MXPA00003552A - Apparatus and method for reclaiming useful oil products from waste oil including hydrogen injection - Google Patents

Abstract

An apparatus and method for reclaiming a useful oil product, from waste oil provides an evaporation chamber in which waste oil is heated and vaporized, preferably at a temperature which causes some cracking of the oil. Hydrogen is injected into the vaporized oil, so to cause saturation of at least some of the olefins in the vaporized oil. The vaporized oil is then condensed and recovered as a useful oil product. The apparatus operates at substantially atmospheric pressure, or a pressure only slightly above atmospheric pressure. Hydrogenation of the vaporized oil stabilizes the recovered oil, and prevents formation of tars and other heavier hydrocarbons, which can cause difficulties in use of the recovered oil.

Description

APPARATUS AND METHOD FOR RECOVERING USEFUL PETROLEUM PRODUCTS FROM WASTE OIL INCLUDING HYDROGEN INJECTION REFERENCE TO RELATED APPLICATION This application is a Continuation in Part of my previous application No. d © Series 08 / 829,526 filed on March 28, 997, which is an application for Envelope Continuation of the No file, series 08 / 199,201 , filed January 21, 1994, which TS a Continuation in Part of Serial No. 07 / 712,775, filed on June 10, 1991, which is a Continuation in Part of No. d? Series 246,834 filed September 20, 1988. In addition, the content of all of these prior applications is hereby incorporated by reference.

FIELD OF THE INVENTION This invention relates generally to an apparatus and method for recovering waste oil, and more particularly relates to the recovery of waste oil from a slurry, i.e. a highly viscous material containing an amount relatively large of pollutants and particulate solids.

In this specification, the term "waste oil" encompasses any suitable oil, for example, mineral oils that have been used as motor oil, or some other lubricating oil, or as hydraulic oil or in some other application. It is expected that these have been derived from mineral oil, but could be, for example, animal or vegetable oil, such as fish oil or oil discarded by restaurants, etc. The mineral oil could be simple crude oil. In use, these lubricating oils are usually charged periodically. Drained and recovered waste oil typically contains substantial amounts of contaminants, which may include dirt, metal particles (including heavy metals, such as molybdenum, chromium, cadmium, vanadium, copper, etc.), oxides and salts, gasoline and gasoline additives (such as tetraethyl lead) as well as detergents and working additives. They can also be contaminated with water, large quantities of this waste oil are produced in industrialized countries, and my previous inventions were directed to methods and apparatus for recovering waste oil, so that it is appropriate for various uses. Contaminants in waste oil usually make it unsuitable for most uses. The term "waste oil" also includes oil-based sludge such as that produced in the apparatus of my prior invention described in application No, of Series 246,834. My previous inventions provided an apparatus in which the lighter hydrocarbons from the waste oil were volatilized and then condensed. Likewise, while the exact mechanism within the apparatus was not fully understood, it is believed that some cracking or splitting of the hydrocarbons from longer chain molecules elongates to shorter occurs, in fact, it is still possible that the contaminants present acted as a catalyst It was discovered that starting with waste lubricant oil, contaminated, approximately 905 of this could become a lighter oil, suitable for use as a diesel fuel. My prior inventions are described in detail in U.S. Patent 5,271,808, which describes a basic refiner. { secondary treater), and 5,286,349, which describes a more advanced process and apparatus identified herein as a preprocessor (primary treater), The contents of these two US patents. they are incorporated herein by reference. The basic process of the refiner provided distillation with some cracking, carried out at substantially atmospheric pressure. This allowed the waste oil to recover as a diesel-grade fuel oil, free of solid impurities and the like. This process left solids and other impurities concentrated like a mud, which presented waste problems. The latest invention, the preprocessor, provided a process in which, when the solids and other impurities had accumulated to a certain level, the additional supply of waste oil is interrupted, and the temperature rises to expel all remaining organic and volatile components. This left a fragile, cake-like material that has been classified as a "non-toxic filtrate," which means that it can be disposed of in almost all jurisdictions. However, a problem with diesel-grade oil or fuel recovered from any of my previous inventions is that it tended to be unstable. Practically, it is believed that the oil contained a number of free radicals and / or olefins, consequently, over a period of time, these free radicals or olefins would combine, forming oil oils and tars. Since the intention was to recover oil as a diesel-grade fuel, this presented considerable problems. Such tar and heavy components tended to be deposited in fuel injection systems and the like, clogging systems and preventing proper operation. Accordingly, it is desirable to provide an improvement or modification to my existing processes, which results in a recovered oil product that is stable, and that can be stored for a significant period of time, typically of the order of 30 days, without any significant degradation or degradation. series or changes in characteristics, more particularly, without deposition of any tars or heavy hydrocarbons.

