CZ20001290A3 - Apparatus and method for reclaiming useful oil products from waste oil comprising hydrogen injection - Google Patents

Abstract

The apparatus includes an evaporation chamber (22) in which it is waste oil is heated by means of heating means and vaporized, preferably at a temperature causing its cracking. The injection oil is injected into the evaporated oil hydrogen gas to saturate at least some olefins present in the evaporated oil. The evaporated oil is then condensed and recovered as a useful oil product. The device operates at substantially atmospheric pressure or beyond pressure only slightly above atmospheric pressure. Hydrogenation the recovered oil stabilizes and prevents the recovered oil creating tars and other heavier hydrocarbons that they can problems in using the recovered oil.

Description

An apparatus and method for recovering useful oil products from waste oil, comprising injecting hydrogen

Cross-reference to related application

For the United States, this application is a partial continuation of my previous application, Serial No. 08 / 829,526, filed May 28, 2008.

March 21, 1997, which is a registered sequential continuation application Serial No. 08/199 201, filed January 21, 1994, which is a partial continuation of application Serial No. 07/712 775, filed on June 10, 1991, which is a partial continuation of application Serial No. 07/1997; No. 246,834, filed September 20, 1988. Furthermore, the contents of all of these earlier applications are hereby incorporated by reference.

Technical field

The present invention generally relates to an apparatus and method for recovering (recovering) waste oil, more particularly it relates to recovering waste oil from sludge, i.e., a highly viscous material containing a relatively large amount of contaminants and particulate solids.

BACKGROUND OF THE INVENTION

In this specification, the term waste oil includes any suitable oil, such as mineral oils, that have been used. · ·

9 9 9 9 9

9 9 99 9 9 9 9 as engine oil, or some other lubricating oil, or as hydraulic oil or in some other application. It is contemplated that these oils will be derived from mineral oil, but could be eg animal or vegetable oil such as fish oil or oil disposed of by restaurants, etc. Mineral oil may be a plain, untreated oil. In use, such lubricating oils are usually replaced periodically. Dewatered and recovered waste oil typically contains substantial amounts of contaminants that may contain dirt, metal particles (containing heavy metals such as molybdenum, chromium, cadmium, vanadium, copper, etc.), oxides and salts, gasoline and additives to it (such as tetraethyl lead) as well as cleaning and operating additives. It can also be contaminated with water. In industrialized countries, large quantities of such waste oil are produced and my previous inventions have been directed to methods and devices for recovering waste oil so as to be suitable for various uses. Pollutants in waste oil usually make it unsuitable for most applications. The term waste oil further includes an oil-based sludge such as that produced in the apparatus of my prior invention described in Serial No. 246,834.

My previous inventions provided a device in which lighter waste oil hydrocarbons were evaporated and then condensed. Also, although the exact mechanism within the device has not been fully understood, it is believed that some cracking or cleavage of hydrocarbons from longer to shorter chain molecules occurs. Indeed, it is also possible for the contaminants present to act as catalysts. It has been discovered that starting with a contaminated, waste lubricating oil, approximately 90% of it could be converted to a lighter oil suitable for use as fhotor diesel.

• · ··· · »· · · · · · · ·

My earlier inventions are described in detail in U.S. Patent Nos. 5,271,808, which discloses a basic purifier (refiner, secondary treatment apparatus), and No. 5,286,349, which discloses a more advanced process and apparatus designated herein as a preprocessor, primary processing equipment). The contents of these two US patents are hereby incorporated by reference.

The basic purifier process provided distillation with some cracking, performed at substantially atmospheric pressure. This allowed the recovery of waste oil as engine oil, free of solid impurities and the like. This process left solid parts and other impurities concentrated as sludge, which presented problems to get rid of it. The latter pretreatment device provided a process in which, when solids and other impurities have accumulated to a certain level, the further supply of waste oil is discontinued, and the temperature is raised to expel all remaining organic and volatile components. Thereafter, the crumbly, cake-like material remains, which is classified as a non-toxic leach, which means that it can be easily disposed of in accordance with the jurisdiction of most countries.

However, the problem with engine-grade oil or fuel obtained from both of my previous inventions is that they tend to be unstable. It is believed that the oil contained a number of free radicals and / or olefins. Subsequently, over time, these free radicals or olefins combine to form heavy oils and tars. Since the aim was to regain oil as a motor-quality fuel, this posed considerable problems. Such tar and heavy components tend to deposit in fuel injection systems and the like, blocking these systems and preventing proper operation.

· · · · · · O · o · o · o · o · o · o · o · o · o · «··· ···· ·· ·

Accordingly, it is desirable to provide an improvement or modification of my existing processes, resulting in a recovered product that is stable and which can be stored for a significant period of time, typically of the order of 30 days, without any serious or significant degradation or characteristic changes, more specifically without settling. no tars or heavy hydrocarbons.

SUMMARY OF THE INVENTION

In accordance with the present invention there is provided a method of recovering a useful oil product from a waste oil, the method comprising the following steps:

(a) heating the waste oil to evaporate the oil therefrom;

(b) injecting hydrogen gas into the vaporized oil to cause saturation of at least some olefins present in the vaporized oil; and (c) recovering the waste oil as a useful oil product.

The waste oil is preferably vaporized at substantially atmospheric pressure, since this eliminates the requirement to provide complex or expensive pressure vessels or the like. Thus, steps (1) and (2) could be performed at a pressure equal to 762 mm water column above atmospheric pressure.

More preferably, the temperature is sufficient to cause at least partial cracking of the oil. The recovered oil is preferably condensed and recovered as a liquid.

