PROCESS FOR THE TREATMENT OF OIL RESIDUES COMING FROM THE OIL INDUSTRY

The present invention relates to a process for the treatment of oil residues coming from the oil industry.

More specifically, the invention relates to a process for the reduction, recovery and declassification of oil sludge and/or tank sediments produced by the oil industry and for the recovery of the oil components .

Waste-products deriving from the oil industry mainly consist of oil sludge coming from wastewater treatment plants (TAS) , sediments coming from the reclamation of tanks containing crude oil, fuel oil, gas oil, etc., from the reclamation of plant equipment and oil residue accumulation basins or ponds.

These waste-products, depending on the origin of the material, have an oil content varying from 20 to 80%, a water content of 10 to 40% and a content of inert products ranging from 5 to 50%.

The national reference regulation for the classification of said waste-products is represented by the Directive of the Ministry for the Environment and Land Protection of April 9, 2002 whose Annex A contains the list of waste-products (European Waste Catalogue) according to the Decision 2000/532/CE and subsequent modifications, in force since January 1 ^st 2002.

In this list, the types of waste-products which can be qualified as hazardous are marked by an asterisk * and are partly represented by isolated items (as the dangerousness is intrinsically linked to the origin of the waste-product) , the remaining part is represented by "specular" items of non-hazardous waste-products (as the dangerousness is linked to the content of dangerous substances present in the waste-product) .

The materials, object of the present invention belong to the waste generator category Nr. 05 00 00: "Waste from oil refining, purification of natural gas and pyrolitic treatment of coal", to the production process Nr. 05 01 00": "Oil Refining Waste" and are qualified as hazardous .

With respect to the final disposal of the waste- products, the Legislative Decree of January 13, 2003 Nr. 36 and the relative Actuation Decree of the Ministry for the Environment and Land Protection of August 3, 2005

concerning the admissibility criteria of waste-products in land dumps, with the aim of preventing or reducing to the maximum negative repercussions on the environment, introduce extremely more restrictive conditions for the disposal of waste-products in land dumps from the point of view of both the quantities, and the categories not admitted for this destination, with respect to both the limits on a series of analytical parameters among which the eluate of heavy metals and the DOC (Dissolved Organic Carbon) parameter, the latter being particularly critical due to the nature of the samples in question.

The intrinsic dangerousness of the waste-products, object of the present invention, also involves the obligation of examining the TOC (Total Organic Carbon) parameter on the sample as such, whose limit of 6%, which can be easily exceeded, makes it necessary to resort to suitable treatment aimed at extracting and recovering the oily fraction contained and stabilizing the solid phase obtained, so as to make it compatible with its disposal in controlled land dumps.

The necessity of treating these materials is therefore determined by both normative restrictions and also by opportunities of an economical nature.

The treatment so far developed has been mainly aimed at recovering the oil component, without specifically

intervening however on the properties of the solid residue in terms of release characteristics.

The recovery of the oil contained in these residues is often effected by resorting to treatment of the thermal type, as described for example in patents US 3,716,474S, EP 022353A1, EP 0330314A1, WO9204424, CN1178777A, EP 1577367A1, with the disadvantage of having to consume energy for removing the aqueous fraction and resort to relatively high temperatures to be able to recover the high-boiling components of which the oil fraction consists.

The treatment described in US patent 5,288,391 uses biodegradable solvents for treating refinery residues, recycling the oil recovered to the refinery, but obtaining a residue which must be treated biologically or used as fuel.

Another treatment approach consists in separating the oil from the solids by means of filtration, as described for example in BE 864352, possibly with the use of additives, as described in EP 0614689A2, where the solid, before being sent for disposal, is treated by extraction with a solvent or by vapour stripping treatment. The separation of the phases starting from the stable system consisting of solid-oil-water, is also obtained with the help of chemical agents such as

surface-active agents (JP 59112808A) , possibly assisted by additives and solvents (US 5,897,767), with the problem of having to subsequently effect the recovery or treatment of the chemicals used.

A thermal/oxidative treatment is also described (WO9925497) which, by used hydrogen peroxide, in addition to recovering the oil, tends to oxidize toxic compounds such as aromatic polycyclic hydrocarbons, this treatment however has the risk of leading to the formation of undesired oxidation compounds.

A process has now been found, which allows the oil residues to be economically and effectively treated by extraction of the oil fraction with solvents having a low environmental impact and subsequent finishing for the declassification of the residual material.

The process is not influenced by the content of water, solids and oil or by the composition of the oil and allows over 90% of oil to be recovered, having a quality which is such as to allow it to be conveniently recycled to the refinery. A residue is also obtained, consisting of deoiled solids with such characteristics as to allow it to be disposed of as a non-hazardous waste- product. The water separated from the process is compatible with the refinery water treatment plants.

The process therefore provides a double advantage:

the recovery of the oil and detoxification of the solid residue .

A further advantage obtained is the weight reduction of the waste-product to be sent for disposal.

