Patent Application
20100179080
1. Field of the Invention
The present invention relates to the removal of contaminants from industrial used lubricating oils and used motor oils by treatment of the used oil with clay at high temperatures, but at lower temperatures than that of “cracking”, and later removing the contaminated clay by filtration and centrifugation.
2. Description of the Prior Art
The recycling of used lubricating oils coming from industrial processes, car motors, transmissions and other sources is an important process, because it avoids contamination by lubricating oils, and allows the recovery of lubricating base oils, which are a scarce product. The oils form a mono-molecular layer on the surface of the water, which it means that a small quantity of oil can contaminate a great volume of water.
The recovered lubricating oil bases have all the properties of the first refining, and they can be used to produce new oils. The recycling process can be done several times.
The contaminants in industrial oils, besides water, are usually iron, chromium, cadmium, nickel, copper, calcium, barium, zinc, aluminum, and phosphorus. Motor oils also have soot, contaminants due to degraded additives, and other contaminants coming from the gasoline, and for that reason they are more difficult to be re-refined.
Several techniques have been used to re-refine used oils, mainly by distillation and treatment with chemical reactives to precipitate the coagulants (principally sulfuric acid and other solvents, which are also contaminants that produce environmental problems).
The treatments with clays at very high temperature have the problem that the later separation becomes difficult because the pores of the felt (cloths, cellulose, synthetic materials or others) of the filter press become plugged, mainly due to soot, colloidal coal, and organic compounds.
The distillation systems require large investments, and the re-refining cost is usually expensive. This is also the case of the other used treatments with sulfuric acid, sulfates, phosphates and other chemicals, which are difficult to extract later on. For example in the separation of sulfuric acid with clays there is the inconvenience of the great production of sludge, besides the large volumes of corrosive acids and the great lost of used original oils. It is necessary to take into account that the pre-heating of the mixtures must not be higher than 250° C. to 300° C., if one wants to avoid the “cracking” of the lubricating oils. (Excessive heat causes hydrocarbon chains in the oil to “crack” and break into smaller chains, which are not suitable for lubricating oil, though they may be suitable for fuel oil.) Other more economic systems use inorganic catalysts mixed with clays in continuous feeding systems.
The present invention has important advantages with respect to these processes.
U.S. Pat. No. 3,625,881, issued on Dec. 7, 1971, to John M. Chambers and Herbert A. Hadley, discloses a process for reclaiming lubricating oils, including flash vaporization to remove water, mixing the used oil with a hydrocarbon oil, using a centrifuge to remove solid precipate, and two fractional distillations. The instant invention is distinguishable, in that in it the used oil is mixed with clay rather than another oil.
U.S. Pat. No. 3,639,229, issued on Feb. 1, 1972, to Darrell W. Brownawell and Remi H. Renard, discloses a process of refining used lubricating oils, in which the used oil is mixed with aliphatic alcohol. There may be a final clay treating step (see claim 9). The instant invention is distinguishable, in that it does not require the use of alcohol.
U.S. Pat. No. 3,819,508, issued on Jun. 25, 1974, to Morton Fainman and Charles Stouse McCauley, discloses a method of purifying lubricating oils, in which the oil is mixed with a predominantly hydrocarbon liquid diluent, then with an alcohol and water mixture, and centrifuging is used to remove sludge and metal compounds. The instant invention is distinguishable, in that in it the used oil is mixed with clay.
U.S. Pat. No. 3,919,076, issued on Nov. 11, 1975, to Louis E. Cutler, discloses a process for re-refining used automotive lubricating oil, including treatment with a saturated hydrocarbon solution, followed by vacuum distillation, followed by catalytic hydrogenation, which are not required in the instant invention.
U.S. Pat. No. 3,930,988, issued on Jan. 6, 1976, to Marvin M. Johnson, discloses a process for reclaiming used motor oil using an aqueous solution of ammonium sulfate or bisulfate, that is not required in the instant invention.
U.S. Pat. No. 4,033,859, issued on Jul. 5, 1977, to Donald Douglas Davidson and Bjorn I. Engesvik, discloses thermal treatment of used petroleum oils under pressure at temperatures to above about 400 to 800 degrees Fahrenheit (or 190 to 412 degrees Celsius). Although there is a small overlap in the temperature range, the instant invention does not require pressure during its heating step.
