NZ208558A - Reducing cloud point of hydrodewaxed mineral oil base stocks - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £08558 208558 Priority Date(s): Complete Specification Filed: Class: .... £jp.fltei/&a P.O. Journal, No //?.%£ Publication Date: NEWZE PATENTS ACT, 1953 K-Z- PATENT OFPIPC 18JUN1984 RECBiypn No.: Date: COMPLETE SPECIFICATION "REDUCING THE CLOUD POINT OF HYDRODEWAXED BASE STOCKS" K/We, MOBIL OIL CORPORATION, a corporation organised under the laws of the State of New York, United States of America, of 150 East 42nd Street, New York, State of New York, United States of America, hereby declare the invention for which i / we pray that a patent may be granted to lJfife/us, and the method by which it is to be performed, to be particularly described in and by the following statement:- (followed by page la) 'uiBtw. ■f aoacKaoio)- - La REDUCING THE CLOUD POINT OF HYDRODEWflXED BASE STOCKS Many hydrodewaxed base oils have relatively high cloud points. While other properties are excellent and the cloud point appears to have no deleterious effect on the performance of formulated oils, nevertheless there are specifications for many oils that require that there be no overnight cloud formation in the base oil at a given temperature.

The high cloud point (or overnight cloud point, ONC) is common to many hydrodewaxed oils. Much processing work, such as selective removal of the haze components and use of crystallization inhibitors, has been done with limited success. Generally, solutions to the haze formation are uneconomic or impractical because the solutions introduce other problems such as lower viscosity, a tendency to emulsify in the presence of water, and poorer oxidation response. It is known to use phosphorus- and sulfur-containing compounds as additives to oils.

This invention relates to a method of lowering the cloud point of a base stock by treating the base stock with a sulfurizing agent, either alone or in the presence of an oil-soluble magnesium, calcium or barium compound or a combination thereof, and adding a portion of the sulfurized base stock to the untreated base stock. The method is applicable to reducing the cloud and/or the hazing characteristics.

While the exact nature of the compounds formed by sulfuriza-tion leading to large improvement is not known, it is believed that various sulfide, disulfide and polysulfide linkages are formed which interface with the wax crystal growth. Sulfurization of mineral oils is an old art. Such sulfurization is used to stabilize the oils against oxidation and to provide antiwear activity.

F-2020(391S} 2 085 58 In accordance with the invention, there is provided a method for lowering the cloud point of a hydrodewaxed mineral oil base stock which comprises reacting sulfur therewith in proportions to provide from 0.013a to 0.20ft by weight thereof in the oil. This may be accomplished through direct addition to the total volume of base stock or by addition to a portion of the base stock to provide an additive level of from 0.10 to 1.0% by weight, followed by the addition of this sulfurized base stock to the balance of the base stock such that a sulfur content of from 0.01ft to 0.20ft by weight thereof in the total oil-additive composition is attained. Alternatively, if color is a problem, the above described sulfurization may be carried out in the presence of an oil-soluble metal compound, such as a calcium, barium or magnesium compound. It is preferred that the metal compound be present during reaction with sulfur, because a principal value of the invention is to provide a product with a light color. There is further evidence that the presence of the metal compounds also aids in improving the hazing characteristics of the oil. The invention also provides a lubricant composition comprising lubricant and the oil-sulfur product, whether comprising a metal compound or not.

The method disclosed herein is generally applicable to any hydrodewaxed mineral oil susceptible to haze formation at lower temperatures. Although, as has been stated hereinabove, such haze formation does not affect other properties of the oil, specifications have been established which require oils to pass an overnight cloud point test at temperatures such as -1°C (30°F) and 4°C (40°F).

In carrying out th* method of this invention, oil is mixed with sufficient sulfur to provide from 0.01ft to 0.2ft thereof in the final oil product, and the mixture is heated at from 150°C to 250°C, preferably from 180°C to 200°C until the reaction is complete. The reaction typically will require from 1 to 5 hours. Alternatively, a metal compound may be present in the oil during reaction. "The metal compound is used in small amounts, usually on the order of from 0.01ft to 1.0ft, and preferably 0.05ft to 0.556, based on the weight of the oil. The amount r-g020(2010) 085 of compound used will depend upon the degree of haze improvement required. Therefore, heavy haze will require more of the sulfur component than trace or light haze. Also, the amount of sulfur will dictate reaction times. Therefore, longer times will be required for higher loads of sulfur.

