DE2821159C2 - Process for making substantially ashless lubricating oil - Google Patents

Description

This invention relates to a process for the production of substantially ashless lubricating oil from needed lubricating oil containing ash-forming components. This process creates impurities from the used lubricating oil, such as metal components and compounds of nitrogen, sulfur and oxygen as well as gasoline.

The oil purified by the method of the invention can be used as an oil base for the production of high quality Lubricating oils can be used.

In the last few years more and more additives such as detergents have been used to reduce the Stoc ': dots, oxidation inhibitors and viscosity index improvers in lubricating oils based on hydrocarbons used. Although these additives have significantly improved the effectiveness of the lubricating oils, they do prepare they have considerable difficulties in recovering the used oils. More specifically, collect When lubricating oils are used, they contain resins, carbon, dirt, worn metals and other impurities which remain suspended in the engine oil by the new detergents. With these Detergents can be calcium and barium salts of alkylbenzenesulfonic acids and ashless detergents act like alkyl substituted succinic imides. These suspended impurities become the largest Part removed from the engine during the oil change and remains in the drained oil.

The economical removal of contaminants from used and detergent-containing lubricating oils Reusable oils have become a difficult problem and so have difficulties increase with the provision of effective detergents.

The novel additives have also created another difficulty in that these additives too must be removed from the base oil in order to allow the recovered oil to be used for reformulating a highly effective lubricating oil is suitable.

This is used to separate carbon and lubricant particles from lubricating oils that do not contain any or only relatively un-. contained effective detergents, processes used can be used to recycle used lubricating oils, containing effective detergents are not used. As today almost all mineral lubricating oils A large number of highly effective detergents contain them all in one when the lubricating oils are drained off Common containers collected today contain all used lubricating oils that are required for reconditioning or recovery, highly effective detergents.

It is therefore an object of the invention to provide a process for the recovery of used lubricating oils, which process is intended to remove both the additives and the solid impurities from the used lubricating oil.
Il This object is achieved according to the invention by a method for the production of essentially

j ^l ashless lubricating oil made from used lubricating oil containing ash-forming components, in which the hotly used lubricating oil is brought into contact with an aqueous solution of an ammonium salt, this salt

'' i is dispersed in the oil and reacted with the ash-forming components, the oil phase from the obtained

ί IW) oil / water reaction mixture is separated and the separated oil optionally hydrotreating treatment "■ a: · is subjected to development, said method being characterized in that the major proportion of water

together with any light hydrocarbons present by distillation from the oil / water ■ '? Reaction mixture is removed and the oil from the remaining mixture of oil and solid Veriinreini-

: gungen is separated.

From US PSS 39 30988 and 3879282 (CPI-Basic Abstracts Journal 1976, 05296 x / 03; CPI-Basic Abstracts Journal 1975. 30 383W / I8; Chemical Abstracts 1975, Vol. 83. No. 14. I18465x). They are methods of recovery containing essentially ash-free lubricating oils made from used, ash-forming components Lubricating oils are known, in which the ash-picture cndcn impurities of the used lubricating oils with a

aqueous solution of an ammonium salt are reacted. This oil / water reaction mixture is made by action separated by gravity, the filled salts going into the aqueous phase and by sedimentation and subsequent filtration are separated. The treated Ölphusc becomes a Kurzwcgdeslillalion subjected to remove water and light hydrocarbons. After that, the residual oil freed from solid impurities by a suitable separation process, for example by filtration.

Compared to these multi-stage and complex procedures, the method according to the invention has the From the fact that it is much simpler and much more economical. To remove the impurities From the oil / water mixture, only the two process steps are required:

1. Distilling off most of the water and any light hydrocarbons present and

2. Separating the solid impurities from the residual oil.

In dur DE PS 664343 is a method for cleaning used lubricating oils by adding water and an aqueous alkali hydroxide solution described. In this process, the impurities accumulate in the aqueous phase and are separated by the action of gravity.

DE AS 1101671 relates to a method for cleaning rolling oils contaminated with abrasion Treatment with concentrated aqueous ammonia solution and introduction of carbon dioxide. The impurities are removed by settling in the aqueous phase.

From DE OS 2426969 a method for reprocessing used oil is known in which the oil is first mixed with a hydrocarbon diluent and then with a water-miscible oil and a small amount of an aqueous ammonium or alkali base. The me. ¹ , colored system is separated by centrifugation.

In the DD PS 42158 a process ^ ar regeneration of used lubricating oils by treatment with Alkali orthophosphate or a salt of orthophosphoric acid described. Also with this procedure will be the impurities are removed with the aqueous phase. ·

DD PS 14793 relates to a process for the regeneration of waste oils by refining with sulfuric acid and subsequent neutralization with ammonia. The precipitated metal hydroxides and soaps separate Some of the oil settles on the bottom of the mixing vessel and the rest is removed by washing the oil with water.

