# Patent

## Title
Five degrees for separation

## Abstract

A process for heating thermally unstable or difficult to heat liquid feeds, e.g., used lubricating oil (ULO) to dehydrate and/or recover distillable components therefrom, is disclosed. The liquid feed is heated by direct contact heat exchange with molten metal, preferably maintained as a bath, operating at a temperature above the boiling point of water and below 600 C. The liquid feed is heated and typically at least partially vaporized in, or above, or by contact with the molten metal to produce a heated liquid. When ULO contaminated with water is the feed, the vapor product of the process will comprise water vapor and/or distillable hydrocarbons. ULO additive decomposition products, such as carbon, may be removed as a solid, semi-solid or liquid residual phase from contact with the molten metal.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit, and is a copy, of my prior provisional application No. 60/500,278, filed Sep. 4, 2003 and incorporated by reference.


FIELD OF THE INVENTION
The invention relates to direct contact heating of normally liquid hydrocarbons and the like, especially those which are thermally unstable or difficult to heat, e.g., processing used motor oil to recover distillable and non-distillable hydrocarbons.
BACKGROUND OF THE INVENTION
Automotive and many industrial lubricating oils are usually formulated from paraffin based petroleum distillate oils or from synthetic base lubricating oils. Lubricating oils are combined with additives such as soaps, extreme pressure (E.P.) agents, viscosity index (V.I.) improvers, antifoamants, rust inhibitors, antiwear agents, antioxidants, and polymeric dispersants to produce an engine lubricating oil of SAE 5 to SAE 60 viscosity.
After use, this oil is collected from truck and bus fleets, automobile service facilities, municipal motor oil recycling centers and retail stores. There is also a significant volume of oil collected from the industrial sector, e.g., cutting, stamping and coolant oils, which is collected on a direct basis or is collected from oily-water dehydrating facilities. This collected oil contains organo-metallic additives such as zinc dialkylthiophosphate from the original lubricating oil formulation, sludge formed in the engine, and water. The used oil may also contain contaminants such as waste grease, brake fluid, transmission oil, transformer oil, railroad lubricant, crude oil, antifreeze, dry cleaning fluid, degreasing solvents such as trichloroethylene, edible fats and oils, mineral acids, soot, earth and waste of unknown origin.
Reclaiming of waste oil is largely carried out by small processors using various processes tailored to the available waste oil, product demands, and local environmental considerations. Such processes at a minimum include partial de-watering and coarse filtering. Some more sophisticated processors may practice chemical demetallizing or distillation. The presence of organo-metallics in waste oils such as zinc dialkylthiophosphate results in decomposition of the zinc dialkyldithiophospnate to form a carbonaceous layer rich in zinc and often other metals such as calcium, magnesium and other metals present as additives and thus difficult if not impossible to process. The carbonaceous layer containing the various metals forms rapidly on heated surfaces and can develop to a thickness of more than 1 mm in 24 hours. This layer not only reduces the heat transfer coefficient of tubular heaters rapidly, it also results in substantial or total occlusion of these tubes within a few days.
Successful reclaiming processes require the reduction of the organo-metallics (or ash) content to a level at which the hot oil does not foul heated surfaces. Such reduction can be carried out by chemical processes which include reacting cation phosphate or cation sulfate with the chemically bonded metal to form metallic phosphate or metallic sulfate. U.S. Pat. No. 4,432,865 to Norman, the contents of which are incorporated herein by reference, discloses contacting used motor oil with polyfunctional mineral acid and polyhydroxy compound to react with undesired contaminants to form easily removable reaction products. These chemical processes suffer from attendant disposal problems depending on the metal by-products formed.
Ash content can also be reduced by heating the used lubricating oil to decompose the organo-metallic additives. However, indirect heat exchange surfaces cannot be maintained above 400.degree. F. (204.degree. C.) for extended periods without extensive fouling and deposition of metals from the additives. Used lubricating oils can be heated to an additive decomposition temperature of 400.degree. F. (204.degree. C.) to 1000.degree. F. (538.degree. C.) by direct heat exchange by mixing with a heated product oil as disclosed in U.S. Pat. No. 5,447,628 to Harrison, et al., the contents of which are incorporated herein by reference. However, dilution of the product oil with used oil requires reprocessing already processed product oil . . . .
UOP's Hy-Lube process, described in U.S. Pat. Nos. 5,244,565 and 5,302,282, and many more, uses a hot circulating hydrogen stream as a heating medium to avoid deposition of decomposed organo-metallic compounds on heating surfaces.
