GB1598723A - Reclaiming used lubricating oils - Google Patents

Description

(54) RECLAIMING USED LUBRICATING OILS (71) We, PHILLIPS PETROLEUM COMPANY, a corporation organised and existing under the laws of the State of Delaware, United States of America, of Bartlesville, Oklahoma, United States of America, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to treatment of used lubricating oils.

In one of its aspects this invention relates to the removal of impurities of used lubricating oils. In another of its aspects this invention relates to the removal of additive systems from used lubricating oils so as to provide a lube oil stock. In still another aspect of the invention it relates to the removal and separation of such specific contaminants as gasoline, metal components, and nitrogen, sulfur and oxygen compounds in a process for treating used lubricating oils.

In one of its embodiments this invention relates to the reduction or removal of contaminants from a used lubricating oil by a series of treatments of the used lubricating oil.

In another embodiment of this invention, oil purified by the overall integrated process of this invention is suitable for use as a high-grade lube oil stock which can be employed in the production of high-grade lubricating oil.

In recent years more and more additives such as detergents, pour point depressants, oxidation inhibitors and viscosity index improvers have been employed in petroleum lubricating oils. While these additives have greatly improved the performance of the lubricating oils, they have also greatly increased the task of reclaiming such oils after use.

More particularly, resins that normally form in the oil while in use, as well as carbon, dirt, wear metals and other impurities, remain suspended in the oil in the engine by means of modern detergent additives, such as calcium and barium salts of alkyl benzene sulfonic acids, and ashless type detergents, such as alkyl-substituted succinimides. Eventually the suspended impurities are thus largely eliminated from the engine during oil changes and remain within the drained oil.

The economic removal of impurities from used high-detergent lubricating oils, so that the oil may be reused, has proven to be no small task for the reclaimer and is becoming increasingly difficult as more effective detergents are being added to the oils.

Moreover, the modern additive systems have presented a further problem in that such additives must also be removed from the oil stock if the resulting lube oil stock is to be suitable for reformulation to a high-grade lubricating oil.

The purification process used in the past for the separation of carbon and dirt particles from lubricating oils containing no or relatively ineffective detergent additives cannot be satisfactorily used to purify today's high-detergent oils. Since nearly all mineral lubricating oil used today is of the high-detergent variety containing numerous additives, and since service stations tend to place all crankcase drainings into a common tank, practically all used lubricating oil available for re-refining or reclaiming processes has high-detergency properties.

In accordance with one embodiment of this invention, an integrated process is provided which is universally applicable to all used lubricating oils in which the used lubricating oil is contacted with an aqueous solution of an ammonium salt treating agent. Following reaction of the treating agent with ash-forming contaminants of the oil, the bulk of the water phase is removed from the resulting mixture along with any light hydrocarbon, such as gasoline, in the oil by distillation of the treated oil/water mixture. The residual oil phase is then treated, preferably by filtration to remove the insolubilised ash-forming contaminants and thereafter subjected to hydrotreating and stripping thereby to provide a high-grade lube oil stock free of both solids and additive systems. The light hydrocarbon and water mixture is cooled and allowed to separate into a light hydrocarbon and a water layer. The hydrocarbon layer is then pumped to storage and the water layer can be reused in the system.

In accordance with another ambodiment of this invention, a method for reducing the ash content of used lubricating oil is provided in which the used oil is contacted with an aqueous solution of an ammonium salt treating agent under conditions such that the ammonium salt treating agent will react with ash-forming metal components present in and entrained in the used oil. Following removal of essentially all of the water and light hydrocarbons present in the reaction mass by distillation, the resulting mixture, being essentially free of water, is then separated to provide an oil phase substantially reduced in ash-producing contaminants.

More specifically, in accordance with one embodiment of this invention we have discovered a universally applicable process for removing solid or ash-forming contaminants from used lubricating oils so as to provide an essentially ash-free oil suitable for various industrial purposes which comprises (a) contacting the used lubricating oil with an aqueous solution of a treating agent consisting essentially of an ammonium salt under conditions of temperature, pressure and time sufficient to disperse the agent in the used lubricating oil and to react the agent with the ash-forming components of the used oil; (b) removing a major portion of water from the resulting mixture of used lubricating oil and treating agent from step (a) by distillation; (c) separating the oil phase from the residual mixture resulting from step (b) and thereafter recovering the resulting oil phase as a product of the process.

In accordance with another embodiment of the present invention, we have discovered a universally applicable integrated process for the reclaiming of essentially all used lubricating oils regardless of the initial additive system contained therein which comprises (a) contacting the used lubricating oil with an aqueous solution of a treating agent consisting essentially of an ammonium salt under conditions of temperature, pressure and time sufficient to disperse the agent in the used lubricating oil and to react the agent with ash-forming components of the used oil; (b) removing a major portion of water from the resulting mixture of used lubricating oil and treating agent from step (a) by distillation; (c) separating the oil phase from the mixture resulting from step (b); (d) subjecting the oil phase to hydrotreating in the presence of hydrogen and a hydrotreating catalyst under conditions of temperature and pressure and time sufficient to produce a hydrotreated oil stock; (e) stripping the resulting hydrotreated oil in a stripping zone and thereafter recovering the resulting hydrotreated lube oil stock as a product of the process.