Bjring the reaction between oil and sulfur, hydrogen sulfide is formed as a by-product. To remove it, oxygen, nitrogen or other inert gas is blown through or over the medium.

The haze component is present in the oil in very small amounts, often less than 0.1% by weight of the oil. It is believed that equally small amounts of sulfur compounds formed in the oil are effective because the sulfur reacts in part with organic structures present to produce small amounts of organo-sulfur compounds, which in turn solubilize the haze component and prevent its crystallization at a given lower temperature.

One specific problem area is Aldelaide MLDW bright stock, which has the properties: 150 95 ° F 1.1% 1.2 2.5 This oil, without the sulfur compound, produces a visible haze on storage overnight at -10°C (30°F), which disappears at higher temperatures but which will reform upon cooling. Several compounds were tested as solubilizers for the haze component, but only a few showed any effect at all. However, such high concentrations of these compounds were required that their use was economically impracticable. Further, the high concentrations required introduced other undesirable properties to the base fluid.

SUB 11 98.9°C (210°F) = VI Pour Point = CCR % S = ASTM Color E 2020(2018)- 208558 Those compounds having some effect were: dioctyl sulfide didodecyl sulfide dimethyl disulfide sulfurized butene -1 sulfurized cis-butene -2 sulfurized trans-butene -2 sulfurized mixed butenes sulfurized octene sulfurized decene sulfurized decene dimer di-t-butyl disulfide Di-t-butyl disulfide showed somewhat more improvement than the other compounds.

Having described the invention in general terms, the following Examples are offered as specific embodiments. It will be understood that they are illustrative of the invention and are not intended to limit its scope.

EXAMPLE 1 Eighty-four grams of Adelaide MLJDW Bright Stock and 0.084 gram of sulfur were charged into a 250 ml, 4 neck round bottom flask equipped with a thermometer, glass "paddle" stirrer and nitrogen inlet tube. The contents were heated to 180°C and held at that temperature for 2 hours with a stream of nitrogen present above the surface. The sulfurized product was cooled to 90°C and filtered through diatomaceous earth.

The product contained 0.1% sulfur. r-2020(201&) . - 5 - EXAMPLE 2 (Ninety-nine and eight tenths grams of Adelaide MLDW Bright Stock and 0.2 gram of sulfur were charged into a 250 ml, 4 neck round bottom flask equipped with a thermometer, glass "paddle" stirrer and nitrogen inlet tube. The contents were heated to 200°C and held at that temperature for 2 hours with a stream of nitrogen present above the surface. The sulfurized product was cooled to 90°C and filtered through diatomaceous earth.

The product contained 0.2% sulfur.

EX/MPLE 3 / Two hundred grams of Adelaide MLDW Bright Stock, 0.4 gram of sulfur and 0.1 gram of magnesium-C^g salicylate were charged into a 500 ml, 4 neck round bottom flask equipped with a thermometer, glass "paddle" stirrer and nitrogen inlet tube. The contents were heated to 180°C and held at that temperature for 2 hours with a stream of nitrogen present above the surface. The sulfurized product was cooled to 90°C and filtered through diatomaceous earth.

The product contained 0.2% sulfur and 0.05% of the Mg compound (0.004% Mg).

EXAMPLE 4 Seventy-nine and two tenths grams of Adelaide MLDW Bright Stock, 0.8 gram of sulfur and 0.2 gram of magnesium-C1Q salicylate were charged into a 125 ml, 2 neck flat bottom flask equipped with a thermometer, magnetic spin bar and nitrogen inlet tube. The contents were heated to 180°C and held at that temperature for 2 hours with a stream of nitrogen present above the surface. The sulfurized product was cooled to 160°C and then air was blown below the surface of the solution for 1.5 hours while it cooled to 87°C. The rate of air 2 085 58 f 2020(26W- introduction was 0.64 CFH. The product was filtered through diatomaceous earth.