The problem of fouling of heated surfaces can be ameliorated to some extent by gentler heating. Some processes, such as the fixed bed version of catalytic cracking, the Houdry process, used a molten salt bath to provide controlled, somewhat gentle heating of vaporized liquid hydrocarbon passing through tubes of catalyst immersed in the salt bath. Molten metal baths have also been used as a convenient way to heat difficult to processes substances to a control temperature, e.g., flammability of some plastics is tested by putting a flask with plastic into a bath of molten metal. Use of molten salt bath, or molten metal bath, or condensing high temperature vapor, could be used to reduce uneven heating of heat exchange surface and thereby reduce dT across a metal surface and perhaps slow the fouling of metal surfaces in ULO service, but the additives in the ULO would still tend to decompose on the hottest surface, which would be the heat exchanger tubes.
Although not related to ULO heating, in addition to the use of molten metal or molten salt for indirect heating as discussed above, there has been use, either commercial, or reported in the patent literature, of use of molten metal for direct contact heating of various substances. The float process for making glass is almost 50 years old. Molten metal, primarily lead, for heating coal or shale has been practiced in one form or another for almost 100 years. There are recent reports and patents on use of molten metal baths for waste pyrolysis, and conversion of latex, by heating ground up plants in a metal bath to make an oily overhead product. Also somewhat related, but even more different than anything discussed above, is the HyMelt® process, using molten iron beds for dissolution of various feed stocks. Temperatures in the HyMelt process are so high that if a liquid hydrocarbon feed is fed to a HyMelt reactor, the feed almost instantaneously dissociates in hydrogen and carbon, with the carbon dissolving in the molten iron. This is an excellent process for dissociating a hydrocarbon into its elemental constituents, but may be overkill for, e.g., reprocessing ULO, when all that is needed is enough heating to vaporize the lube boiling range components.
Some researchers took the position that fouling of metal surfaces during ULO processing was going to happen, and that the best way to deal with it was to inject something into the ULO which would scrub the metal clean, i.e., injecting an abrasive material.
Solvent extraction with light paraffin solvents such as propane, butane, pentane and mixtures thereof have been practiced by Interline and others. Details of the Interline Process are provided in U.S. Pat. No. 5,286,380 and U.S. Pat. No. 5,556,548. While the extraction approach seems like an elegant solution to the problem of processing ULO, the process may be relatively expensive to operate. Their quarterly report of May 15, 2002, reports that “It has become evident that demanding royalties based on production is impractical in many situations and countries. Unless and until the re-refined oil produced in a plant can be sold at prices comparable to base lubricating oils, collecting royalties based on production will be difficult. This reality was experienced in Korea, where the royalty was terminated for the first plant, and in England where the royalties were reduced and deferred until the plant becomes profitable.
A breakthrough in ULO processing occurred with direct contact heating of the ULO with steam or a non-hydrogenating gas. This approach solved the problem of zinc additive decomposition fouling of hot metal surfaces, by ensuring that the metal surfaces holding the ULO were always relatively cool. The hottest spot in these ULO process was the point of vapor injection. Decomposing additives had only themselves to condense upon. Such a vapor injection ULO process was disclosed in my earlier patent, U.S. Pat. No. 6,068,759, Process for Recovering Lube Oil Base Stocks from Used Motor Oil . . . and in U.S. Pat. No. 6,447,672, Continuous Plural State Heated Vapor Injection Process for Recovering Lube Oil Base Stocks from Used Motor Oil . . . Other variations on the theme of ULO vapor injection processes are disclosed in U.S. Pat. No. 6,402,937 Pumped Recycle Vapor and U.S. Pat. No. 6,402,938, Vaporization of Used Motor Oil with Non-hydrogenating Recycle Vapor, which are incorporated by reference.
The “state of the art” of used motor oil processing could be summarized as follows:
Chemical additive and extraction approaches can be used to react with, or extract everything but, zinc additives, but costs associated with such processes are apparently high, as evidenced by little commercial use. Additives could be extracted, but the operating costs are high.
Indirect heating, in a fired heater, causes rapid fouling of metal surfaces. Using milder heating, via a double boiler approach or molten metal heating medium, can minimize but not eliminate fouling on hot metal surfaces.
Direct contact heating with high pressure hydrogen may eliminate fouling but requires high capital and operating expenses.
Direct contact heating, with recycled product oil, helps but requires processing the ULO twice.