In accordance with this, an object of the present invention relates to a process for the treatment of oil residues coming from the oil industry comprising, with reference to figure 1:

(i) sending the oil residue to an extraction phase (A) by mixing with a solvent, for the recovery of the oil component ;

(ii) sending the mixture of oil residues-solvent to a solid-liquid separation phase (B) and collecting a supernatant and a solid fraction;

(iii) sending the supernatant separated in phase (B) to a thermal recovery phase (G) of the oil and solvent used for the extraction, and recycling the same to the process;

(iv) sending the solid fraction separated in phase (B) to a washing phase (D) by mixing with water,-

(v) sending the solid fraction-water mixture of the washing phase (D) to a solid-liquid separation phase (E) and collecting an aqueous supernatant and a final solid residue .

The washing phase (D) allows both the removal of the

residual solvent and the extraction of the polar compounds present in the oil component.

Downstream of the extraction with the solvent, before washings with water, a low-temperature thermal desorption step (C) can be inserted for recovering the extraction solvent from the solid.

The aqueous component of the residue possibly- extracted is separated from the extraction solvent by- sedimentation (F) .

The solid/liquid separation (B) , (E) takes place by centrifugation, cycloning, or by sedimentation.

The solvents used can consist of either hydrocarbon fractions, pure or in a mixture, such as for example fractions consisting of aromatic solvents with a boiling point ranging from 100 to 140 ⁰ C, or solvents characterized by a greater polarity such as ethyl acetate or acetone, pure or in a mixture, or a combination of said solvents .

In the preferred configuration, the apolar solvent consists of toluene, the polar solvent of ethyl acetate. The extraction and solid-liquid washing ratio varies from 1:0.5 to 1:10 by weight and, preferably, from 1:1 to 1:5. The contact time with the solvent and the washing time with water varies from 5 to 60 minutes, and preferably from 10 to 30' .

The extraction steps with a solvent, n _e , and washing with water, ni, can vary from 1 to 10, generally being 2- 3.

The recovery of the solvent takes place by evaporation at 50-150 ⁰ C, 0.01-1 atm, and preferably at 60-90 ⁰ C and 0.1-0.8 atm.

If the solid deoiled material is characterized by the presence of leachable metals, during the washing with water, reagents can be added, capable of stabilizing said metals, such as compounds containing S° or S ^2" , such as for example sulfides and polysulfides .

Said washing is preferably effected using the same procedure described above, with contact times between the solid residue and the solution containing sulfide or polysulfide, varying from 30 minutes to 24 h, preferably 2-8 hours .

The concentration of reagents based on S° or S ^2" can vary from 0.01 to 5% in water, and preferably ranges from 0.05 to 2 %. The washing with the solution of S° or S ^2" is followed by 1-10 washings with water, preferably 1-2, with the procedure described above.

The use of organic solvents having a different polarity, possibly followed by washings with water, offers the advantage of both recovering high percentages of oil, which can be reused in the refinery, and also of

removing the polar organic components possibly present in the residue, which can be strongly jeopardized in relation to the disposal options of the same.

One of the parameters which determine the disposal options of a waste-product, in fact, consists of the quantity of organic carbon that this releases in water.

As the process also envisages the extraction of polar compounds, it reduces the quantity of leachable organic carbon from the waste-product, allowing it to be disposed of as non-hazardous according to the legislation in force.

Some examples are now provided, which represent applications of the present invention, which should not be considered as limiting the same. EXAMPLE 1 Treatment of tank sediments with toluene

A sample of tank sediment was first characterized in terms of oil content, water and inert products.

The oil proved to be equal to 67.4%, the water 17.6% and the inert products 15.0%.

The sample was extracted with toluene in the proportions (weight/weight) sediment : toluene = 1:3, under stirring x 15' to favour the extraction of the oil fraction on the part of the solvent. The solid-liquid separation was then effected with the use of a centrifuge

operating at 3,000 r x 20'.

The water content was determined on the supernatant, which is separated in a separator funnel (proving to be equal to 1.8%), and the oil content, extracted by- weighing the boiler deposit deriving from the distillation of the toluene at 80 ⁰ C at 0.8 atm in a rotating evaporator (equal to 16.2%).

The solid residue separated by the centrifugation was treated with the same procedure as the first extraction step, undergoing a further 2 mixing and centrifugation steps for each of which the water content was re-determined (1.4% at the 2 ^nd step and 0.6% at the 3 ^rd step) together with the oil content (1.4% at the 2 ^nd step and 0.2% at the 3 ^rd step) extracted from the supernatant. The final solid residue downstream of the third extraction step was dried in an oven at 110 ⁰ C to remove the toluene contained therein and was subsequently washed by mixing with water x 15' in a residue: water weight ratio = 1:3. The mixture was centrifuged at 3,000 r x 20' and the solid residue subjected to a further two analogous washings with water. An analytical characterization according to DM 3/08/2005 was effected on the final solid residue of the treatment, determining the TOC parameter on the material as such, which proved to be equal to 4.6% (lower than the 5% limit for disposal

in land dumps for non-hazardous waste-products) and effecting the leaching test according to the regulation UNI 10802 for measuring the DOC parameter on the eluate, which proved to be equal to 36 mg/1 (lower than 80 mg/1 the limit for disposal in land dumps for non-hazardous waste-products) and heavy metals, whose values, indicated in the following table, all proved to be lower than the specification limits, except for the mercury.