DE-OS 2613878 (WiIa Part I 1976, ClOM-11/00) relates to a cleaning process for rolling oils by treatment with a strongly alkaline aqueous solution of an inorganic salt.

This prior art does not provide any teaching for the method according to the invention and its advantages derive.

Preferred embodiments of the invention will now be described.

In a preferred embodiment of the invention, substantially all of the water and hydrocarbons are removed by a short path distillation. It is advantageous, these short path distillation at a temperature ranging from 60 to 200 ⁰ C and at a pressure in the range from 0.14 to 1.4 atm. perform.

According to a further preferred embodiment of the method according to the invention, the treated Oil separated from the remaining mixture of oil and solid impurities by filtration.

According to another preferred embodiment of the invention, the treated separated oil becomes a Subjected to treatment with hydrogen. To do this, the oil phase in the presence of hydrogen and a Hydrotreating catalyst subjected to such temperature, pressure and Zt.tbedingungen that a hydrogen-treated Base oil is created. The oil so obtained is then in a stripping zone of light components freed and one then obtains as a process product a water-treated which is suitable as a base for lubricating oils Oil.

Another advantageous embodiment of the invention provides that the finish from the treatment with Hydrogen, which contains sulfur and hydrogen, is brought into contact with zinc oxide or iron oxide, to remove sulfur.

The used lubricating oils used in the invention are primarily used oils from machines for internal combustion, such as oils from crankcases of e.g. gasoline engines or diesel engines. Other sources of used oils include steam turbine, transmission and gear oils, Steam engine oils, hydraulic oils, and heat transfer oils.

Refined lubricating oil cuts based on paraffin, mixed base or made from naphthenic crude oils are used for processes according to the invention. Their viscosities iisgen generally in the range of about 20 to 400 Ccniisloke at 38 ⁰ C. These oils also contain various additives such as antioxidants (for example, barium, calcium and Zinkalkylthiophosphaie and di-t-butyl-p-cresol). verschleißverhiiidernde means (for example, organic lead compounds such Blcidiorganophosphordithionme and zinc dialkyldithiophosphates), rust inhibitors (for example calcium and Nairiumsulfonatc), dispersing agents (eg, calcium and barium sulfonates and phenoxides), viscosity index improvers { '.. B. polyisobutylenes, poly (alkylstyrcle)), detergents e.g. . B. calcium and barium salts of alkylbenzenesulfonic acids) and ashless detergents such as alkyl-substituted succinic acid m> imides.

If desired, the water carried along in the untreated used oil can be used before proceeding! ¹ according to the invention can be removed. Such a separation can be achieved by removing the water phase. for example in the storage containers for the used lubricating oil.

Examples of suitable ammonium salts which come into consideration as treatment agents in the invention, are ammonium sulfate, ammonium bisulfate, ammonium phosphate. Diammonium hydrogen phosphate, ammonium dihydrogen phosphate and mixtures of these salts.

If desired, the precursor of such an ammonium salt can also be used instead of part or the

total ammonium salts * can be used. Some examples of such precursors are ammonium thiosulfate. Ammonium polyphosphates such as ammonium metaphosphate. Urea sulfate, guanidine sulfate, urea phosphate and guanidine phosphate. Other suitable precursors are reactive combinations of ammonia and / or ammonium hydroxide with sulfuric acid and / or phosphoric acid and / or ammonium hydrogen sulfate 5 or ammonium hydrogen phosphate, d. H. Ainmoniiimbisiilfal, Dutmmoniumhydrogenphosphat and / or Ammoniumdihydrogenphosphai. If the precursor contains a combination of such components which are reactive toward one another and which produce the desired salt “in situ”, the components of the combination can be introduced at the same time, or one of the components can be introduced before the introduction of the other components be introduced.

Although the concentration of the treatment agent in the aqueous solution is not essential to the invention and also dilute solutions can be used, the economics of the process by using increased by relatively concentrated solutions, so that the amount of water to be removed afterwards does not increase is great. In general, the concentration of the treating agent in the aqueous solution is in the range of 30 to 95% by weight, typically about 80% by weight, of that of one treated with the treatment agent at 25 ° C.

saturated solution. Often there is some water in the used oil and in such cases it can the concentration of the treatment agent can be adjusted accordingly.