SUMMARY OF THE PRESENT INVENTION In accordance with the present invention, there is provided a method for recovering a useful petroleum product from a waste oil, the method comprising the steps of: (1) heating the waste oil to vaporize oil from the waste oil; same; (2) inject hydrogen gas into the steamed oil, to cause saturation of at least some olefins present in the steamed oil; and (c) recover the waste oil as a useful oil product. Preferably, the waste oil is vaporized at substantially atmospheric pressure, and this then eliminates the requirement to provide complex or expensive pressure vessels or the like. In this way, steps (1) and (2) could be carried out at a pressure equivalent to up to 76.20 centimeters of water - above atmospheric pressure. More preferably, the temperature sufficient to cause at least partial cracking of the oil. Advantageously, the recovered oil is condensed and recovered as a liquid. Advantageously, the waste oil is heated in an evaporation chamber and the oil is continually supplied to the evaporation chamber, and the level of waste oil in the evaporation chamber is monitored, to keep the level within desired limits. In a preferred embodiment, the vaporized oil is passed through a connecting duct from the evaporation chamber to a condensation chamber and, for step (2), hydrogen is injected into the petroleum vapor in at least one of the chamber of evaporation and the connection. Advantageously, the hydrogen passes through a duct that extends through the liquid waste oil into the evaporation chamber, to preheat the hydrogen to a temperature inside the evaporation chamber. In accordance with my previous preprocessor invention, the method may include an additional step (5): after a period of time, finish the supply of waste oil to the evaporation chamber and continue heating the vaporization chamber and the oil of waste therefrom in a baking mode to a substantially higher temperature, to vaporize substantially all of the residual waste oil in the evaporation chamber, to leave a solid residue inside the evaporation chamber. In accordance with another aspect of the present invention, and provides an apparatus for recovering a useful petroleum product from a waste oil, the apparatus comprising: an evaporation chamber, including an inlet for the waste oil, and an outlet for vaporized oil, as a useful oil product; a heating element to heat the camera d? evaporation to vaporize oil from waste oil; an element for injecting hydrogen into the waste oil vapor; and an element for recovering vaporized oil. Preferably, the apparatus includes a condensing element and a connection duct connecting the outlet of the evaporation chamber to the condensing element. The element for injecting hydrogen advantageously comprises a duct that opens towards at least one of an upper portion of the evaporation chamber and the connection duct. A portion of the duct can extend through a lower portion of the evaporation chamber, whereby the hydrogen in the duct is heated by the waste oil to the temperature inside the evaporation chamber. In accordance with my previous inventions, the evaporation chamber may include an inlet for waste oil, and the apparatus then includes a pump element for supplying waste oil to the evaporation chamber, and a level control element for monitoring the level of waste oil inside the evaporation chamber, and a level control element that is connected to the pump element and which actuate the pump element to maintain the level of waste oil within the desired limits.

For operation as a preprocessor, the heating element is preferably connected to element d? level control and, in a normal mode of operation, ST incapacitated if the oil level goes outside the desired limits, and the apparatus also includes an element to disable the level control element and terminate the oil supply of waste, to allow the continuous operation of the heating element in a baking mode, in which the evaporation chamber ST heats at an elevated temperature to vaporize the remaining hydrocarbons.

BRIEF DESCRIPTION OF THE FIGURES OF THE DRAWING For a better understanding of the present invention, and to show more clearly how it can be carried out, reference will now be made, by way of example, to the accompanying drawings showing a preferred embodiment of the apparatus. , and in which: Figure la is a side view of a primary preprocessor or treater in accordance with the present invention; Figure Ib is a side view of a secondary refiner or treater in accordance with the present invention; Figure 2a is a side view, on an amplified scale, of a heat exchanger of the apparatus of Figure 1; Figure 2b is a perspective view of a layer of heat exchange ducts; Figure 3 is a front view of the apparatus; Figure 4 is a view of the right side of the apparatus; and Figure 5 is a view of the left side of the apparatus.

