HIGH TEMPERATURE DRILLING FLUIDS BASED ON SULPHONATED THERMOPLASTIC POLYMERS

Abstract: The present invention concerns oil-based drilling muds for oil and gas wells. These muds comprise water, an emul­ sifier, a wetting agent, a weighting material and a neutral­ ised sulphonated thermoplastic polymer. The sulphonated thermoplastic polymers have 5 to 100 milli-equivalents of sulphonate groups per 100 grams of the sulphonated ther­ moplastic polymer, wherein the sulphonated groups are neutralized with a metallic cation or an amine or ammonium counterion.

Description: The present invention concerns oil-based drilling muds which are used during operation of gas and oil wells, e.g., to maintain pressure, cool drill bits and lift cuttings from the holes. The oil-base drilling muds of the present invention minimally comprise (but can also include other additives) an organic liquid such as an oil; fresh water or salt water; an emulsifier; a wetting agent; a weighting material and a sulfonated polymer, the latter acting as a viscosification agent. In general, the oil-based drilling mud has a specific gravity of 7 Ib/gallon to 20 lb/gallon, more preferably, 10 to 16, and most preferably 12 to 16 lb/gallon. A typical oilbased drilling mud as envisaged by the present invention comprises : an oil; 1 to 10 parts by weight of water per 100 parts by weight of the oil, more preferably 3 to 5; and 20 to 50 lb/bbl of an emulsifier; 1/2 to 5 lb/bbl of a wetting agent; and weighting material (Barium sulfate or Barite) necessary to give the desired mud density; which comprises less than 800 lb/bbl of Barium sulfate, more preferably 5 to 750, and most preferably 10 to 700 lb/bbl; and .25 to 4 lb/bbl of sulfonated polymer. The oil employed in the oil-based drilling mud is generally a No. 2 diesel fuel, but it can be other commercially available hydrocarbon solvents such as kerosene, fuel oils or selected crude. If crudes are used, they should be weathered and must pie free of emulsion breakers. Typical, but non-limiting examples of suitable emulsifiers which can be readily employed are magnesium or calcium soaps of fatty acids. Typical, but non-limiting examples of a suitable wetting agent which can be readily employed is an alkylaryl sulfonate. Typical, but non-limiting examples of a weighting material which can be readily employed is barite or a barium sulfate which may optionally be surface treated with other cations, such as calcium. The neutralized sulfonated thermoplastic polymers employed in the oil base drilling muds are preferably derived frcr polystyrene type thermoplastics polymers selected from polystyrene, polyt-butyl-styrene, polychlorostyrene, polyalpha methyl styrene, cc- or terpolyiners of the aforementioned with acrylonitrile or vinyl toluene, polystyrene, poly-t-butylstyrene, polychlorostyrene, polyvinyl toluene, polyalpha methyl styrene and or terpolymers of the aforementioned with acrylonitrile methyl methacrylate butadiene. Although sulfonated thermoplastics are-the preferred form of this invention, there are a large number of sulfonate-containing polymers which fall within the scope of this invention. These are described in U.S. Patents 3,870,841 and 3,931,021. Such polymers can be prepared by direct sulfonation of the preformed polymer or by copolymerization with a sulfonate-containing monomer. Particularly desirable polymers are those derived from vinyl monomer or comonomer, except propylene. The polystyrene thermoplastics suitable for use in the practice of the invention have a glass transition temperature from 700C to 1500C, more preferably 900C to 140"C and most preferably 90"C to 1200C. These polystyrene resins have a weight average molecular weight, as measured by GPC, of 5,000 to 500,000, more preferably 20,000 to 350,000 and most preferably 90,000 to 300,000. These base polystyrene thermoplastic resins can be prepared directly by any of the known polymerization processes. The term "thermoplasti" is used in its conventional sense to mean a substantially rigid Cflexus modulus > 10,000 psi) material capable of retaining the ability to flow at elevated temperatures for relatively long times. The preferred polystyrene thermoplastic resin is a homopolymer of styrene having a number average molecular weight of 180,000, and an intrinsic viscesity in toluene of 0,8, These polymers are widely available commercially in large volume. A suitable material is Styron 666 manufactured by Dow Chemical Co., which affords a suitable number average molecular weight of 105,000. The thermoplastic polymers