In the method of the invention, the treating agent should be used in an amount that is at least sufficient. to react with all of the ingredients in the used oil. Though that Weight ratio of the treatment medium to the oil used, depending on the nature and the

: o The concentration of the metal-containing components in the oil and the specially used treatment agent can vary widely, it is generally in the range from 0.002: 1 to 0.05: 1, preferably in the range from 0.005: 1 to 0.015: 1 and typically around 0, 01: 1. Although larger amounts of the treatment agent can be used, in most cases it will not be used as it would be wasted.
The invention will now be explained in more detail with reference to the drawing.

: 5 According to FIG. 1, used oil is fed from the storage tank 1 via the line 2 to the heater 3. Aqueous treatment agent containing diammonium hydrogen phosphate is from the dressing tank 8 via the Line 7 in a slight excess over the amount required to react with the ash-forming constituents in the used oil is required. into the line? introduced. After going through the heater 3 is the obtained hot mixture of oil and treatment agent via line 4 in a

v> Touch device 5 initiated, in which there is sufficient stirring, e.g. by stirring paddles 6, in order to ensure a careful Dispersion of the aqueous treatment agent in the oil phase of the mixture fed into the device 5 is initiated to ensure. It is presently preferred to have the aqueous treating agent above the heater 3, since a relatively small volume of this agent is used. The aqueous treatment agent but can also either after the heater 3 into the line 4 or directly into the touch device 5

.15 are initiated.

The mixture of used oil and aqueous treatment agent is in the touch device 5 held for a period of time and under conditions of temperature and pressure sufficient to cause the reaction between the treating agent with essentially all of the ash-forming components present bring about in the used oil.

• ίο After a sufficient reaction of the ash-forming components in the hot oil with the treatment agent the reaction mixture obtained, which has a continuous oil phase, is transferred via line 9 introduced into the upper part of a distillation device 10. In one embodiment of the invention a suspension of a filter aid before the emulsion enters the distillation device 10 in oil or in a light hydrocarbon. e.g. from the phase separator 44, the system from the Serving tank 11 is added via line 12.

Suitable auxiliaries in the process according to the invention are diatomaceous earth, perlite and cellulose fibers. Diatomaceous earth is currently preferred.

In one embodiment of the invention, the upper end of the distillation device 10 is at a Maintained temperature and pressure sufficient to short-path distillation of the majority of the

5 <) Components to effect water and light hydrocarbons of the mixture. These components are then passed via line 13 into a phase separation device 14, where a hydrocarbon layer 1 and a water layer 16 are formed. The water layer can be removed via line 19 and discarded, or it can optionally be used for other purposes. e.g. for steam generation.

The remaining mixture obtained, which has a sulfated ash value of about 0.3 to about 10% by weight ASTM D 847-72 with no filter aid or excess treating agent present is one hot oil phase. which is essentially free of water, but excess treating agent, some residual Water and any filter aid used in addition to or from those originally present contains resulting ash-forming solids in the used oil. It is going down through the still guided.

m Although it is not required. it is currently preferred. Introduce water vapor via line 40 into the distillation device 10 while the oil is still at an elevated temperature in order to promote the removal of the light components and the remaining water from the system. The oil, which has been freed of volatile constituents and is still hot, is then passed via line 20 to a filter 21 in order to separate off suspended and entrained ash-forming materials.

As already stated, a filter aid can be added to the emulsion before the volatiles are driven off be added to the later separation of the solids from the essentially anhydrous To facilitate oil phase. However, it is preferred that the filter 21 with one of the mentioned filter aids is coated beforehand, these filter aids being applied directly to the filter. If desired.

the filter aid can be added to the emulsion before the volatile constituents are removed as well as for the previous covering of the filter.

In a preferred embodiment of the invention, the filter cake is discharged from filter 21 via line 47 removed and optionally fed to a furnace, where the diatomaceous earth, which the retained ashes contains, is burned or calcined and then discharged via the waste line 49 or in the circuit the dressing tank 11 is performed for further use in the system.

The filtered oil is essentially free of any ash-forming components previously contained in it. In dei .iegel it has a sulfated ash value of about 0.01 to about 0.3 wt .-% according to ASTM D 847-72. without excess treatment agent and filter aid that has inadvertently passed through the filter could be. This recovered oil is suitable for a wide variety of industrial applications, e.g. as heating oil, in lubricant formulations or in the production of certain types of Lubricating oil. If desired, the oil can be removed from the system via line 23.

In a preferred embodiment of the invention, however, the hot oil after filtration through the Line 22 fed to heater 25 to raise its temperature to 200 to 480 ° C. If desired, a first portion of hydrogen is supplied via line 24. The hot oil obtained with the deposited Hydrogen is then passed through the touch device 26, where a decomposition of the contained in the oil Sulfonates occurs.

