EP0835298A1

EP0835298A1 - Alkaline treatment method for refining used oils

Info

Publication number: EP0835298A1
Application number: EP96924004A
Authority: EP
Inventors: Bernard Chavet
Original assignee: Individual
Current assignee: Individual
Priority date: 1995-06-22
Filing date: 1996-06-21
Publication date: 1998-04-15
Anticipated expiration: 2016-06-21
Also published as: NO976008L; ES2125208T1; WO1997000928A1; DK0835298T3; DE69612978T2; ES2125208T3; DE69612978D1; EP0835298B1; FR2735785B1; US6072065A; CA2222704A1; FR2735785A1; NO976008D0; ATE201438T1

Abstract

PCT No. PCT/FR96/00974 Sec. 371 Date Apr. 20, 1998 Sec. 102(e) Date Apr. 20, 1998 PCT Filed Jun. 21, 1996 PCT Pub. No. WO97/00928 PCT Pub. Date Jan. 9, 1997An alkaline treatment method for refining used oils, wherein (a) the used oils are distilled; (b) the resulting distillate is treated with an alkaline agent in the presence of a solvent selected from water, a monoalcohol, a polyalcohol and a mixture of said a alcohols, said alkaline agent being present in a percentage by weight, based on the weight of the distillate, equal to the product Fx(IA+IS), where F is a multiplier between 2 and 50 and IA and IS are the acid value and the saponification value respectively of said distillate, at a temperatue of around 80-330 DEG C. for 2-200 minutes; (c) the reaction medium is washed with water then decanted to recover the oily phase; and (d) said oily phase is distilled. The method is useful for producing refined oils having excellent properties in that they are odorless and nearly colorless and in that they have a very low chlorine, phosphorus and sillicon content.

Description

Process for refining used oils by alkaline treatment.

The present invention relates to a process for refining used oils which makes it possible to obtain refined oils which can be reused in particular as base oil, as fuel, or in an oil refinery.

According to the present application, the expression used oils is understood to mean an oil or a mixture of oils in variable proportions, of various origins originating in particular from industrial applications.

As is well known, oils intended for industrial uses or for engines contain various additives intended to give them the specific properties required for the envisaged applications. These additives are either organic (so-called "ashless" additives) or organometallic. In all cases, in addition to their specific function (such as anti-corrosion, anti-wear, anti-oxidant, dispersant, etc.), they are characterized by very good solubility in base oils (hydrocarbons having boiling points higher than 350 ° C), thermal stability as high as possible and finally volatility as low as possible.

Oils after use or used oils contain as additives such as impurities, either intact or in the form of decomposition products as well as sediments (wear particles from moving metal parts, air dust, carbon, etc.) and hydrocarbons not present in the original oils and which are undesirable. These are gasoline and diesel fractions, oxidation products (such as organic acids) and pyrolysis products. The presence of these various impurities makes it particularly difficult to refine used oils.

Generally, industrial used oils as defined above have the characteristics given in Table I below: TABLE I

Chlorine content (mg / kg) 150-2000

Phosphorus content (mg / kg) 300-1300

Silicon content (mg / kg) 8-80

Color (ASTM D 1500) d> 8

Odor (sensory measurement) Strong-very strong

Water content (% by weight) 0.2-12

Sediments (% by weight) 0.1-0.5

Viscosity at 40 ° C (mm ² / s) 35-140

Acid number (IA; mgKOH / g) 0.9-4.5

Saponification index (IS; mgKOH / g) | 4-17

In Table I above, the phosphorus and silicon contents were measured by plasma, the chlorine contents either by X-ray fluorescence (above 50 mg / kg) or by coulometry (below 50 mg / kg), the acid number was determined according to French standard NFT 60112, the viscosity was measured at 40 ° C according to the NFT 60100 method, the color was measured according to the ASTM D 1500 method, the odor was measured from sensory by the experimenter and the saponification index was measured by potentiometry.

In order to separate the main contaminants from used oils, and to improve their color and odor, several methods of treatment by physical and / or chemical separation as well as refining methods have been developed, this with the aim of regenerate them and reuse them as base oil, as fuel, or in an oil refinery.

