Patent Grant
10190067
Field of the Invention
The present embodiments herein relate to the field of high-performance environmentally-acceptable hydraulic fluid blend containing fluids from up to four different classes of environmentally-acceptable hydraulic fluids, plus additives.
Discussion of the Related Art
The purpose of a lubricant is generally to minimize friction and wear of metals. Lubricants generally consist of a base fluid and additives selected to improve the lubricating properties or other properties of the lubricant (e.g., stability, performance at low or high temperature, etc.). With industrialization, mineral based lubricants became important in the market. Most existing heavy duty lubricating oils used for construction equipment and the like contain mineral oils as a main a component. For example, hydraulic systems found in farm tractors, backhoes, excavators, garbage trucks, snow plows and other heavy equipment generally use mineral oil based fluids as lubricants. Mineral oils have the advantages of lubricity, longevity, and corrosion resistance.
The drawbacks of mineral based lubricants are that they are toxic, they have long term residual properties making them difficult to dispose of safely (i.e., long term, they have very low biodegradability), and they are very difficult to clean if there is an accidental spill. In particular, they are environmentally unacceptable. Thus, unauthorized release and spill of mineral oil based lubricants can have significant adverse impacts on terrestrial and aquatic environments, as well as underground sources of drinking water. Furthermore, scattering and leakage of oil is generally difficult to avoid during usage; hence, mineral oil usage inevitably leads to at least some contamination of the environment. Spillage clean up can require removing the top layer of the grass or soil and containment for proper disposal which involves significant labor hours and additional costs.
Accordingly, because of the foregoing problems with respect to mineral-oil derived hydraulic fluids, there is a desire in the industry for Environmentally-Acceptable (EA) hydraulic and lubricating fluids to protect the environment but still offer beneficial lubricating properties. Generally, there are four basic types of environmentally friendly hydraulic and lubricating fluids that are commonly used individually. Each have different chemistries and each are derived from different stocks and thus have different applications and thus may necessitate a designed composition to address lubricating a material (e.g., seals) that it is to interact with during particular operations.
In particular, one of the four of such fluids is a hydraulic environmental ester synthetic (HEES) fluid, which is a water-insoluble synthetic ester derived from either petroleum, animal oils, or vegetable (typically rapeseed) oil feedstocks. Petroleum-sourced HEES fluids combine an organic acid and alcohol, whereas vegetable sourced fluids combine a fatty acid and alcohol. A second of such fluids includes hydraulic environmental triglyceride (HETG), which are water insoluble triglycerides derived from vegetable or animal oils with soybean, sunflower, and rapeseed (Canola) being the most common sources, wherein they often can contain soluble thickeners to increase viscosity. A third of such fluids includes hydraulic environmental poly glycols (HEPG), which are often but not necessarily water-soluble (e.g., oil-soluble) polyalkylene glycols (PAG), polymers made from reacting alkylene-oxide monomers such as ethylene oxide, propylene glycol, or propylene oxide with glycol. The fourth basic type of environmentally friendly hydraulic and lubricating fluid includes hydraulic environmental polyalphaolefin and related products (HEPR) fluids, which are water-insoluble polyalphaoletins (PAO) and related hydrocarbon-based fluids. Such synthetic hydrocarbons are made by polymerizing alpha olefins to produce PAO.
With respect to illustrative but not exhaustive example properties of such fluids, HEES fluids have a broad viscosity range and have high thermal and oxidative stability and good fluidity at low temperatures. However, they hydrolyze in the presence of water. HETG fluids are highly biodegradable and nontoxic and are noncorrosive. However, high-temperature operation can cause undesired fast oxidation and aging, extreme thickening and gumming, and they are vulnerable to water effects, causing hydrolysis and increased acidity. HEPG fluids have been found to be incompatible with polyurethane seals, and pumps and motors often utilized in systems requiring lubricants. HEPR fluids have outstanding oxidation stability, corrosion protection, beneficial lubricity, desired aging characteristics, and good viscosity performance over a wide temperature range. Nonetheless, much like HEPG fluids, they have been found to be incompatible with many seal and gasket materials.
It is to be noted however, that while each of the above four basic environmentally acceptable fluids have beneficial properties (in addition of course to deleterious properties), none of them can compete with unacceptable environmental (i.e., mineral based) fluids in all performance categories and thus when utilized, often require special system design and maintenance considerations.