The touch device 26 preferably includes bauxite or a bed of absorbent activated carbon, however other absorbents can also be used in it, such as silica gel, clay, activated alumina or mixtures thereof. The absorbents initially cause the ammonium salts to decompose: o the sulfonic acids and ashless detergents in the oil. In addition, a small part collects on them of the resulting products, which prevents undesired decomposition products from entering the hydrotreater is prevented. Such absorbents can be regenerated and reused by customary measures will.

In a less preferred embodiment, the touch device 26 is omitted and the small amount of the ash-forming components and the very polar materials which are present in the filtered low-ash oil, by heating the oil to a temperature between 300 to 400 ⁰ C, e.g. about 38O ⁰ C, removed in the presence of hydrogen and a suspended in the oil-absorbent. After such a treatment, the oil is heated to a temperature in the range from 60 to 200 ^° C., for example about 150 ^° C., and filtered again. The absorbents already mentioned for the touch device can be used and similar results are achieved.

The absorbent preferably contains 0.2 to 20% by weight of at least one metal from groups VIA and VIII based on the total weight of the modified absorbent. This modified absorbent is preferred by impregnating the absorbent with an aqueous solution of a water-soluble compound of a Metal of the named groups of the periodic table of the elements and subsequent · evaporation of the water manufactured. Currently preferred water-soluble compounds for this purpose are iron compounds, such as iron !!! - ammop.iurr.oxalat, Ε! $ βη-! Π = ;; ΓπΓτ.οηίΐ! ΓΓ; ο: ίΓ ;; ί, iron-! !! - Sulphate and Iron-II-AiTiniüniumsuifai.

The treated oil is fed from the contact device 26 via the line 27 to the hydrotreater 28, which is kept at an elevated temperature and in which the various systems of additives that were contained in the original oil, can be destroyed. In the hydrotreater is used for the desired hydrotreatment conversion Hydrogen via line 29, which is in communication with line 27, introduced. The hydrogen can also be fed directly to the hydrotreater 28. In the hydrotreater 28, the oil Exposed to hydrogenation conditions in the presence of a catalyst which is sufficiently effective to remove the undesired compounds and the unsaturated materials and cause decomposition bring about the remaining sulfur-containing, oxygen-containing and nitrogen-containing substances.

Suitable catalysts for use in the Hydrotreater 28 are the Group VIA and VIII metals and mixtures thereof on a refractory support commonly used in hydrodesulfurization processes be used.

After the hydrotreating treatment, the oil obtained is passed through line 30 to a separating reflux column 31 supplied to remove the water and other by-products from the previous treatments so of the oil. If desired, and especially when hydrogen chloride is present, water can be added to the Column 31 is injected to remove most of any hydrogen chloride present and a portion of hydrogen sulfide and ammonia as water soluble salts. The one on the head of the column 31 outgoing fraction, which contains hydrogen, hydrogen sulfide, ammonia and water, is fed via line 32 to unit 33 for the removal of sulfur. This unit has for example a bed of zinc oxide, which is used to remove hydrogen sulfide. The obtained sulfur-free hydrogen §

current is then passed via line 34 to cooler 35. Then ammonia becomes e.g. by washing with Water removed in a unit not shown. Hydrogen is then transferred to line 29 via line 36 returned.

An example of another material that can be used in unit 33 to good effect is Iron oxide. Alternatively, a solution method can be used in which alkanolamines and / or others Amines are used, with hydrogen sulfide subsequently being converted to sulfur in a process like the Claus process is oxidized.

The residues from the column 31 are fed to the distillation device 38 via line 37, where a further steam treatment takes place, with steam being supplied via line 39.

The driving off of the volatile constituents of the oil, preferably by means of steam, is an essential feature a preferred embodiment of the invention, since it reduces the light hydrocarbons, the lower boil as the oil, such as kerosene or heavy gasoline, is removed. Such light carbon

Hydrogen products can either be contained in the used oil or they can also be found as by-products the hydrogenation treatment occur. Alternatively, these volatile constituents can also be removed with gases such as hydrogen.

The warm and volatilized product obtained, which is essentially pure Base oil for lubricating oils is, after cooling, e.g. in a heat exchanger as in 25, via the Line 41 is fed to a storage tank, not shown, for storage and can then be used as of additives free base oil can be used to reformulate a lubricating oil with additives.

The distillate '' at the top of the device 38, which consists essentially of heating oil and water, is over the line 42 is passed to the settling device 43, where there is a hydrocarbon phase 44 and a water layer 45 trains. The hydrocarbon layer 44 is removed via line 46 and optionally combined with the hydrocarbon phase in the storage tank 18 for further use. The small amount of Gases contained in line 46 can be burned.

In the following, more detailed information on the conditions of the procedure is given, whereby in the first column Reference is made to the units in fig. I.

