling operations—whether drilling a vertical or directional or horizontal borehole, conducting a sweep, or running casing and cementing—may be conducted as known to those skilled in the art with other drilling fluids. That is, a drilling fluid of the invention is prepared or obtained and circulated through a wellbore as the wellbore is being drilled (or swept or cemented and cased) to facilitate the drilling operation. The drilling fluid removes drill cuttings from the wellbore, cools and lubricates the drill bit, aids in support of the drill pipe and drill bit, and provides a hydrostatic head to maintain the integrity of the wellbore walls and prevent well blowouts. The specific formulation of the drilling fluid in accordance with the present invention is optimized for the particular drilling operation and for the particular subterranean formation characteristics and conditions (such as temperatures). For example, the fluid is weighted as appropriate for the formation pressures and thinned as appropriate for the formation temperatures.
The foregoing description of the invention is intended to be a description of preferred embodiments. Various changes in the details of the described fluids and methods of use can be made without departing from the intended scope of this invention as defined by the appended claims.

## Claims

1. A method of thinning an aqueous based drilling fluid for use in drilling a borehole in a subterranean formation, comprising adding to the drilling fluid an additive comprising an acrylic copolymer comprising a hybrid/graft lignosulfonate multipolymer, containing carboxylate and sulfonate functional groups, with synthetic polymer side chains covalently linked to a base lignosulfonate material, and having a molecular weight in the range of 1,000 to 15,000 and a high anionic charge density as indicated by a zeta potential of about 18 to 19 mV.

2. The method of claim 1 wherein the copolymer has a molecular weight of 5000 to 10,000.

3. The method of claim 1 wherein the copolymer has a molecular weight of 4,000 to 8,000.

4. The method of claim 1 wherein the aqueous base is brine or saltwater.

5. The method of claim 1 wherein the aqueous base is fresh water.

6. The method of claim 1 wherein the fluid contains no chromium or other heavy metals.

7. The method of claim 1 wherein the additive also provides filtration control.

8. The method of claim 1 wherein the additive provides rheology control at temperatures in the range of 350° F. to 400° F.

9. A method for drilling a borehole in a subterranean formation having water-sensitive formations and temperatures greater than 350° F., said method comprising:
providing an aqueous based drilling fluid thinned with an additive comprising a sulfonated acrylic copolymer having a hybrid/graft lignosulfonate multipolymer structure containing carboxylate and sulfonate functional groups with synthetic polymer side chains covalently linked to a base lignosulfonate material, wherein the copolymer has a molecular weight in the range of 4000 to 10,000, and has a high anionic charge density as indicated by a zeta potential of about 18 to 19 mV; and
drilling with the drilling fluid in the subterranean formation.

10. The method of claim 9 wherein said drilling fluid has a pH in the range of 8.0 to 10.5 and the copolymer enhances the rheological stability of the drilling fluid in the presence of fluid contaminants.

11. The method of claim 9 wherein said drilling comprises drilling through at least one producing zone in said formation.

12. The method of claim 9 wherein said drilling comprises stabilizing the wellbore.

13. New. The method of claim 9 wherein said thinned drilling fluid is stable at temperatures as low as 40° F. and as high as 400° to 450° F.