The used lubricating oils treated by the process of this invention are primarily the discarded oils that have been used for internal combustion lubrication purposes such as crankcase oils, e.g., in gasoline engines or diesel engines. Other sources of used oils include steam-turbine oils, transmission and gear oils, steam-engine oils, hydraulic oils, heattransfer oils and the like.

The oils for the purposes named above are the refined lubricating cuts from paraffin-base, mixed-base, or naphthenic crudes. Their viscosities are generally in the range of from about 100 to about 1,800 SUS at 1000F. The oils also contain various additives such as oxidation inhibitors (e.g., barium, calcium and zinc alkyl thiophosphates, di-t-butyl-pcresol, etc.), antiwear agents (e.g., organic lead compounds such as lead diorganophosphorodithioates, zinc dialkyldithiophosphates, etc.), rust inhibitors (e.g., calcium and sodium sulfonates, etc.), dispersants (e.g., calcium and barium sulfonates and phenoxides, etc.), viscosity index improvers (e.g., polyisobutylenes, poly-(alkylstyrenes), etc.), deter gents (e.g., calcium and barium salts of alkyl benzene sulfonic acids) and ashless-type detergents such as alkyl-substituted succinimides, etc.

If desired, water entrained in the untreated used lubricating oil can be removed before use of same in the process of this invention. Such a separation can be readily achieved by removal of the water phase which may occur in the storage tanks for the used lubricating oil.

The ammonium salt treating agents which are useful in the process of the present invention are those selected from ammonium sulfate, ammonium bisulfate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, as well as mixtures thereof.

In addition, if desired, precursors of said ammonium salts can be employed instead of part or all of the ammonium salt. Some examples of said precursors include ammonium thiosulfate, ammonium polyphosphates such as ammonium metaphosphate, urea sulfate, guanidine sulfate, urea phosphate, and guanidine phosphate. Other applicable precursors include reactive combinations of ammonia and/or ammonium hydroxide with sulfuric acid and/or phosphoric acid and/or an ammonium hydrogen sulfate or phosphate, i.e., ammonium bisulfate, diammonium hydrogen phosphate, and/or ammonium dihydrogen phosphate. When the precursor comprises a combination of such components reactive with each other to give the desired salt in situ, the components of the combinations can be introduced at the same time, or either component can be added prior to the introduction of the other component.

Although the concentration of treating agent in the aqueous solution of treating agent is not critical and more dilute solutions can be used, the economics of the process are enhanced by the use of relatively concentrated solutions in order that the amount of water to be removed subsequently will not be great. Generally the concentration of treating agent in the aqueous solution will be within the range of about 30 to about 95 weight percent, typically about 80 weight percent, of that in an aqueous solution at 250 C. saturated with the treating agent. Frequently some water will be found in used oil, and in these instances the concentration of the treating agent can be adjusted accordingly.

In the process of this invention, the treating agent should be employed in an amount at least sufficient to react with all of the metal constituents in the used oil. Although the weight ratio of the treating agent to the used oil can vary greatly, depending in part upon the nature and concentration of metal-containing components in the oil and on the particular treating agent employed, generally it will be within the range of about 0.002:1 to about 0.05:1, most often being within the range of about 0.005:1 to about 0.015.1, and typically being about 0.01:1. Although larger amounts of treating agent can be used, in most instances this would be wasteful of treating agent.

To illustrate further the overall process of the present invention, the following descriptions are provided which, taken in conjunction with the attached drawings of which Figures 1 and 2 are schematic representations of the process of this invention, set forth the presently preferred modes of operation.

Referring now to Figure 1, used oil from storage tank 1 is passed via line 2 to heater 3.

Aqueous treating agent containing diammonium hydrogen phosphate from makeup tank 8 is introduced via line 7, in an amount in slight excess of that required to react with the ash-forming constituents in the used oil, into admixture in line 2. Following heating in heater 3, the resulting hot admixture of oil and treating agent is passed via line 4 into a contactor 5 wherein sufficient agitation is provided, such as by the action of paddles 6, to assure thorough dispersion of the aqueous treating agent into the oil phase of the mixture introduced into the stirred contactor 5. While it is presently preferred that the aqueous treating agent be added upstream of heater 3 due to the relatively small volume of agent being employed, the aqueous treating agent can be added either downstream of heater 3 into conduit 4 or directly to the contactor 5.

The admixture of used oil and aqueous treating agent is maintained in contactor 5 for a period of time and under conditions of temperature and pressure sufficient to effect reaction of the treating agent with essentially all of. the ash-forming components present in the used oil.