Figure I symbol No. 3 7 5

10

Figure I symbol no.14 21

48 12

24 25 26 28

29 31 33 35 38 43

unit

typical

Preferred areas

Heater Beh. -Medium touch. -Fitting.

distillation

unit

Temperature 16O ⁰ C pressure 14.6 atm.
Weight ratio medium: oil 0.01: 1 temperature 160 ° C pressure 14.6 atm.
Time 30 min.
head

Temperature 160 ° C pressure 1.1 atm. floor

Temperature 115 ° C pressure 1.1 atm.

typical

60-200 ° C 1 -17 atm.

0.005: 1-0.05: 1 60-200 ° C 1-17 atm. 10 min.-2 h.

60-200 ⁰ C 0.14-1.4atm.

60-200 ° C 0.14-1.4 atm.

Preferred areas

Phase separator Temperature 40 ° C 0-80 ° C Pressure 1 atm. 1 -3.1 atm. filter Temperature 115 ⁰ C 60-200 ° C Pressure difference Plate and Frame filter 5.4 atm. 0.3-6.80 atm. continuous Rotation filter 0.7 atm. 0.14-0.95 atm. oven Temperature 760 ⁰ C 650-870 ⁰ C Pressure 1 atm. about 1 atm. Filter aids Weight ratio Medium: Ö! 0.01: 1 0: 1-0.15: 1 H, feed 111 vol / vol oil 80-3000 v / v oil Heater Temperature 370 ⁰ C 200-480 ° C Pressure 50 atm. 10.2-204.1 atm. Touch setup Temperature 370 ⁰ C 200-480 ° C Pressure 50 atm. 10.2-204.1 atm. Hydrotreal Temperature 360 ° C 200-430 ° C Pressure 49.7 atm. 10.2-204.1 atm. H, feed 222 vol / vol oil 80-3000 v / v oil Reflux Temperature 325 ° C 290-400 ° C Pressure 48 atm. 40.8-54.4 atm. Sulfur removal Temperature 290 ⁰ C 150-430 ° C Pressure 47.6 atm. 6.80-204.1 atm. cooler Inlet temperature 29 ° C ⁰ 260-370 ° C Outlet temperature 55 ° C 40-95 ⁰ C distillation Temperature 370 ⁰ C 280-395 ° C Pressure 1.4 atm. 1-3.4 atm. Weaners Temperature 55 ° C 0-80 ⁰ C Pressure 1.1 atm. 1-3.1 atm.

In the following Table I typical compositions of matter for the main streams are shown below the operating conditions specified in the overview above.

per slrom day 70 9 20th 28 21 159 30th 32 34 37 42 46 41 Tiihjüc 1 2 7 6644 6644 6325 32 32 6293 32 32 6261 0.45 kg healing 6644 Stream no. 51 13th 13th 22nd 24 29 <1 <l <1 oil 15th 45 45 6645 <l <1 <1 Metals plus P * 50 10 10 <0, l <0.1 <0.1 ίο S * 10 557 13th 54 54 61 320 O** 417 140 44 20th 20th 20th N * IO 14th 14th H, O 1 2 NH, 300 150 4th 4th 275 185 185 90 90 90 15th H ₂ S 300 light coals 137 132 132 5 5 5 hydrogen 150 115 114 114 I. 1 I. (NH ₄ J ₂ HPG ₄ 128 128 CH ₄ 70 67 67 H ₂ 66 67 insoluble in oil Diatomaceous earth

* Available in combined form in the used oil
** Available in a combined form in the used oil, excluding H ₂ O

In another embodiment of the invention according to FIG. 2, used oil is fed from the storage tank 101 via the line 102 to the heater 103 and then to the touch device 106. The aqueous treating agent, which contains diammonium hydrogen phosphate, is passed into line 104 from the dressing tank 105 . Optionally, treatment agent precursors such as ammonia, phosphoric acid, and water can be introduced into the heated oil after heater 103 , with the treatment agent forming "in situ" in line 102 and in touch device 106 . The oil is fed from the heater 103 in mixture with the treating agent into the stirrer-equipped contact device 106 where the mixture is kept under stirring for a time sufficient to react with the ash-clad components of the oil. Preferably, a recycle stream is passed through line 152 to pump 153 and then through heater 154 before being returned to touch device 106 , thereby heating and agitating its contents. Other stirring devices can also be used.

Thereafter, the mixture is fed via line 107 to a second contact device 109 , which is maintained at a temperature in the range from about 110 to about 140 ^° C. for a period of time sufficient to distill a major part of the water and at least a part of the light present To effect hydrocarbons. As a result, while in touch device 109 , substantially all of the water and at least some of the light hydrocarbon components of the mixture are removed via line 110 and go to separator 111, where a hydrocarbon layer and a water layer are formed. The hydrocarbon layer can then be fed into the storage container 113 via the line 112. The water layer can be removed and discarded or used for other purposes. Preferably, a recycle stream is passed via line 155 to pump 158 and then through heater 108 before being introduced into contact device 109 , thereby heating and moving the contents of this reactor. In this case, too, other stirring devices can be used.

