US3425940A - Non-staining liquid lubricant - Google Patents

Description

11 Claims Int. Cl. (310m 1/40 ABSTRACT OF THE DISCLOSURE A liquid mineral oil-free lubricating composition that is particularly suited for use in the drilling of earth formations with a diamond coring bit, and which is superior to previous lubricants for this purpose in that it does not cause staining of the earth cores, comprises from 3 to 25 weight percent of a salt of an alkylated aromatic sulfonic acid, from 3 to 25 weight percent of a solubilizing agent, from 1 to 10 weight percent of a rust inhibitor and from 40 to 93 weight percent of water. The composition can be added to the circulating stream of water used in the drilling operation at the rate of 1 volume of lubricant per 200 to 1000 parts of the circulating water.

This application is a continuation-in-part of application Ser. No. 476,664, filed Aug. 2, 1965, now abandoned.

The present invention relates to a water-based liquid lubricating composition. In general, it concerns a nonstaining liquid lubricating composition particularly useful for diamond core drilling. In particular, it concerns a nonstaining liquid lubricating composition containing an alkyl aryl metal organic sulfonate as a lubricity agent and the use of such a composition in the drilling of earth formations with a diamond drill coring bit.

In many industrial lubricating applications, staining of surfaces coming in contact with the lubricant is a problem. For example, in the Canadian mining industry where exploratory drilling is carried out using diamond core drilling apparatus to search for ore bodies, lubrication of the apparatus with conventional lubricants generally results in staining of the cores of rock and ore that are bored out by the diamond drill bit. Diamond bit coring is conventionally conducted by rotating a reamer and diamond drill bit on a string of drill pipe in a bore hole. It is the rotary action of the diamonds grinding against the rock and the weight of the drill rod assembly bearing down on the rock at the bottom of the hole which causes the assembly to penetrate into the rock. The doughnut-shaped diamond drill bit grinds out a smooth-surfaced cylindrical rock core (about one inch in diameter) which is pushed up into the inner core tube. The drill pipe is removed from the hole after every 10 to 20 feet of drilling to recover the rock cores. Recently a new technique has been perfected whereby a line equipped with a special clamp to fasten onto the core samples is lowered down through the drill pipe and the core samples are recovered without the necessity of raising and uncoupling the many feet of drill pipe. This new technique makes it especially mandatory that a non-staining lubricant be used.

In diamond core drilling, water, usually called fresh sludge water, is pumped down the drill pipe to flush the debris formed around the diamond bit back up through the annulus between the drill pipe and the walls of the hole and to serve as a coolant for the cutting diamonds. It also provides some lubrication to the rotating drill line. A string of drill rods or pipe which are not properly lubricated will cause the inherent vibrations common to a long rod or pipe to become severe. This condition creates impact forces that are transmitted to the diamond bit with nited States Patent 3,425,940 Patented F ch. 4, 1969 damaging effects. The recovery of the cores is also adversely affected under such conditions, since the vibration breaks the cores into smaller pieces. The rate of penetration of the bit is greatly reduced and will cease if the vibrations become too severe.

For some years a special grease has been marketed to coat the outside of the drill pipe to provide extra lubrication and to seal the hole where caving conditions are encountered due to fragile rock. The use of grease did permit greater drilling speed and provided some rust protection to the rods under these conditions. The use of a grease applied to the drilling apparatus so as to lubricate only the external surface of drill rods or pipe will result innon-staining of the cores, but at the same time neither the internal surface of the core barrel or tube nor the diamond drill bit is lubricated with the grease; thus, there is no internal lubrication and the life of the bit is decreased. In a like manner, when water alone is used as a lubricant, no core staining occurs. However, lubrication, both external and internal, is very poor, and in many instances vibrations are so great that drilling must cease.

More recently it was found that a soluble oil, e.g., an emulsifiable oil comprising a major proportion of a mineral lubricating oil and a minor proportion of one or more anionic emulsifiers, when metered into the fresh sludge water, markedly increased the cutting speed and bit life.

In most instances however, use of the soluble oils caused deposition of a tenacious insoluble film on the surface of the rock cores. This film prevented the geologist from identifying, by visual inspection, the ores and rocks contained in the core. An analysis of the deposit showed that it was composed of 50% of a black magnetic iron oxide (of such fine crystalline structure as to make identification by X-ray Diffraction techniques difiicult), and 50% of a resinous organic binder. The iron oxide appeared to have been ground into the pores of the rock core.