Following adequate reaction of the ash-forming components in the hot oil with the treating agent, the resulting reaction mass having a continuous oil phase is passed via conduit 9 to the upper portion of stripper 10. In one embodiment of the invention, prior to the entry of the emulsion to stripper 10, a slurry of a filter aid in oil or in light hydrocarbon, e.g., from phase 44, can be added to the system from makeup tank 11 via line 12.

Filter aids which are useful in the practice of the process of this invention are those selected from the group consisting of diatomaceous earth, perlite, and cellulose fibers.

Presently preferred is diatomaceous earth.

In one embodiment of the invention, the upper end of stripper 10 is maintained at a temperature and a pressure sufficient to effect flash distillation of the bulk of the water and light hydrocarbon components of the mixture, which are thereafter removed and passed via line 13 to phase separator 14 wherein a hydrocarbon layer 15 and a water layer 16 are allowed to form. The hydrocarbon layer can then be transferred via line 17 to storage 18.

The water layer 6 can be removed via line 19 and discarded or employed for any desired purpose, such as, for example, use in a steam boiler.

The resulting residual mixture, which has a sulfated ash value of about 0.3 to about 10 weight percent (ASTM D 847-72) exclusive of any filter aid or excess treating agent present, comprising a hot oil phase which is essentially free of water but which has excess treating agent, some residual water, and filter aid, if used, in addition to the ash-forming solids originally present in or derived from the used oil, is passed downwardly through stripper 10.

While not required, it is presently preferred that while the oil is still at an elevated temperature, steam is introduced via line 40 to stripper 10 to assist in removal. of light components and residual water from the system. Thereafter, the resulting stripped hot oil is passed via line 20 to filter 21 to remove suspended and entrained ash-forming matter.

While a filter aid can be added to the emulsion prior to stripping, as described above, to assist in the subsequent separation of the solids from the essentially water-free oil phase, it is preferable that the filter 21 be precoated with a filter aid selected from those named above and applied directly to the filter. If desired, the filter aid can be used both to add to the emulsion prior to stripping and to precoat the filter.

In the presently preferred embodiment of the invention, filter cake from filter 21 is removed via line 47 and optionally passed to furnace 48 from which, following burning or calcination, the resulting ash comprising diatomaceous earth can be passed to waste via line 49 or recycled to slurry makeup tank 11 for further use in the system.

The filtered oil, being essentially free of ash-forming constituents previously contained therein, i.e., now having a sulfated ash value of about 0.01 to about 0.3 weight percent (ASTM D 847-72) exclusive of excess treating agent or any filter aid which inadvertently might have passed through the filter, is suitable for a variety of industrial uses such as fuel oils without further treatment in accordance with the integrated overall process of this invention. For example, the used oil at this point in the overall treating system of the invention can be used as a fuel oil, in grease formulations or in the preparation of some types of lubricating oil formulations. When so desired, the oil can be removed from the system via line 23.

However, in the presently preferred integrated process of this invention, the hot oil following filtration is passed via line 22 to heater 25 so as to raise the oil to a temperature in the range of 200"-480" C. If desired, a first portion of hydrogen is added thereto via line 24.

The resulting hot oil having added hydrogen therein is then passed through contactor 26 wherein decomposition is effected of the sulfonates contained in the oil.

While it is presently preferred that contactor 26 contain bauxite or an activated carbon adsorbent bed therein, this unit can employ other adsorbents such as those selected from the group consisting of silica gel, clay, activated alumina, combinations thereof, and the like. The adsorbent serves to effect breakdown and decomposition of the ammonium salts of sulfonic acids and the ashless detergents contained in the oil. The adsorbent further serves to collect a small portion of the resulting products and thus precludes passage of such undesirable decomposition products to the hydrotreater. Such adsorbents can be regenerated by conventional means and reused.

While less preferred, it is also possible to omit contactor 26 and to remove the small amount of ash components and highly polar materials present in the low-ash, filtered oil by heating the oil to a temperature within the range of about 300 -410 C., e.g., about 380" C., in the presence of hydrogen and an adsorbent suspended in the oil. After such treatment, the oil is cooled to a temperature within the range of about 60 -200 C., e.g., about 1500 C., and refiltered. The same adsorbents cited above for use in fixed contactors are suitable for this contact-treating process and give similar results.

Preferably, the adsorbent contains about 0.2 to about 20 weight percent of at least one metal selected from the group consisting of Group VIB and Group VIII metals, this weight percent being based on the total weight of modified adsorbent. This modified adsorbent can eand often preferably is prepared by impregnation of the adsorbent with an aqueous solution of a water-soluble compound of a Group VIB or Group VIII metal, followed by evaporation of water. Water-soluble compounds presently preferred for this use are iron compounds such as ferric ammonium oxalate, ferric ammonium citrate, ferric sulfate, and ferrous ammonium sulfate.

The resulting treated oil is thereafter passed from contactor 26 via line 27 to hydrotreater 28, which is maintained at an elevated temperature, which serves to effect destruction of various additive systems previously added to the original oil stock. Hydrogen for the desired hydrotreating reaction is introduced to the system via line 29 in communication with line 27 or, if desired, directly to the hydrotreater 28.