When these are intended to serve as base oils, they must have a very low coloration (at least less than 4 in measurement according to standard ASTM D 1500).

When they are intended to be used as fuel, for example in industrial heating systems, they must be odorless and have a low acidity (i.e. an IA acid number of less than about 0.2 mgKOH / g) as well low chlorine content, a source of combustion pollutants. Finally, when they are intended to be treated in an oil refinery (catalytic cracking or hydrogenation) they must have a very reduced level of phosphorus, chlorine and silicon in order to avoid the destruction of the catalysts (namely preferably a content of phosphorus less than 5 mg / kg, a chlorine content less than 35 mg / kg and a silicon content less than 5 mg / kg).

Among the known processes for the preliminary treatment of waste oils by physical separation, mention may be made of vacuum distillation, precipitation using a solvent such as propane (or "deasphalting") or ultrafiltration. These processes have a certain efficiency in separating sediments and to a certain extent demetallizing or clarifying used oils. However, such physical pre-treatment methods do not make it possible to separate all the impurities present in the used oils. Thus, for example, after distillation, the oils obtained still have a very strong odor, a notable acidity and contain non-negligible quantities of volatile compounds, chlorine, phosphorus and silicon. Among the known methods of prior treatment by chemical separation, mention may in particular be made of those using an alkaline agent. However, these processes, most of which are intended to facilitate coagulation of the sediments and then their separation, essentially aim at improving the behavior of the equipment (distillation, and exchangers by reducing their fouling). Here again, oils are obtained which are entirely unsuitable for use as a base oil for formulating new lubricants. Thus, for example, the alkaline treatments applied to used oils before their vacuum distillation, although they effectively reduce the odor and the acidity of the resulting oils, do not, however, quantitatively eliminate undesirable contaminants such as chlorine, taking into account the conditions under which alkaline agents are used. From the used oils thus pretreated, they can be refined according to various processes, in particular by catalytic hydrogenation at high pressure, or by treatment with concentrated sulfuric acid, by treatment with an activated earth or by the combination of these last two treatments. and in some cases by distillation after one of these treatments. High pressure catalytic hydrogenation cannot, however, be used without raising catalyst deactivation problems if the oils subjected to this type of treatment are not rigorously free of contaminants such as phosphorus, chlorine and silicon. Treatment processes based on sulfuric acid / activated earth cause the production of acidic sludge and used earth which is difficult to absorb.

The known processes for refining used oils therefore exhibit performance shortcomings or difficulties in removing by-products. There was therefore a definite need for the development of a process making it possible to obtain, in a simple and economical manner, from used oils, refined oils having all the qualities and properties required.

The present invention thus relates to a process for refining used oils which makes it possible to obtain refined oils capable of meeting the various criteria of quality and purity set out above, this process being characterized in that it comprises a determined series of steps consisting of: a) distilling said used oils, b) treating the resulting distillate with an alkaline agent and in the presence of a solvent chosen from water, a monoalcohol, a polyalcohol and a mixture of these alcohols, said alkaline agent being present in a proportion, in percentage by weight relative to the weight of the distillate, equal to the product F x (IA + IS), F being a multiplying factor of between 2 and 50, IA and IS being respectively the acid number and the saponification number of the distillate, said treatment being carried out at a temperature of approximately 80 to 330 ° C and for a time of approximately 2 to 200 min, c) to be washed with water the reaction medium and then leave to settle to recover the oily phase, and d) to carry out the distillation of said oily phase. The method according to the invention has the particular advantage of being very flexible in so far as it can be adapted, as regards its characteristics, to the required quality of the finished products. In particular, the process according to the invention can be implemented following one or more prior treatment processes, physical and / or chemical, and / or upstream of one or more refining processes, such as than those mentioned above.