The waste oil is preferably heated in the evaporation chamber and is continuously supplied to the chamber, and the level (level) of the waste oil in the evaporation chamber is monitored to maintain its level within the desired limits.

····································

4 9 4 9 9 9 9 • Hi 4 9 ··

9 ·· · ♦ ··

In a preferred embodiment, the vaporized oil passes through the connecting line from the evaporation chamber to the condensation and, in step (2), hydrogen is injected into the oil vapor in the at least one evaporation chamber and the connecting line.

Preferably, the hydrogen passes through a conduit that passes through the liquid waste oil into the vaporization chamber to preheat the hydrogen to a temperature inside the vaporization chamber.

In accordance with my prior invention of the pretreatment apparatus, the method may comprise an additional step (5): after a period of time interrupting the supply of waste oil to the evaporation chamber and continuing to heat the evaporation chamber and waste oil therein in the baking process to a substantially higher temperature; to evaporate substantially all of the residual waste oil in the evaporation chamber and leave a solid residue (residue) inside the evaporation chamber.

In accordance with another aspect of the present invention there is provided an apparatus for recovering a useful oil product from a waste oil, the apparatus comprising: an evaporation chamber with a waste oil inlet and a vaporized oil outlet as a useful oil product; heating means for heating an evaporation chamber to evaporate oil from the waste oil; means for injecting hydrogen into the waste oil vapor; and means for recovering the evaporated oil.

Preferably, the apparatus comprises condensation means and a connecting line connecting the outlet of the vaporization chamber to the condensation means. The hydrogen injection means preferably comprise an opening of the conduit into at least one upper part of the vaporization chamber and the connecting conduit. A portion of the conduit may extend through the lower portion of the evaporation chamber, whereby the hydrogen in the conduit is heated by the waste oil to a temperature inside the evaporation chamber.

• · φ ··· ··· ♦ ·· * · · · · · · · ·

For continuous operation and in accordance with my previous inventions, the vaporization chamber may comprise an inlet for waste oil and the apparatus then includes a pump means for supplying the waste oil to the vaporization chamber; and a level control means for monitoring the level of waste oil within the evaporation chamber, the means being connected to the pump means and actuating it to maintain the level of waste oil within the desired limits. For operation as a pretreatment device, the heating means is preferably coupled to the waste oil level of the control means and locked in normal mode of operation if the oil level exceeds the desired limits, and the apparatus further includes means for blocking the level control means and interrupting the waste oil supply. operating the heating means in a firing method in which the evaporation chamber is heated to an elevated temperature to evaporate the remaining hydrocarbons.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to better understand the invention and to more clearly illustrate its commissioning, further reference will be made, by way of example, to the accompanying drawings showing a preferred embodiment of the device, in which:

Giant. 1a - a side view of a pretreatment device or primary processing device in accordance with the invention.

Giant. 1b is a side view of a cleaner or secondary processing apparatus in accordance with the invention.

Giant. 2a is an enlarged side view of the heat exchanger of the apparatus of FIG. 1.

• ·

Giant. 2b is a perspective view of a heat exchange conduit layer.

Giant. 3 is a front view of the device.

Giant. 4 is a right side view of the device.

Giant. 5 is a left view of the device.

DETAILED DESCRIPTION OF THE INVENTION

Giant. 1a shows a device according to the invention, generally indicated by 1. The device 11 comprises two basic elements, namely an evaporator unit 2 and a condensing unit or heat exchanger 4, which are further described below. Since the details of this basic device do not form part of the present invention, the assembly of the device 1a is merely indicated herein and complete details are provided in my earlier U.S. Patent No. 5,286,349. The invention is mainly described herein in relation to my processing device or primary processing device. . For completeness, FIG. 1b illustrates a cleaner or secondary processing apparatus to illustrate the application of the present invention to such apparatus, and useful reference numerals are indicated in FIG. lb. In addition, FIG. 1a and 1b are based on current versions of the device, while the other figures are based on U.S. Patent No. 5,286,349.

As shown in FIG. 3, the vaporizer unit 2 has a generally rectangular cross section and has a depth slightly less than its length or width. The vaporizer unit 2 has two longitudinal support portions 10 for supporting it and facilitating transportation of the unit 2. The unit 2 has a housing 11 comprising outer side walls 12, end walls 14, 16, a bottom wall 18 and an upper wall 20. Inside the unit 2 is a distillation the waste oil chamber 22, which is located inwardly from all outer walls of the unit 2. The chamber 22 is supported at 0 · 0 0

0 0 »0 ·

0 0 * * 0 0 0000 ··· 00 000 0 »00 number of support rollers (not shown) to allow the free movement of 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 both ends and the chamber 22 is freely mounted on the top plates to allow thermal expansion and contraction. The waste oil chamber 22 has a flat bottom 24. The chamber is made of 304L stainless steel. The side walls 26 extend therefrom and connect to the top wall 28. These walls 24, 26, 28 extend to the end walls 29 of the chamber. In one end wall 29 there is a chamber access door 34 for access opening extending through the respective end wall 14 into the chamber 22 to allow the solid cake material remaining in the chamber 22 to be removed. The respective access door may be provided for the combustion chamber . The chamber 22 also has, in a known manner, longitudinal and transverse reinforcing bars to withstand the internal pressure of the full waste oil charge.