In hydrotreater 28 the oil is subjected to hydrogenation conditions in the presence of a catalyst sufficient to remove unwanted compounds and unsaturated materials and to effect decomposition of residual sulfur, oxygen and nitrogen bodies so as to yield an oil product suitable for further purification to a lube stock.

Suitable catalysts for use in hydrotreater 28 are those selected from the group consisting of Group VIB and Group VIII metals and combinations thereof, on a refractory support, used in conventional hydrodesulfurization processes.

Following hydrotreating, the resulting oil is passed via conduit 30 to separator-reflux column 31 which serves to remove water and various other by-products of the previous treatments from the oil. If desired, and particularly when HCI is present, water can be injected into column 31 to aid in removal of most of any HCI and part of the H2S and NH3 as water-soluble salts. Overhead from column 31 comprising hydrogen, H2S, NH3, and water is passed via line 32 to sulfur removal unit 33. This unit. for example a bed of zinc oxide, serves to remove H2S (sulfur) from the hydrogen stream. The resulting sulfur-free hydrogen stream is thereafter passed via line 34 to cooler 35. Ammonia is then removed, for example by water washing in an ammonia removal unit (not shown) in conduit 36.

Hydrogen is then recycled via conduit 36 to line 29.

An example of another material useful in unit 33 is iron oxide. Alternatively, a solvent process can be employed using substances such as alkanolamines and/or other amines, the H2S being subsequently oxidized to sulfur in a Claus-type process.

The bottoms product from column 31 is passed via line 37 to lubestock stripper 38 wherein a further steam treatment is carried out by introduction of steam via line 39.

Stripping, preferably steam stripping, of the oil is essential to the integrated process of this invention since it serves to remove those light hydrocarbon products boiling below the oil, such as kerosene or heavy gasoline, which have remained entrained in the oil or which are by-products of the hydrogenation treatment. Alternatively, gas stripping such as with hydrogen can be employed.

The resulting hot stripped product, consisting essentially of a pure lube oil stock, following cooling such as by use in heat exchanger 25, is thereafter passed via line 41 to a lube oil stock product tank (not shown) for storage and subsequent use as an additive-free lube oil stock suitable for reformulation with additives as desired.

Overhead from stripper 38, which consists essentially of fuel oil and water, is passed via line 42 to settler 43, where a hydrocarbon phase 44 and a water layer 45 are allowed to form. The hydrocarbon layer 44 is removed via line 46 and combined, if desired, with the hydrocarbon phase in storage tank 18 for further use. The small amount of gases present in line 46 can be removed by flashing.

Depending upon the feedstock, treating agent and other characteristics of a particular operation, as one skilled in the art in possession of this disclosure will understand, the specific conditions of operation given below can vary, preferably within the approximate ranges which are also given.

Calculated Operation Fig. 1 Unit Approximate Ref. No. Description Typical Preferred Ranges 3 Heater Temperature 1600 C. 60-200 C.

Pressure 215 psia atmospheric-250 psia 7 Treating Agent Weight ratio agt.oil 0.01:1 0.005:1-0.05:1 5 Contactor Temperature 1600 C. 60-200 C.

Pressure 215 psia atmospheric-250 psia Time 30 minutes 10 minutes-2 hours 10 Stripper Top Temperature 1600 C. 60-200 C.

Pressure 16 psia 20-2 psia Bottom Temperature 115 C. 60-200 C.

Pressure 16 psia 20-2 psia 14 Phase Temperature 40 C. 0-80 C.

Separator Pressure atmospheric atmospheric-45 psia 21 Filter Temperature 115 C. 60-200 C.

Pressure differential Plate and frame filter 80 psi 5-100 psi Continuous rotary drum filter 10 psi 2-14 psi 48 Furnace Temperature 760" C. 650-870 C.

Pressure atmospheric substantially atmospheric 12 Filter Aid Weight ratio aid:oil 0.01.1 0:1-0.15:1 Calculated Operation (continued) Fig. 1 Unit Approximate Ref. No. Description Typical Preferred Ranges 24 Hydrogen Charge 111 vol/vol oil 80-3000 vol/vol oil 25 Heater Temperature 370 C. 200-480 C.

Pressure 735 psia 150-3000 psia 26 Contactor Temperature 370 C. 200-480 C.

Pressure 735 psia 150-3000 psia 28 Hydrotreater Temperature 360 C. 200-430 C.

Pressure 730 psia 150-3000 psia 29 Hydrogen Charge 222 vol/vol oil 80-3000 vol/vol oil 31 Reflux Temperature 325 C. 290-400 C.

Pressure 705 psia 600-800 psia 33 Sulfur Temperature 290 C. 150-430 C.

Removal Unit Pressure 700 psia 100-3000 psia 35 Cooler Inlet temperature 290 C. 260-370 C.

Outlet temperature 55 C. 40-94 C.