Accordingly, there is a need to provide environmentally-acceptable hydraulic fluid blends that addresses environmental and system performance/cost concerns. The embodiments herein address such a need by providing a novel high-performance environmentally-acceptable hydraulic fluid blend containing fluids from up to four of the different classes of environmentally-acceptable hydraulic fluids discussed above, plus additives. By selecting relative concentrations of such Environmentally-Acceptable (EA) fluids in a novel fashion, resultant desired performance properties acting in a synergistic way are optimized, making them competitive with non-Environmentally-Acceptable (EA) fluids.
It is to be appreciated that the present example embodiments herein are directed to high performance environmentally acceptable fluid (e.g., a biodegradable hydraulic fluid) that can include synthetic oils, and optionally stable vegetable and animal oils (unsaturated), and additives. The synthetic oil often but not necessarily includes trimethylolpropane trioleate (TMPTO) esters of predominantly mono unsaturated vegetable oils. By “predominantly mono unsaturated”, it should be understood that at least 50% of the fatty acid moieties are mono unsaturated fatty acids. The synthetic oil may also be formed from vegetable oils or vegetable oil blends or animal oils or animal oil blends, which have low levels of saturated fatty acids (i.e., no carbon carbon double bonds) and/or low levels of polyunsaturated fatty acids (i.e., two or more carbon carbon double bonds).
The present embodiments are thus directed to a hydraulic fluid that includes a contribution of a range of 10% up to about 85% by weight of at least one of: natural esters, synthetic esters, polyols, a vegetable oil, 1% up to about 40% by weight of polyalphaolefin (PAO), 1% up to about 40% by weight of polyalkylene glycol (PAG), and mixtures thereof; and wherein up to about 10% by weight quantity of one or more additives are introduced to provide desired properties that include at least one of: a high viscosity index, a low pour point, a hydrolytic stability, and an oxidative stability, as part of the hydraulic fluid contribution.
Accordingly, the fluid blends disclosed herein thus exhibit the following beneficial properties:
In the description of the invention herein, it is understood that a word appearing in the singular encompasses its plural counterpart, and a word appearing in the plural encompasses its singular counterpart, unless implicitly or explicitly understood or stated otherwise. Furthermore, it is understood that for any given component or embodiment described herein, any of the possible candidates or alternatives listed for that component may generally be used individually or in combination with one another, unless implicitly or explicitly understood or stated otherwise. It is to be noted that as used herein, the term “adjacent” does not require immediate adjacency. Moreover, it is to be appreciated that the figures, as shown herein, are not necessarily drawn to scale, wherein some of the elements may be drawn merely for clarity of the invention. Also, reference numerals may be repeated among the various figures to show corresponding or analogous elements. Additionally, it will be understood that any list of such candidates or alternatives is merely illustrative, not limiting, unless implicitly or explicitly understood or stated otherwise. In addition, unless otherwise indicated, numbers expressing quantities of ingredients, constituents, reaction conditions and so forth used in the specification and claims are to be understood as being modified by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the subject matter presented herein. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the subject matter presented herein are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical values, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
Specific Description
The embodiments herein are directed to a hydraulic fluid formulation and method for its production. In particular, the embodiments herein are directed to a new class of high-performance environmentally acceptable hydraulic fluids. According to IS015380, environmentally acceptable hydraulic fluids can be divided into four categories: (1) Hydraulic Environmental Synthetic Esters (HEES), which include for example trimethylolpropane triesters (TMPTEs) which may or may not be genetically or synthetically modified, polyols wherein the polyols with varying numbers and fatty acids chain lengths such as neopentyl glycol dioleate (diester), trimethylolpropane trioleate (TMPTO) (triester), pentaerythritol tetraoleate (tetraester) from vegetable oils or animal oils; (2) Hydraulic Environmental Tri-Glycerides (HETG), which include for example vegetable oils and animal oils; (3) Hydraulic Environmental Polyalphaolefins and Related products (HEPR); and (4) Hydraulic Environmental Poly-Glycols (HEPG). It is also to be noted that as used herein, natural oils include both vegetable and animal based oil that are genetically or synthetically modified but that nonetheless can exclude synthetic or genetic modification.
Fluids from each of these four categories offer a certain set of properties, as briefly discussed above, that are not necessarily exhibited by fluids from other categories. For instance in addition to what was previously discussed, fluids in the HETG category have a high viscosity index and are readily biodegradable, but have a high pour point and are prone to hydrolysis and oxidation. Fluids in the HEES category are more hydrolytically and oxidatively stable than fluids in the HETG category, but they tend to have a lower viscosity index. Fluids in the HEPR category are oxidatively stable and have a low pour point, while fluids in the HEPG category are hydrolytically stable. Fluids in the HETG and HEES categories are derived from renewable resources, whereas fluids in the HEPR and HEPG categories are derived from non-renewable resources (petroleum).