According to a particular embodiment of the process according to the present invention, the distillation step (a) is firstly carried out under atmospheric pressure, at a temperature of approximately 130 to 180 ° C., to remove the water and recover a fraction of essences. The distillation is then continued, under a pressure of about 650 to 12,000 Pa and at a temperature of about 240 to 345 ° C, to recover a small fraction of diesel and then a large fraction, greater than 60% of the used waste oil. Although the whole of the distillate can be subjected to the subsequent step, the only significant fraction of the distillate is preferably used according to the invention.

This prior distillation step is particularly important because it allows almost all of the tars to be removed.

The alkaline agent used in step (b) of the process is either soda or potash, but never a mixture of soda and potash. Preferably, potash is used according to the invention. Given the proportion of alkaline agent added indicated above, the pH of the reaction medium (distillate + solution of alkaline agent) is greater than 8 and preferably between 9.5 and 13.

When the solvent used in step (b) of the process is water, the concentration of the alkaline agent in aqueous solution is preferably between 50 and 96% by weight relative to the weight of the aqueous solution. Advantageously, the aqueous solution of alkaline agent is in the form of the potassium / water eutectic (86.7 / 13.3). The aqueous solution of alkaline agent is prepared beforehand and is then added with continuous stirring to the distillate resulting from step (a). It can be "solid" at room temperature, as is notably the case for the potassium / water eutectic (86.7 / 13.3), the use of which constitutes a particularly preferred embodiment. In this case, the "solid" solution becomes fluid at the reaction temperature. When the solvent used in step (b) is a monoalcohol, a polyalcohol or a mixture of these, the alcoholic solution used is preferably such that the molar ratio of said solvent to said alkaline agent is between 2 and 20, and more particularly between 2.5 and 5.

According to a preferred embodiment of the invention, an amount of alcohol or an alcohol mixture sufficient to ensure in the reaction medium a concentration of alkaline agent close to saturation is used.

The monoalcohol or the polyalcohol preferably contains from 2 to 8 carbon atoms, and more particularly from 2 to 5 carbon atoms. Among the monoalcohols preferred according to the invention, mention may be made of ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, isobutanol, pentanols, hexanols and octanols. Among the preferred polyalcohols according to the invention, mention may be made of ethylene glycol, di- and tri-ethylene glycol. It is preferred, according to the invention, to use alcohols having a boiling point lower than the initial boiling point of the distillate and / or having a high solubility in water since their subsequent elimination by distillation or washing with water is easier.

The reaction medium is preferably prepared either by dissolving the alkaline agent in alcohol, then introducing it into the distillate, or by hot mixing the distillate and the alcohol then adding the alkaline agent in the form of solid pellets. According to a particular embodiment of step (b) of the process according to the invention, when an alcohol or a mixture of alcohols is used as solvent, the distillate is treated with the alkaline agent at reflux of alcohol or mixture of alcohols, however, provided there is no risk of loss by evaporation. According to another particular embodiment of step (b) of the process according to the invention, when operating at high temperature, and in particular when the solvent comprises an alcohol with a boiling point below the reaction temperature chosen, the distillate is treated with the alkaline agent at a pressure of about 10 ⁵ to 50 x 10 ⁵ Pa, preferably under a pressure of 10 ⁵ to 25 x 10 ⁵ Pa, in order to avoid losses by evaporation.

After the end of the alkaline treatment, at least one washing of the reaction medium is carried out using 1 to 15% of water approximately at a temperature between ambient temperature and approximately 100 ° C. The washing operation with water or step (c) of the process according to the invention makes it possible to remove the excess of alkaline agent, possibly the alcohol if it has been used as solvent as well as all the products soluble from contaminants and generated by alkaline treatment.

When the step of washing with water is carried out in a single operation, this is generally carried out using approximately 10% of water at a temperature of approximately 100 ° C. However, according to a particularly preferred embodiment, the washing step is carried out in two separate operations. The first consists in treating the reaction medium obtained after step (b) with an amount of water of approximately 1 to 10% and at a temperature as low as possible, between 20 and 90 ° C. The second is, after decanting, treating the reaction medium again with an amount of water of between 1 and 10% and at a temperature as high as possible and at least equal to that of the first operation.