38 Stripper Temperature 370 C. 280-395 C.

Pressure 20 psia atmospheric-50 psia 43 Settler Temperature 55 C. 0-80 C.

Pressure 16 psia atmospheric-45 psia In the table below there are given typical compositions of the principal streams for the operating conditions above set out.

TABLE I Pounds per Steam Day Stream No. 2 7 9 20 22 24 29 30 32 34 37 42 46 41 Oil 6644 6644 6644 6445 6325 32 32 6293 32 32 6261 Metals plus P* 51 S* 15 13 13 13 < 1 < 1 < 1 O** 50 45 45 44 < 1 < 1 < 1 N* 10 10 10 10 < 0.1 < 0.1 < 0.1 H2O 417 140 557 2 2 54 54 61 320 NH3 4 4 20 20 20 H2S 14 14 Light hydrocarbons 300 300 150 150 275 185 185 90 90 90 (NH4)2HPO4 70 CH4 67 67 137 132 132 5 5 5 H2 66 67 115 114 114 1 1 1 Oil-insolubles 128 128 Diatomaceous earth 70 * Present in combined form in the used oil.

** Present in combined form in the used oil, excluding H2O.

In another embodiment of this invention as shown in Figure 2, used oil from storage tank 101 is passed via line 102 to heater 103 and contactor 106. Aqueous treating agent containing diammonium hydrogen phosphate from makeup tank 105 is introduced via line 104. If desired, agent precursors ammonia, phosphoric acid, and water can be introduced into the heated oil downstream of heater 103, thereby forming the treating agent in situ in line 102 and contactor 106. The oil from heater 103 is passed in admixture with treating agent into the first agitated contactor 106 wherein the mixture is maintained under agitation for a time sufficient to react with the ash-forming components in the oil. Preferably, a recycle stream is passed through conduit 152 to pump 153 and then through heater 154 before its return to contactor 106, thereby providing heat and agitation to the contents of the contactor. Stirring means also can be employed.

Thereafter the mixture is passed via conduit 107 to second contactor 109, which is maintained at a temperature in the range of about 110 to about 140"C., for a time sufficient to effect distillation of a major portion of the water and at least some of the light hydrocarbons present therein. Thus, while retained in contactor 109, essentially all of the water and at least a portion of the light hydrocarbon components of the mixture are removed via line 110 and passed to separator 111 wherein a hydrocarbon layer and a water layer are allowed to form. The hydrocarbon phase can then be transferred via line 112 to storage 113. The water layer can be removed and discharded or employed for any desired purpose. Preferably, a recycle stream is passed through conduit 155 to pump 158 and then through heater 108 before its return to contactor 109, thereby providing heat and agitation to the contents of the reactor. Stirring means also can be employed.

The resulting residual mixture comprising a hot oil phase which is essentially free of water is passed via conduit 114 to a third contactor 116 wherein the mixture is admixed with diatomaceous earth which is introduced to contactor 116, preferably as a slurry in light hydrocarbons recovered from the integrated process, via conduit 118 from makeup tank 119. Preferably, a recycle stream is passed through conduit 157 to pump 158 and then through heater 115 before its return to contactor 116, thereby providing heat and agitation to the contents of the contactor. Any residual water and light hydrocarbon components are removed from contactor 116 via line 159.

If desired, any one or two or all of contactors 106, 109 and 116 can be provided with jackets heated by steam or other source of heat to aid in maintaining the contents of the contactors at the desired temperatures. Any one or two or all of contactors 106, 109 and 116 can be equipped with stirrers to provide additional agitation. In an operable but presently less preferred arrangement, a stirrer in any one or more of the three contactors can be used instead of the recycle system employed with the corresponding one or more of the three contactors, any additional heating being provided by heaters in the line ahead of the contactors and/or by heated jackets around the contactors. Furthermore, if desired, the process can be conducted without contactor 116, in which instance the diatomaceous earth can be passed through conduit 118 into conduit 114 from which the resulting mixture comprising oil, solid impurities and diatomaceous earth can be passed directly to filter 121.

Also, if desired, any one or two or all of conduits 102, 107 and 114 can feed into the recycle stream for contactors 106, 109 and 116, respectively, i.e., into conduits 152, 155 and 157, respectively, instead of directly into the respective contactor as shown in Figure 2.

Following admixture of diatomaceous earth, the resulting hot mixture is passed via line 117 to filter 121, which optionally can be precoated with diatomaceous earth. If desired, other filter aids such as perlite or cellulose fibers can be used.

Filter cake from filter 121 is removed via line 147 and optionally passed to furnace 148 from which, following burning or calcination, at least a portion of the resulting ash compr wherein decomposition is effected of the sulfonates contained in the oil.

While it is presently preferred that contactor 126 contain bauxite or an activated carbon adsorbent bed therein, this unit can employ other absorbents such as those selected from the group consisting of silica gel, clay, activated alumina, combinations thereof, and the like. The adsorbent serves to effect breakdown and decomposition of the ammonium salts of sulfonic acids and the ashless detergents contained in the oil. The adsorbent further serves to collect a small portion of the resulting products and thus precludes passage of such undesirable decomposition products to the hydrotreater. Such adsorbents can be regenerated by conventional means and reused.