The remaining mixture obtained contains the oil phase and is essentially free of water. It is fed via line 114 to a third touch device 116 where it is mixed with diatomaceous earth, which is introduced into device 116, preferably as a slurry in light hydrocarbons, via line 118 from dressing tank 119 . As light hydrocarbons, those obtained by this integrated process can be used. A recycle stream is preferably conducted through conduit 157 to pump 158 and then through heater 115 before it is introduced into the contact device 1 16, wherein the content of the device heated by the recycle stream and is moved. Any amounts of water and light hydrocarbons still present are removed from device 116 via line 159 .

If desired, any one or two or all Berührungseinrichiungen 106, 109 and 1 16 is provided with jackets in order to be heated by steam or any other heat source so that the contents of the contact means can be maintained at the desired temperatures. Any or two or all of the devices 106, 109 and 116 can be equipped with stirrers. At a currently Less preferred embodiment of the invention, instead of the circulatory system, a stirrer is used in one or more of the contact devices, additional heating being effected by heating in the line in front of the contact device and / or by heating jackets of the contact devices. In addition, if desired, the method can also be carried out without the touch device 116 , in which case the diatomaceous earth is introduced through the line 118 into the line 114 , from where the resulting mixture of oil, solid impurities and diatomaceous earth is fed directly to the filter 121. If desired, any or two or all of the lines 102, 107 and 114 can also be introduced into the circuit streams for the touch devices 106, 109 and 116 , ie into lines 152, 155 and 157, rather than directly as in FIG. 2, to be introduced into the corresponding touch device.

After the diatomaceous earth has been mixed in, the hot mixture obtained is passed through the line 117 to the filter | s

121 supplied, which can optionally be coated beforehand with diatomaceous earth. In this case, too, Q-

other filter aids such as perlite or cellulose fibers can be used. *;

The filter cake from filter 121 is removed via line 147 and is optionally passed through oven 148 | j

guided. After burning or calcining, at least some of the ash obtained, which contains the diatoms, is used

contains earth, fed to the Aofall via line 149 or via lines 120 and 160 to the dressing tank ||

119 for further use in the system. Fresh Diatomecnerdc is approached on line 160 §;

guided. Light hydrocarbons can be used to make the slurry in tank 119, £ 5

which are deposited in the integrated process and which are brought in via line 151 v. earth. K

ir> When carrying out this embodiment of the invention, an advantageous increase in the Filtra- ä;

The speed of the oil through the filter 121 is reached when the mixture of oil and the treatment f |

medium for a period of at least 10 minutes at a temperature of 60 to 120 ⁰ C before the further j |

Treatment is held. G

The hot-filtered oil is essentially free of any ash-forming components previously contained therein

goods, and is suitable for a wide variety of industrial uses. This treated oil can be obtained from the -g

System can be removed via line 123. £

In the preferred integrated process of the invention, however, the hot oil is after filtration S

fed via the line 122 to the heater 125 in order to raise its temperature to 200 to 480 ⁰ C for a further | §

Increase treatment in a manner similar to that in FIG. If desired, a first part of hydrogen Sh

are supplied via line 124. The hot hydrogen-containing oil is then released through the '· *'

dirmng 126, where a decomposition of the in the O! containing sulfonates occurs. ~

It is presently preferred that the touch device 126 have bauxite or a bed of adsorbent Contains activated carbon. However, other adsorbents such as silica gel, Clay, activated alumina and mixtures thereof. The adsorbents are used to decompose the ammonium salts the sulfonic acids and ashless detergents contained in the oil. The adsorbents hold also return a small proportion of the products obtained and thereby prevent the continuation of such products - unwanted decomposition products to hydrotrater. Such adsorbents can be regenerated in the usual way and be reused. ι

Less preferred, it is to omit the touch device 126, the small amount of ash-forming components and highly polar materials in the filtered oil with a low ash content by heating the oil to a temperature in the range of about 300-410 ⁰ C, for example about 380 ° C , in the presence of hydrogen and an adsorbent suspended in the oil. After such treatment, the oil to a temperature in the range of 60 is - 200 ⁰ C, for example 150 ^c Eiwa cooled C. and filtered again. The adsorbents already mentioned can also be used in this case and similar results are achieved.