According to the first washing operation, the temperature should preferably be as low as possible so as to minimize the hydrolysis phenomena but sufficient to lower the viscosity of the oily reaction medium of step (b) and guarantee a sufficient decantation speed .

On the other hand, for the second washing operation, the temperature should be as high as possible in order to ensure good removal of the residual alkaline agent. The total amount of water used according to this particular embodiment is preferably between 5 and 15%.

According to a variant of this washing step in two separate operations, the second washing operation can be carried out using a weakly acidic aqueous solution, for example using 0.1 to 1 N hydrochloric acid. washing and decanting step of the oily phase, this is then subjected to the distillation step (d) consisting first of all of a distillation at atmospheric pressure and at a temperature of about 70 to 270 ° C, to remove any remaining solvent, then at a pressure of about 1350 to 650 Pa and at a temperature of about 210 to 375 ° C in order to obtain a refined oil and a residue which represents less than 5% of the charge of departure.

According to a variant of the process according to the invention, step (c) of washing the oily phase with water can be followed by at least one treatment of said oily phase by catalytic hydrogenation at high pressure, by contacting with a sulfonating agent and / or by contacting with activated carbon or an activated earth. Preferably, the sulfonating agent is chosen from concentrated sulfuric acid and chlorosulfonic acid.

The activated earth is preferably a mineral earth of the silico-aluminate type activated by an acid treatment.

In the case of the treatment of the oily phase by contacting with a sulphonating agent, this treatment is preferably followed by neutralization of the oily phase, for example by adding the washing water from step (c) and preferably by addition of ammonia. The refined oil or the base oil obtained by the process according to the invention has excellent properties, both physical and chemical. It is practically free of odor, of low coloring and has very low chlorine contents, but also phosphorus and silicon

The main characteristics of the refined oils obtained by the process according to the invention are as follows:

TI TABLE

Chlorine content (mg / kg) <35

Phosphorus content (mg / kg) <5

Silicon content (mg / kg) <5

Color (ASTM D 1500) <3

Odor (sensory measurement) Very weak

Water content (% by weight) <10 ^"2

Sediments (% by weight) Absence

Viscosity at 40 ° C (mm ² / s) <85

Acid number (IA, mgKOH / g) <0.05

Saponification index (IS, mgKOH / g) <0.20

As can be seen by comparing Tables I and II, the treatment process according to the invention is particularly effective in reducing the main contaminants of used oils

We will now give by way of illustration several examples of implementation of the method according to the invention, from used oils, the characteristics of which have been given previously in Table I on page 1 of this description.

EXAMPLES 1 FT 2: From used oils of various industrial origins, first of all a distillation was carried out at atmospheric pressure and then, after increasing the temperature, at a pressure of about 1350 Pa This distillation allowed to obtain the following fractions TABLE III

Fraction j Pressure (Pa) j Temperature ι ° C) Proportion (% by weight)

1 1.013 x lO ⁵ 130/180 7.5% (water + petrol)

2 d 5300-10700 240/285 9% (diesel)

3 i 650-2000 285/345 65%

The distillation residue represented approximately 18.5% and consisted mainly of tars.

The fraction representing 65% had the following characteristics:

TABLE IV

Chlorine content (mg / kg) 60

Phosphorus content (mg / kg) 27

Silicon content (mg / kg) 9

Color (ASTM D 1500) 6.5

Odor (sensory measurement) Very strong

Water content (mg / kg) <80

Sediments (% by weight) Absence

Viscosity at 40 ° C (mm ² / s) 31.24

Acid number (IA; mgKOH / g) 0.26

Saponification index (IS; mgKOH / g) 1.30

A part of the distillate fraction representing approximately 65% was treated under the conditions given in Table V below using an aqueous potassium hydroxide solution.

50% by weight relative to the weight of the solution, at a temperature of 300 ° C and under a pressure of 14 x 10 ⁵ Pa and another part of this distillate using the potassium / water eutectic (86, 7 / 13.3), at a temperature of 220 ° C. and under a pressure of 10 ⁵ Pa. After the alkaline treatment, the reaction medium was washed several times with water brought to a temperature of approximately 90 °. C in order to eliminate the excess of alkaline agent and the various soluble products originating from the alkaline treatment.