While less preferred, it is also possible to omit contactor 126 and to remove the small amount of ash components and highly polar materials present in the low-ash, filtered oil by heating the oil to a temperature within the range of about 300 -410 C., e.g., about 380" C., in the presence of hydrogen and an adsorbent suspended in the oil. After such treatment, the oil is cooled to a temperature within the range of about 60 -200 C., e.g, about 1500 C., and refiltered. The same adsorbents cited above for use in fixed-bed contactors are suitable for this contact-treating process and give similar results.

Preferably, the adsorbent contains about 0.2 to about 20 weight percent of at least one metal selected from the group consisting of Group VIB and Group VIII metals, this weight percent being based on the total weight of modified adsorbent. This modified adsorbent can be prepared by irnpregnation of the adsorbent with an aqueous solution of a water-soluble compound of a Group VIB or Group VIII metal, followed by evaporation of water.

Water-soluble compounds presently prefered for this use are iron compounds such as ferric ammonium oxalate, ferric ammonium citrate, ferric sulfate, and ferrous ammonium sulfate.

The resulting treated oil is thereafter passed from contactor 126 via line 127 to hydrotreater 128, which is maintained at an elevated temperature, which serves to effect destruction of the various additive systems previously added to the original oil stock.

Hydrogen for the desired hydrotreating reaction is introduced to the system via line 129 in communication with line 127 or, if desired, directly to the hydrotreater 128.

In hydrotreater 128 the oil is subjected to hydrogenation conditions in the presence of a catalyst sufficient to remove unwanted compounds and unsaturated materials and to effect decomposition of residual sulfur, oxygen and nitrogen bodies so as to yield an oil product suitable for further purification to a lube stock.

Suitable catalysts for use in hydrotreater 128 are those selected from the group consisting of Group VIB and Group VIII metals and combinations thereof, on a refractory support, used in conventional hydrodesulfurization processes.

Following hydrotreating, the resulting oil is passed via conduit 130 to separator-reflux column 131 which serves to remove water and various other by-products of the previous treatments from the oil. If desired, and particularly when HCI is present, water can be injected into column 131 to aid in removal of most of any HCI and part of the 1125 and NH3 as water-soluble salts. Overhead from column 131 comprising hydrogen, H2S, NH3, and water is passed via line 132 to sulfur removal unit 133. This unit, for example a bed of zinc oxide, serves to remove H2S (sulfur) from the hydrogen stream. The resulting sulfur-free hydrogen stream is thereafter passed via line 134 to cooler 135. Ammonia is then removed, for example by water washing in an ammonia removal unit (not shown) in conduit 136.

Hydrogen is then recycled via conduit 136 to line 129.

An example of another material useful in unit 133 is iron oxide. Alternatively, a solvent process can be employed using substances such as alkonalomines and/or other amines, the H2S subsequently being oxidized to sulfur in a Claus-type process.

The bottoms product from column 131 is passed via line 137 to lubestock stripper 138 wherein a further steam treatment is carried out by introduction of steam via line 139.

Stripping, preferably steam stripping, of the oil is essential to the integrated process of this invention since it serves to remove those light hydrocarbon products boiling below the oil, such as kerosene or heavy gasoline, which have remained entrained in the oil or which are by-products of the hydrogenation treatment. Alternatively, gas stripping such as with hydrogen can be employed.

The resulting hot stripped product, consisting essentially of a pure lube oil stock, following cooling such as by use in heat exchanger 125, is thereafter passed via line 141 to a lube oil stock product tank (not shown) for storage and subsequent use as an additive-free lube oil stock suitable for reformulation with additives as desired.

Overhead from stripper 138, which consists essentially of fuel oil and water, is passed via line 142 to settler 143, where a hydrocarbon phase 144 and a water layer 145 are allowed to form. The hydrocarbon layer 144 is removed via line 146 and combined, if desired, with the hydrocarbon phase in storage tank 113 for further use or recycled to filter aid makeup tank 119 via line 151. The small amount of gases present in line 146 can be removed by flashing.

Depending upon the feedstock, treating agent and other characteristics of a particular operation, as one skilled in the art in possession of this disclosure will understand, the specific conditions of operation given below can vary, preferably within the approximate ranges which are also given.

Calculated Operation Fig. 2 Unit Approximate Ref. No. Description Typical Preferred Ranges 103 Heater Temperature 95 C. 60-120 C.

Pressure 17 psia atmospheric-250 psia 104 Treating Agent Weight ratio agt:oil 0.01:1 0.005:1-0.05:1 106 Contactor Temperature 95 C. 60-120 C.

Pressure 17 psia atmospheric-50 psia Time 30 minutes 10 minutes-2 hours 109 Contactor Temperature 125 C. 110-140 C.