Direct contact heating with steam or non-hydrogenating vapor, as reported in my U.S. Pat. No. 6,068,759 and the related patents discussed above, is believed to be the best available technology. This approach requires only moderate capital investment and moderate operating expense when steam is the injected vapor, but the process can create a water disposal problem and is thermally less efficient because the latent heat of water is lost when the steam is condensed against cooling water or air in a heat exchanger. When other vapors are injected for heating e.g., propane, the water problem goes away but large volumes of vapor are needed to provide sufficient heat input, so costs increase to heat and recycle such vapor streams.
Although my earlier work, steam injection for direct contact heat exchange, solved the worst problem, fouling on hot metal surfaces, it had some deficiencies as briefly noted above. I wanted an even better approach.
I thought about steam injection. The steam injection process seemed nice and simple, because it was easy to heat water to make steam. Unfortunately, using large amounts of water created a potential water disposal problem and produced a relatively “wet” plant, with many potential areas for corrosion as the steam condensed. Re-using the condensed water was possible, but there are concerns about the amount of water treatment required to remove chlorides, etc, so that corrosion and/or plugging of the tubes in the fired heater would not be a problem. Large volumes of steam were required, which resulted in relatively large plant volumes, at least until some or all of the injected steam was condensed. I realized that although the use of steam was a great advance in the art, it might not be the best approach.
The “pumped vapor” approach, use of propane or other recycle hydrocarbon vapor eliminates many concerns about water, but required a more complicated plant to recycle the hydrocarbon vapor. Large molar volumes of injected vapor are needed because of the relatively low heat capacity of hydrocarbon vapors. Condensation and separation of multiple hydrocarbon species, both injected heating vapors and recovered lubricating components, is more complicated than cooling everything and allowing water and oil to separate as separate phases.
I wanted to retain the beneficial features of heating the ULO by injecting something hot into it, but avoid the problems created by using either steam or a light hydrocarbon vapor as the heating medium. I found a way to overcome these deficiencies, by using a non-pyrolizing molten metal as the heating fluid.
There are several metal alloys available which are fluid at relatively low temperatures which have ideal properties for use herein. They are non-corrosive. They are highly conductive, permitting compact furnace design to heat the metal. The metals are dense and carry of lot of energy per volume of fluid, so the used lubricating oil (ULO) re-processing plant can be small. They are not volatile, so they do not contribute to air or water pollution. They have a high surface tension, which means that decomposition products and trash found in the ULO will not stick to or stay with the molten metal, permitting extended use of the metal bath. Molten metal also permits a flexible design approach, permitting injection of the metal into the oil or vice versa, though not necessarily with equivalent results. When oil is injected into a molten metal bath, it is easy to increase or decrease process severity by changing the depth of molten metal in the bath or the temperature of the metal or the pressure in the molten metal bath.
BRIEF SUMMARY OF THE INVENTION
Accordingly, the present invention provides a process for heating a liquid feed stream comprising a normally liquid hydrocarbon comprising direct contact heating of said liquid feed by contact with molten metal to produce heated liquid.
In another embodiment, the present invention provides a method of refining used lubricating oil (ULO) containing lubricant boiling range hydrocarbons and thermally decomposable additives to recover as a hydrocarbon liquid product at least a portion of said lubricant boiling range hydrocarbons comprising heating said ULO by direct contact heat exchange with molten metal having a temperature of 100 to 500 C for a time sufficient to vaporize at least a portion of said lubricant boiling range hydrocarbons and removing as a vapor product said lubricant boiling range hydrocarbons.
In yet another embodiment, the present invention provides, in a process for heating a thermally unstable liquid feedstock which cokes and/or rapidly fouls metal surfaces such as tubes in a fired heater, heat exchanger tubes, or the like, the improvement comprising heating said thermally unstable liquid feedstock by direct contact heat exchange with molten metal to produce a heated feed as a product of the process.
The invention will be more fully understood from the following description of the preferred embodiment taken in conjunction with the figures.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a simplified schematic drawing of a preferred embodiment wherein used oil is refined by direct contact heating with a continuous phase of molten metal
FIG. 2 is similar to FIG. 1, but differs in that ULO, rather than molten metal, is the continuous phase.
FIG. 3 shows an embodiment with a dehydration station upstream of the molten metal heating zone.



DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
In FIG. 1, as-received Used Lube Oil (ULO) flows from a feed storage system, 10, through line 12 to the feed pump, 13, into the contactor vessel, 14, at or near its bottom. A heat transfer fluid, 15, that is immiscible with and much denser than ULO circulates from the bottom of the contactor vessel, 14, by line 16 to a heater, 18, that raises the temperature of the heat transfer fluid to the desired value. Heating may also be accomplished by operating electrical resistance elements in the heat transfer fluid phase in the contactor vessel, 14. The heat transfer fluid flows back to the contactor vessel by line 20. Flow of the heat transfer fluid through the heater, 15, may be by natural convection, as shown, or the fluid may be caused to flow through the heater, 18, by use of an appropriate pump. The total liquid level in the contactor, 14, is maintained by a vertical outlet pipe, 22, through which all gas, vapor and liquid leave the vessel and flow through line 22, to the separator vessel, 26. The inventory of heat transfer fluid sets its level in the contactor, 14. When the level of the heat transfer fluid, 15, is relatively high as shown in FIG. 1, ULO is the predominately dispersed phase and the heat transfer fluid is the predominately continuous phase. When the level of the heat transfer fluid is relatively low as shown in FIG. 2, ULO is the predominately continuous phase and the heat transfer fluid is the predominately dispersed phase.
The liquid and vapor entering the residue separator vessel, 26, separate into a liquid stream, 28, and a vapor stream 32. The liquid stream, 28, flows to a residue storage system 30. The vapor stream, 32, flows through a cooler, 34, that may use air as shown in FIGS. 1 and 2 as the cooling fluid or some other cooling media such as boiling water, cooling water or some other fluid. The outlet temperature of the cooler 34 should be low enough to condense substantially all of the oil in the feed, 10. Usually an outlet temperature of less than 150° F. (65.5° C.), causes nearly all of the feed to condense. The condensed stream flows by line 36 to an overhead separator vessel, 38, where any water in the feed, 10, separates and flows out through line 40 to a water storage system, 42. Liquid oil in stream 36 flows out through line 44 to an overhead oil storage system, 46. Any non-condensable gases flow out through line 48 to a gas handling system, 50. For extremely low flows of non-condensable gas and slightly above atmospheric pressure for the operating pressure of the overhead separator vessel 38, the gas handling system may be simply a vent. For larger flows, a flare, or some other appropriate gas treatment system may be required. The gas handling system may also incorporate a vacuum system to cause the contactor, 14, the residue separator, 26, and the overhead separator 38 to operate at sub-atmospheric pressure.
FIG. 3 shows a more preferred embodiment of the subject invention. Feed ULO, 10 flows by line 12 to a charge pump, 13 to a partial condenser, 50, that heats it by partially condensing vapor from the overhead separator vessel, 42, to a temperature of approximately 350° F. (176.7° C.). The heated feed flows through line 14 to a pressure-reducing valve, 16, and then to a flash vessel 18. All water and approximately 1% of the hydrocarbons contained in the feed, 10, vaporize and flow by line 22 to a thermal oxidizer, 24, or some other appropriate treatment system where the hydrocarbons are converted to carbon dioxide and water and vented through line 26.
The dried feed flows by line 20 to the feed pump, 28, where it enters the bottom of the contactor vessel, 30, where it is contacted with a heat transfer fluid phase, 31. The heat transfer phase may be the continuous or dispersed phase as described earlier. The vertical outlet pipe, 32, maintains the total liquid level in the contactor vessel, 14. All gas, vapor, and liquid exit the contactor through line 34 to the residue separator vessel, 42. Liquid residue flows through line 44 to a residue storage system 46. Vapor flows through line 48 to the partial condenser, 50, where it is partially condensed by heating the feed as described earlier. The partially condensed vapor flows through line 51 to a cooler, 52 where its temperature is reduced to at least 150° F. (65.5° C.) by heat exchange with a cooling fluid. The condensed stream flows through line 53 to the overhead separator, 54. Liquid overhead flows out by line 56 to an overhead storage system, 58. Any non-condensable gases flow by line 60 to a gas handling system. The gas handling system may include a vacuum system so that the contactor, 30, the residue separator, 42 and the overhead separator, 54 can operate at sub-atmospheric pressure.
DESCRIPTION OF PREFERRED EMBODIMENTS
Any metal can be used as part or all of the molten metal bath, so long as it is in a liquid phase at the desired operating temperature. Metals which can be used include lead, tin, antimony, mercury, cadmium, sodium, potassium, bismuth, indium, zinc, gallium. Preferably, for ULO the metal used melts below 600° F. (315.5° C.) or forms an alloy that does. Not all metals will give equal results and some present significant safety concerns, e.g., lead or mercury, but they can be included as part of the molten metal bath, if desired.
Any feed containing a normally liquid hydrocarbon can be heated using the process of the present invention. The normally liquid hydrocarbons include C5 and heavier hydrocarbons, e.g., naphtha boiling range up through residual fractions. Heavy feeds are contemplated for use herein, including those which are so heavy that they are not liquid at room temperature, e.g., a grease, wax, petrolatum or indeed any hydrocarbon having a high melting point may be used as feed. These materials will, upon heating, form liquids and may be used as feed. Treatment of solids is outside the scope of the present invention, i.e., treatment of coal or dirt contaminated with oil is outside the scope of the present invention. What is essential for the practice of the present invention is direct contact heat exchange of a liquid by a liquid. The liquid must contain hydrocarbons and can even be a pure hydrocarbon. The liquid feed usually will be contaminated with undesired lighter or heavier components which can be removed by heating, either to vaporize a desired feed component from a residue fraction or to remove an undesired lighter contaminant from a desired residue product fraction.
When processing ULO, the ULO will frequently contain both light and heavy contaminants. Light contaminants include water, naphtha and some impurities introduced during the ULO collection process. Heavy contaminants include the additive package. When processing ULO, the economic incentive is to vaporize as much of the feed as possible. This can create a problem as the residue will not flow when more than 83 to 85% of the feed is vaporized. I believe that a practical limit is 80% vaporization of the dry oil.
A surprising feature of the use of molten metal to heat ULO and vaporize the lube oil boiling range components therefrom, is that it is easy to achieve deep de-oiling of the ULO. The metal temperature at the bottom of a molten metal continuous bath and the oil temperature at the top of the contactor, the oil floating on the surface of the molten metal, are very close. I have never seen more than 5° F. difference in them. There is evidence that no fouling has yet occurred.
The invention contemplates the use of a range of molten metals for the high-intensity drying and/or heating process. These include low-melting point metal alloys. When simple drying or only a modest amount of thermal processing is desired, the candidate molten fluids may have melting points typically ranging from 60.degree.–230.degree. C.
It is essential that the heating fluid be immiscible with the ULO and substantially denser.
It is preferred that the interfacial surface tension between the molten metal heat transfer media, or other fluid which is immiscible with the feed being treated, and the liquid feed be sufficiently high to avoid sticking of the molten fluid to the wet surface. The thermal conductivity of the molten fluid should also be sufficiently high to ensure that the molten fluid remains in a liquid state, at least during the process, so that fluid does not solidify to form a solid film or freeze cone at the point of contact with the ULO.
When the thermal conductivity of the fluid is sufficiently high, the fluid conducts heat from the body of the molten bath to the interface contact region between drops or streams of ULO and molten heating medium, or drops or streams of molten heating medium when the ULO is the continuous phase. The use of molten metal alloys is preferred due to their high interfacial surface tension with decomposition products that may form from, and trash that may be found in, the ULO. Metals are also preferred over other immiscible fluids due to their high thermal conductivity. An additional benefit is the high density of molten metal relative to ULO, which promotes rapid transit of one fluid through the other and plenty of motive force should baffles or column packing be used.
Table 1 summarizes some estimated properties for several recommended molten metal eutectic alloy materials, when only moderate severity heating is required. This alloy information is taken from information reported in U.S. Pat. No. 5,619,806, which is incorporated by reference.







