Biodegradable fluids

Abstract

The incorporation of highly refined, low viscosity index base oils along with a polymeric thickener produces a final readily biodegradable fluid with a significantly high viscosity. The present invention allows the formulation of a high viscosity readily biodegradable fluid where the vast majority of the fluid is mineral oil. Previous uses of mineral oils only allowed for formulation of substantially lower viscosity readily biodegradable fluids.

Claims

1. A readily biodegradable fluid, comprising: a mineral oil base fluid portion, wherein the mineral oil base fluid portion comprises one or more highly refined mineral oils having a ratio of paraffin content to cycloparaffin content of at least 3:2 and a viscosity index of at least 110; and a polymeric thickener portion, wherein the polymeric thickener portion comprises polymethacrylate, wherein the readily biodegradable fluid is readily biodegradable, and wherein a readily biodegradable fluid is readily biodegradable when at least 60% of organic carbon in the readily biodegradable fluid is converted to carbon dioxide in 28 days when exposed to freshwater microorganisms.

2. The readily biodegradable fluid of claim 1, wherein the readily biodegradable fluid comprises about 80 to about 97 wt % of the mineral oil base fluid portion and about 3 to about 20 wt % of the polymeric thickener portion.

3. The readily biodegradable fluid of claim 1, further comprising one or more highly refined, high viscosity mineral oils having a ratio of paraffin content to cycloparaffin content of less than 1:1 and a viscosity index of less than 110.

4. The readily biodegradable fluid of claim 1, wherein the readily biodegradable fluid has an ISO viscosity grade of 32.

5. The readily biodegradable fluid of claim 1, wherein the biodegradable fluid has an ISO viscosity grade of 46.

6. A method for preparing a readily biodegradable fluid, comprising: preparing a mineral oil base fluid portion, wherein the mineral oil base fluid portion comprises one or more highly refined mineral oils having a ratio of paraffin content to cycloparaffin content of at least 3:2 and a viscosity index of at least 110; and mixing a polymeric thickener portion into the mineral oil base fluid portion, wherein the polymeric thickener portion comprises polymethacrylate, and wherein the mixing is carried out at a temperature of about 20° C. to about 65° C., to produce the readily biodegradable fluid, wherein the readily biodegradable fluid is readily biodegradable, and wherein a readily biodegradable fluid is readily biodegradable when at least 60% of organic carbon in the readily biodegradable fluid is converted to carbon dioxide in 28 days when exposed to freshwater microorganisms.

7. The method of claim 6, wherein the readily biodegradable fluid comprises about 80 to about 97 wt % of the mineral oil base fluid portion and about 3 to about 20 wt % of the polymeric thickener portion.

8. The method of claim 6, wherein the mineral oil base fluid portion further comprises one or more highly refined, high viscosity mineral oils having a ratio of paraffin content to cycloparaffin content of less than 1:1 and a viscosity index of less than 110.

9. The method of claim 6, wherein the readily biodegradable fluid has an ISO viscosity grade of 32.

10. The method of claim 6, wherein the readily biodegradable fluid has an ISO viscosity grade of 46.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a schematic of an exemplary hydrotreating/hydrocracking and hydroisomerization process.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

(2) The present disclosure relates to biodegradable fluids.

(3) In preferred embodiments, the biodegradable fluids are readily biodegradable mineral oil based fluids. Preferred embodiments of the biodegradable fluids comprise highly refined, highly paraffinic mineral oils and polymeric thickener. Additional preferred embodiments of the biodegradable fluids may comprise highly refined, high viscosity base oils which are of lower paraffin content.

(4) Mineral oil biodegradability is significantly impacted by degree of refining, with more severely refined mineral oil base fluids (base oils) showing higher levels of biodegradability. Preferred mineral oil base fluids used herein are prepared from highly paraffinic feedstocks having a high viscosity index (VI) and subjected to a severe hydrotreating/hydrocracking and hydroisomerization process. FIG. 1 shows a schematic of an exemplary hydrotreating/hydrocracking and hydroisomerization process. In the hydrotreating/hydrocracking process feedstocks are reacted with hydrogen in the presence of a catalyst at high temperatures (>300° C., but preferably near 400° C.) and high pressures (>2000 psi, but preferably near 3000 psi). The principle reactions occurring in this process are the 1) removal of unwanted polar compounds containing sulfur, nitrogen and oxygen, 2) conversion of aromatic hydrocarbons to saturated cyclic hydrocarbons and 3) the conversion of heavy polycyclo-paraffins into light, saturated hydrocarbons. The hydroisomerization process, operating in series with the hydrotreating/hydrocracking process employs an additional catalyst to selectively isomerize wax molecules (long chain n-paraffins present in the feedstock) to high viscosity index, low pour point isoparaffinic base oil molecules. The combined processes are capable of producing highly paraffinic base oils with viscosity indexes in excess of 130. The enhanced degree of refining is seen as an increased paraffin to cycloparaffin content and increased viscosity index (VI) (increased resistance to change in viscosity with change in temperature) in the given series of base oils. The preferred mineral oil base fluids show unexpectedly high levels of biodegradability as compared to similar viscosity grades of less refined mineral oil base fluids.