In the upper wall 20 there is an exhaust port 36, which is connected to a suitable exhaust chimney 37. For the evaporation chamber 22, the outlet 38 is connected to the connecting pipe 40. FIG. 1a shows a connecting pipe 40 which shows the distinct shape of the inverted U that continues through the elbow 41 to the condensation unit 4. As indicated in 39, a vent is provided that is connected to the pressure relief valve when any excess pressure is generated. The system normally operates at a low positive pressure of about 3.4 kPa (0.5 psi) and the pressure relief valve is set to open at about 17 kPa (2.5 psi). As shown in FIG. 1, for the cleaner and in the other figures for the processing device, the connecting line 40 may also include an overall straight vertical part and then a sloped part running downwardly towards the capacitor. In both cases, the design should be such as to avoid the dead • · 9 ·

9 to 999 9999 points, i.e., to ensure that any oil that condenses out of the conduit 40 either runs back into the re-vaporization chamber or flows towards the condensation collecting unit 6.

As indicated in 43, a downstream portion of the connecting line 40 may be provided with a reactive bed that has not been found to be essential and the hydrogenation of the oil occurs without it. The reactive bed 43 may include any suitable material that promotes the reaction of hydrogen with oil vapor. It should include, for example, nickel-cadmium.

At both ends of the vaporizer unit 2, and mounted on each side wall 12, there is a blower 42 for the respective burner within the combustion chamber 32. Associated with each blower 42 is the supply of suitable fuel (not shown). This could be a 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 FIG. 3, the support portions 10 extend on one side of the distillation unit 2 at a greater distance than they extend on the other side. This is due to adaptation to the delivery system securing the waste oil inlet.

The apparatus 1 comprises means for supplying waste oil to the chamber 22 and for maintaining the desired level (s) of oil in the chamber. Initially, these were provided by a float tank, with a number of floats and an associated control circuit connected thereto. However, any suitable means may be provided to monitor the oil level and control the operation of the pumps, burners and associated equipment, and dependence on the detected oil level. Typically, they will include safety devices, for example, interrupting the operation of the oil burners when the oil level rises beyond the prescribed limits.

In accordance with aspects of the pretreatment apparatus of my invention, the control circuit also provides blocking of safety switches that interrupt the burner operation when the oil level drops to a certain level. With these locked switches, the burners are operated in the firing method to expel all remaining hydrocarbons and volatile components from the material in the chamber until only solid cake material remains. The burner operation is then discontinued and the chamber 22 is allowed to cool and then opened to remove solid residual material therefrom.

Another aspect of the vaporizer unit described in detail in my earlier patent is to provide a flow baffle assembly to promote the flow of sintered gases from the burners around the chamber 22 and to promote efficient heat transfer.

Turning to the condensing unit 6, it likewise has a pair of support portions 70 to support the unit and facilitate its transportation. It comprises a frame 72 which carries an array of condensation or heat exchanger tubes, generally indicated by reference numeral 74.

Giant. 1a and 1b show a preferred and simultaneous form of a condensing unit. The other figures show an earlier version of the condensing unit, although the same principles apply to both units.

In FIG. 1a and 1b, the condensation unit A has support portions 170 and a frame 172 carrying transverse condensation tubes 174.

As with all embodiments, the assembly of condensation tubes 174 is intentionally left simple to provide a large transfer surface. This avoids the complexity of problems with more complex arrangements, including complex fin designs, etc. Here are four layers of cross tubes 176, designated as 178, 180, 182, and 184. Worst Pipe Layer ·

• * - · * 9 9 9 9 9

0 0 · 0 0 0 · 0 <0 0 0 0 0 0 0 0 0 0 0 0 »» »» »» »»

178 has two channels at each end. The other two layers of tubes 180, 182 each have six conduits connected so that the condensed oil flow flows back and forth across the condensation unit 4. The lowest conduit layer 184 is substantially horizontal and includes three transverse conduits.

As desired, the conduits may be provided with an end access door, drain valves and the like. Specifically, the fifteenth transverse tube 176 is designated in 186, this being the first tube in the lowest layer 184. This conduit 186 is provided with a drain valve to allow, for example, the sampling of condensed oil.

The outlet of the last pipe in the row is connected to the final product pump 190 to supply condensed oil to the tank.

Giant. 2a and 2b show an alternative embodiment of a condensing unit. The assembly of condensation tubes 74 is intentionally maintained here by simple, while providing a large heat transfer surface, in order to avoid the problems associated with complex designs, for example, complex rib designs. Thus, condensation tubes include a plurality of transverse tubes 76 arranged in two sloped layers designated 78 and 82. The layers 78 and 82 are generally similar, although the size of the tubes varies between these layers. The first layer comprises a first portion 79 of larger tubes and a second portion 80 of smaller tubes similar to the second layer 82. The reason for this is that a greater percentage of steam is required in the first portion 79 requiring a larger volume. Otherwise, the arrangement in the different layers is generally similar and is described in relation to the topsheet 78.

In the first part 79 of the upper layer 78 the tubes are of larger size 76 and in the second part 80 the tubes are smaller 77. These tubes 76 and 77 extend transversely, i.e. perpendicular to the plane of FIG. 2.