Pressure 16 psia 5-25 psia Time 30 minutes 10 minutes-2 hours 116 Contactor Temperature 1600 C. 140-200 C.

Pressure 16 psia 5-25 psia Time 30 minutes 10 minutes-2 hours 111 Phase Temperature 40 C. 0-80 C.

Separator Pressure atmospheric atmospheric-45 psia 121 Filter Temperature 115 C. 60-200 C.

Pressure differential Plate and frame filter 80 psi 5-100 psi Continuous rotary drum filter 10 psi 2-14 psi 148 Furnace Temperature 760" C. 650-870 C.

Pressure atmospheric substantially atmospheric 118 Filter Aid Weight ratio aid:oil 0.01:1 0:1-0.15:1 124 Hydrogen Charge 111 vol/vol oil 80-3000 vol/vol oil 125 Heater Temperature 370" C. 200-480 C.

Pressure 735 psia 150-3000 psia 126 Contactor Temperature 370 C. 200-480 C.

Pressure 735 psia 150-3000 psia 128 Hydrotreater Temperature 360 C. 200-430 C.

Pressure 730 psia 150-3000 psia 129 Hydrogen Charge 222 vol/vol oil 80-3000 vol/vol oil 131 Reflux Temperature 325 C. 290-400 C.

Pressure 705 psia 600-800 psia 133 Sulfur Temperature 290 C. 150-430 C.

Removal Unit Pressure 700 psia 100-3000 psia Calculated Operation (continued) Fig. 1 Unit Approximate Kef. No. Description Typical Preferred Ranges 135 Cooler Inlet temperature 290 C. 260-370 C.

Outlet temperature 55 C. 40-95 C.

138 Stripper Temperature 370 C. 280-395 C.

Pressure 20 psia atmospheric-50 psia 143 Settler Temperature 55 C. 0-80 C.

Pressure 16 psia atmospheric-45 psia In the table below there are given typical compositions of the principal streams for the operating conditions above set out.

TABLE II Pounds per Stream Day Stream No. 102 104 107 117 122 124 129 130 132 134 137 142 146 141 Oil 6644 6644 6644 6445 6325 32 32 6293 32 32 6261 Metals plus P* 51 S* 15 13 13 13 < 1 < 1 < 1 O** 50 45 45 44 < 1 < 1 < 1 N* 10 10 10 10 < 0.1 < 0.1 < 0.1 H2O 417 140 557 2 2 54 54 61 320 NH3 4 4 20 20 20 H2S 14 14 Light hydrocarbons 300 300 150 150 275 185 185 90 90 90 (NH4)2HPO4 70 CH4 67 67 137 132 132 5 5 5 H2 66 67 115 114 114 1 1 1 Oil-insolubles 128 128 Diatomaceous earth 70 * Present in combined form in the used oil.

** Present in combined form in the used oil, excluding H2O.

As used herein, the term "flash distillation" is meant to represent distillation in which all or substantially all of the heat used to convert liquid to vapor in the distillation process is provided as sensible heat to the mixture comprising the liquid while the mixture is under a given pressure, with vaporization of liquid subsequently occurring upon reduction in pressure. Thus, "flash distillation" is employed in the process of Figure 1 in the removal of water and light hydrocarbons from the mixture which leaves contactor 5. As used herein, the term "distillation" is meant to represent that process wherein at least the major amount of heat required to convert liquid to vapor is applied to the mixture comprising the liquid while the mixture is substantially at the pressure at which vaporization occurs. Thus, "distillation" is employed in the process of Figure 2 in the removal of water and light hydrocarbons from contactors 109 and 116.

Reasonable variations and modifications are possible within the scope of the foregoing disclosure, the drawings, and the appended claims of the invention, the essence of which is that there has been provided a method for treating used lubricating oil so as to produce an intermediate product of reduced ash content and a final lube oil stock.

Claims (35)

WHAT WE CLAIM IS:

1. A process for the recovery of ash-free lubricating oil stock from used lubricating oil containing ash-forming components, which comprises treating the used lubricating oil with an aqueous solution of an ammonium salt reactive with the ash-forming components of the oil, such treatment being effective to disperse said salt throughout the oil for reaction with said ash-forming components; distilling the oil/water mixture thus produced thereby to remove by distillation at least a major proportion of the water introduced into the mixture by said treatment and also any light hydrocarbon components of the used lubricating oil; and separating the oil phase from the mixture remaining after the distillation of said water and light hydrocarbon.

2. A process according to claim 1, wherein the water and light hydrocarbon are removed from the oil/water mixture by flash distillation.

3. A process according to claim 1, wherein the ammonium salt is ammonium sulfate, ammonium bisulfate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate or a mixture of two or more thereof.

4. A process according to claim 1, or 3, wherein water initially present in said used lubricating oil is removed from said oil prior to contact with said solution.

5. A process according to claim 1, 3 or 4, wherein the used lubricating oil is treated with said solution at a temperature in the range 60 to 2000C and a pressure in the range atmospheric to 250 psia.