(5) In preferred embodiments, one or more of the mineral oil base fluids making up the mineral oil base fluid portion of the biodegradable fluid contains at least 1:1 paraffins relative to cycloparaffins, with regard to wt %. In additional preferred embodiments, one or more of the mineral oil base fluids making up the mineral oil base fluid portion of the biodegradable fluid contains paraffins relative to cycloparaffins in at least a 3:2 ratio, with regard to wt %. In further preferred embodiments, the mineral oil base fluid portion of the biodegradable fluid includes one or more highly refined, high viscosity base oils which may be of lower paraffin content, or less than a 1:1 ratio of paraffins relative to cycloparaffins, with regard to wt %. In preferred embodiments, one or more of the mineral oil base fluids making up the mineral oil base fluid portion of the biodegradable fluid should have a VI of at least 110. In further preferred embodiments, the mineral oil base fluid portion of the biodegradable fluid further comprises one or more highly refined, high viscosity base oils having a viscosity index of less than 110. Different refining techniques may be used to prepare suitable base oil compositions that are expected to produce the same high levels of biodegradability of the base oils. A wide variety of highly paraffinic, high viscosity index feed sources are suitable for producing these highly biodegradable base oils. Preferred examples of the mineral oil base fluids include the mineral oil base fluids identified in Table 1 below as Mineral Oil Base Fluid A-E.

(6) TABLE-US-00001 TABLE 1 Mineral Oil cSt @ cSt @ kg/L@ ppm wt % wt % wt % Base Fluid 40° C. 100° C. VI 15° C. sulfur paraffins cycloparaffins aromatics A - N100DW 21.5 4.4 117 0.839 <2 52.8 47.2 <0.1 B - N100VHVI 21.3 4.5 128 0.832 <1 60.9 39.1 <0.1 C - N100XV 19.0 4.2 135 0.828 <1 67.9 32.1 <0.1 D - N325DW 52.5 8.2 128 0.846 <1 51.7 48.3 <0.1 E - N650HT 106 11.8 99 0.870 <1 21.4 78.6 <0.1

(7) Preferred embodiments of the biodegradable fluids also include polymeric thickeners. A significant and unexpected synergy, in regards to increased biodegradability, can be obtained by blending mineral oils with selected polymeric thickeners. The level of biodegradability of the mineral oils and polymeric thickener alone is significantly lower than a mixture of both. This synergy from the polymeric thickener is wholly unexpected as the polymer itself shows low levels of biodegradability. Preferred examples of the polymeric thickeners include polymethacrylate thickeners. Polymethacrylate thickeners may be in the form of viscosity modifiers and pour point depressants. Other polymethacrylate additives such as anti-foaming additives can be included in the biodegradable fluids and also contribute to the unexpected synergy. Polymethacrylate thickeners typically include polymethacrylate at about 60-100 wt % and solvents and diluents at about 0-40 wt %.

(8) Preferred embodiments of the biodegradable fluids may contain one or more additional, optional ingredients, such as antiwear additive, antioxidants, and corrosion inhibitors, in an amount of less than 5 wt %, preferably less than 2 wt %.

(9) In preferred embodiments, the biodegradable fluids comprise about 80 to about 97 wt % of a mineral oil base fluid portion and about 3 to about 20 wt % of a polymeric thickener portion. In additional preferred embodiments, the mineral oil base fluid portion comprises one or more highly refined mineral oils having a ratio of paraffin content to cycloparaffin content of at least 3:2 and a viscosity index (VI) of at least 110. In further preferred embodiments, the mineral oil base fluid portion of the biodegradable fluid further comprises one or more highly refined, high viscosity mineral oils having less than a 1:1 ratio of paraffin content to cycloparaffin content and a viscosity index (VI) of less than 110. In further preferred embodiments, the polymeric thickener comprises polymethacrylate.