TABLE 1







Properties of Candidate Molten Materials















Surface



Melting
Therm. Cond.
Spec. Heat
Tension



Temp. C.
(Btu/ft2/h/F)
(Btu/lb/F)
(dyne/cm)















In/Sn (52/48)
118
19.6
0.060
580


Bi/Pb (55/45)
124
7.7
0.035
391


Bi/Sn (58/42)
138
11.6
0.046
447


Sn/Pb (63/37)
183
14.5
0.051
528


Sn/Zn (92/8)
199
20.0
0.061
594


“Tin Foil”
227
19.0
0.061
587


Sn/Cu (99/1)









The metallic material of the bath may consist of an alloy selected from the group that includes:

    i) Ga/In
    ii) Bi/In
    iii) In/Sn
    iv) Bi/Pb
    v) Bi/Sn
    vi) Sn/Pb
    vii) Sn/Zn
    viii) Sn/Cu.


A spectrum of molten metal temperatures can be used, from high to low. Based on the float bath process for making plate glass, tin has ideal properties when a relatively high temperature bath is desired. Tin has a melting point of 232 C and a boiling point of 2623 C. This means that a range of temperatures can be achieved in the molten metal bath, ranging from temperatures near the boiling point of water (when a low melting alloy like Wood's metal is used, to temperatures above 500 C. For ease of startup, i.e., a relatively low melting point, a tin-bismuth alloy is preferred.
Experiments
The experiments were conducted in a length of 4′′ schedule 40 stainless steel pipe. The metal alloy used was a tin-bismuth eutectic that is 42% tin and 58% Bismuth. The depth of molten metal was about 20′′, with about 12′′ of freeboard or vapor space above the molten metal. The stainless steel pipe was heated by a cylindrical heater, an electric jacket with a thermostat. The initial series of tests on ULO was conducted at about 600 F molten metal bed temperature. The ULO feed was fed into the bottom of the molten metal bath via a 1⁄4′′ nipple to which a length of 1⁄8′′ SS tubing was affixed. The tubing did not extend into the molten metal bath. The process ran under vacuum, which is customary for lube oil recovery processes. I estimate that the pressure was about 0.5–1 psia, but the pressure gage used was not very accurate at these low pressures.
The first tests were run with a poor sample of ULO, which had about 10 wt % water, much more than is present in any automobile engine. I do not know where all the water came from, but it was there, and caused considerable processing difficulties, perhaps due to slugging addition of an aqueous phase, which caused the apparatus to shake and the metal to splash out. A significant quantity of metal was lost due to the unusual water level of the feed, but the process worked to vaporize lube oil components from the ULO.
The next set of tests was run after dehydration of the ULO feed, to remove essentially all of the water. This series of tests would approximate the process flow shown in FIG. 3, i.e., dehydration before “distillation” of the ULO in the molten metal bath. The process worked smoothly, with none of the rumbling and spattering associated with the initial series of tests. The overhead product was a golden clear liquid, which looked almost like honey. There was some odor associated with both the overhead and the liquid residue, but the liquid residue had less smell than the ULO feed.
One problem was encountered in early runs, freezing of metal near the point of feed injection. This was overcome by adding some heat tape to the stainless steel tubing. This will probably not be a problem in commercial sized units, but if it is some form of heating of the feed injection means can be used to overcome it.
The experiments represent actual work done in a laboratory, but should not be construed as either a limitation on the process nor an optimization thereof. ULO re-refiners may operate at even lower temperatures, using a molten metal bath merely to remove water and/or “light ends” which may be present. This mild use of the technology would permit a fleet operator to periodically condition the motor oil used in vehicles, by removing water and crankcase dilution, and return the conditioned motor oil to the vehicle, perhaps with some additional additives. Some re-refiners, especially those with no market for a heavy liquid residue product, may want to use higher temperatures, to maximize production of distillable hydrocarbons and minimize production of “ash” or sludge from the ULO, to simultaneously improve product recovery and minimize disposal costs.