6. A process according to any one of claims 1, or 3-5, wherein the concentration of ammonium salt in said aqueous solution is in the range 30 to 95 weight per cent of that in an aqueous solution at 25"C saturated with the same salt.

7. A process according to any one of claims 1, or 3-6, wherein the weight ratio of ammonium salt to used oil is in the range 0.005:1 to 0.05:1.

8. A process according to any one of claims 1, or 3-7 wherein the oil phase is separated from the mixture remaining after the removal of the water and light hydrocarbon by filtration.

9. A process according to any one of claims 1, or 3-8, wherein the used oil is mixed with said solution in a first zone at a temperature in the range 50 to 1200C and the mixture then passed to a second zone maintained at a temperature in the range 110 to 1400C for a time sufficient to distill off substantially all of the water and the light hydrocarbon.

10. A process according to any one of claims 1, or 3-9, wherein oil separated from said remaining mixture is further purified by a hydrotreatment.

11. A process according to claim 10, wherein the hydrotreatment is carried out at a temperature in the range 200 to 430" C and a pressure in the range 150 to 3000 psia.

12. A process according to claim 11, wherein the hydrotreatment is performed in the presence of a catalyst comprising a Group VIB or Group VIII metal on a refractory support.

13. A process according to claim 10, 11 or 12, wherein the gaseous effluent from the hydrotreatment step is contacted with zinc oxide or iron oxide to remove any sulfur therein.

14. A process according to any one of claims 10 to 13, wherein prior to hydrotreating, the oil is admixed with hydrogen and then contacted with an adsorbent selected from activated carbon. silica gel, clay, bauxite and activated alumina, at a temperature in the range 200 to 480" C.

15. A process according to claim 14, wherein said adsorbent contains from 0.2 to 20 weight per cent of at least one Group VIB or Group VIII metal, based on the total weight of modified adsorbent.

16. A process according to any one of claims 10 to 15, wherein the hydrotreated oil is subsequently steam-stripped at a temperature in the range 280 to 395"C and a pressure in the range atmospheric to 50 psia.

17. A process according to claim 1, substantially as hereinbefore described with reference to Figure 2 of the accompanying drawings.

18. A reclaimed hydrocarbon lubricating oil stock when obtained by a process claimed in any one of the preceding claims.

19. A process according to claim 2, wherein the ammonium salt is ammonium sulfate, ammonium bisulfate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate or a mixture of two or more thereof.

20. A process according to claim 2 or 19, wherein any water initially present in said used lubricating oil is removed prior to treatment with said solution.

21. A process according to claim 2, 19 or 20, wherein the used lubricating oil is treated with said solution at a temperature in the range 60 to 200"C and a pressure in the range atmospheric to 25() psia.

22. A process according to claim 21, wherein the mixture of oil and said solution is maintained at said temperature and pressure for a period of from l() to 12() minutes.

'3. A process according to any one of claims 2 or 19 to 22, wherein the concentration of ammonium salt in said aqueous solution is in the range 30 to 95 weight per cent of that in an aqueous solution at 25"C saturated with the same salt.

24. A process according to claim 23, wherein the weight ratio of said salt to the used lubricating oil is in the range 0.005:1 to 0.05:1.

25. A process according to any one of claims 2 and 19 to 24, wherein water and light hydrocarbon in said mixture are flashed at a temperature in the range 60 to 2()() C and a pressure in the range 20 to 2 psia.

26. A process according to any one of claims 2 and 19 to 25, wherein said oil is separated from said residual mixture by filtration.

27. A process according to any one of claims 2 and 19 to 26, wherein the recovered oil is further processed by hydrotreating in the presence of hydrogen and a hydrotreating catalyst.

28. A process according to claim 27, wherein the hydrotreatment is carried out at a temperature in the range 200 to 430"C and a pressure in the range of 15() to 3000 psia.

29. A process according to claim 27 or 28, wherein the hydrotreating catalyst comprises a Group VIB or Group VIII metal on a refractory support.

30. A process according to any one of claims 27 to 29, wherein the gaseous effluent from said hydrotreatment is contacted with zinc oxide or iron oxide to remove any sulfur therein.

31. A process according to any one of claims 27 to 30, wherein, prior to hydrotreating, the oil phase is heated to a temperature in the range 200 to 480"C in admixture with hydrogen and the resulting mixture is contacted with an adsorbent comprising activated carbon, silica gel, bauxite or activated alumina.

32. A process according to claim 31, wherein said adsorbent contains from 0.2 to 20 weight per cent of a Group VIB or Group VIII metal, based on the total weight of modified adsorbent.

33. A process according to any one of claims 27 to 32, wherein the hydrotreated oil is subsequently steam stripped.

34. A process according to claim 2, substantially as hereinbefore described with reference to Figure 1 of the accompanying drawings.

35. A reclaimed lubricating oil stock when obtained by a process claimed in any one of claims 19 to 34.