In accordance with the present invention, there is provided a liquid lubricant which does not stain and which possesses very good lubricity properties. This lubricant is employed in the same manner as with the prior practice when using the so-called soluble oils, i.e., it is also metered into the fresh sludge water used in the diamond drilling operation. Usually about 1 part by volume of the composition of the present invention will be employed with about 200 to 1000 parts, and preferably 200 to 400 parts, by volume of water (e.g., fresh sludge water).

The composition of the present invention comprises a metal salt of an alkyl aryl su-lfonie acid, as the lubricity additive; a n0n-staining solubilizing agent, which solubilizes the sulfonate in water; a non-staining rust inhibitor; and water, as a carrier.

The alkyl aryl metal sulfonate employed as the lubricity additive of the present invention is well known to the art as a surface active agent. The metal portion of the sulfonate can be sodium, potassium, lithium or ammonium, preferably sodium. The alkyl portion of the sulfonate contains about 6 to 18 carbon atoms, preferably 10 to 14 carbon atoms, e. g., dodecyl. The aryl portion of the sulfonate can be benzene, diphenyl, or naphthalene. Benzene is particularly preferred. Examples of sulfonates suitable for use in the present invention include, but are not limited to, sodium dodecyl benzene sulfonate, potassium nonylbenzene sulfouate, ammonium octyl benzene sulfonate, sodium cetyl naphthalene sulfonate, lithium decyl benzene sulfonate, etc. The above-described sulfonates are anionic surface active agents and their methods of preparation are well known to the art. Such sulfonates are readily available for example under the trade names Deltamin AB 80, Sorapon SX Slurry, etc.

The solubilizing agent employed in the present invention must be water-soluble and must also be non-staining. One such solubilizer is Triton X-l02, which is isooctylphenyl polychtoxy ethanol, i.e., the reaction product of isooctylphenol and ethylene oxide. This reaction product has an average of 12 to 13 oxyethylene units. Another non-limiting example of a suitable solubilizer is urea.

P-articula-rly effective solubilizers are the alkyl phenyl polyalkoxy alkanols, which are obtained by reacting to 15 molar proportions of a C to C alkylene oxide with one molar proportion of an alkyl phenol having a C to C alkyl group, e.g., the reaction product of 6 moles of propylene oxide with one mole of dodecyl phenol, the reaction product of a mixture of 5 moles of ethylene oxide and 5 moles of propylene oxide with one mole of nonyl phenol, and the reaction product of 8 to 10 moles of ethylene oxide with one mole of isooctyl phenol. These are included within a broader class of solubilizers having the formulas:

where R is a C to C hydrocarbon group, A is oxygen or sulfur and x is 8 to 20, which would include, in addition to the alkyl phenol derivatives described above, the alkyl thiophenol derivatives and the higher alcohol ethers and higher mercapto ethers of the alkylene oxides or the polyglycols.

Still other suitable solubilizers include the sodium, potassium, or ammonium salts of toluene sulfonic acid or of xylene sulfonic acid. Another solubilizer comprises a mixture of 1 to 10 parts by weight of the tetrasodium salt of ethylene diamine tet-racetic acid with 1 part of the sodium salt of N, N-di-(Z-hydroxyethyl) gylcine and/or 1 part of the sodium salt of hydroxyethyl ethylene diamine triacetic acid.

The composition of the present invention employs a non-staining water-soluble rust inhibitor to provide rust protection for the container during shipment and for the drill rods during use. Suitable rust inhibitors include, but are not limited to, sodium benzoate, sodium nitrite, triethanolamine, sodium borate, sodium dichromate, thiourea, etc. Sodium benzoate is preferred.

In general, the above-described three components of the composition of the present invention will be used with a Water carrier in the following general proportions:

Weight percent The above weight percentages are based upon 100 percent active ingredient. Sulfonates suitable for use in the present invention are often supplied in concentrate form. For example, Sorapon SX Slurry is a concentrate of about 45% by weight of sodium dodecyl benzene sulfonate in 55 weight percentage water. The dodecyl group is derived by alkylating benzene with tetrapropylene.

Various other ingredients may be added to the compositions of the present invention. For example, antifoamants such as silicone fluid DC 200 (350 centistokes), dyes such as Disuphine Blue VN 150, and other conventional additives may be employed for their known effects.