Discussion

The most surprising result, to me, of the experiments, was the low temperature difference between the top and bottom of the molten metal bath and of the residual liquid oil fraction, all were within 5 F. In a conventional refinery process, using a metal walled heat exchanger or a fired heater with metal tubes, temperature differences at any point on the metal surface are typically 10 to 50 F, with huge temperature differences between the inlet and the outlet of the device. As an example, if a fired heater was used to heat and vaporize a ULO feed, the oil feed temperature at, or just inside of the inlet to the heater, would be ambient, or perhaps 150 F if some heat exchange was practiced on the ULO feed. The temperature on the furnace side of the tube would be 400–500 F or higher. At the heater exit, the ULO would be at the desired process temperature, typically 500–750 F, and the temperature on the furnace side of the tube would be 550–900 F, to give enough dT to drive heat through the tube walls and into the ULO. Relatively large dTs are needed to reduce the surface area of heat exchange tubing, or heater tube, to an affordable amount, because heat transfer is relatively slow across a solid metal surface, the BTU's have to pass from the hot furnace interior by convection and radiation to the outer surface of the heater tube, through the metal tube (and this is typically efficient), across the interface between the inner tube wall and the layer of vapor/liquid in close proximity to the tube wall, and eventually into the bulk stream of ULO feed. There are many “pinch points”, which slow down the overall rate of heat transfer. Part of the problem in a fired heater is that the relatively hot metal tube surfaces cause vaporization and fouling, both of which drastically reduce heat transfer. Vaporization reduces heat transfer because it is roughly an order of magnitude more difficult to heat a gas than a liquid. Fouling reduces heat transfer because the thin, but growing, layer of carbonaceous deposits acts like an insulator, while providing a relatively porous place to hold hydrocarbon liquids and vapors a long time, permitting thermal cracking and more fouling.
In the process of the invention, especially when practiced with a metal bath continuous phase, the natural phenomenon which occur during heating become virtues rather than vices. ULO, when injected into the base of the bath, is almost instantly heated, causing some vaporization and disruption of any large droplets of ULO that may try to form. The ULO vapors produced are much lighter than the residual ULO liquid, and are believed to form something like a three phase bubble, with a vapor top, liquid oil bottom in a molten metal shell. If a large bubble forms, the light vapor portion will either break away from the residual ULO liquid, or at the least cause some form of vigorous agitation as the large three phase bubble rises. If the vapor portion breaks away, that leaves the residual ULO liquid to form a new bubble, but of liquid, or at least much more liquid than before the vapor phase broke away, and this denser bubble will not rise as quickly in the molten metal bath, giving more time for the molten metal to heat the ULO.
Radiant heat transfer is also believed to play a significant part, in that the lens shaped oil pool in the lower portion of a bubble has a large surface area to volume ratio, one or more orders of magnitude more favorable for heat transfer than can occur when the ULO is passed through a metal tube of 4′′–6′′ or similar diameter, in a fired heater. Radiation heat transfer is considered to play a negligible part of transferring heat from a hot metal heat exchange surface to oil flowing within, or around, the surface. In my process, the bubbles are small enough and can “see” enough hot molten metal so that a significant amount of radiant heat transfer occurs.
Based on the work done to date, the preferred metal composition is the tin-bismuth eutectic that is 42% tin and 58% Bismuth. It looks like the optimum conditions for temperature and pressure will be around 600 to 620° F. and 1 to 1.5 psia. There are actually an infinite number of temperature pressure combinations that will give the 80% overhead yield desired. For ULO, the limits on the combinations of pressure and temperature may range from 580° F. at 0.01 psia to 800° F. at near atmospheric pressure. Either of these extremes could result in an inoperable situation. The key parameter is vaporizing 75 to 80% of the feed without causing problems that make the process inoperable.
The ultimate use of the products, both the overhead lube oil fraction and the residue fraction, can have an important influence on operating conditions. When the process is being practiced to recover a high quality lubricating oil base stock, or a material which can be subjected to further conventional processing to make it a base stock, relatively low temperatures and somewhat lower product recoveries may be optimum. When the residue product is going to be an asphalt extender, the desire to preserve as much as possible of the plastic present in the ULO, primarily the viscosity modifier, to improve asphalt properties. When the overhead product will be FCC feed, a much lower quality product can be tolerated, so higher temperatures and higher recovery may be optimum. To minimize production of low value waste, and this will usually be the residual fraction of the ULO, after the lubricant boiling range hydrocarbons have been removed, it may be important to have very high temperatures and/or lower pressures, to reduce the resid fraction as much as possible.
General Consideration
It is important to use a molten fluid, with a “heat range” within that required for the desired process objectives. When simple dehydration of ULO is all that is required, and this will usually be a first or preliminary treatment rather than the entire process, molten metal which is molten in the 80 C+temperature range is suitable. When distillation of lubricating oil boiling range components from the ULO is desired, the metal must remain molten at temperatures above 100° C. to say 600 C. When some carbonization or “coking” of a residue fraction is desired, even higher temperatures may be required, typically 200 C to 700 C.
The upper limit on temperature/choice of the metal alloy is determined by volatility and process constraints. The preferred molten metals will have a low vapor pressure at the temperatures used, so that loss of molten metal due to “dusting” or for any other reason is less than 1% a day. The metals chosen should not be corrosive under process conditions and preferably are non-toxic, for safety.
This invention permits drying and/or recovering lube oil base stocks and/or other hydrocarbons from used motor oil. The process and apparatus of the present invention also permits efficient processing of other waste or low value oil streams that contain so much emulsified water and/or additives that conventional processing is impractical.
When used to process ULO, this invention permits the separation of metallic additive packages from valuable distillable hydrocarbons in the waste motor oil with limited, or no, decomposition of these distillable hydrocarbons. When the residual fraction from the ULO is destined for use as an asphalt extender, it may be beneficial to have some or most or even all of the additive package intact. The plastic viscosity modifiers used in some lube oils may have beneficial effects on the asphalt, so it is good to have a process which gives re-refiners the option to decompose, or not decompose, the additive package.
The process and apparatus of the present invention may also be used to heat other thermally unstable, or difficult to heat, liquids.
While our tests were conducted at relatively low pressure, re-refiners may wish to operate under a harder vacuum, to maximize recovery of lube oil components and minimize decomposition of additives. Others may wish to operate above 1 atm up to 100 atm pressure, or more, to minimize vapor volumes and facilitate processing of streams with large amounts of water. Higher pressures permit a more compact facility to be built.
The experiments were conducted using a single molten metal bath, but the invention is not limited to this embodiment. Multiple molten metal baths may be used, much as product fractionators use multiple distillation trays, each operating at a slightly different temperature.