DESCRIPTION OF THE PREFERRED MODALITY The Figure shows an apparatus according to the present invention, indicated generally by reference 1. The apparatus 1 includes two basic elements, namely an evaporation unit 2 and a condensing unit or an exchanger 4 thermal, which are described in turn below. Since the details of this basic apparatus are not part of the present invention, the structure of the apparatus is only delineated here and full details are provided in my U.S. Pat. previous 5,286,349. The invention here ST describes mainly in relation to my processor or primary processor. For purposes of completeness, Figure Ib shows a refiner or secondary processor, to show the application d? the present invention to said device, and the applicable reference numbers are indicated in Figure Ib. Additionally, Figures la and Ib are based on the current versions of the apparatus, while the other Figures are based on the U.S. Patent. 5,286,349. As ST shows in Figure 3, evaporation unit 2 is d? generally rectangular section and has a depth slightly less than its length or width. The evaporation unit 2 has two members 10 d? longitudinal supports to support the unit, and facilitate the transport of the unit 2, the unit 2 has a housing 11 that includes external side walls 12, end walls 14, 16, a bottom wall 18 and a top wall 20. Within unit 2, there is a waste oil distillation or evaporation chamber 22, which is spaced inward from all the outer walls of the unit 2, the chamber 22 is supported on a plurality of support cylinders (not shown) ), d? way to allow the free movement of the hot gases around the waste oil chamber 22 and inside the outer walls 12-20. Each support cylinder is provided with a metal plate at either end, and the chamber 22 is freely mounted on the upper plates, to allow thermal expansion and contraction. The waste oil chamber 22 has a flat bottom 24. The camera is made from 304L stainless steel. Extending upwardly therefrom are the side walls 26 which connect to a top wall 28. These walls 24, 26, 28 ST extend upwards to the chamber end walls 29. On an end wall 29 there is a chamber access door 34, for an access opening extending through the respective end wall 14 to the chamber 22, to allow the solid, cake-like material left in the chamber 22 to be removed. Appropriate access doors can be provided for the combustion chamber. The chamber 22 also has, in a known manner, longitudinal and transverse reinforcing bars or permanence, to withstand the internal pressure of a complete load of waste oil. In the upper wall 20, there is a discharge opening 36 which is connected to an appropriate discharge stack 37. For the camera 22 d? evaporation, an outlet 38 is connected through a connecting duct 40. The Figure shows a connection duct 40 illustrating a different inverted U configuration, which continues through an elbow 41 to the condensation unit 4. As indicated at 39, ventilation is provided which is connected to a pressure relief valve, in case any excessive pressure condition arises. The system normally operates at a small positive pressure of about 0.04 kg / cm2, and the release valve d? Pressure is adjusted to open at a pressure d? 0.18 kg / cm2, As shown in Figure 1, for the refiner, and in other Figures for the processor, the duct 40 d? The connection may also comprise a generally straight vertical portion and then an inclined portion running downward toward the capacitor. In any case, the configuration must be such as to avoid dead spots, ie, in order to ensure that any oil that condenses out of the duct 40 runs back into the chamber d? evaporation for further boiling, and flow to the condensation unit 4 for collection. As indicated at 43, a reactive bed may be provided in a downward portion of the connecting duct 40. This reactive bed 43 has been found to be non-essential, and the hydrogenation of the oil occurs without it. Reactive bed 43 may comprise any suitable material that promotes the reaction of hydrogen with petroleum vapor. Could you understand, for example, nickel-cadmium, anywhere d? the evaporation unit 2, and mounted on each side wall 12, there is a blower 42 for a respective burner inside the combustion chamber 32, associated with each blower 42 is a fuel supply (not shown) for an appropriate fuel . This could be fuel derived from the method of the present invention, or the method of my previous application, or alternatively some completely separate fuel source. As shown in the front view of Figure 3, the support members 10 extend on one side of the distillation unit 2 at a greater distance than the one ST extends on the other side, This is to accommodate a delivery system of waste oil that provides an entry for waste oil. The apparatus 1 includes an element for supplying waste oil to the chamber 22 and for maintaining a desired level of oil in that chamber. Originally, this was provided by a flotation tank, with a series of floats and appropriate control circuits connected to the floats. However, any appropriate element can be provided to supply the oil level and to control the operation d? the pumps, burners and associated equipment, and the dependence on the level of oil detected. Typically, this would include various fail-safe devices, for example, interrupting the operation of the burners if the oil level falls outside the prescribed limits. In accordance with the preprocessor aspects of my invention, the control circuit also provides means for disabling the safety switches that interrupt the operation of the burner, if the oil level falls below a certain level. When these d? decouple, the burners are operated in a baking mode, to expel all remaining hydrocarbons and volatile constituents of the material in the chamber, until just a solid cake material is left. The operation of the burner is then terminated, and the chamber 22 is allowed to cool, and the chamber is then opened, to allow the removal of the solid residue. Another aspect of the evaporation unit detailed in my prior patent TS is the provision of a bypass assembly, to promote the flow of hard gases from the burners around the chamber 22, and to promote efficient thermal transfer. Going back to unit 4 d? condensation, this has d? similarly a pair of support members 70, to support the unit for and facilitate the transportation thereof. It includes a frame 72 that supports an arrangement of condensation or heat exchange pipes, generally indicated by reference 74. Figures la and Ib show a preferred and current form of the condensation unit. The other figures show an earlier version of the condensing unit, even though the principles are the same for the two units. In Figures la and Ib, the condensing unit 4 has support members 170 and a frame 172 that supports transverse condensation pipes or ducts 174. As for all modalities, the structure of the pipes 174 d? ST condensation kept deliberately simple, in order to provide a large transfer surface. This avoids the complexities d? problems with more complicated configurations, including complex fin designs, etc. here, there are four layers of transverse ducts 176, labeled 178, 180, 182 and 184. The uppermost duct layer 178 has just two ducts at either end. The next two layers of ducts 180, 182 each have six ducts. connected so that the flow d? Condensed oil flow back and forth through the condensing unit 4. The lowermost layer of ducts 184 is essentially horizontal and includes three, transverse ducts. As required, ducts can be provided with end access doors, drain valves and the like. In particular, the fifteenth transverse conduit 176 is indicated at 186, this Q being the first conduit in the lowermost layer 184. This duct 186 is provided with a drain valve, to allow a sample of the condensed oil to be taken. The output of the last duct in the series connected to a pump 190 of fine product.1, to deliver the condensed oil to a tank. Figures 2a and 2b show an alternative configuration for unit d? condensation, Here, the structure of condensation pipes 74 is kept deliberately simple, while providing = one or large surface d? thermal transfer in order to avoid problems associated with complex designs, e.g., complex fin configurations. In this way, the condensation tubes comprise a plurality d? transverse ducts 76 arranged in two inclined layers, 5 indicated at 78 and 82. Layers 78 and 82 are generally similar, even though the size of the ducts varies between the layers. The first layer includes a first section 79 of major ducts and a second section 80 of minor ducts, similar to the second layer 82. The reason for this is that in the first section 79 there is a higher percentage of present vapor that requires a volume higher. Otherwise, the arrangement in the various layers is generally similar and is described in relation to the upper layer 78. In the first section 79 of the upper layer 78, there are the ducts 76 of larger size and the smaller ducts 77 in the second section 80. These ducts 76, 77 extend transversely, i.e., perpendicular to the plane of Figure 2. The ducts 76, 77 are each provided with an access plate 75 that are provided at the alternate ends of the ducts. ducts. Only the access plates on one side are shown in Figure 2a, The alternate ends of the dutes 76, 77 are connected through each other, d? way to provide a sinuous or zigzag path. In other words, the steam that enters the topmost duct 76 from the connecting duct 40 will flow to one end of the duct, and then through the next duct 76 transverse. The steam then travels along the length of that duct 76 before flowing down to the next transverse duct 76, and so on. A connection pipe 81 is provided between the duct layers 78, 82. Consequently the vapor flows. in a zigzag or sinuous path to c- through ducts 76, 77 and upper layer 78 and then through d? connecting pipe 81 to the upper end of layer 82 where the process is repeated, this layer comprising only minor ducts 77. The lower layer 82 ends at an outlet 84 for oil recovered, which ST picks up in collection tank 86, This tank is adjusted with a float switch, to limit the level of oil recovered in tank 86, as detailed below. Even when Figure 2a shows ducts of In the case of thermal exchange extending transversely, the configuration of FIGS. 1a and 1b is preferred. Figure 2b shows an example arrangement of ducts of large section for the upper section of said heat exchanger. As before, the 76 ducts have 2nd access doors 75, which would be used for cleaning, to prevent the accumulation of a carbon deposit. Between pairs of adjacent ducts, there is a short connecting duct 94, and brackets or spacing reinforcements 96; these features would be present in all the duct layers, but they are only clearly shown in Figure 2b. The upper layer 78 is enclosed within a housing 90 (Figure 1). About the accommodation, there are six individual fans 92 arranged C) to draw air from the ambient atmosphere and blow it over the duct layers 78, 82. In this way it will be seen that the flow of cooling air, to effect the condensation of the vapor is effectively in the same direction as the vapor flow, IQ In use, any water vapor present is condensed in the heat exchange ducts, the Small drainage taps (not shown) are provided for this "and the corresponding drainage channels lead to a collection tank of 1 $ water (also not shown). If large amounts of water are generated, a removal pump may be provided, and the water may be treated in a water / oil separator. It is preferred to treat the waste oil in a pretreatment to remove water vapor or water before processing. A pretreatment simply heats the waste oil to a temperature above the boiling point of water, to expel the water vapor. An additional alternative, where water does not separate in the condenser, is to separate water from the recovered oil.