• 9 • • t t t 9 t t 9 9 9 9 # 9 # # # # # # # # # # 9 9 9

9 9 9 9 9

9999 9999 9 9 9 99 9 9 9 ·

The tubes 76, 77 are each provided with one access plate 75 which are secured at alternating ends of the tubes. In FIG. 2a only the access plates on one side are shown. The alternating ends of the tubes 76, 77 are connected through one another to provide a meandering or zigzag path. In other words, the steam entering the uppermost tube 76 from the connecting tube 40 will flow to one end of the tube and then through the next cross tube 76. The steam then moves along the path of the tube 76 before flowing down into the next cross tube 76 and so on. gave. A connecting pipe 81 is provided between the layers of the pipes 78, 82. Subsequently, the steam flows in a zigzag or sinusoidal path through the pipes 76, 77, and the topsheet 78 and then the connecting pipe 81 to the upper end of the layer 82 where the process is repeated. this layer comprises exclusively smaller tubes 77. The bottom layer 82 terminates at the recovery 84 for the recovered oil that is collected in the recovery tank 86. This tank is equipped with a float switch to limit the level of recovered oil in the tank 86, as detailed below.

While FIG. 2a shows a heat exchange conduit that extends transversely, preferably the embodiment of FIG. la a lb. Giant. 2b shows an exemplary arrangement of large cross-sectional tubes for the upper portion of such a heat exchanger. As before, the tubes 76 have an access door 75, which will be used for cleaning, to prevent the build-up of carbon deposits. Between adjacent pairs of tubes there is a short connecting tube 94 and spacer brackets 96, these features being present in all layers of the pipeline, but are clearly shown only in FIG. 2a.

The topsheet 78 is enclosed within the housing 90 (FIG. 1). At the top of the casing are six individual fans 92, arranged to draw air from the ambient atmosphere and blow it through layers of this tube 78, 02. So, that the cooling air flow to effect steam condensation is effectively in the same direction as the steam flow.

In use, any steam present is condensed in the heat exchange conduit. For this purpose, small drainage taps (not shown) are provided and the corresponding drainage channels lead to a water collection tank (also not shown). If large amounts of water are generated, a pump can be supplied to remove them and the water can be treated in a water / oil separator. It is preferred to treat the waste oil in a pretreatment device to remove water vapor prior to treatment. This pretreatment device simply heats the waste oil to a temperature above the boiling point of water to remove water vapor. Another alternative where the water is not separated in the condenser is to separate the water from the recovered oil.

In use, the device is operated for a period of time, with the waste oil continuously fed to the evaporation chamber 22. At the same time as the tank 86 is provided, this is periodically emptied as it is filled. This causes the level of solids or pollutants in the evaporation chamber 22 to increase. During this time, the temperature controller 128 is set at a desired temperature, e.g. between 315.5 ° C to 426.6 ° C, as taught in my earlier patent No. 5,271,808. It has been found practically that the device will operate at an almost constant temperature , depending on the material supply, and the actuator may be set to a certain limit above the actual operating temperature.

·· ···· · · · · · · · · · · · · · · · · · · · · · · · · ·

(modified sheet)

It will be appreciated that, notwithstanding the issue of handling the accumulated solids, as described below, the entire process is essentially a continuous, flow-through process, without tanks or vessels requiring significant residence times therein.

After some time, the accumulation of solids in the chamber 22 requires the device to be turned off. Means may be provided for monitoring the accumulation of solids, for example by providing them for regular samples and controlling the contents of the chamber 22. The exact level of solids that can be tolerated will depend on the formation of the chamber 22, and particularly on the means of supplying heat therein. The accumulation of solids acts as an insulator and limits heat transfer from the hot gases around the fluid chamber 22 therein. It is proposed to provide tubes running through the chamber 22 through which hot gases will pass. This would improve heat transfer and allow more solids to accumulate within the chamber 22.

Once it has been determined that the maximum permissible solids level is present, the waste oil supply is then switched off and the firing mode is started. At this time, the burners can continue to operate. The low level switch is blocked so that the waste oil level (level) can be lowered below that normally allowed. The fans continue to operate as long as the temperature sensor continues to sense temperatures above this setting.

When the heat exchanger 4 is sufficiently cooled, indicating that oil production has almost stopped, the heat sensor and the control circuit will start a firing cycle. The temperature in the evaporation chamber 22 is then raised to a final, firing temperature to remove as much volatile or liquid components in the evaporation chamber 22 as possible. This temperature is set by the control panel. temperature. The temperature controller could initially be set at 482.2 ° C. For the final firing step where the sludge supply is off, the temperature could be set to 704.4 ° C.

The effect of this is to leave behind a solid, cake-like material that can easily be extracted from the evaporation chamber 22. This firing step is carried out until no more volatile substances are condensed and collected in the condensing unit as determined by the firing timer.

When the device is sufficiently cool, the access door 34 is opened to remove solid residual matter. The access door 30 will then be closed and the process can be restarted with the next batch of sludge.

In accordance with the present invention, there is provided means for injecting hydrogen into gases or vapors at the top of the vaporization chamber 22. This has been accomplished by providing a source of hydrogen denoted by 100 and a supply line 102 connected to the chamber 22. As shown, section 104 of this the supply line passes through oil and / or evaporation in the chamber 22, has an extended length and opens next to the top of the chamber 22. The supply pipe 104 is shown schematically and includes a portion next to the bottom of the chamber 22 that provides multiple passages of liquid oil to ensure proper heating of hydrogen . This ensures that the hydrogen is preheated to the temperature of the chamber 22 before being injected into the steam stream exiting the chamber 22 and through the outlet 38 to the connecting line 40. At three different levels, in the perpendicular part of the outlet 38 and / or vertical part of the connecting line 40 is

• ·

15A (treated sheet) body of nozzle arrangement 106.

The arrangement of the nozzles may be such that hydrogen is injected into the steam stream. When the oil evaporates, the waste oil tends to foam to some extent. However, the formation is such that the lower nozzles 106 are out of the foam so that hydrogen is injected just into the vapor phase.