After separation of the oily phase, it was subjected to distillation first under atmospheric pressure and then under a vacuum of between 650 and 1350 Pa. We thus recovered 96% of the starting distillate

The characteristics of the refined oils obtained are also given in Table V. As can be seen, these two processes by alkaline treatment lead to a refined oil having identical characteristics as regards the reduction in the contents of phosphorus, silicon and chlorine.

It should however be noted that the pure potash to be used to achieve the result is 7.2% or about 45 times the stoichiometry (IA + IS) if an aqueous potassium solution of 50% and 0 is used. , 47% or about three times the stoichiometry if the potassium / water eutectic is used.

It is also important to note that in the latter case, the treatment temperature is much lower since it is 220 ° C instead of 300 ° C.

We can therefore deduce a greater reactivity of the potash / water eutectic (86.7 / 13.3).

TABLE V

EXAMPLES 3 TO 11:

By following the same operating mode of the process as described in the previous examples and starting from the same distillate, step (b) of the alkaline treatment of the process according to the invention was carried out at temperatures varying between 175 and 300 °. C for a period of 10 to 60 minutes with n-octanol under the conditions indicated in Table VI below. The amount of alkaline agent used was in all cases at least equal to twice the stoichiometry (IA + IS) and all the tests according to these examples were carried out under atmospheric pressure with the exception of examples 10 and 11 which were carried out under a pressure of 10 × 10 ⁵ Pa.

It follows from Table VI that at equal temperature, the potash leads to more satisfactory results as regards the reduction in phosphorus, silicon and chlorine.

TABLE VI

EXAMPLE 12:

From waste oils of various origins, a distillate having the following characteristics was obtained, after distillation according to the technique of the preceding examples:

Chlorine content (mg / Kg) 72.00

Phosphorus content (mg / Kg) 18.00

Silicon content (mg / Kg) 23.00

Color (ASTM D 1500) 7.00

Acid number (IA; mg KOH / g) 0.49

Saponification index (IS; mgKOH / g) 2.90 Half of the distillate was treated with 2.5% 85% potash (i.e. 2% dry potash) and the other half was treated with 4.71% 85% potash (i.e. 4% dry potash) ). The treatments were carried out at a temperature of 250 ° C for approximately 30 minutes. The first half resulting from the treatment with 2% dry potash was divided into two equal parts.

The first was subjected to a single washing with 10% water at 100 ° C, and the second to the following two washing operations:

(i) a first wash using 5% water at 65 ° C and after decantation in (ii) a second wash using 5% water at 100 ° C.

Likewise, the second half resulting from the treatment with 4% of dry potash was divided into two equal parts.

The first was subjected to a single wash using 10% water at 100 ° C, and the second to the following two washing operations: (i) a first wash using 5% water at 65 ° C and after decantation at

(ii) a second wash using 5% water at 100 ° C. After decantation, the four oily residues obtained were subjected to fractional distillation under a pressure of 1,300 Pa with a view to obtaining for each of them the following four fractions (corrected temperatures reduced to 1 Atm.): Fraction I: 264 - 370 ° C

Fraction II: 370 - 441 ° C Fraction III: 441 - 475 ° C Fraction IV: 475 - 558 ° C The colors of the different fractions obtained were then measured according to the ASTM D 1500 method and the results are collated in Table VII below . - 1:

TABLE VII

As can be seen, washing in two operations leads to oils having a markedly improved color, which is a particularly unexpected result.

It has also been found that, in order to optimize the yields of oily products before the distillation step, it was advisable to use in the washing process in two operations, a quantity of water during the first washing, greater or less. equal to 2% but less than or equal to 10% and preferably between approximately 4 to 6% in order to obtain yields of the order of 90 to 98%.