In use, the apparatus is operated for a certain period of time, with the waste oil being continuously supplied to the evaporation chamber 22. Simultaneously, tank 86 is emptied periodically, as it is filled. This causes: that the quantity or level d? solids or contaminants in the evaporation chamber 22 accumulates, During this time, the temperature controller 128 is set to a desired temperature. Practically, it has been found that the apparatus will operate at an almost constant temperature, depending on the feedstock, and the controller may adjust to some margin above the actual operating temperature. After some time, the accumulation of solids in the chamber 22 will require that the apparatus be interrupted. Elements can be provided to monitor the accumulation of solids, eg, by providing a regular sampling and checking of the contents of the chamber 22. The exact level of solids that can be tolerated will depend on the configuration of the chamber 22, and in particular, the elements for supplying it with heat. The accumulation of solids acts as an insulator to inhibit thermal transfer from the hot gases around the chamber 22 to the liquid therein. It is proposed to provide pipes that go through the chamber 22 through which the hot gases would pass. This would improve thermal transfer and allow a higher level of solids accumulated within chamber 22., - Once it is determined that the maximum permissible level of solids is present, then the waste oil supply is disconnected and a baking mode. At this time, the burners can continue the operation. He becomes disabled I Q a low level switch, so that the level of waste oil can be lowered to less than usually allowed. The fans will continue working, as long as the temperature sensor continues to perceive a temperature in excess of that ! tight When the thermal exchanger 4 has been sufficiently cooled, indicating that the oil production has almost been completed, the temperature sensor and the control circuit will start the cycle 2nd of baking. The temperature in the evaporation chamber 22 will then rise to a final bake temperature to remove as much as possible of the volatile or liquid components in the evaporation chamber 22. This temperature is adjusted by a temperature controller. The temperature controller could be adjusted initially for a temperature of 482SC. For the final bake step, where the sludge supply is disconnected, the temperature controller could be set to 704SC. The effect of this is to leave behind a cake-like material, solid that can be easily removed from the evaporation chamber 22. This step d? baking is carried out until no more condensers are condensing and collecting more volatiles in the condensing unit 4, as determined by a bake timer. When the apparatus is sufficiently fresh, the access door 34 is opened, to allow the solid residue to be removed. The access door 34 will then be closed, and the process can be restarted with another batch of mud. In accordance with the present invention, there is provided an element for injecting hydrogen into the gases or vapors in the upper part of the evaporation chamber 22. This was achieved by providing a hydrogen source indicated schematically at 100 and a supply line 102 connected to the chamber 22. As shown, a portion 104 of the supply line passes through the oil and / or steam in the chamber 22, is of extended length, and opens near the top of the chamber 22, the supply line 104 is shown schematically, and would include a portion near the bottom of chamber 22, which provides multiple passes through the liquid petroleum to ensure adequate heating of the hydrogen. This ensures that the hydrogen is preheated to the temperature in the chamber 22 before being injected into the vapor stream leaving the chamber 22 and through the outlet 38 into the connecting duct 40. A nozzle arrangement 106 is provided at three different levels, in a vertical portion of the outlet and / or a Vertical portion of the connecting duct 40. The nozzle arrangement may be such that the hydrogen is injected into the vapor stream, A As oil vaporizes, oil d? waste tends to foam to a certain degree. However, the configuration is such that the lowermost nozzles 106 are free of any foam, so that the hydrogen is just injected into the vapor phase. To test the efficiency of this hydrogen injection treatment, tests were carried out in a preprocessor, as shown in the drawings that ST accompanies, and also in a refiner, as in Figure Ib and in accordance with the invention described in U.S. Patent, 5,271,808. The details of these tests are provided below. In both cases, the hydrogen was previously heated, in the manner described above, by the hot oil in the evaporation chamber, and then added to vapors above the hot oil in the chamber. The tests were carried out with a preprocessor and refiner that had been thoroughly cleaned to ensure the removal of tar deposits. For both units, the samples collected IQ during the hydrogen addition were collected after the units had been operating for a sufficient time, approximately six hours, to reach a steady-state condition. For samples collected without addition d? hydrogen, the units of 1 ST device operated for one to two hours after stopping the hydrogen, before samples were taken d? liquidated and gas. For the preprocessor shown here, oil d? waste supplied was oil from waste of a variety of industrial forces, mainly waste crankshaft oil, For the refiner, the feed material was oil that had been processed through the processor shown and described herein. 