The arrangement of the nozzles may be such that hydrogen is injected into the steam stream. When the oil evaporates, the waste oil tends to foam to some extent. However, the formation is such that the lower nozzles are outside the foam so that hydrogen is injected into the vapor phase.

To test the efficiency of this hydrogen injection treatment, tests were carried out on a pretreatment apparatus as shown in the accompanying figures, as well as on a scrubber as shown in FIG. 1 and in accordance with the invention disclosed in U.S. Patent No. 5,271,808. Details of these assays are provided below. In both cases, the hydrogen was preheated as described above, with hot oil in the evaporation chamber, and then fed to the vapor, above the hot oil in the chamber.

• tt tttt * · tttt ·· tttt tttt

Tests were carried out with a pretreatment equipment and a cleaner that had been thoroughly cleaned to ensure that tar deposits were removed. For both units, samples were collected during the hydrogen addition after these units had operated for a sufficient time, about six hours, to achieve a steady state condition. For samples collected without the addition of hydrogen, before the liquid and gas samples were taken, the unit units operated for one or two hours after closing the hydrogen.

In the pretreatment apparatus illustrated herein, the waste oil supplied was a waste oil from a variety of industrial uses, primarily crankcase waste oil. Oil was supplied to the cleaner and was pretreated with the pretreatment apparatus shown and described herein.

Liquid and gas product samples were collected for both units working with and without hydrogen injection. Liquid samples were taken from the oil feed pump to the pretreatment equipment and from the product outlet port. In the cleaner, since the inlet was the outlet of the pretreatment device, a liquid sample was taken from the outlet of the product. For the pretreatment equipment, a sample was additionally collected from the drain valve on the condensation line 186.

In addition, in an attempt to obtain a representative sample of the total purifier product containing any volatile substances that could be vented to the atmosphere, a sampling system was used to collect samples from the transition conduit 40 connecting the evaporator chamber to a condenser in a pretreatment apparatus and the like. cleaner. The steam sample taken from this location was passed through a water-cooled condenser. Condensed liquids collected • 9 99 ·· 9999 99 99

9999 9 · 9999

9,999 99 · · · ·

0 9 9 9 999 99 · • 9 99 9999 «• 999 9999 <9 999 99 99 in a glass container. All remaining gases were passed through a quartz wool plug and either vented or collected in a gas bag. For both units, a sample was collected from the connecting tube and fed to a collecting condenser. The tube leading to the collecting condenser was insulated, with the intention of preventing vapor condensation, until it reached the condenser of this sampling system.

The pretreatment device or primary processing device has been found to have a gas flow from the sampling system after fluid condensation. A sample of this gas was collected in a gas bag, both with and without hydrogen. This gas bag was then sent for analysis to a research facility. As for the pretreatment cleaner or apparatus, there was no pressure in the transfer line so that no sample could be collected.

The following Table 1 summarizes the operating conditions of the pretreatment equipment and cleaner during sampling and testing:

• · · · · · ·

Cleaner

Model 320 ··

9 1 1

11 1 1111 19 9 119 • 911 9199 1 · 911 1 · ··

TABLE 1: Operating conditions during sampling

Preliminary equipment. pracov.

Model 510

Preliminary equipment. pracov.

Model 510

Cleaner Model 320

FLOWS without H ₂ with H ₂ without H ₂ with H ₂ supplied oil 946.3 1 / hr 1514 1 / hour ¹ 1097.7 1 / hour sludge 151.4 1 / hour 264.9 1 / hour ¹ 121.1 1 / hour product 757 1 / hour 1078.8 1 / h ¹ 946.3 1 / hr levels. oils (evaporation chamber 22) 508 mm 647.7 mm 508 mm TEMPERATURES bottom (Evaporation chamber 22) 687 ° C for ³ N / A ⁴ 307 ^u C ² oil in evaporator. 387 ° C to chamber 22) 360 ° C 265 ° C output 38 385 ° C 373 ° C ON connecting pipe 40 207 ° C 294 [deg.] C ON input cond. Unit 4 207 ° C 393 ° C 207 ° C cond output unit 4 Deň: 27 ° C Deň: 18 ° C Deň: 31 ° C PRESSURES evaporate. Chamber 22 27 9 mm H ₂ O 406, 4 mm H ₂ 0 0 cond. Unit 4 228.6 mm H ₂ O 330.2 mm H ₂ O 0

• 9 ··· 9

94

9 4 9 4 4 9 9 4 4 9

4 9 9 444 4 9 9 4 • · · · 9 4 4 4 9 9

9 9 4 4 4 4 4 · ¹⁾ The difference between these digits is due to the changing oil level in chamber 22.

²⁾ This temperature is much lower than that of the pretreatment equipment because much lighter oil is processed.

³⁾ Note that this is for normal, uninterrupted operation and not for the firing method.

⁴⁾ N / A - Not available.

During these tests, for the pretreatment equipment, 80 liters of hydrogen per minute were supplied in addition to the outlet of the evaporation chamber 22. Assuming a product flow of 1097.7 liters / hour (comparable to 1078.7 liters / hour in Table 1) from the outlet of the evaporation chamber 22 and a boiling point distribution between 70 ° to 400 ° C, hydrogen will be present at an estimated concentration of 3.2% If all of the hydrogen had reacted to the product oil, the addition of hydrogen to the oil would be about 0.04% by weight.