are sulfonated by a process in a non-reactive solvent such as a chlorinated aliphatic solvent, chlorinated aromatic hydrocarbon, or an aliphatic hydrocarbon such as carbon tetrahcloride, dichloroethane or chlorobenzene. The preferred solvents are the lower boiling chlorinated hydrocarbons. A sulfonating agent is added to the solution of the polymer and a non-reactive solvent at a temperature of -1000C to 1000C for a period of time of 1 to 60 minutes, most preferably at room temperature for 5 to 45 minutes; and most preferably 15 to 30. Typical sulfonating agents are described in U.S. Patents 3,642,728 and 3,836,511. These sulfonating agents are selected from an acyl sulfate, a mixture of sulfuric acid and an acid anhydride or a complex of sulfur trioxide donor and a Lewis base containing oxygen, sulfur or phosphorus. Typical sulfur trioxide donors are SO3, chlorosulfonic acid, fluorosulfonic acid, sulfuric acid, oleum, etc. Typical Lewis bases are: dioxane, tetrahydrofuran, tetrahydrothiopene or triethyl phosphate. The most preferred sulfonation agent for this invention is an acyl sulfate selected from benzoyl, acetyl, propionyl and-butyryl sulfate. The acyl sulfate can be formed in situ in the reaction medium or pregenerated before its addition to the reaction medium in a chlorinated aliphatic or aromatic hydrocarbon. It should be pointed out that neither the sulfonating agent nor the manner of sulfonation is critical, provided that the sulfonating method does not degrade the polymer backbone. The reaction is quenched with an aliphatic alcohol such as methanol, ethanol or isopropanol, with an aromatic hydroxy compound, such as phenol, a cycloaliphatic alcohol such as cyclohexanol or with water. The unneutralized sulfonated thermoplastic polymer has 5 to 100, more preferably 8 to 60; and most preferably 10 to 45 meq. sulfonate groups per 100 grams of sulfonated polymer, The range of sulfonate content which can be considered does vary over an extremely broad latitude; however it has been observed that in those systems of high sulfonation level that there is great difficulty in dissolving the sulfonated polymers and there can be very adverse effects in terms of the interaction of the sulfonated polymer with the barite weighting agent and with the other components of the drilling mud. Therefore, there is clearly an optimum level of sulfonation content which may vary from one sulfonated backbone to another but for sulfonated polystyrene it is in the most preferred embodiment of the invention as described above. The meq. of sulfonate groups/ 100 grams of sulfonated thermoplastic polymer is determined by both titration of the polymeric sulfonate acid and Dietert Sulfur analysis. In the titration of the unneutralized sulfonate, the polymer is dissolved in solvent consisting of 95 parts by volume of toluene and 5 parts by volume of methanol at a concentration level of 50 grams per liter of solvent. The unneutralized sulfonate is titrated with ethanolic sodium hydroxide to an Alizarin Thymolphthalein end-point. The unneutralized sulfonated thermoplastic polymer is gel free and hydrolytically stable. Gel is measured by stirring a given weight of polymer in a solvent comprising 95 vol. toluene-5 vol.methanol at a concentration of 5 wt. X, for 24 hours, allowing the mixture to settle, withdrawing a weighed sample of the supernatant solution and evaporating to dryness. Hydrolytically stable means that the unneutralized sulfonate will notbe eliminated under neutral or slightly basic conditions to a neutral moiety which is incapable of being converted to highly ionic functionality. The unneutralized sulfonate groups of the sulfonated thermoplastic polymer are neutralised by the addition of a solution of a basic salt to the unneutralized sulfonated polymer dissolved in the mixture of the alipathic alcohol and non-reactive solvent. The basic salt is dissolved in a binary solvent system consisting of water and/or an aliphatic alcohol. The counterion of the basic salt may be selected from antimony, iron, aluminum, lead and Groups IA, IIA, IB and IIB of the Periodic Table of Elements and mixtures thereof as well as ammonium and amine counterions. The preferred cations include zinc, magnesium, sodium, lead, barium, calcium, and ammonium cations, wherein zinc, magnesium and sodium are the most preferred cations. The anion of the basic salt is selected from a carboxylic acid having from 1 to 4 carbi atoms per irolecule, a hydroxide, or alkoxide and mixtures thereof. The preferred neutralizing agent is a metal acetate, more