U.S. Pat. No. 4,383,915, issued on May 17, 1983, to Conrad B. Johnson, discloses a clay contacting process for removing contaminants from waste lubricating oil, in which the oil is contacted with decolorizing clay at a temperature in the range of 650 to 725 degrees Fahrenheit (or 329 to 370 degrees Celsius). The instant invention is distinguishable, in that it uses a lower temperature range, and a different type of clay (see column 3, lines 21 to 31).
U.S. Pat. No. 4,502,948, issued on Mar. 5, 1985, to Donald C. Tabler, discloses a procedure for treating demetallized used oil using an acid such as sulfuric acid. In the instant invention, no sulfuric or other acid is used.
U.S. Pat. No. 5,112,479, issued on May 12, 1992, to Vichai Srimongkolkul, discloses an oil purification unit with a cyclonic (centrifuge) reservoir section and a filtration section. The second embodiment of the instant invention is distinguishable, in that in it the oil is first mixed with clay before being centrifuged.
U.S. Pat. No. 5,759,385, issued on Jun. 2, 1998, to Marcel Aussillous et al., discloses a process and plant for purifying spent oil, including vacuum distillation, which is not required by the instant invention.
U.S. Pat. No. 5,968,370, issued on Oct. 19, 1999, to Mark E. Trim, discloses a process for removing hydrocarbons bound to solid particles in contaminated sludge, such as from oil refineries, supertankers, and drill cuttings. A treatment fluid is applied, comprising water, a silicate, a nonionic surfactant, an anionic surfactant, a phosphate builder and a caustic compound. Later, the treatment fluid is removed, to be used again. In the instant invention, the products to be treated are different, namely lubricating oils contaminated with small amounts of metals and other products, as a result of their use as lubricants. In the instant invention, only clay is used; no fluid treatment is used, and no treatment fluid is recovered, but only the lubricating oils themselves.
U.S. Patent Application Publication No. 2006/0000787, published on Jan. 5, 2006, to Louis Galasso III et al., discloses purification of impure oil by centrifugation, without first mixing the oil with clay as in the instant invention.
U.S. Patent Application Publication No. 2002/0166794, published on Nov. 14, 2002, inventors Alexander P. Bronhstein, Moshe Gewertz and Vladimir M. Rozhansky, discloses a process for producing standard and used fuels from lubricating oils and several other waste products. It produces a mixture of water and other products to be added to petroleum-based waste. Later, dewatered matter is skimmed, and what remains is processed by thermocatalytic cracking. The instant invention produces a lubricating oil basis (not fuel) from used lubricating oils. In the instant invention, no water as a carrier of products is used. Instead, most of the water is taken out by methods such as decanting and heating, before treatment with clay in the reactor. In the instant invention, no skimming of a watered mixture is performed, nor is thermocatalytic cracking used, thus it has a final product different from that of Bronhstein et al. Instead of fuel products, it obtains a lubricating oil basis, which can be used to obtain new lubricating oil by adding appropriate additives.
French Patent No. 2 690 924, published on Nov. 12, 1993, to Virgulino Antonio Digilo, discloses a method of re-cycling of used or contaminated lubricating oils, including adding clay to the oil in a reactor, and also adding water containing a dissolved sulphur based catalyst and filtration aid. The instant invention is distinguishable, in that it does not require adding water containing a catalyst.
Japanese Patent No. 2-4898, published on Jan. 9, 1990, to Kyoho Seisakusho and Toyota Jidosha, discloses a process of reclaiming lubricating waste oil, including a thermal reaction treatment in which an aqueous solution of caustic alkali is added to the oil, a centrifugation process after diatomaceous earth and activated clay are added to the oil, and a filtration process. The instant invention is distinguishable, in that it does not require that the addition of a solution of caustic alkali to the oil.
Clay Amended Soilless Substrates: Increasing Water and Nutrient Efficiency in Containerized Crop Production by James Stetter Owen, Jr. (2006) (cited by the Examiner in the parent application) does not disclose the use of clay for cleaning used lubricating oils, as in the instant invention.
None of the above inventions and patents, taken either singly or in combination, is seen to describe the instant invention as claimed.
We can summarize the prior art process for recovering used lubricating oil as having three parts or stages:
First there is the adaptation or preparation process, which consists in the separation of solids and water, usually by filtration and flash distillation, respectively, or other process.
In a second stage there is a treatment to eliminate the contaminant products, such as metals, soot, organic refuse, additives, oligogenic compounds, etc. This elimination process is done: i) by chemical methods, such as adding sulfuric acid, calcium sulfate, hydroxides, phosphoric acid, etc.; ii) by physical-chemical methods as vacuum distillation; or iii) by other methods.