25 Samples of the liquid and gas product were collected for both units operating with and without the addition of hydrogen. The liquid samples were collected from the feed pump that supplies oil to the preprocessor and from the product outlet. For the c-refiner, since the feed was the output of the preprocessor, just a liquid sample was taken from the output of the product. For the processor, additionally a sample was collected from the drain valve in the condensation duct 186. In addition, in an effort to obtain a representative sample of the total refiner product, including any volatiles that may have been vented to the atmosphere, ST used a sampling system to collect samples from the duct 40 d? transition or connection, which connects the evaporation chamber to the condenser in the preprocessor, and similarly for the refiner. The vapor sample taken from this location was passed through a condenser cooled with water. The condensed liquids were collected in a glass jar. Any remaining gases were passed through a quartz wool plug and ventilated or collected in a gas bag. For both units, the sample was collected from the connection duct and fed to a collection condenser. The line leading to the collection condenser was isolated, with the intention of preventing the condensation of vapors until they reached the condenser of the system of sampling. For the first processor or primary processor, it was found that there was a flow d? gas from the mucking system after the condensation of liquids. A sample of this gas was collected in a gas bag, both when operating with hydrogen and without hydrogen. This gas bag was shipped to an installation. of research for analysis. In the refiner or secondary treater, there was no pressure in the transition duct, so that a gas sample could not be collected. The following table summarizes the operating conditions of the preprocessor and refiner during sampling and testing: TABLE 1: CONDITIONS OF OPERATION DURING SAMPLING FLOWS Preprocessed - Preprocessing - Refiner Refiner Model Model Model 510 without H2 510 with H2 320 without 320 with Feeding oil 946.24 1 / h 1,514 1 / h1 1,097.65 1 / h Mud 151.40 1 / h 264.95 1 / h1 121 .12 1 / h product 757 1 / h 1,078.73 1 / h1 946 .24 1 / h FLOWS Preprocessed- Preprocessing- Refiner Refiner Model Dor Model Model 510 without H2 510 with H2 320 without 320 with H2 H2 oil level (22 evaporation chamber) 50.80 cm 64.77 cm 50.80 cm TEMPERATURES (evaporation chamber 22) 687aC3 NO 307SC2 Petroleum in chamber 22 of evaporation 387aC 360aC 265CC Output 38 385aC 373aC DO NOT connect 40 connection 207HC 2949C NO inlet of condensation unit 4 207flC 393aC 207aC Output of condensing unit 4 27ßC 23aC 31ßC PRESSURES evaporation chamber 22 27. 94 cm H20 40. 64 cm H20 Condensing Unit 4 22. 86 cm H20 33. 02 cm H20 1 The difference between these figures is due to the level of variable oil in chamber 22. 2 This temperature is much lower than that for the Pr? Processor since oil is being processed much lighter, 3 Note that this is for continuous, normal operation and not the baking mode. During these tests, for the first 80 μl hydrogen processor, they were added near the outlet of the evaporation chamber 22. Assuming a product flow of 1,097.65 liters / hour (comparable to-a figure of 1,078.73 in Table 1) from the outlet of evaporation chamber 22 and a boiling point distribution between 70a and 400aC, hydrogen will be C >; present at a calculated concentration of 3.2% by volume in the vapor and the outlet of the chamber 22. If all the hydrogen reacted to the petroleum product, the addition of hydrogen to the oil would be approximately 0.04% by weight. o During the test with the addition of hydrogen, the temperature of the gas at the outlet 38 of the evaporation chamber 22 was 309C higher than the oil temperature in chamber 22, while without the addition of hydrogen, the temperature of the gas was 2aC lower than the 5 temperature d? petroleum, This should be expected since hydrogenation is an exothermic reaction. The typical heats of reaction for hydrogenation of olefins either from the scale of -133kJ / gmol to -125kJ / gmol of hydrogen reacted. Using the flow rates, - above and assuming that all hydrogen reacted with olefins, the temperature of the gas leaving the preprocessor could be expected to increase by 8SC. A higher temperature rise would occur if part of the hydrogen were reacting with compounds that contain oxygen to form water, giving a greater heater reaction. The temperature of the increased outlet gas shown in Table 1 indicates that the hydrogenation was occurring, taking into account the large number d? reactions that could be occurring _5 the temperature rise of 13aC is consistent with a calculated elevation of 8SC if all the hydrogen reacted with all the compounds, As noted, the gas samples were collected in gas pockets from a connecting duct 40 for the preprocessor, one when the or hydrogen was being added and one without it. The samples were collected in gas bags after condensing the vapor liquids. For these tests, it was necessary to ship the gas, in gas bags, to a separate test facility, ideally 5 for a precise analysis of the gas. gas, a gas chromatograph must be connected directly to the apparatus, but this was not possible.In addition, the gas collected must be analyzed immediately, which again was not possible here.The gas analysis is shown in the following table. samples appear to indicate contamination there, as indicated by the high content of 02 and N2, and due to this reason should be viewed with caution.Table 2 provides the concentrations as analyzed and after normalizing the air and the missing components (eg, volatile light or gas that was heated). Even though these analyzes may not be completely accurate; but, some general observations can be made from the standardized concentrations. The concentration of hydrogen was three ! - • times higher in the gas phase when hydrogen was added at 80 1 / min. There were also a number of gas composition differences, strongly indicative that the hydrogen was reacting with products from the evaporation chamber, to say; 2o the ratio of CO to C02 dropped from about 4: 1 without hydrogen to about 1: 4 with hydrogen; the methane concentration dramatically from more than 50% to less than 4%; the ratio of ethane to ethane was 1: 1 without hydrogen and approximately 6: 1 with hydrogen; H2S u other sulfur-containing compounds were not detected in the analysis d? gas with or without hydrogen.