During the hydrogen addition test, the temperature in the outlet 38 of the evaporation chamber 22 was 30 ° C higher than the oil temperature in the chamber 22, while without hydrogen addition the gas temperature was 2 ° C lower than the oil temperature. This is to be expected since hydrogenation is an exothermic reaction. Typical reaction heats for olefin hydrogenation range from 133 kJ / gmol to 125 kJ / gmol of reacted hydrogen. Using the above flow rates and assuming that all of the hydrogen reacted with the olefins, the temperature of the gas leaving the pretreatment equipment would be expected to increase by 8 ° C. A higher temperature rise would occur if part of the hydrogen reacted with oxygen-containing compounds to form water, providing a reaction with greater heat. The elevated outlet temperature shown in Table 1 indicates that hydrogenation has occurred. Bearing in mind the large number of reactions that could have occurred, a temperature rise of 13 ° C is this this •·· • this •·· totototo • · ········ · · ··· ················································································································ compounds. As noted, gas samples were collected into the gas bags from the pre-treatment connection pipe 40, one when hydrogen was added and the other without hydrogen. Samples were collected in gas bags after condensation of vaporized liquids. For these tests, it was necessary to send this gas, in gas bags, to a separate test facility. Ideally, for accurate gas analysis, a gas chromatograph should be attached directly to the device, but this was not possible. In addition, the collected gas should be analyzed immediately, which in turn was not possible. The gas analysis is presented in the following Table 2. These samples appear to indicate contamination as indicated by the high content of O ₂ and N ₂ and should therefore be considered with caution. Table 2 provides the concentrations as analyzed and after normalization in air and missing components (for example, light volatile components or gas that have been fired). Even then, these analyzes may not be quite accurate; however, some general observations can be made from normalized concentrations. The hydrogen concentration was three times higher in the gas phase when hydrogen was added at a rate of 80 liters per minute. There are also many differences in gas composition, which strongly suggests that hydrogen has reacted with products from the evaporation chamber, namely: the CO to CO ₂ ratio has decreased from about 4: 1 without hydrogen to about 1: 4 without hydrogen; methane concentration dropped dramatically from more than 50% below 4%; the ratio of ethane to ethene was 1: 1 without hydrogen and about 6: 1 with hydrogen; H ₂ S or other sulfur-containing compounds were not captured with or without hydrogen in the gas analysis.

• 0 00 0 * 0 · 00 0 · 00 0000 00 00 0000

0 0 000 · 0 00 »• 00

TABLE 2: Composition of gas sample from transition pipe of Model 510 or Purifier equipment

Normalized composition (volume%) CM WHAT 90.34 3.84 0.91 vO tn cn 0.26 1.80 2.81 CM rc N Φ ri 29.46 1.20 j 5.03 i 1 1 WHAT r— < what tn 5.45 1 5.00 0.72 Composition (volume%) WHAT [5.26 O i — t O 0.04 0.15 0.01 80Ό 0.12 19.03 76.70 -1.56 CM rc N φ Λ tx tx c4 0.11 1 tx O 5.00 0.51 0.47 0.07 11.82 1 1 67.89 10.89 • Component CM £ ï at WHAT £ O in £ CM at O £ CM at Also other HC'S CM O CM £ and missing 1

fefe fefe fefe fefefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe

The following Table 3 lists the collected samples, together with comments on their physical appearance. There was insufficient pressure on the Cleaner Model 320 to obtain a fluid sample from the manifold. One sample of 150 ml was taken during the hydrogen addition operation by applying a slight vacuum to the sample. Table 3 additionally contains visual perception notes about collected liquid samples immediately after collection. As with the other samples taken, the sample containers were purged with nitrogen and maintained from exposure to light. Since the samples were sent to a remote examination facility, they were eventually received seven days after they were collected and during this time no observable change was observed on their physical appearance.

· 0 «0 00 00

0 0 0 0 0 0

00 »» 0 0 0 • 0 000 00 0

0 0 0 0 0 ·

000 00 40

TABLE 3: liquid samples taken * · • 00 »·· ·

0 0

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Comment:

Unit 510 - pretreatment equipment

Unit 320 - Cleaner (For Sample 9, this sample was taken from a location around the fourth or fifth condensation piping, counted from the top of the condensation unit 4).

The following Table 4 shows the results of the analysis of liquid samples taken from the primary or pre-treatment equipment, Model 510, while Table 5 shows the corresponding results of analysis of liquid samples taken from the secondary treatment or cleaner, Model 320.

• ·

• * »» 9 · · · · · · · · · · · · · · · · · · · · · · ·

TABLE 4: Analysis results of liquid samples taken from the primary processing equipment (Model 510)

Elemental analysis (weight%) 1- O* 1.05 1 m 00 O τ— < in O 0.42 and oo r-l O Ch ix MO 00 87.90 t / 5 1.29 89Ό 0.56 0.59 0.48 0.16 80 * 0 OF 0.27 0.037 0.036 1 0.041 0.029 0.322 0.182 12.20 13.18 13.03 12.80 1 13.01 10.83 rn at 85.19 85.27 85.86 86.15 86.30 ί 1.90 i 0.74 x: o \ o x o w to> 1 ω x what x <-t Λ 0> o> o X> 4-1 - 1.41 0.007 0.026 0.042 1 i 0.025 0.17 1 0.036 (0 » x υ CO -χ. x it W 8906Ό 0.8215 0.8360 0.8628 0.8524 1.0309 1.0097 j W o o e o O · rH 5-1 O> 4 «Z á * 10 j 20.5 12.3 7.3 5.4 0.3 0.37 ₍ Number r-H tx M0 CM Condenser # 15 (mainly water) m WHAT Sample 1 1 AND | '' supply Connecting pipes 40 CM rc N Φ x CS | TO what Product CM TO N Φ rt CM w what CM W N $ Ux CM rc <0

oxygen content determined by difference • ·

TABLE 5: Results of analysis of liquid samples taken from secondary processing equipment (Model 320)