The third stage is the process of whitening and taking out the smell. Here there are also use different methods, but the most common is the use of clay or activated carbon.
The main difference of our method compared with the prior art, is that the second and third stages are integrated in a unique process using only clays, and there is not any chemical process or vacuum distillation. In this way there is only two process or stages: the first one and a second one using only clays. The separation of the clays from the recovered lubricating oil is performed by filtering as in the prior art. Filtering is adequate for industrial used lubricating oil. However for used lubricating oil with contaminant soot, as in the case of used oil coming from the cars and other vehicles, the soot usually plugs the pores of the filters, and it is necessary to use an additional centrifugation process in order to avoid this problem.
In our search for a process for the recovery of used lubricating oils that was economic and did not require high investments, a fact to be considered appeared immediately. It was necessary to separate the treatment of industrial oils, with mainly watery and metallic contaminants, from those with organic contaminants and soot, such as those coming from the internal combustion motors. For this reason, the present invention has two preferred embodiments: the first for recovery of used industrial lubricating oils, and the second for recovery of oils coming from internal combustion motors (including used lubricants oils of explosion and diesel motors, automatic transmissions, and in general, every kind of oils coming from filling and service stations for cars).
The first preferred embodiment of the present invention is suitable for used industrial oils, and it includes the steps of: (a) Mixing the used lubricating oils with clay in a reactor, and heating the mixture to temperatures from 80° C. to 200° C., in a batch type system. The temperatures are low enough that the cracking of the lubricating oils in the mixture does not take place or at least is minimized. (b) Keeping the mixture of clay and used lubricating oil for a certain residence time in the reactor. (c) Filtration by a system of filter presses, wherein the clay sticks to the filtering cloths, and the filtered oil goes through free of impurities. This system is shown in
An important observation in this process is that, if this is performed in a continuous way, with feeding of used oil and preheated clay through the bottom of the reactor and gathering of recovered oil from the upper side, then the oil still contains a large amount of contaminants, and is not suitable for future use. In continuous systems in the prior art, they use catalysts or chemical reactives to obtain suitable results, which complicate and increase the cost of the process.
On the other hand, it is important also to point out that the amount of water contained in some oils is high, and in these cases before adding the clay it is convenient to eliminate the water with a “flash” distillation process from 80° C. to 100° C., prior to treatment with the clay.
The second preferred embodiment of the invention is designed for the removal of metallic contaminants, soot and organic contaminants from the used lubricating oils coming from automotive market. It includes the steps of: (a) Mixing the used lubricating oils with clay in a reactor, and heating the mixture to temperatures from 80° C. to 200° C. Again, the temperatures are low enough that the cracking of the lubricating oils in the mixture does not take place or at least is minimized. (b) Keeping the mixture of clay and used lubricating oil is for a certain residence time in the reactor. (c) Using a centrifuge to separate a large part of the oils to be recovered from the clay containing organic and metallic contaminants. (c) Filtration of the oils coming from the centrifuge, by passing them through a filter press as described above for the industrial used oils. The second preferred embodiment is illustrated in
For both embodiments, the heating system which was found most economic for the process of the present invention, consists of a boiler heated with gas and a transference fluid (e.g., hydraulic oil), which carries the heat from the boiler to a heating jacket in the reactor containing the used oil and clay. The heating is done by conduction. The used lubricating oils are loaded in the reactor with movable and diaphragm electric pumps, or by gravity. Before the used oils are placed into the reactor, they may be passed through a gross filter (for instance, 200 mesh) to remove large particles. After passing them through the gross filter, there can also be a flash distillation from 80° C. to 120° C. to remove excessive quantities of water. Next, the right amount of clay is added, and after some residence time determined by the type of oil and laboratory analysis, the mixture in the reactor is discharged. During the residence time the clay reacts with the contaminants, creating chemical bonds between them. For this, it is necessary to have good control of the temperature (in order to avoid cracking the oils) and of the amount of clay and the residence time in the reactor. All these conditions are previously determined by the laboratory analysis. After that the filtering process is performed.
Accordingly, it is a principal object of the invention to provide an improved process for recycling industrial lubricating oils.
It is another object of the invention to provide an improved process for recycling automotive lubricating oils.
It is a further object of the invention to reduce pollution to the environment from discarded used lubricating oils.