preferably sodium acetate. Sufficient metal salt of the carboxylic acid is added to the solution of the unneutralized sulfonated thermoplastic polymer to effect neutralization. It is preferable to neutralize at least 958 of the sulfonate groups, more preferably 98%, most preferably 100%. Examples of metal oxides useful in preparing metal sulfonates are MgO, CaO, BaO, ZnO, Ag2O, PbO2 and Pb304. Useful examples of metal hydroxides are NaOH, KOH, LiOH, Mg(OH)2 and Ba (OH)2. In addition to the sulfonation/neutralization of polystyrene, an alternative approach to such polymers involves the copolymerization of sulfonate-containing monomers with styrene to yield polymers having the appropriate levels of sulfonate groups. The sulfonate-containing polymers obtained via this approach are also effective in this invention. Alternatively, a latex of a sulfonated polymer as described in U.S. Patents 3,912,683 and 4,007,149, could be readily employed as a convenient method of introducing the sulfonated polymer into the oil-based drilling mud. A polar cosolvent can optionally be added to the oil drilling mud, wherein the polar cosolvent increases the solubility of the sulphonated polymer in the oil drilling mud by decreasing the strong ionic interactions between the sulphonate groups of the sulphonated polymer. EXAMPLE I Oil-based drilling muds were prepared using conventional laboratory methods. The muds contain No. 2 diesel oil, fresh or salt water, emulsifier, supplementary emulsifier, a wetting agent, weighting agent and a 1.7 mole percent sodium salt of sulfonated polystyrene. The muds were aged overnight at 1500F to ensure chemical equilibrium. Aliquots of the mud were aged in pressurized cells at 3000 and 4000F for 16 hours. The cells were cooled at room temperature, depressurized, and then the rheological properties of the mud were measured on a Fann Model 35 viscometer at 1150F. Muds containing 0.5 and 1.0 lbs/bbl of sulfonated polystyrene is presented in Table I. TABLE I Rheological Properties of Several Oil-Based Muds Containing 1.7 Mole Percent Sulfonated Polystyrene Designation lbs/bbl(A) Water 600(B) 300(C) PV(D) YP(E) Gels(F) Temp. F. 1M 0.5 Fresh 63 35 28 7 2-10 150 58 32 26 6 1-11 300 69 40 29 11 5-27 400 2M 1.0 Fresh 62 36 26 10 3-12 150 62 35 27 8 2-18 300 88 54 34 20 10-26 400 3M 0.5 Salt 41 23 18 5 2-3 150 41 22 19 3 1-2 300 44 23 21 2 1-4 400 4M 1.0 Salt 44 24 20 4 1-3 150 49 27 22 5 2-4 300 55 30 25 5 1-3 400 (A) Polymer concentration in lbs/bbl. (B) Reading taken on a Fann &commat; rotational viscometer at 600 rpm. (C) Reading taken on a Fann &commat; rotational viscometer at 300 rpm. (D) Plastic viscosity in centipoise units: Difference between the 600 rpm and 300 rmp measurements. (E) Yield point in units of lbs/100 ft.2: Difference between the 300 rpm measurement and plastic viscosity. (F) First number is the initial value (expressed as lbs/100 ft.2) on the viscometer at 3 rpm, while the second number corresponds to the value after 10 minutes has elapsed. Table I shows the effectiveness of 1.7 mole percent sodium salt of sulfonated polystyrene as a viscosifier and gel strength additive for oil-based muds. The data show that mud containing fresh water can be treated with the sulfonated polymer to enhance both the viscosity and gel strength characteristics. These desirable properties are maintained after subjecting the mud to high temperatures (3000-4000F). In addition, the data show that the sulfonated polystyrene is not effective as a viscosifier and gel strength additive for oil muds -¯¯containing calcium chloride water. EXAMPLE II Oil-based drilling muds, formulated with the additives employed in Example I (except the 1.7 mole percent sulfonated polystyrene) and containing 2.65 and 4.19 mole percent sodium salt of sulfonated polystyrene, were prepared using conventional laboratory methods. These results are shown in Table II. TABLE II Rheological Properties of Several Oil-Based Drilling Muds Containing 2.65 or 4.19 Mole Percent Sulfonated Polystyrene Sulfonation Designation Level (mole %) bbl H2O 600(A) 300(A) PV(A) YP(A) Gels(A) Temp, F 1 2.65 0.5 Fresh 61 37 24 13 5-13 150 47 25 22 3 2-13 300 58 38 20 8 3-17 400 2 2.65 1.0 Fresh 59 34 25 9 3-10 150 50 28 22 6 3-17 300 60 34 26 8 6-21 400 3 4.19 0.5 Fresh 54 32 22 10 4-10 150 44 22 22 0 1-1 300 50 25 25 0 1-9 400 4 4.19 1.0 Fresh 57 33 24 9 4-11 150 47 24 23 1 1-6 300 57 30 27 3 2-14 400 5 2.65 0.5 Salt 43 25 18 7 3-6 150 46 24 22 2 1-4 300 53 28 25 3 2-8 400 6 2.65 1.0 Salt 37 20 17 3 1-3 150 42 21 21 0 1-2 300 53 26 27 0 