TABLE 2: GAS COMPOSITION SAMPLED FROM THE TRANSITION DUCT IN THE MODEL 510 PROCESSOR OR REFINER TREATMENT Composition Composition Standard (% by volume) lized (% by volume) Co nent without H2 with H2 without H2 with H2 H2 2.77 5.26 29.46 90.34 C02 0.11 0.16 1.20 3.84 co 0.47 0.04 5.03 0.91 CH4 5.00 0.15 53.13 3.56 C2H < 0.51 0.01 5.45 0.26 C2Hs 0.47 0.08 5.00 1.80 other HC S 0.07 0.12 0.72 2.81 0. 11.82 19.03 N2 67.89 76.70 missing 10.89 -1.56 The following Table 3 lists samples collected along with comments on the physical appearance of the samples. There was insufficient pressure in the Model 320 refiner to extract a liquid sample from the connecting duct. A 150 mL sample was collected during the test with addition of hydrogen by applying a slight vacuum to the sample. Table 3 additionally includes visual notes on liquid samples collected immediately after sampling. As for other samples taken, the sample vessels were purged with nitrogen and kept out of exposure to light. Since the samples were sent to a remote location for examination, they were possibly received several days later? that the samples were taken, and during that time, no noticeable change in physical appearance was observed.

TABLE 3: COLLECTED SAMPLES COLLECTED Unit No. Time H2 Location Comments Sample dark coffee tank /, crude feed fuel black 510 21:47 yes pump 190 color of engine oil used to clean 510 (pre-22.00 yes pipeline) of yellow, color processed with a thickening, light dor) 186 with fine sediment suspended without tar on the walls of the jar, fine powdery settled sediment TABLE 3 (Continued) Unit No. Time H2 Location Comments Sample Sample 4 510 10:30 - yes it shows oil color 10:45 total motor power, something each of the water separaducto 40 gives during the conenoche, sedimenxión to, some tar stuck to the jar 510 24:15 no duct 186 dark condense beer color, tar and pitch tar glosser adhered to the jar, higher amount of tar than the sample 3 510 24:23 no pump 190 color of motor oil used to clean, fine black sediment in the background 510 24: 23- does not show light yellow. 24:38 total oil color each of the new engine, pipeline 40 some water and conealquitrán sexión dimentado during the night, similar in appearance to the sample 4 320 01:47 if pump 190 clear, color (refine- de produc- green yellow dor) to clear, fine black sediment TABLE 3 (Continued) Unit No. Time H2 Location Sample Comments 9 320 03:30 no half more foggy pipeline with condensate-tar deposits when compared to the sample 8 10 320 02:23 does it show clear total liquid light with globule of alkylate 40 and alkyd? They are attached to the walls of the jar [For sample # 9, the sample was taken from around the fourth or fifth condenser, as counted from the top of the condensation unit 4] The following Table 4 lists the results analytical samples for liquid samples collected from the primary processor or the 510 processor, while the Table 5 lists the corresponding analytical results for samples collected from the secondary treater or refiner model 320 TABLE 4: ANALYTICAL RESULTS FOR LIQUID SAMPLES PICK-UP OF THE PRIMARY TREATER (MODEL 510) Sample # No. of Dens ¿Conté Elemental Analysis (% in Bromine weight density) (g / (g / of Só lOOg) cm3) lidos (% by weight) C H N S 0 * Alimen- 1 10 0.9068 1.41 85.19 12.20 0.27 1.29 1.05 tion Connection pipeline No H2 7 20.5 0.8215 0.007 85.27 13.18 0.037 0.68 0.83 With H2 4 12.3 0.8360 0.026 85.86 13.03 0.036 0.56 0.51 Product Without H2 6 7.3 0.8628 0.042 86.15 12.80 0.041 0.59 0.42 With H2 2 5.4 0.8524 0.025 86.30 13.01 0.029 0.48 0.18 Condenser # 15 (mainly water) Without H2 5 0.3 1.0309 0.17 1.90 10.83 0.322 0.16 86.79 With H2 3 0.37 1.0097 0.036 0.74 11.1 0.182 0.08 87.90 * oxygen content determined by difference TABLE 5: ANALYTICAL RESULTS FOR LIQUID SAMPLES COLLECTED FROM THE SECONDARY TREATER (MODEL 320) Sample # Densi No.. Conté Elemental Analysis (% in Bromine weight ratio) (g / (g / d? Só- 100 g) cm3) lidos (% by weight) C H N S O * Power 2 5.4 0.8524 0.025 86.30 13.01 0.029 0.48 0.18 Connection Pipe 40 Without H2 No - With H210 6.5 0.8286 0.008 86.19 13.35 0.019 0.22 0.22 Product Without H2 9 5.2 0.8307 0.003 85.78 13.23 0.019 0.23 0.74 With H2 8 8.6 0.8335 0.003 85.97 13.19 0.025 0.22 0.59 * oxygen content determined by difference These analyzes revealed that samples 3 and 5 collected from one of the condensation ducts in condensing unit 4 were mainly water, containing a small amount of hydrocarbons, for the refiner model 320, the differences significant with and without hydrogen were not large. For the preprocessor, comparison d? Samples numbers 1, 2, 4, 6 and 7 show the effect of the addition of hydrogen. The sample d? oil d? Product from the processor with addition of hydrogen was a lighter liquid than the sample collected without the addition of hydrogen, This is consistent with the lower density measured in the product with addition of hydrogen. Olefins can be unstable compounds that result in the formation d? tars in petroleum products. The analytical technique of bromine number, made in accordance with ASTN D 1159, measures the amount of bromine in grams reacted per 100 grams of oil sample. The bromine will react with double-bonding carbon, except aromatics, in the hydrocarbon liquid and provides a measure of the amount of olefins in the sample. Changes in bromine number greater than + or - 1 are significant. Here, the samples removed from the connecting duct 40 in the model 510 preprocessor show the greatest difference in bromine number, as between samples with and without hydrogen addition. The bromine number increased from 12.3 to 20.5 when the hydrogen flow stopped, The product's bromine number also increased slightly without hydrogen addition, from 5.4 to 7.3. The reduction of the bromine number when hydrogen is used indicates that the olefins are being saturated by the addition of hydrogen. Here, it can be seen that both the preprocessor and the tested refiner retain significant volumes of product oil in their capacitors. As such, the unit may not have to be operated sufficiently without hydrogen flow to purge all of the product oil from the condensers and to reach a constant state without hydrogen. A longer period of operation without flow d? Hydrogen gas would be necessary to ensure that the product oil sample taken from the condensation of the unit in case was truly representative. Note that liquid samples taken from the connection duct between the evaporation chamber and the condensing unit, which show a significant change in bromine number, probably better reflect the addition effect d? hydrogen, since they were not affected by the relatively large liquid volumes of the condensing units. This oil d? retained product can explain why the bromine number differences. The change in bromine number for the product oil samples was not so great for the samples d? transition pipeline. The differences in oil density were not great with or without hydrogen flow. The feed oil density of 0.9 was reduced to 0.85 in the preprocessor model 510 and to 0.83 after further processing in the model 320 refiner. The lower density of 0.82 to 0.83 in samples number 4 and 7 collected from the connection pipeline 40 suggests that the sampling procedure did not effectively recover the heavier liquid products. The higher boiling components would probably condense in the connecting duct. The lower density of the liquid samples for the model 510 preprocessor when hydrogen was added is consistent with the transformation d? olefins to paraffins, which have a lower density. As for the solid contents filtered d? the samples in tables 4 and 5, in addition d? . the food that, as is known, has a content d? relatively high solids, the different concentrations were low and not significant. Regarding the elemental analysis, no STs found large differences in the elemental composition with or without hydrogen in the samples collected from the model 510 processor unit. The sulfur and oxygen content were slightly reduced both in the connection pipe 40 and the samples of petroleum, of product with the addition of hydrogen. The oxygen content of the samples was not measured directly but was determined by difference of the analyzed C, H, N and S analysis. The increase in H / C ratio for the preprocessor liquids when hydrogen was added is again consistent with the addition of hydrogen to liquids. There was little significant difference in the product oils d? elementary analysis from, the refiner model 320 with or without addition d? hydrogen. The following Table 6 provides a simulated distillation of the feeds, and indicates the boiling point distribution. In this way, IBP indicates the initial boiling point and FBB indicates the final boiling point, and numbers 10, 20, etc. indicate? l point d? boiling after 10%, 20%, etc. that the initial ST sample had evaporated.