Metals (μg/l) Example 1 analyte ref. limit np ref. limit P

As 200 2500 35

Ba 10000 30000 0.3

Cd 20 200 2

Cr tot 1000 7000 5

Cu 5000 10000 4.7

Hg 5 50 65.6

Mo 1000 3000 6

Ni 1000 4000 668.4

Pb 1000 5000 15.7

Sb 70 500 1.7

Se 50 700 < 50

Zn 5000 20000 160.9

The whole treatment allows an oil recovery of about 91% and a reduction in the material to be disposed of, of about 66%. EXAMPLE 2 Treatment of tank sediment with toluene + Na ₂ S

In order to stabilize the leaching of the metal mercury to lower its concentration in the eluate within

specification limits, the final solid residue downstream of the third extraction step and drying in an oven at HO ⁰ C according to example 1, was washed with a solution of sodium sulfide at 0.1% x 8 hours in a solid: liquid weight ratio of 1:3. The mixture was centrifuged at 3,000 r x 20' and the solid residue was subjected to a further two washings with water for a mixing time of 15' in the same residue: water weight ratio = 1:3. The leaching test was effected again on the final solid residue of the treatment for measuring the metals on the eluate, whose values, indicated in the following table, all proved to be lower than the specification limits.

Metals (μg/l) Example 2 analyte ref. limit np ref. limit P

As 200 2500 35

Ba 10000 30000 12.1

Cd 20 200 2.7

Cr tot 1000 7000 5.3

Cu 5000 10000 4.1

Hg 5 50 2.5

Mo 1000 3000 70.3

Ni 1000 4000 442.2

Pb 1000 5000 31.2

Sb 70 500 21.1

Se 50 700 <50

Zn 5000 20000 33.3

EXAMPLE 3

Treatment of TAS oil sludge with ethyl acetate

A sample of oil sludge was first characterized in terms of content of oil, water and inert products.

The oil proved to be equal to 23.1%, the water 28.0% and the inert products 48.9%; in addition, the content of dry substance was determined, as a complement to 100 of the weight loss at 105 ⁰ C, which proved to be equal to 63.1%, and the content of volatile substance at 550 ⁰ C which proved to be equal to 23.8%. An analytical characterization was also effected according to the DM 3/08/2005, by carrying out the leaching test according to the regulation UNI 10802 for measuring the eluate of the DOC parameter, which proved to be higher than 100 mg/1 (limit for granting the disposal of waste-products in land dumps) : in order to be disposed of in land dumps, the material must therefore undergo suitable treatment .

The sample was extracted with ethyl acetate in the proportions (weight/weight) sludge: ethyl acetate = 1:3 under stirring x 15' to favour the extraction of the oil fraction on the part of the solvent. The slurry was then subjected to solid- liquid separation with the use of a centrifuge operating at 3,000 r x 20'.

The content of water which is separated in a separator funnel was then determined on the supernatant

(equal to 0.0%) and the content of oil extracted by weighing the boiler deposit deriving from the

distillation of ethyl acetate at 80 ⁰ C at 0.6 atm in a rotating evaporator (which proved to be equal to 6.9%) .

The solid residue separated by the centrifugation was treated with the same procedure used in the first extraction step undergoing a second mixing and centrifugation step for which the water content (0.0%) and oil content (0.5%) extracted from the supernatant was re-determined. The solid residue was then dried in an oven at 105 ⁰ C to remove the ethyl acetate contained therein and was subsequently washed by mixing with water x 15' in a residue : water weight ratio = 1:3. The mixture was centrifuged at 3,000 r x 20' and the solid residue underwent an analogous washing with water.

An analytical characterization according to DM 3/08/2005 was effected on the final solid residue of the treatment, determining the TOC parameter on the material as such, which proved to be equal to 4.8% (lower than the 5% limit for disposal in land dumps for non-hazardous waste-products) and effecting the leaching test according to the regulation UNI 10802 for measuring the DOC parameter on the eluate, which proved to be equal to 62 mg/1 (lower than 80 mg/1, the limit for disposal in land dumps for non-hazardous waste-products) and heavy metals, whose values, indicated in the following table, all proved to be lower than the specification limits.

Metals Example 3 analyte ref. limit np ref. limit P

As 200 2500 35

Ba 10000 30000 304.5

Cd 20 200 2.7

Cr tot 1000 7000 5.3

Cu 5000 10000 63.9

Hg 5 50 2

Mo 1000 3000 625.7

Ni 1000 4000 88.8

Pb 1000 5000 31.2

Sb 70 500 21.1

Se 50 700 <50

Zn 5000 20000 15.8

The whole treatment allows an oil recovery of about 97% with a slight increase in the material to be disposed of, equal to about 7%.