Elemental analysis (weight%) O* ί 0.18 0.22 with O 0.59 <Λ 00 in* O 0.22 1 0.23 0.22 1 OF 0.029 0.019 Ch r- < O O 0.025 X 13.01 13.35 13.23 13.19 at 86.30 86.19 85.78 i 85.97! Content solid bodies (weight%) 0.025 - 1 800Ό 0.003 what O O O «3 2 6 what 3 to 0.8524 1 0.8286 0.8307 IO what what 00 O Bromové No. (g / g) ί 5.4 1 6.5 5.2 8.6 Number CM ON O rH Ch 00 Sample Ϊ Ό O > mH fa · Connecting 1 pipe 40 1 Ol N <D Λ 1 Ή what Product 'Ol w N Φ Λ Ol w w

• · · ·

These analyzes revealed that Samples of Nos. 3 and 5 taken from one of the condensation lines on condensation unit 4 were predominantly water containing a small amount of hydrocarbons. For Model 320 there were no significant differences with and without hydrogen.

In the pretreatment apparatus, the effect of hydrogen addition shows a comparison of Samples 1, 2, 4, 6 and 7. The oil sample of the product from this hydrogen addition apparatus was a lighter liquid than the sample taken without the addition of hydrogen. This is consistent with the lower density measured in the hydrogen addition product.

The olefins can be unstable compounds that lead to the formation of tar in petroleum products. The bromine number analytical method, performed in accordance with ASTN D 1159, measures the amount of bromine reacted in grams per 100 grams of oil sample. Bromine reacts with double bonded carbon, except aromatics, in a hydrocarbon liquid and provides a measurement of the amount of olefins in a given sample. Changes in bromine number greater than + or -1 are important.

Here, the samples taken from the connecting line 40 on the Model 510 pre-treatment apparatus exhibit the greatest differences in bromine number, as between samples with and without the addition of hydrogen. The bromine number increased from 12.3 to 20.5 when the hydrogen flow was stopped. The bromine oil number of the product also increased slightly without the addition of hydrogen, from 5.4 to 7.3. Decreasing the bromine number using hydrogen indicates that the olefins become saturated by the addition of hydrogen.

Here it can be noted that both the pretreatment device and the purifier tested retain large volumes of product oil in their capacitors. As such, the unit may not have been operated long enough without hydrogen flow to empty all product oil from the capacitors and to achieve a steady state without hydrogen. A longer period of operation without hydrogen gas flow will be necessary to ensure that the product oil sample taken from the condensation of the unit in question is truly representative. Note that liquid samples taken from the connecting line between the evaporation chamber and the condensing unit, which show a significant change in bromine number, are likely to better reflect the effect of hydrogen addition because they were not affected by the relatively large liquid volumes of the condensing units. This product oil retention can explain why there are changes in bromine number. The change in bromine number for the product oil samples was not as great as the transition line samples.

The differences in oil density were not great with or without hydrogen flow. The oil supply density of 0.9 was reduced to 0.85 in the Model 510 and 0.83 after further treatment in the Model 320 cleaner. Lower density 0.82 to 0.83 in Samples Nos. 4 and 7 taken from the manifold 40 indicates that the sampling procedure did not effectively recover heavier liquid products. Higher boiling components are likely to condense in the manifold. The lower density of liquid samples in the pretreatment apparatus, Model 510, when hydrogen was added, is consistent with the conversion of olefins to paraffins having a lower density.

Regarding the filtered solids content of the samples in Tables 4 and 5, despite the raw material, which is known to have a relatively high solids content, various concentrations were low and insignificant.

With respect to elemental analysis, there are no large differences in elemental composition with or without hydrogen in the samples taken from the pretreatment unit unit 510. The sulfur and oxygen contents were slightly reduced in both the connecting line 40 and the oil samples of the hydrogen-added product.

• ·

The oxygen content was not measured directly, but determined by the difference from the analyzed C, Η, N and S. The increase in the H / C ratio of the pretreatment equipment liquids when hydrogen was added is again consistent with the addition of hydrogen to the liquids. There was little difference in the elemental analysis product oils taken from the Model 320 purifier with or without the addition of hydrogen.

The following Table 6 provides a simulated distillation of the products supplied and indicates the boiling point distribution. Thus, the IBP indicates the initial boiling point and the FBB indicates the final boiling point, and the numbers 10, 20, etc. indicate the boiling point after 10%, 20% etc. of the original sample have evaporated.

TABLE β: _Simulated distillation of supplied raw material and products

Distillation results Ph CQ U- < > 615 1 511 514 395 IX CN WHAT 90 and 1 414 389 310 307 80 1 1 380 j 350 ' 285 281 70 539 352 319 266 264 09 / 466 326 294 250 250 ί 50 and 1 and 412 302 265 236 236 40 1 1 358 in CM 3 CM 220 222 30 and 306 249 178 203; 207 20 May 258 220 and 72 183 189 1 01 212 181 41 159 164 CQ A ►— <Ph 100 ALIGN! 90 <36 87 1 1 87 J Sample no. Ί r-t O CM CN oo - Delivered waste, oil Model 510 (preprocessing) 04 / w N <D d 04 / TO it Model 320 (cleaner)) 04 / w N Φ d 04 / w ra

Which is a treatment cleaner; valve

The cleaner product oil, Model 320, had a lower boiling point than the oil supplied as shown in Table 6. There was little or no difference in the boiling point distribution for the cleaner product, Model 320, with or without the addition of hydrogen. In the pretreatment equipment, Model 510, the initial boiling points for the lower fractions were greatly reduced, although the final boiling point was slightly higher.