When the liquid lubricating composition is diluted with water in the proportion of 1 volume of the composition and 200 to 1,000 volumes of water, there will be obtained a circulating fluid which will consist essentially of about 200 to 1,000 parts by weight of water, from 0.03 to 0.25 part by weight of the sulfonate, from 0.03 to 0.25 part by Weight of the solubilizing agent, and from about 0.01 to 0.1 part by Weight of the rust inhibitor.

The present invention will be further described by reference to the following examples.

Example 1 A non-staining lubricant composition of the present invention was prepared by simple mixing of 20 weight percent Sorapon SX Slurry, 10 weight percent Triton X-102, 5 weight percent sodium benzoate and 65 weight per-cent water. To this was added about 0.002 weight percent disulphine blue dye VN 150 for identification purposes. The resulting viscous blue liquid composition had a specific gravity of 1.06 at 60 F., a solids content (by evaporation) of 24 weight percent and a viscosity at F. of about 360 SUS. It had good low-temperature stability, there being no separation of components after several hours storage at 0 F.

This composition was found to be eminently suitable for use in diamond drilling operations by metering about 1 gallon of the composition into about 400 gallons of water. For example, when Water is circulating through the drill pipe at 1,200 gallons per hour, 3 gallons per hour of the described composition is metered into the circulating water.

In a typical operation a rock formation in an exploration hole at a depth between 6,600 and 10,000 feet below the surface Was cored with a diamond bit, using circulating water to which the above composition had been added in the proportion of 1 gallon per 400 gallons of water. There was essentially no staining of the recovered cores and lubrication of the drill pipe was good as evidenced by lack of vibration.

Example 2 A lubricant composition is prepared by simple mixing of 13 weight percent of ammonium isooctyl benzene sulfonate, 14 weight percent of nonylphenyl polypropoxy propanol, 4 weight percent of triethanolamine, and 69 weight percent of water. The isooctyl benzene sulfonate is derived from benzene that has been alkylated with diisobutylene. The nonylphenyl polypropoxy propanol is the reaction product of mixed nonylphenols with 8 to 9 molar proportions of propylene oxide. The mixed nonylphenols consist of 76 Weight percent of monononylphenol and 24 weight per-cent of dinonylphenol resulting from alkylation of phenol with tripropylene.

The lubricant composition thus prepared is mixed with Water in the proportion of 1 part of lubricant to about 500 parts of water to constitute the circulating and lubricating fluid for coring a rock formation in -a bore hole in the earths surface using a diamond coring bit.

While the lubricating composition of the present invention has been described primarily as a non-staining lubricant for diamond core drilling operations, the composition also finds utility in other liquid lubricating ap plications. For example, it can be used without further dilution as a way lubricant, i.e., as a fabrication lubricant applied to the cooling beds for the lubrication of hot steel bars as they slide down the bed and onto the ways. In this respect it is superior to the more expensive gr-aphited lubricants and acidless tallows commonly employed as way lubricants. The composition can also be employed as a metal cutting fluid, or as a roll oil in the fabrication of metal sheets. Colloidal graphite may also be added to this composition for specific applications.

It is to be understood that the examples presented herein are intended to be merely illustrative of the invention and not as limiting it in any manner; nor is the invention to be limited by any theory regarding its operability. The scope of the invention is to be determined by the appended claims.

What is claimed is:

1. A non-staining liquid mineral-oil-free lubricating composition consisting essentially of from 3 to 25 Weight percent of a sulfonate salt selected from the group consisting of the sodium, potassium, lithium, and ammonium salts of alkylated aromatic sulfonic acids wherein the alkyl groups have about 6 to 18 carbon atoms, from 3 to 25 weight percent of a Solubilizing agent, from 1 to 10 weight percent of a rust inhibitor and from 40 to 93 weight percent of water, said solubilizing agent being selected from the group consisting of urea, 21 sodium, po-

tassium, or ammonium salt of toluene sulfonic acid, a sodium, potassium, or ammonium salt of xylene sulfonic acid, a phenyl polyalkoxy alkanol obtained by reaction of 5 to 15 moles of a C to C alkylene oxide with one mole of an alkyl phenol having a C to C alkyl group, a mixture of ethylene diamine tetrasodium tetra acetate and sodium salt of N, N-di-(Z-hydroxyethyl) glycine, and a mixture of ethylene diamine tetrasodium tetra acetate and sodium salt of hydroxyethyl ethylene diamine triacetic acid, said rust inhibitor being a water-soluble rust inhibitor selected from the group consisting of sodium benzoate, sodium nitrite, triethanol amine, sodium borate, sodium dichromate, and thiourea.