Hydraulic fluids derived from vegetable oils and animals oils belong to the HETG category. These fluids are appealing due to their biodegradability, low ecotoxicity, and are derived from renewable resources. Triglycerides display good hydraulic fluid properties, but they are prone to hydrolysis, have a poor oxidative stability, and a poor low-temperature performance. To improve the properties of triglycerides, the glycerol backbone can be replaced by other polyols to yield synthetic esters (HEES). One example of such fluids is trimethylolpropane triester (TMPTE), which displays improved hydrolytic stability and low-temperature performance. High-oleic HETG and HEES fluids are known to exhibit improved pour point, and hydrolytic and oxidative stability. The properties of HETG and HEES ester fluids can be further improved by adding polyalphaolefin (PAO), a HEPR fluid, which is known to enhance oxidative stability. Addition of polyalkylene glycol (PAG), a HEPG fluid, is known to improve hydrolytic stability.
Fluid Development
Optimum combination of properties (including a high viscosity index, a low pour point, a high oxidative stability, and a high hydrolytic stability) are determined by blending fluids from up to four categories. Other inadequate properties are compensated for by using chemical additives. The main component of the blend often includes ester base fluids, while PAO and PAG are diluents.
As part of this determination, a three part study provided for improving the oxidative stability of the hydraulic fluid blend. Part I and part II in particular was directed to improving the oxidative stability of the hydraulic fluid blend, which is mainly composed of TMPTO base fluid, while in part III, the role of PAG on improving the hydrolytic stability is assessed. The following are brief non-limiting descriptions of the three part study.
Part I: Optimization of Oxidative Stability
Parameters include: High-oleic vegetable oil (soybean vs. canola); Influence of PAO; and Influence of different antioxidants (F323/57 (Functional Products, Inc.), NA-L (King Industries, Inc.), and VAN (Vanderbilt Chemicals, LLC.)). It was determined that the addition of PAO desirably lowers the pour point and improves the oxidative stability. The formulation containing NA-Lube BL-1208 (NA-L) shows the highest oxidative stability. Furthermore, the formulation with the optimum combined properties contains high oleic canola oil derived TMPTO base fluid. Therefore, all subsequent formulations contain PAO, NA-L, and high oleic canola oil based TMPTO. From here onwards, TMPTO refers to high oleic canola oil derived trimethylolpropane trioleate base fluid.
Part II: Optimization of Oxidative Stability
Parameters include: Influence of PAO in combination with PAG. To further improve the oxidative stability, another non-ester type fluid, PAG, is incorporated. The percentage of the non-ester type fluids is varied and the results are compared with those of the TMPTO base fluid (synthetic ester) and our vegetable oil base fluid (natural ester).
The role of PAO as an oxidative stability improver was confirmed, and we obtained hydraulic fluid formulations showing comparable or higher oxidative stability performance than Bio-Ultimax™ 1000. PAG is also found to improve the oxidative stability, but not as much as PAO.
Part III: Optimization of Oxidative and Hydraulic Stability (Parameters Include: Vegetable Oil (VO), PAO, and PAG.
While the effect of PAG on improving the oxidative stability of ester base fluids is smaller than that of PAO, PAG beneficially can improve hydrolytic stability. This aspect is especially important, since ester base fluids are known to degrade via hydrolysis to give acid in the presence of water. As an example but a non-limiting blend, a vegetable oil/PAG blend is available commercially as Dow Symbio™ (Dow Chemical Co.). Accordingly, the role of PAG was confirmed as a hydrolytic stability improver and a fluid formulation with a high viscosity index, a low pour point, and a good hydrolytic and high oxidative stability is obtained.
Table 1.1 shown below summarizes the role of each base fluid component when added to TMPTO as determined from the experiments performed in parts I, II, and III. The comparison of the antioxidants shows that NA-L results in the best oxidative stability improvement for the ester base fluids (TMPTO or VO). The concentration of the pour point depressant (Viscoplex 10-171) and the antifoam additive (Viscoplex 14-520) are fixed throughout the study. It is seen that each of these components contribute to the overall property of the fluid. It is to be noted that while both PAG and PAO contribute to oxidative stability, the oxidative stability improvement due to PAG is not as significant as that due to PAO.
Table 1.2 shown below compares selected properties of various fluid blends and compares them with those of a commercially available fluid, i.e., Bio-Ultimax™ 1000.