This product contained 1% sulfur and 0.25% of a Mg compound (0.0016% Mg).

EXAMPLE 5 Ninety-nine and eight tenths grams of Adelaide MLDW Bright Stock, 0.2 gram of sulfur and 0.05 gram of a magnesium-C1Q . salicylate were charged into a 125 ml, 2 neck flat bottom flask equipped with a thermometer, magnetic spin bar and a nitrogen inlet tube. The contents were heated to 200°C and held at that temperature for 2 hours with a stream of nitrogen present above the surface. The sulfurized product was cooled to 150°C and then air was blown below the surface of the solution for 2.5 hours while it cooled to 93°C. The rate of air introduction was 0.64 CFH. The product was filtered through diatomaceous earth.

The product contained 0.2% sulfur and 0.05% of a Mg compound (0.064% Mg).

EXAMPLE 6 Ninety-nine and five tenths grams of Adelaide MLDW Bright Stock, 0.4 gram of sulfur and 0.1 gram of a magnesium-C^0 salicylate were charged into a 125 ml, 2 neck flat bottom flask equipped with a thermometer, magnetic spin ^ar and a nitrogen inlet tube.

The reaction conditions were the same as for Example 5.

The product contained 0.4% sulfur and 0.1% of a Mg compound (0.008% Mg). >£-2020(2010)- 2 085 5 8 EXAMPLE 7 Ninety-eight and seventy-five hundredths grams of Adelaide MLDW Bright Stock, 1.0 gram of sulfur and 0.25 gram of a magnesium-C10 salicylate were charged into a 125 ml, 2 neck flat bottom flask equipped with a thermometer, magnetic spin bar and a nitrogen inlet tube.

The reaction conditions were the same as for Examples 5 and 6.

The product contained 1% sulfur and 0.25% of a Mg compound (0.02% Mg).

EXAMPLE 8 Ninety-nine grams of Adelaide MLDW Bright Stock and 1.0 gram of sulfur were charged into a 125 ml, 2 neck flat bottom flask equipped with a thermometer, magnetic spin bar and a nitrogen inlet tube.

The reaction conditions were the sane as for Example 7.

The product contained 1% sulfur and is the same as Example 7 except that no Mg compound was present.

Samples of the oils were heated to 100°C (212°F) for 45 minutes and were then placed in a cold room, maintained at -1°C (30°F), overnight for a total of about 16 hours and were then evaluated for haze by-nephelometric determination. Numbers higher than 10 indicate visible haze in the oils.

Results are shown in the following table. r-2020(20l0) 2 O- TABLE 1 OVERNIGHT CUDUD POINT TEST RESULTS WITH ALDELAIDE MLDW BRIGHT STOCK (HYDRODEWAXED) Adelaide Bright Siock Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Wt. % Cone. In Adelaide Bright Stock 10 1 2 4 10 1 5 1 2 1 2 Overnight Cloud Point, °C/°F 0.56/33 -12. 2/10 -7.2/19 -12.8/9 -12.2/10 -8.3/17 -10.6/13 -12.8/9 -13.9/7 -13.9/7 -12.8/9 -12.2/10 -12.8/9 -12.8/9 -10/14 -10.6/13 j=^g020(20l9^ 208558 TABLE 2 VISIBLE CLOUD POINT TEST RESULTS WITH MLDW STOCKU) Additive None Example 3 Example 3 Example 3 Wt. % in MLDW Stock 1.0 5.0 10.0 Observed Haze at 21.1°C (70°F)(Overnight) Light Haze Clear and Bright Clear and Bright Clear and Bright 4 0 0 3 (1) - 100" solvent paraffinic neutral mineral oil. in ih oo SI I o Additive None Example 3 3 3 3 3 3 3 TABLE 3 GUDUD POINT OBSERVATIONS WITH GULF CANADA HYDRODEWAXED BRIGHT STOCKS Base Oil A, hydrodewaxed 170 Bright Stock Feed* B, hydrodewaxed 170 Bright Stock Feed** A A A A B B B Observed Haze at Wt. % Room Temp. 21.1°C — Heavy Haze Overnight — Light Haze Overnight Clear Overnight Clear Overnight 2.5 Trace Haze Overnight 1.0 Trace Haze Overnight Clear Overnight Clear Overnight 1 Trace Haze Overnight Overnight Cloud, 21.1°C 48 16 24 22 * Properties of Bright Stock A **Properties of Bright Stock B o c-l N. / C) C 1 < 5 C 4 IH KV <! 40°C @ 100°C SUS @ 37.8°C 98.9°C VI Pour Point °C Color (ASTM) S (ppm) 462.2 32.27 2468 158 102 -15 D 3.5 <10 KV © 40°C ® 100°C SUS® 37.8°C @ 98.9°C VI Pour Point °C Color (ASTM) S (ppm) 395.7 29.25 2106 144 102 -15 D 0.0 1.0