Still another object of the invention is to reduce the depletion of nonrenewable resources used in making lubricating oils.
It is an object of the invention to provide improved elements and arrangements thereof in an apparatus for the purposes described which is inexpensive, dependable and fully effective in accomplishing its intended purposes.
These and other objects of the present invention will become readily apparent upon further review of the following specification and drawings.
Similar reference characters denote corresponding features consistently throughout the attached drawings.
The present invention an improved process for recycling used lubricating oils, having two preferred embodiments.
In
The system described in
Once the recovered bases are obtained, the corresponding analysis has to be performed in order to determine that the amount of contaminants is below the wanted level, as well as to determine the characteristics of the recovered base lubricating oils, such as their viscosity, total basic number (TBN), flash point, etc.
The following examples are given for illustration:
A treatment of 1,800 liters of used oil of industrial origin was performed, to show the effectiveness of the present invention.
1,800 liters of lubricating oils for industrial gears coming from Carbonorca Enterprise C.A.
1. Color: Opaque brown, non-translucent.
2. Presence of free water and/or in emulsion: (10-50% v/v).
3. Presence of solid suspended particles (>1000 mg/Kg, 0-30% v/v)
4. pH: >7
5. Aromatics: <1 mg/Kg.
Activated clays, hybrid type of hormite and smectite, with acid characteristic, with pH (5% solids diluted in H2O) equal to 2.5-3.0, density of 336-416 g/l, and particle size, by sieve analysis (Tyler Standard), particles with sizes less than 150 μm: 100%, and particles with sizes less than 45 μm: of 73-76%.
Once the removal of contaminants is finished the procedure is:
Table 1 shows the analysis of properties of industrial used oil:
Table 2 presents the properties of the recovered lubricating base oils obtained through this process:
A laboratory experiment was performed, with a sample of used motor oil. The following is a description of the details of the experiment:
800 ml of used oil, coming from a Fiat “Ritmo” car, 1987 model, 1600 ml motor, with 45 days of running, and a total of 55,000 km passed over. The original oil was PDV (Petroleum of Venezuela) brand, 20W-50W multigrade (Experiment No. 1). There was also used 800 ml of a mixture of used oils coming from an workshop for oil change, located in Maracay, Aragua State-Venezuela (Experiment No. 2).
Activated clays, hybrid type of hormite and smectite, with acid characteristic.
A sample of 800 grams of used motor oil was put in a glass beaker, with a magnetic stirrer inside, and was placed on an electric heating plate with continuous magnetic stirring.
The heating of the sample was between 100-120° C. during 30 minutes, in order to eliminate the water, until the crepitating or crackling test was negative. The amount of clay was prepared in approximately 20% m/m of used oil. (By “m/m” is meant the mass of the clay divided by mass of the used oil.) The oil was added with stirring of 800 to 1200 rpm, during one hour, and reaching temperatures of 180° C.
The mixture oil-clay was passed through a filtration process at vacuum with a Buchnner funnel, using two cycles of filtering: first with 35 mesh, and second with Watman No. 5 cellulose. In this way, the contaminants retained with the clay are separated from the filtered oil.
Tables 3 and 4 show the results obtained, giving the characteristics of the used oils in the experiments, and the recovered lubricating base oils after applying the experimental procedure.
The laboratory tests have shown that with the process described, a removal takes place of metallic and organic contaminants of used industrial lubricating oils and those oils coming from internal combustion motors. The level of removal is such that the recovered lubricating oil bases can be used again with confidence in motor oils, automatic transmissions and other required uses. Our system is simple and economic compared to other systems, and the quality of the recovered oils is similar. Note that in our system, only clay (without the use of other substances) is used to remove contaminants from the oil.
It is clear that the process and the product of the present invention will find wide use in the recovery and recycling of used industrial oils as well as those oils coming as wastes from internal combustion motors and transmissions. The foregoing describes only some embodiments of the present invention and obvious modifications to those skilled in the art can be made thereto without departing from the scope of the invention. It is to be understood that the present invention is not limited to the embodiments described above, but encompasses any and all embodiments within the scope of the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 06-02147 | Sep 2006 | VE | national |
This application is a Continuation-In-Part of U.S. Regular Utility patent application Ser. No. 11/856,813, filed Sep. 18, 2007, which claimed priority from and included a certified copy and translation of Venezuelan patent application 06-02147, filed in Venezuela on Sep. 18, 2006, which are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 11856813 | Sep 2007 | US |
| Child | 12731366 | US |