Claims

1. A process for refining used oils, characterized in that it comprises the stages consisting of: a) distilling said used oils, b) treating the resulting distillate with an alkaline agent and in the presence of a solvent chosen from water, a monoalcohol, a polyalcohol and a mixture of these alcohols, said alkaline agent being present in a proportion, in percentage by weight relative to the weight of the distillate, equal to the product F x (IA + IS), F being a multiplying factor between 2 and 50, IA and IS being respectively the acid number and the saponification number of said distillate, said treatment being carried out at a temperature of about 80 to 330 ° C for a time d '' approximately 2 to 200 min, c) washing the reaction medium with water and then leaving to settle to recover the oily phase, and d) proceeding to the distillation of said oily phase.

2. Method according to claim 1, characterized in that step (a) of distillation of the used oils is carried out under atmospheric pressure and at a temperature of about 130 to 180 ° C, then under a pressure of about 12000 at 650 Pa and at a temperature of around 240 to 345 ° C.

3. Method according to any one of the preceding claims, characterized in that the alkaline agent is either sodium hydroxide or potassium hydroxide.

4. Method according to any one of the preceding claims, characterized in that the alkaline agent is potash.

5. Method according to any one of the preceding claims, characterized in that when said solvent is water, the concentration of alkaline agent is between 50 and 96% by weight relative to the weight of the aqueous solution.

6. Method according to any one of the preceding claims, characterized in that the alkaline agent is in the form of the potassium / water eutectic (86.7 / 13.3).

7. Method according to any one of claims 1 to 4, characterized in that when said solvent is chosen from a monoalcohol and a polyalcohol or a mixture thereof, the alcoholic solution of alkaline agent used is such that the molar ratio of said monoalcohol or polyalcohol to said alkaline agent is between 2 and 20.

8. Method according to claim 7, characterized in that the molar ratio of said monoalcohol or polyalcohol to said alkaline agent is between 2.5 and 5.

9. Method according to any one of claims 1 to 4, 7 and 8, characterized in that said monoalcohol or polyalcohol has from 2 to 8 carbon atoms.

10. Method according to any one of the preceding claims, characterized in that step (c) of washing the reaction medium with water is carried out using 1 to

15% water at a temperature between room temperature and around 100 ° C.

1 1. Method according to any one of the preceding claims, characterized in that step (c) of washing the reaction medium with water is carried out in two separate operations, the first consisting in treating said medium with a quantity of water from about 1 to 10% and at a temperature between 20 and 90 ° C and the second consisting, after decantation, in treating the resulting medium with an amount of water between 1 and 10% and at a temperature high.

12. Method according to claim 11, characterized in that the second washing operation is carried out using a weakly acidic aqueous solution.

13. Method according to any one of the preceding claims, characterized in that step (d) of distillation is carried out firstly at atmospheric pressure and at a temperature of about 70 to 270 ° C, then under pressure from about 1350 to 650 Pa and at a temperature of about 210 to 375 ° C.

14. Method according to any one of the preceding claims, characterized in that the oily phase resulting from the washing step (c) is further followed by at least one treatment by catalytic hydrogenation at high pressure, and / or by setting in contact with a sulfonating agent or with activated carbon or activated earth.

15. The method of claim 14, characterized in that said sulfonating agent is chosen from concentrated sulfuric acid and chlorosulfonic acid.

16. The method of claim 14, characterized in that said activated earth is a silico-aluminate activated by acid treatment.

17. The method of claim 14, characterized in that the treatment of the oily phase by contacting with a sulfonating agent is followed by neutralization of the oily phase.

18. The method of claim 17, characterized in that said neutralization of the oily phase is carried out by addition of ammonia.

19. Refined oil obtained by the process according to any one of the preceding claims, characterized in that it has the following characteristics:

- chlorine content (mg / kg) <35 - phosphorus content (mg / kg) <5

- silicon content (mg / kg) <5

- color (ASTM D 1500) <3

- very weak odor (sensory measurement)

- water content (% by weight) <IO ^"2 - sediments (% by weight) absent

- viscosity at 40 ° C (mm7s) <85

- acid number (IA; mgKOH / g) <0.05

- saponification index (IS; mgKOH / g) <0.20