Claims (13)

w P-2020( 201Q) - 11 - 208558 TABLE 4 OVERNIGHT CLOUD POINT TESTS WITH VARIOUS MLDW STOCKS 'j Base Stock (2) (2) (2) (3) (3) (3) (4) (4) (4) (5) (5) (6) (6) Additive Example 3 Example 3 Example 3 Example 3 Example 3 Example 3 Example 3 Example 3 Wt. % Additive 5 10 5 10 5 10 ONC at -1°C (30°F) 3 1 0 120 63 101 15 16 10 13 ... ,7 ' 11 25 Observed Haze at -1°C (30°F) Haze Bright & Clear Bright & Clear Haze Trace Haze Trace Haze Haze Lt. Haze Bright & Clear Haze Bright & Clear Haze Haze (2) - 200" solvent paraffinic neutral mineral oil. (3) - 700" solvent paraffinic neutral mineral oil (VI-100; 75 SUS at 210°F). (4) - 700" solvent paraffinic neutral mineral oil (VI-95, 695 SU5 at 210°F). (5) and (6) - Highly refined turbine oil stocks. .WHAUAVE CLAJM ISf -CLAlHSr

1. A method for lowering the cloud point of a hydrodewaxed mineral oil base stock comprising reacting sulfur with the base stock in sufficient quantity to provide from 0.0135 to 0.235 by weight of sulfur therein.

2. The method of Claim 1 further comprising reacting sulfur with a portion of the base stock in sufficient quantity to provide from 0.0135 to 1.035 by weight therein and adding a sufficient amount of this sulfurized stock to the balance of the base stock such that the "V sulfur concentration in the total composition is from 0.0135 to 0.2035 ^ by weight.

3. The method of Claim 1 wherein there is present during sulfurization from O.G135 to 1.035 by weight of an oil soluble calcium, barium or magnesium compound.

4. The method of Claim 3 wherein the oil soluble compound is an oil soluble magnesium compound.

5. The method of Claim 4 wherein the magnesium compound is magnesium decyl salicylate.

6. The method of Claim 1 wherein the reaction takes place at -> from 150°C to 250°C. ? • "

7. A lubricant composition comprising a major proportion of a hydrodewaxed mineral oil base stock and an amount of a hydrodewaxed mineral oil - sulfur reaction product containing from 0.1035 to 1.035 by weight of sulfur sufficient to give a concentration of sulfur in the lubricant composition of from 0.0135 to 0.235 by weight thereof. F-2020(2018) - 12 - 208558 --e^g0ge£20±8-) 13

8. The composition of Claim 7 wherein there is present the residue of an oil soluble calcium, barium or magnesium compound used in the reaction to form the the reaction product.

9. The composition of Claim 8 wherein the oil soluble compound is an oil soluble magnesium compound.

10. The composition of Claim 9 wherein the magnesium compound is magnesium decyl salicylate.

11. The composition of Claim 7 wherein the reaction to form the the reaction product is carried out at from 150°C to 250°C.

12. A method for lowering the cloud point of a hydrodewaxed mineral oil base stock substantially as herein described with reference' to the Examples.

13. A lubricant composition substantially as herein described with reference to the Examples. ByJdfe^Their Authorised Agents, A. J. PARK & SON N.Z. PATENT OFFICE 18JUNI984 RECEIVED