Preferably, the adsorbent contains about 0.2 to about 20 wt .-% of at least one of the metals from the Groups VIA and VIII of the Periodic Table of the Elements, these percentages by weight based on the total weight of the modified adsorbent. This modified adsorbent can by impregnating the adsorbent with an aqueous solution of a water-soluble compound of one of the metals mentioned and then Evaporation of the water can be produced. The currently preferred compounds are also in in this case iron compounds such as ice-III-ammonium oxalate, iron-III-ammonium citrate. Ferrous sulfate and Ferrous ammonium sulfate.

The treated oil obtained is then released from the touch device 126 via the line 127

Hydrotreater 128 fed, which is maintained at an elevated temperature, so that the various systems the additives that have been added to the original oil are destroyed. For hydrotrcating treatment the hydrogen is added to the system via line 129 in communication with line 127 or if desired fed directly to the hydrotreater 128.

In the hydrotreater 128, the oil becomes so under hydrogenation conditions in the presence of a catalyst treated for a long time until the unwanted compounds and unsaturated materials are removed and the residues 5 <> of sulfur-containing, oxygen-containing and nitrogen-containing compounds are decomposed, so that an oil product arises that for further purification for a base oil for lubricating oil is suitable.

Suitable catalysts for the treatment in the Hydrotreater 128 are those made from metals from Group VIA and VIII and combinations thereof on a refractory support as used in conventional hydrodesulfurization processes be used.

After the hydrotreating treatment, the resulting oil is passed via line 130 to a separating reflux column 131 where water and various other by-products from previous treatments of the oil are removed. If desired, and particularly when hydrogen chloride is present, water can be injected into column 131 to facilitate removal of most of any hydrogen chloride and some of the hydrogen sulfide and ammonia as water soluble salts. A stream exits at the top of column 131. the hydrogen. Contains hydrogen sulfide, ammonia and water, and which is passed via line 132 to the sulfur removal unit 133. This unit, which can contain, for example, a bed of zinc oxide, removes hydrogen sulfide. The sulfur-free hydrogen stream is then directed to cooler 135 via line 134. Ammonia is then removed, for example by washing with water in a unit (not shown) in line 136. Via line 136, hydrogen is then returned 6; led to line 129.

Another example of a suitable material in unit 133 is iron oxide. Alternatively, a solvent process can be used can be used in which alkanolamines and / or other amines are used and Hydrogen sulfide is subsequently oxidized to sulfur in a Claus process.

The bottom product from column 131 is via the line. 137 is fed to a disinfection device 138 , where a further water vapor treatment is carried out by introducing water vapor via line 139 .

The driving off of the volatile constituents of the oil, especially the driving off with water vapor, is essential for the integrated process of the invention as it serves to remove those light hydrocarbons remove that boil lower than the oil, such as B. kerosene or heavy fuel. These are hydrocarbons present in the used oil or arise as by-products of the hydrogenation. Alternatively comes the volatile constituents can also be driven off with gases such as hydrogen.

The product obtained, freed from volatile components, consists essentially of pure base oil for lubricating oils. It is used after cooling, e.g. B. in a heat exchanger 125 via the line 141 to a storage container, not shown, and can then be used as a base oil free of additives for the reformulation with additives.

The top outlet of the distillation device 138, which consists essentially of heating oil and water, is passed via the line 142 to a settling device 143 , where a hydrocarbon phase 144 and a water layer 145 are formed. The hydrocarbon layer 144 is combined via the line 146 and fails desired, combined with the hydrocarbon phase in the storage tank 113 for further processing or circulated to the serving tank 119 via the line 151 . The small amount of gas present in line 146 can be removed by incineration.

The following is a summary of the typical and preferred reaction conditions in the given different units of the system according to FIG.