Additional formulations of environmentally acceptable hydraulic fluids can be prepared using various grades of esters derived from animal-based oils or plant-based oils. Also various grades of PAO, PAG, antioxidants and other additives can be used. Example additives include N,N′ di sec butyl p-phenylenediamine, Vanlube NA, Vanlube 81, Vanlube 961, Vanlube SS, NA Lube AO-142, NA Lube AO-242, Naugalube 640, Naugalube 438 L, Naugalube TMQ, BHA, TBHQ, BHT, Ethanox 470, Ethanox 4716, NA Lube AO-210, Lauryl Gallate, and Propyl Gallate. Different viscosity grades of environmentally acceptable hydraulic oil blends also can be developed with the aid of commercially available viscosity improver additives and/or by varying the concentration of individual components in the final blend. Moreover, the properties shown above are non-limiting examples of the beneficial properties of the hydraulic fluids disclosed herein. For example, the pour point temperature can vary down to −55° C. and up to about −30° C. for particular compositions.
Example but desired recipes within the practice of the invention is set forth as shown in Table 1.3 below:
Accordingly, in a novel but non-limiting fashion, Table 1.2 clearly demonstrates beneficial unlimiting example compositions (e.g., example nomenclature ASL 1) that demonstrate the workings of the inventions disclosed herein. In particular, Part 1 of the study yielded ASL 1, which exhibits a high viscosity index, a low pour point, and a high oxidative stability. Part II of the study yielded ASL 2a, ASL 2b, and ASL 3. ASL 2a shows a lower pour point than ASL 2b, but a slightly lower RPVOT value. The difference in RPVOT, however, is only about 5%. ASL 3 shows better combined properties than ASL 1, ASL 2a, and ASL 2b. Part III of the study yielded ASL 4 and ASL 5, which pass the hydrolytic stability test with a copper appearance of 1b. ASL 4 shows properties that are on par with those of ASL 2a, ASL 2b, and ASL 3. ASL 5 shows a significantly higher oxidative stability than all other ASL formulations, a high viscosity index, and a low pour point. It is also to be appreciated that although particular percentages are shown for the example compositions in Table 1.3, such percentages can vary in providing for the non-limiting example compositions, as disclosed herein. As an illustration, trimethylolpropane trioleate (TMPTO), ASL1 shown by example only in Table 1.3, can be as high as up to about 85% by weight or down to about 40% by weight in the example compositions disclosed herein when desired. Even more particular, from 10% up to about 40% by weight of polyalphaolefin (PAO), and up to about 20% by weight of polyalkylene glycol (PAG) can also be beneficial configurations. Moreover, a vegetable oil contribution in a range of up to about 70% by weight can be mixed in the hydraulic fluid.
Comparing the performance properties of fluids ASL 1 through ASL 5 with those of Bio-Ultimax™: 1) The viscosity indices are comparable with one another, 2) The pour points are comparable or better than that of BioUltimax™. When measured by the same vendor (Petrolube), the RPVOT numbers are at least comparable or significantly better (up to 41% for ASL 5) to that of Bio-Ultimax™.
Effect of PAO and PAG on TMPTO Fluid
1. Optimizing the Synergistic Effect of PAO and PAG
PAO and PAG play different roles in enhancing the properties of TMPTO fluid. PAO significantly increases the oxidative stability and maintains a low pour point, but it has an adverse effect on hydrolytic stability. PAG improves the hydrolytic stability and slightly increases the oxidative stability, but undesirably increases the pour point, as discussed in detail below. It is also to be noted that when used together, both PAO and PAG can compensate for each other's inadequate properties.
A composition to optimize PAO and PAG contribution to the property of the TMPTO fluid, asymmetric PAO/PAG ratios was assessed, wherein the amount of PAG is fixed. As an example TMPTO fluid formulation, such a fluid formulation contains antioxidant (NA-Lube BL-1208), 2 wt %, pour point depressant (Viscoplex 10-171), 1 wt %, and antifoam additive (Viscoplex 14-520), 0.1 wt %.
Overall, PAO/PAG ratios between 0.2 and 5 are expected to demonstrate desired properties with the 30/15 of PAO/PAG composition showing the best combined properties with a relatively low pour point and highest oxidative stability. The viscosity index is lowest, but differs only by 8.8% from the TMPTO fluid. The RPVOT value of the fluid containing 30/15 of PAO/PAG is significantly higher than the TMPTO fluid by 71.7%.