## Claims

1. A process for refining a used lubricating oil (ULO) liquid feed comprising lubricant boiling range hydrocarbons and non-distillable or thermally decomposable additives comprising:
a. heating said ULO by direct contact heat exchange with non-pyrolizing molten metal to vaporize at least a majority of said lubricant boiling range hydrocarbons;
b. recovering said vaporized lubricant boiling range hydrocarbons as a vapor product of the process; and
c. recovering a liquid product comprising said additives or decomposition products thereof.

2. The process of claim 1 wherein said direct contact heat exchange occurs at a temperature and residence time sufficient to decompose at least a majority of said decomposable additives and vaporize at least a majority of said lubricant boiling range hydrocarbons.

3. The process of claim 1 wherein at least a majority of said ULO is recovered as a vapor fraction which is essentially free of motor oil additives and at least a majority of said additives, or decomposition products thereof, are recovered as a separate liquid, phase from said molten metal.

4. The process of claim 1 wherein said ULO is dehydrated before step a).

5. The process of claim 4 wherein said ULO is dehydrated by contact with a molten metal bath.

6. A method of refining used lubricating oil (ULO) containing lubricant boiling range hydrocarbons and thermally decomposable additives to recover as a hydrocarbon liquid product at least a portion of said lubricant boiling range hydrocarbons comprising:
a. heating said ULO by direct contact heat exchange with non-pyrolyzing molten metal having a temperature of 100 to 500° C. for a time sufficient to vaporize at least a portion of said lubricant boiling range hydrocarbons and
b. removing as a vapor product said lubricant boiling range hydrocarbons.

7. The method of claim 6 wherein said molten metal is maintained as a continuous phase.

8. The method of claim 7 wherein said molten metal is disposed as one or more baths of molten metal and said ULO is injected into, or bubbles up through, said molten metal.

9. The method of claim 6 wherein said ULO is maintained as a continuous phase and said molten metal is poured, sprayed or otherwise passed down through said continuous ULO phase.

10. A process for refining a used lubricating oil (ULO) liquid feed comprising water, lubricant boiling range hydrocarbons and non-distillable or thermally decomposable additives comprising:
a. dehydrating said ULO in a dehydration stage by beating at a temperature and pressure sufficient to vaporize said water from said ULO and produce dehydrated ULO;
b. heating said dehydrated ULO by direct contact heat exchange with non-pyrolizing molten metal at a temperature and pressure sufficient to vaporize at least a majority of said lubricant boiling range hydrocarbons in said dehydrated ULO and produce a vaporized lubricant boiling range hydrocarbon fraction and a residue liquid phase containing at least a majority of said non-distillable or thermally decomposable additives or decomposition products thereof;
c. cooling and condensing said vaporized lubricant boiling range hydrocarbons to produce a liquid product stream containing at least a majority of the lubricant boiling range hydrocarbons present in said ULO feed; and
d. removing said residue liquid from contact with said non-pyrolizing molten metal as a product of the process.