Figure 2 unit typical Preferred areas Symbol no. Heater Temperature 95 ° C 60-120 ⁰ C. 103 Pressure 1.2 atm. 1-17 atm. Treatment Miucl Weight ratio 104 Medium: oil 0.01: 1 0.005: 1-0.05: 1 Touch device Temperature 95 ° C 60-120 ⁰ C. 106 Pressure 1.2 atm. 1-3.4 atm. Time: 30 minutes 10min-2h Touch device Temperature 125 ° C 110-140-C 109 Pressure 1.1 atm. 0.3-1.7 atm. Time: 30 minutes 10min-2h Touch device Temperature 160 ⁰ C 140-200 ⁰ C. 116 Pressure 1.1 atm. 0.3-1.7 atm. Time: 30 minutes 10min-2h Phases! runner Temperature 40 ⁰ C 0-80 ⁰ C 111 Pressure 1 atm. 1-3.1 atm. filter Temperature 115 ° C 60-200 ⁰ C. 121 Pressure difference Plate and Frame filter 5.4 atm. 0.3-6.80 atm. continuicrl. Rotation filter 0.7 atm. 0.14-0.95 atm. oven Temperature 76O ° C 650-870 ⁰ C 148 Pressure 1 atm. about 1 atm. Filter aids Weight ratio 118 Medium: oil 0.01: 1 0: 1-0.15: 1 H ₂ clock 111 vol / vol oil 80-3000 v / v oil 124 Heater Temperature 370 "C 200-480 ° C 125 Pressure 50 atm. 10.2-204.1 atm. Touch setup Temperature 370 ⁰ C 200-480 ° C 126 Pressure 50 atm. 10.2-204.1 atm. Hydrotreal Temperature 360 ° C 200-430 ⁰ C. 128 Pressure 49.7 atm. 10.2-204.1 atm. H ₂ supply 222 vol / vol oil 80-3000 v / v oil 129 Reflux Temperature 325 ⁰ C 290-400 ⁰ C 131 Pressure 48 atm. 40.8-54.4 atm. Sulfur removal Temperature 29O ° C 150-430 ° C 133 Pressure 47.6 atm. 6.80-204.1 atm. cooler HinlaBicmperatur 290 ⁰ C 260-370 ⁰ C. 135 Outlet temperature 55 ° C 40-95 ° C distillation Temperature 37O ° C 280-395 ° C 138 Pressure 1.4 atm. 1 -3.4 atm. Weaners Temperature 55 ° C 0-80 ° C 143 Pressure 1.1 Ulm. 1-3.1 atm.

In the following Table II typical compositions of matter for the main streams under the operating conditions specified in the overview above.

Table II 102 Electricity day 70 128 117 122 124 129 130 132 134 137 142 320 146 141 6644 104 107 6644 6645 6325 32 32 6293 32 32 6261 0.45 kg units per 51 6644 Stream no. 15th 13th 13th <1 <1 <1 oil 50 13th 45 44 <1 <I. 90 90 <1 ίο .Metals plus P * 10 45 10 10 <0, l <0.1 <0, l S * 417 10 2 2 54 54 61 5 5 ο * 140 557 4th 4th 20th 20th 20th 1 1 N * 14th 14th 'H ₂ O 15 NH ₃ 300 150 150 275 185 185 90 H ₂ S 300 light coals 67 67 137 132 132 5 hydrogen 66 67 115 114 114 1 (NH ₄ ) ₂ HPO ₄ 128 20 CH ₄ 70 H ₂ insoluble in oil Diatomaceous earth

* Present in a combined form in the used oil. ** Available in combined form in the used oil, excluding H ₂ O.

Short-path distillation (flash distillation) is understood here to mean a distillation in which the entire or essentially all of the heat used in the distillation process to convert the liquid to vapor is used, is supplied as sensible heat to the mixture containing the liquid, the mixture is under a certain pressure and the evaporation of the liquid afterwards with lowering of pressure occurs. The "short path distillation" is consequently used in the method according to FIG. 1 for removal of water and light hydrocarbons from the mixture used by the touch device 5 leaves. The term "distillation" is used here to denote the process in which at least the bulk of the heat required to convert liquid wedge into vapor of the mixture that makes up the Contains liquid, is supplied, ν; at the mixture is essentially at the pressure at which the Evaporation occurs. As a result, the "distillation" in the process of FIG. 2 is used to remove Water and light hydrocarbons from the touch device mixes 109 and 116 are used.

For this purpose 2 sheets of drawings

Claims (6)

Patent claims: 1. A process for the production of substantially ash-free lubricating oil from used, ash-forming oil Component-containing lubricating oil, in which the used lubricating oil with an aqueous solution of a Ammonium salt is brought into contact, this salt is dispersed in the oil and with the ash-forming Components is reacted, the oil phase is separated from the resulting oil / water reaction mixture and the separated oil is optionally subjected to a hydrotreating treatment, thereby characterized in that the main proportion of water together with any light hydrocarbons present is removed by distillation from the oil / water reaction mixture and the oil from the ίο remaining mixture of oil and solid impurities is separated. 2. The method according to claim 1, characterized in that substantially all of the water and all hydrocarbons are removed by a short path distillation. 3. The method according to claim 2, characterized in that the short-path distillation at a temperature in the range from 60 to 200 ⁰ C and a pressure in the range from 0.14 to 1.4 atm. is carried out. 4. The method according to any one of claims 1 to 3, characterized in that the treated oil by Filtration is separated from the remaining mixture of oil and solid impurities. 5. The method according to any one of claims 1 to 4, characterized in that the separated oil is a Is subjected to treatment with hydrogen. 6. The method according to claim 5, characterized in that the waste from the treatment with hydrogen, which contains sulfur and hydrogen, is brought into contact with zinc oxide or iron oxide To remove sulfur.