TABLE 6: SIMULATED FEED DISTILLATION AND PRODUCTS Mue_ Distillation Results tra # IB 10 20 30 40 50 60 70 80 90 EBP P Oil 100 212 258 306 358 412 466 539 - - < 615 Waste Disposal Model 510 (pre-processor Without H2 6 90 181 220 249 275 302 326 352 380 414 511 With H2 2 < 36 41 72 178 234 265 294 319 350 389 514 Model 320 (refiner) Without H2 9 87 159 183 203 220 236 250 266 285 310 395 With H2 8 87 164 189 207 222 236 250 264 281 307 397 The petroleum product collected from the model 320 refiner had a lower boiling point than the feed oil, as shown in Table 6. There was little or no difference in the boiling point distribution for the product collected from the refiner 320 with or without the addition of hydrogen. For the 510 model processor, the initial boiling temperatures for the lower fractions were very small, even though the final boiling point was slightly higher. The control system for supplying hydrogen preferably includes a number of safety features . These may include: location of the hydrogen tanks outside the main building housing the refiner or preprocessor as the case may be; interruption valve d? supply d? hydrogen placed in the hydrogen supply tanks, which can be operated remotely from a controller; check valves on line d? supply of hydrogen to prevent the flow of oil back to the hydrogen supply line; integration with a refiner or preprocessor control system, to include automatic interruption of hydrogen during startup, disconnection and interruption or disturbance conditions, d? way to minimize the introduction of hydrogen when hydrocarbon vapors are not present; Adequate ventilation of buildings and insulation, to ensure the dissipation of any ventilated hydrogen, and hydrogen detectors at the highest point in a building.