2. Effect of PAO and PAG on Viscosity Index, Pour Point, Oxidative Stability, and Hydrolytic Stability of TMPTO Fluid
Effect of PAO and PAG on Viscosity Index, Pour Point, and Oxidative Stability
The TMPTO base fluid is known to exhibit higher viscosity index than PAO and PAG. Reduction in the viscosity index due to addition of PAO and PAG is therefore expected. However,
Effect of PAO and PAG on Hydrolytic Stability of TMPTO Fluid
While PAG has adverse effects on pour point and viscosity index, the main function of PAG is to improve the hydrolytic stability of ester base fluids (i.e., TMPTO fluid). In order to determine the effect of PAO and PAG on the hydrolytic stability of TMPTO fluid, the different fluid formulations were tested according to the beverage bottle method (ASTM D2619). The post-test change in the acidity, weight of copper, acid number, amount of insoluble, viscosity (%) copper, and copper appearance are noted. The copper appearance are the same for all fluid compositions, 1b (as per ASTM D 130) and the % change in viscosity are all less than 1.0%.
Synergistic Effect of PAO and PAG
It is to be appreciated that the fluids belonging to such different categories are characterized by certain properties. For example, fluids in the HEES and HETG categories are more biodegradable than fluids in the HEPR and HEPG categories. However, fluids in the HEPG category are characterized by a higher hydrolytic stability, and fluids in the HEPR category are characterized by a higher oxidative stability. The novel class of high-performance environmentally acceptable hydraulic fluids disclosed herein combines components from two or more of these categories in such a manner that the overall properties of the fluid such as a high viscosity index, low pour point, good hydrolytic stability, and good oxidative stability are derived from a synergistic interaction between the individual components. As examples of such fluids, the embodiments herein include evaluated properties of fluid blends containing the following major components: Trimethylolpropane trioleate (TMPTO) derived from canola oil (HEES). Vegetable oil (VO), (canola oil), obtained from Cargill, Inc. (HETG). Polyalphaolefin (PAO), (SPECTRASYN) obtained from Exxon Mobil Corp. (HEPR) Polyalkylene glycol (PAG), (UCON-OSP) obtained from Dow Chemical Co. (HEPG). In addition, various additives (e.g., NA-L, V 10-171, V 14-520) are used in desired quantities to further enhance or modify certain properties.
The invention is directed to a hydraulic fluid formulation and method for its production. The hydraulic fluids herein use natural or synthetic esters derived from vegetable or animal oils, or mixtures of the same, which are preferably highly unsaturated. Natural vegetable oils are glyceride esters, i.e., tri-, di- or monoesters of glycerol and straight chain saturated and unsaturated fatty acids. Exemplary vegetable oils which may be suitable for use in the formulation include rapeseed, rape, soybean, castor, olive, coconut; palm, tall, maize, walnut, flaxseed, and cotton, sunflower, safflower, sesame, almond, and canola oil. Desired base oils used in the invention include mixtures of oils obtained from chemical products producers such as Cargill. The vegetable oils and/or animal oils used in the practice of this invention will be predominantly monosaturated (i.e., they have only one carbon-carbon double bond in the fatty acid moiety); however, in some formulations, low levels of polyunsaturated vegetable oil may be employed.
Various additives can be added to the final mixture to comply with state and federal laws or to adjust the properties of the biohydraulic fluid include antioxidants, antiwear agents (e.g., zinc dithiophosphates, etc.), corrosion inhibitors, pour point depressants, and antifoam agents.
Antioxidants inhibit the oxidation of hydraulic oils by scavenging free radicals. Vegetable and animal oil based hydraulic fluids often contain substantial amounts of polyunsaturated oils to lower the pour point, and these oils are highly reactive with free radicals. When free radical react with polyunsaturated oils, cross linking or polymerization can occur, which increases viscosity. In extreme cases a rubbery residue is formed. Thus, because antioxidant additives have synergistic effects when mixed together, the embodiments herein can provide synergistic improvement.
Moreover, pour point additives can be beneficial utilized with the hydraulic liquids disclosed herein. Such polymer additives co-crystallize with the saturated oils, thereby dispersing them as particles small enough to avoid gelling. The co-crystallization process is sensitive to the chemical structures of the fluid and additive.
It is to be understood that features described with regard to the various embodiments herein may be mixed and matched in any combination without departing from the spirit and scope of the invention. Although different selected embodiments have been illustrated and described in detail, it is to be appreciated that they are exemplary, and that a variety of substitutions and alterations are possible without departing from the spirit and scope of the present invention.
This application claims priority to the U.S. Provisional Application No. 62/299,159 filed Feb. 24, 2016, the complete content of which are herein incorporated by reference.
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