11. The process of claim 10 wherein said molten metal is maintained as a continuous phase.

12. The process of claim 10 wherein said molten metal has a temperature of 100 to 600° C.

13. The process of claim 10 wherein direct contact heat exchange of dehydrated ULO occurs under vacuum.

14. The process of claim 13 wherein direct contact heat exchange occurs at a pressure of 0.01 to 1.5 psia.

15. A process for refining a used lubricating oil (ULO) liquid feed comprising water, lubricant boiling range hydrocarbons and non-distillable or thermally decomposable additives comprising:
a. dehydrating said ULO by heating at a temperature and pressure sufficient to vaporize water from said ULO and produce dehydrated ULO;
b. heating said dehydrated ULO by direct contact heat exchange with molten metal at a temperature and pressure sufficient to vaporize at least a majority, but no more than 80 LV %, of said lubricant boiling range hydrocarbons in said dehydrated ULO to produce a vaporized lubricant boiling range hydrocarbon fraction and a residue liquid phase;
c. cooling and condensing said vaporized lubricant boiling range hydrocarbons to produce a liquid product stream containing at least a majority of the lubricant boiling range hydrocarbons present in said ULO feed; and
d. removing from contact with said molten metal a liquid residue phase as a product of the process.

16. The process of claim 15 wherein heating of dehydrated ULO with molten metal occurs under vacuum.

17. The process of claim 16 wherein heating occurs at a pressure of 0.01 to 1.5 psia.

18. A process for refining a used lubricating oil (ULO) liquid feed having an odor and comprising lubricant boiling range hydrocarbons and non-distillable or thermally decomposable additives comprising:
a. heating said ULO having an odor by passing said liquid feed up through a molten metal continuous bath having a surface and a temperature high enough and operating at a pressure low enough to vaporize at least a majority of said lubricant boiling range hydrocarbons in said liquid feed to produce a vapor phase and a residue oil phase floating on said surface of said molten metal bath;
b. recovering said vapor phase containing at least a majority of the lubricant boiling range hydrocarbons present in said ULO feed as a vapor product of the process; and
c. withdrawing said oil floating on said surface of said molten metal as a liquid product of the process.

19. The process of claim 18 wherein said liquid residue product has an odor and said odor is less than the odor of said ULO feed.

20. The process of claim 18 wherein said molten metal bath has a temperature at a bottom portion thereof and said oil floating on said surface of said molten metal bath has a temperature and there is no more than a 5° F. difference.

21. A process for distilling a used lubricating oil (ULO) liquid feed comprising lubricant boiling range hydrocarbons and a non-distillable residue fraction to produce two liquid product streams comprising:
a. heating said ULO liquid feed by injecting said feed into a molten metal bath operating at a temperature of 100–600° C. and pressure of 0.01 to 1.5 psia, wherein said temperature and pressure are sufficient to vaporize at least a majority of said lubricant boiling range hydrocarbons present in said liquid ULO feed but vaporizing no more than 85 LV % of said ULO liquid feed and produce a vapor fraction comprising at least a majority of the lubricant boiling range hydrocarbons within said ULO liquid feed and a liquid phase residue comprising said non-distillable residue fraction;
b. removing from contact with said molten metal bath said vapor fraction as an overhead vapor stream;
c. cooling and condensing said overhead vapor stream to produce a first liquid phase product comprising at least a majority of said lubricant boiling range hydrocarbons in said ULO feed; and
d. removing from contact with said molten metal bath said liquid phase residue as a second liquid phase product.

22. The process of claim 21 wherein said first liquid phase product comprising at least a majority of said lubricant boiling range hydrocarbons in said ULO feed is a golden clear liquid.

23. In a process for heating a thermally unstable liquid feedstock which cokes and/or rapidly fouls metal surfaces such as tubes in a fired heater, heat exchanger tubes, or the like, the improvement comprising heating said thermally unstable liquid feedstock by direct contact heat exchange with non-pyrolizing molten metal to produce a heated liquid feedstock as a product of the process.

24. A process for heating and partially vaporizing a thermally unstable liquid feedstock which cokes and/or rapidly fouls metal surfaces such as tubes in a fired heater, heat exchanger tubes, or the like, comprising:
a. injecting liquid droplets of said thermally unstable feed into a non-pyrolyzing molten metal bath operating at a temperature of 100 to 500° C. and a pressure;
b. heating said injected droplets by direct contact heat exchange with said molten metal bath to a temperature, at the pressure in said bath, sufficient to vaporize at least a portion of said feed in each droplet and form bubbles rising up through said molten metal bath, each bubble having a vapor phase top and a residual liquid feed bottom in a molten metal shell;
c. heating said residual liquid in said bubble by direct contact heat exchange with said molten metal and by radiant beat transfer with said molten metal shell, to produce rising heated bubbles comprising heated residual liquid feedstock stock and a vapor phase;
d. removing from above said molten metal bath said vapor phase as an overhead vapor product; and
e. removing from above said molten metal bath said heated residual liquid phase as a liquid phase product.