The data collected during the experiments in the pr? Processor 510 model indicate that the gas d? Hydrogen injected into the evaporation chamber 22 was reacting with the product vapors. The addition of hydrogen had the following measured effects: (1) increase in gas temperature in the connection duct 40; (2) reduced ol? Fine content in oil samples collected from the 40 d duct? Connection; (3) reduced density and boiling point distribution of the final petroleum product: (4) slight reduction in sulfur content and probably oxygen content in the product oil; (5) reduced concentration of ethylene and increased ethane in the product gas.

Claims (1)

1. CLAIMS 1. - A method for recovering a useful oil product from waste oil, the method comprising the steps of: (1) heating the waste oil to vaporize the oil thereof; (2) inject hydrogen gas into the vaporized oil, to cause saturation of at least some olefins present in the vaporized oil, and (3) recover the vaporized oil as a useful petroleum product. 2.- A method of conformity with claim 1, which includes vaporizing the waste oil at substantially atmospheric pressure 3. A method according to claim 1, which includes vaporizing the oil at a temperature sufficient to cause at least partial cracking of the oil. - A method according to claim 2, including vaporizing the oil at a temperature sufficient to cause at least partial cracking of the oil 5. A method according to claim 2, which includes as a step (4), after step (3) condensing the recovered oil 6. A method according to claim 5, which includes vaporizing the oil to a enough temperature to cause when • less partial cracking of the oil. 7. A method according to claim 6, comprising heating the waste oil in an evaporation chamber, continuously supplying waste oil to the evaporation chamber and monitoring the level of waste oil in the evaporation chamber, for keep the level within desired limits. 8, - A method according to claim 7, comprising passing the vaporized oil through a connecting duct from the evaporation chamber to a condensing unit and condensing the petroleum vapor in the condensing unit, where step (2) comprises injecting hydrogen into the petroleum vapor in at least one of the evaporation chamber and the connecting duct. 9. A method according to claim 8, which comprises passing the hydrogen through a pipe that ST extends through the liquid waste oil in the evaporation chamber, to preheat the hydrogen at a temperature inside the evaporation chamber, and subsequently inject the hydrogen into the petroleum vapor in at least one of the evaporation chamber and the connecting duct. 10. A method according to claim 2, which includes preheating the hydrogen at the temperature of the vaporized oil. 11. A method according to claim 9, which includes an additional step (5): after a period of time, terminate the supply d? waste oil to the evaporation chamber and continue heating the evaporation chamber and the waste oil therein in a baking mode to a substantially higher temperature, to substantially vaporize? all residual waste oil in the evaporation chamber, to leave a solid residue inside d? the evaporation chamber. 12. A method according to claim 11, including an additional step (6); After all the waste oil has been vaporized from the evaporation chamber, allow the evaporation chamber to cool, opening the evaporation chamber and removing the solid residue. 13. - An apparatus for recovering a useful petroleum product from a waste oil, the apparatus comprising; an evaporation chamber, which includes an inlet for waste oil, and an outlet for vaporized oil, as a useful oil product; a heating element to heat the evaporation chamber to vaporize the oil from the waste oil; an element for injecting hydrogen into the waste oil vapor; and an element for recovering vaporized oil, 14. An apparatus according to claim 13, which includes a condensing element and a connecting duct which? connects the outlet of the evaporation chamber to the condensation element. 15. An apparatus according to claim 14, wherein the element for injecting hydrogen comprises a conduit opening to at least one of an upper portion of the evaporation chamber and the connecting duct. 16. An apparatus according to claim 15, wherein part of the conduit extends through a lower portion of the evaporation chamber, whereby the hydrogen in the conduit is heated by the waste oil to the temperature inside. of the evaporation chamber. 17. An apparatus according to claim 16, wherein the evaporation chamber includes an inlet for waste oil, and the apparatus includes a pump element for supplying waste oil to the evaporation chamber.; and a level control element for monitoring the level of waste oil within the evaporation chamber, the level control element being connected to the pump element and driving the pump element to maintain the level of waste oil inside. of desired limits. 18. An apparatus according to claim 17, wherein the heating element is connected to the level control element, and in a normal mode of operation, is incapacitated if the level of oil exceeds the desired limits, and which includes an element for incapacitating the level control element and terminating the waste oil supply, to enable the continuous operation of the heating element in a baking mode, in which the evaporation chamber is heated to = an elevated temperature to vaporize the remaining waste oil.