1-5 400 7 4.19 0.5 Salt 37 20 17 3 2-4 150 40 20 20 0 1-2 300 46 24 22 2 1-8 400 8 4.19 1.0 Salt 39 21 18 3 1-3 150 40 20 20 0 1-2 300 42 21 21 0 1-2 400 (A) The meaning of the symbol is given in Table I. Table II shows the effectiveness of two different sulfonate levels of polystyrene as a viscosifier for oil-based muds containing either fresh or calcium chloride water. The data indicates that the 2.65 mole percent sulfonate level functions well as a viscosifier and gel strength additive for muds containing fresh water. Also, the data indicates that the 4.19 mole percent sulfonated polystyrene does not perform as well as the 2.65 mole percent sulfonated polystyrene material in fresh water. The reduced performance of the former material is due essentially to its very low solubility in the mud formulation. When calcium chloride water is present, the rheological properties of the muds containing either polymer is found to have deteriorated. EXAMPLE III An oil-based drilling mud was produced (as described in Example I) with a 2.65 mole percent sodium sulfonated polystyrene and a nonionic surfactant (PluronicF-68 is manufactured by the BASF Wyandotte Corporation). The rheological properties of this mud in both fresh and calcium chloride water is presented in Table III. TABLE III Rheological Properties of an Oil-Based Mud Containing 2.65 Mole Percent and a Nonionic Surfactant Designation lbs/bbl H2O 600(A) 300(A) PV(A) YP(A) Gels(A) Temps. F 1 0.5-SPS Fresh 65 42 23 19 7-16 150 0.5-F88 49 27 22 5 1-10 300 52 30 22 8 4-20 400 3 0.5-SPS Fresh 47 27 20 7 3-7 150 1.0-F88 47 26 21 5 2-10 300 61 35 26 9 5-16 400 2 0.5-SPS Salt 47 28 19 9 3-7 150 0.5-F88 54 29 25 4 1-5 300 59 33 26 7 3-10 400 4 0.5-SPS Salt 42 26 16 10 3-6 150 1.0-F88 48 27 21 6 1-5 300 55 30 25 5 3-13 400 (A) The explanation of these symbols is given in Table I. The data in Table III shows that the 2.65 mole percent sulfonated polystyrene along with the nonionic surfactant produced an oil-drilling mud possessing excellent rheological properties. Both the viscosity and gel strength characteristics of the oil mud is enhanced in either fresh or calcium chloride water. In addition, the sulfonated polystyrene and nonionic surfactant is capable of maintaining these characteristics after being subjected to high temperatures (3000-4000F).

Claims: CLAIMS 1. An oil-based drilling mud which comprises: (a) an organic liquid; (b) 1 to 10 parts by weight of water per 100 parts by weight of the organic liquid; (c) 20 to 50 lb/bbl of an emulsifier; (d) a wetting agent; (e) a weighting material in sufficient quantity to achieve a density of 7 to 20 lb/gallon; and (f) 0.25 to 4.0 lb/bbl of a neutralized sulphonated thermoplastic polymer, said neutralized sulphonated thermoplastic polymer having 5 to 100 meq. of sulphonate groups per 100 grams of the neutralized sulphonated thermoplastic polymer. 2. A drilling mud according to claim 1, in which the sulphonate groups of said neutralized sulphonated thermoplastic polymer are neutralized with a counterion selected from antimony, iron, aluminum, lead and metals of Groups IA, IIA, Is and IIB of the Periodic Table of Elements. 3. A drilling mud according either of claims 1 and 2, in which said neutralized sulphonated thermoplastic polymer is derived from polystyrene. 4. A drilling mud according to either of claims 1 and 2, in which said neutralized sulphonated thermoplastic polymer is derived from poly-t-butyl-styrene, polychlorostyrene, polyalpha methyl styrene, polyvinyl toluene, Co- or terpolymers of styrene with acrylonitrile, methyl methacrylate, butadiene or mixtures thereof. 5. A drilling mud according to any of the preceding claims in which said wetting agent is an alkylaryl sulphonate. 6. A drilling mud according to any one of the-preceding claims in which said weighting material is Barite or barium sulfate. 7. A drilling--mud ccording- to any one of the preceding claims in which the concentration level of said weighting material is sufficient to give said drilling mud a specific gravity of 10 to 16 pounds per gallon. 8. A drilling mud according to any one of the preceding claims in which said organic liquid is an oil. 9 A drilling mud according to any one of the preceding claims which includes a polar cosolvent. 10. A drilling mud according to any one of the preceding claims in which said water is salt water.

Inventors: LUNDBERG, ROBERT DEAN, PEIFFER, DENNIS GEORGE, WALKER, THAD OSCAR
Applicants: EXXON RESEARCH AND ENGINEERING COMPANY
Application year: 1982
Main classification: C09K7
IPC codes: C09K8