The hydrogen delivery control system preferably comprises a number of safety features. These may include: placing the hydrogen tanks outside the main building, or, optionally, a hydrogen supply pre-closing device located in the hydrogen supply tanks, which may be operated remotely from the control panel; check valves in the hydrogen supply line to prevent oil return to the hydrogen supply line; integration with a purge control system or pretreatment device to include automatic shut-off of hydrogen during start-up, stopping conditions and interruptions or difficulties to minimize hydrogen supply when hydrocarbon vapors are absent; adequate building ventilation and insulation to ensure that any vented hydrogen is dispersed, and hydrogen detectors secured at the highest point in the building.

The data collected during the pre-treatment experiments, Model 510, indicate that the hydrogen gas injected into the vaporization chamber 22 reacted with the product vapors. The addition of hydrogen had the following measured effects:

increasing the gas temperature in the connecting line 40; a reduced olefin content in the oil samples taken (1) (2) from the connecting line 40;

99 99 99 99 999 99 99 99 99 9 99

9 9 9 9 999 9 ··

9 99 9 · 9 9 9 (3) reduced density and boiling point distribution of the final oil product;

(4) a slight reduction in the sulfur content and possibly oxygen content of the product oil;

(5) reduced ethylene concentration and increased ethane concentration in the product gas.

Claims (15)

PATENT CLAIMS (Adjusted Claims) A method for recovering a useful oil product from a waste oil, the method comprising the following steps: (a) heating the waste oil to evaporate the oil therefrom; (b) injecting hydrogen gas into the vaporized oil to cause saturation of at least some olefins and free radicals present in the vaporized oil; and (c) recovering the evaporated oil as a useful oil product; wherein the process is carried out at substantially atmospheric pressure. 2. The method of claim 1, comprising vaporizing the waste oil at a temperature sufficient to cause at least partial cracking of the waste oil. Method according to claim 1 or 2, characterized in that it comprises as step (4), after step (3), condensation of the evaporated oil. A method according to any one of the preceding claims, comprising heating the waste oil in the evaporation chamber, continuously supplying the waste oil to the evaporation chamber, and monitoring the level of the waste 9 · 99 ··> oil in the evaporation chamber to maintain its level within the specified limits. The method of claim 4, comprising passing the vaporized oil through a conduit from the vaporization chamber to a condensing unit and condensing oil vapor therein, wherein step (2) comprises injecting hydrogen into the oil vapor in at least one vaporization chamber and connecting pipes. 6. The method of claim 5, comprising passing hydrogen through a conduit passing through the liquid waste oil in the evaporation chamber to preheat the hydrogen to the temperature in the evaporation chamber, and then injecting hydrogen into the oil vapor in the at least one evaporation chamber and the coupling. conduit. The method of claim 5 or 6, further comprising providing a catalyst in the manifold, and passing hydrogen gas and vaporized oil through the catalyst to promote hydrogenation of at least some olefins and free radicals. Method according to claim 6, characterized in that it comprises an additional step (5): after a certain period of time, interrupting the supply of waste oil to the evaporation chamber and continuing to heat the evaporation chamber and the waste oil therein in the firing method to a substantially higher temperature to essentially all of the residual waste oil was evaporated and a solid residue (residue) remained inside the evaporation chamber. • · The method of claim 8, comprising the additional step (6): after all the waste oil has been evaporated from the evaporation chamber, allowing the evaporation chamber to cool, opening the evaporation chamber and removing the solid residue therefrom. 10. An apparatus for recovering a useful oil product from a waste oil comprising: an evaporation chamber with a waste oil inlet and a vaporized oil outlet as a useful oil product; heating means for heating an evaporation chamber to evaporate oil from the waste oil; means for injecting hydrogen into the waste oil vapor; means for recovering evaporated oil; and means for maintaining the evaporation chamber at substantially atmospheric pressure. Apparatus according to claim 10, characterized in that it comprises condensation means and a connecting line connecting the outlet of the evaporation chamber to said condensation means. 12. The apparatus of claim 10 or 11, wherein the means for injecting hydrogen comprises an opening of the conduit into at least one upper portion of the evaporation chamber and the connecting conduit. Apparatus according to claim 12, characterized in that a portion of the conduit extends through the lower portion of the evaporation chamber, whereby the hydrogen in the conduit is heated by the waste oil to a temperature inside the evaporation chamber. ♦ · · · · ί ί ί ί ί ί ί ί ί Apparatus according to any one of claims 11 to 13, wherein the vaporization chamber comprises an inlet for waste oil and the apparatus comprises a pump means for supplying the waste oil to the vaporization chamber; and a level control means for monitoring the level of waste oil within the evaporation chamber, the oil level control means being connected to the pump means and actuating the pump means to maintain the level of the waste oil within the desired limits. 15. The apparatus of claim 14, wherein the heating means is connected to the oil level of the control means and, in normal mode of operation, is blocked if the oil level exceeds the desired limits and which comprises means for blocking the waste oil level control means and interrupting the supply of waste oil to allow the heating means to continue to operate in the firing method in which the evaporation chamber is heated to an elevated temperature to evaporate the remaining waste oil.