(10) In preferred embodiments, the combination of highly refined mineral oils and select polymeric thickener allows the formulation of the present readily biodegradable mineral oil based fluids having a higher viscosity than can be achieved using a base oil blend alone. In particular, it is expected that the maximum viscosity of a readily biodegradable fluid blended from mineral oils alone would be approximately 22 cSt at 40° C. In preferred embodiments, the formulation of a readily biodegradable mineral oil based fluid has at least an ISO viscosity grade of 32 (28.8-35.2 cSt at 40° C.). In other preferred embodiments, the formulation of a readily biodegradable mineral oil based fluid has at least an ISO viscosity grade of 46 (41.4-50.6 cSt at 40° C.). The ability to formulate a higher viscosity fluid, while maintaining ready biodegradability, is key, as most industrial equipment requires higher viscosity oils in order to adequately protect moving parts with a hydrodynamic lubricating film.

(11) Ready biodegradability, as measured by OECD (Organization for Economic and Co-operation and Development) 301B, is the breakdown or mineralization of at least 60% of an organic substance in 28 days when exposed to freshwater microorganisms. OECD 301B measures this breakdown or mineralization by monitoring the degree to which the organic carbon in a test substance is converted to carbon dioxide by the microorganisms.

(12) Further aspects of the present invention will become apparent from the following description given by way of example only.

Example 1

(13) Preferred examples (Formula 1, 2, 3, and 4) of the biodegradable fluids were prepared having the compositions set forth in Table 2 below.

(14) TABLE-US-00002 TABLE 2 Formula 1 Formula 2 Formula 3 Formula 4 ISO VG Class 32 46 46 46 Component Description wt % wt % wt % wt % Base mineral A - N100DW 46.43 oil B - N100VHVI 64.18 45.38 46.20 C - N100XV 9.72 D - N325DW 31.30 29.80 29.83 E - N650HT 18.73 19.74 39.05 Performance Ashless Hydraulic 1.65 1.65 1.65 1.65 Additive Performance Package Package (LUBRIZOL AH93SA, Lubrizol, Wickliffe, OH) Polymeric Polymethacrylate Viscosity 2.43 2.95 2.95 2.95 Thickener Modifier (Viscoplex 8-440, Evonik, Essen, Germany) - cSt @ 100° C. = 1250 Polymeric Polymethacrylate Pour 0.42 0.42 0.42 0.42 Thickener Point Depressant (Viscoplex 1-153, Evonik, Essen, Germany) Anti-foaming Polymethacrylate Anti- 0.02 0.02 0.02 0.02 Additive foamer (PC-1244, Allnex, Frankfurt, Germany)

(15) All components were blended together at a temperature between room temperature (about 20-22° C.) and 65° C. Preferably the temperature should be between 40° C. and 50° C. The mixing should be simple low to moderate shear mechanical mixing.

(16) Table 3 below shows the Measured Biodegradability of Formulas 1-4 (OECD 301B-28 Day Biodegradability, wt %), the total weight percent of base mineral oil, in each formulation, and, for comparison, the expected biodegradability of the base oil portion. In each case, the exemplary biodegradable fluid (Formula 1-4) showed a biodegradability greater than expected based on the base mineral oil. Formulas 1, 3 and 4 demonstrated ready biodegradability.

(17) TABLE-US-00003 TABLE 3 Formula 1 Formula 2 Formula 3 Formula 4 Measured 62.8 58.8 75.2 79.0 Biodegradability, wt % wt % Base Oil 95.48 94.96 94.95 94.97 Expected 49.0 35.9 44.1 48.6 Biodegradability of Base Oil Portion

(18) Table 4 below shows compositions for additional preferred examples of the biodegradable fluids (Formulas 5, 6, and 7).

(19) TABLE-US-00004 TABLE 4 Formula 5 Formula 6 Formula 7 ISO VG Class 46 46 46 Component Description wt % wt % wt % Base Mineral Oil B - N100VHVI 47 46 48.5 D - N325DW 30 30 30 E-N650HT 20 20 21.5 Polymeric Polymethacrylate Viscosity 3 Thickener Modifier (Viscoplex 8-440, Evonik, Essen, Germany) - cSt @ 100° C. = 1250 Polymethacrylate Viscosity 4 Modifier (Viscoplex 0-219, Evonik, Essen, Germany) - cSt @ 100° C. = 830

(20) Table 5 below shows the Measured Biodegradability of Formulas 5-7 (OECD 301B—28 Day Biodegradability, wt %), the total weight percent of base mineral oil, in each formulation, and, for comparison, the expected biodegradability of the base oil portion. Tests were duplicated and results were averaged. Formulas 5 and 6 both showed higher biodegradability than what was expected. Formula 5 demonstrated ready biodegradability.

(21) TABLE-US-00005 TABLE 5 Formula 5 Formula 6 Formula 7 Measured 75.3 53.0 34.1 Biodegradability, wt % wt % Base Oil 97 96 100 Expected 45.2 44.6 46.6 Biodegradability of Base Oil Portion