2. Composition as defined by claim 1 wherein said alkyl groups range from about to 14 carbon atoms.

3. Composition as defined by claim 1 wherein said sulfonate is sodium dodecyl benzene sulfonate.

4. Composition as defined by claim 1 wherein said solubilizing agent is the product of alkoxylation of a C to C alkyl phenol with from 5 to moles of a C to C alkylene oxide.

5. Composition as defined by claim 1 wherein said solubilizing agent is isooctyl phenyl polyethoxy ethanol having 12 to 13 oxyethylene units.

6. Composition as defined by claim 1 wherein said rust inhibitor is sodium benzoate.

7. In the drilling of a well bore in the earth wherein a core sample is obtained by a coring device at the lower end of a string of drill pipe and wherein said drill pipe and said coring device are lubricated by circulation of Water through the drill pipe and the coring device, the improvement which comprises adding to said circulating water one volume, per 200 to 1000 volumes of said water, of the liquid lubricating composition defined by claim 1.

8. A circulating fluid for the lubrication of a string of drill pipe and an earth coring device suspended therefrom in a well bore which consists essentially of a mixture of from 200 to 400 volumes of water and 1 volume of the lubricant composition defined by claim 1.

9. Circulating fluid as defined by claim 8 wherein said lubricant composition consists essentially of: (1) about weight percent of a slurry of 45 weight percent of sodium dodecyl benzene sulfonate, about 55 weight percent of water; (2) about 10 Weight percent of isooctyl phenyl polyethoxy ethanol having from 12 to 13 oxyethylene units; (3) about 5 weight percent sodium benzo-ate; and (4) about 65 weight percent of water.

10. A mineral oil-free circulating fluid for the lubrication of a string of drill pipe and an earth coring device suspended therefrom in a well bore which consists essentially of about 200 to 1000 parts by weight of water, from about 0.03 to 0.2 part of a sultonate salt selected from the group consisting of the sodium, potassium, lithium and ammonium salts of alkylated aromatic sultonic acids wherein the alkyl groups have from about 6 to 18 carbon atoms, from about 0.03 to 0.2 part of a solubilizing agent and from 0.01 to 0.1 part of a rust inhibitor, said solubilizing agent being selected from the group consisting of urea, a sodium, potassium, or ammonium salt of toluene s-ulfonic acid, a sodium, p0- tassium, or ammonium salt of xylene sulfonic acid, a phenyl polyalkoxy alkanol obtained by reaction of 5 to 15 moles of a C to C alkylene oxide with one mole of an alkyl phenol having a C to C alkyl group, a mixture of ethylene diamine tetrasodium tetra acetate and sodium salt of N, N-di-(Z-hydroxyethyl) glycine, and a mixture of ethylene diamine tetrasodium tetra acetate and sodium salt of hydroxyethyl ethylene diamine triacetic acid, said rust inhibitor being a water-soluble rust inhibitor selected from the group consisting of sodium benzoate, sodium nitrite, triethanol amine, sodium borate, sodium dichromate, and thiourea.

11. Fluid as defined by claim 10 wherein said solublizing agent is the product of alkoxylation of a C to C alkyl phenol with from 5 to 15 moles of a C to C alkylene oxide.

References Cited UNITED STATES PATENTS 2,568,992 9/1951 Doscher 252- 2,610,151 9/1952 Putman et a1. 252-333 2,617,296 11/1952 W'isenbaker 252-85 X 2,832,736 4/1958 Jezl 252-333 3,112,799 12/1963 GalluS 252-85 X 3,150,085 9/1964 Mallory 252-85 3,308,068 3/1967 Jones 252-85 X 2,796,429 6/1957 Kreps et a1. 252-161 X 3,282,843 11/1966 Alburger 252-495 X OTHER REFERENCES Rogers, Composition and Properties of Oil Well Drill ing Fluids, Third Edition, pub. 1963 by Gulf Pub. Co. of Houston, Texas, pp. -121.

HERBERT B. GUYNN, Primary Examiner.

US. Cl. X.R.