Method for treating fossil-origin hydrocarbons followed by fractionation in the presence of waste oil

Abstract

The invention relates to a method concerning hydrocarbon fluids from a fossil hydrocarbon feedstock and a waste oil, the method comprising: a) a first step of treating the fossil hydrocarbon feedstock in a first treatment section producing a hydrocarbon effluent, b) a second fractionation step in which the hydrocarbon effluent is fractionated in a second fractionation section into at least one liquid hydrocarbon fraction, and optionally into at least one gaseous fraction, and wherein: - the first treatment section is chosen from a first desalting section producing a desalted hydrocarbon effluent and a first atmospheric-pressure distillation fractionation section producing at least one bottom fraction, and - the desalted hydrocarbon effluent or the at least one bottom fraction is fractionated in the presence of at least part of the waste oil in the second fractionation section.

Description

[0001] DESCRIPTION

[0002] TITLE: PROCESS FOR TREATMENT OF FOSSIL-DERIVED HYDROCARBONS FOLLOWED BY FRACTIONATION IN THE PRESENCE OF USED OIL

[0003] technical field

[0004]

[0001] The present invention relates to a process for treating fossil hydrocarbons followed by fractionation in the presence of used oil from industrial applications or engines, such as engine oils, hydraulic oils, gear oils, and / or industrial oils. The invention relates in particular to a process for manufacturing hydrocarbon fluids from a fossil feedstock and used oil.

[0005] Previous art

[0006]

[0002] Used or spent oils, sometimes referred to by the acronym U LO for "Used Lubricant Oils" or UMO for "Used Motor Oils", are derived from mineral or synthetic, lubricating or industrial oils.

[0007]

[0003] These oils typically correspond to mixtures of hydrocarbons, most often but not exclusively of petroleum origin. These oils also contain various additives that enhance their intrinsic properties or provide additional properties for a specific use.

[0008]

[0004] Among the additives commonly used in oils, particularly in engine oils, we can mention:

[0009]

[0005] - antioxidant additives whose function is to slow down the oxidation phenomena of the oil and thus extend its lifespan;

[0010]

[0006] - detergent additives whose function is to keep clean the parts intended to be in contact with oil;

[0011]

[0007] - dispersing additives, for example alkyl-succimides, which serve to suspend in the oil solid impurities present in the engine oil such as soot, dust, wear metals;

[0012]

[0008] - anti-wear additives contributing to the formation of a protective film on the surfaces of the parts in contact with said oil, for example organo-metallic compounds such as zinc alkyl-dithio-phosphates;

[0013]

[0009] - rust-preventative additives, detergents for example sulfonates or phenolates,

[0014]

[0010] - additives improving the viscosity index or anti-foaming additives, emulsifiers, pour point depressants, etc.

[0015]

[0011] During their use, particularly in an industrial machine or an internal combustion engine, oils are subjected to stresses which will cause their degradation leading to an increase in the level of contaminating elements in said oils, these contaminating elements may come from a degradation of the aforementioned additives, such as antioxidant additives, anti-wear agents; or from external pollutants, such as dust; or from wear metals emanating, for example, from the parts with which the oil is in contact during its use; or even from fuel fractions (diesel or gasoline) more or less oxidized or thermally cracked and which may be in liquid or solid form, in particular soot;or even contaminants related to the storage of used oils, which sometimes contain substances constituting light fractions that are generally water, or chlorinated or petroleum solvents.

[0016]

[0012] The result is a polluted oil with a color that is generally stronger than the original clean oil.

[0017]

[0013] Two main categories of used oils can thus be distinguished:

[0018]

[0014] - black oils, including engine oils and certain industrial oils

[0019] (quenching, rolling, wire drawing oils and other neat metalworking oils); these oils are highly degraded and contaminated, for example due to the presence of oxidation or fuel cracking products in the case of engine oils;

[0020]

[0015] - clear oils, coming from transformers, hydraulic circuits and turbines. They are slightly contaminated and generally loaded with water and particles.

[0021]

[0016] For economic, environmental, and resource conservation reasons, these used oils are recovered and processed for reuse as oil or in other hydrocarbon fluids. Today, a fraction of used oils is recycled to form new products (lubricants). To be recycled, used oils must meet specifications (contaminant levels) that depend on the recycling processes used. Used oils that do not meet these specifications, particularly the heavier fractions, are generally used as fuel.

[0022]

[0017] There is therefore a need to better valorize used oils, in particular the most polluted and / or heaviest fractions of these used oils.

[0023] Description of the invention

[0024]

[0018] The invention proposes a process for manufacturing hydrocarbon fluids from a fossil hydrocarbon feedstock and used oil. The process comprises:

[0025]

[0019] a) a first stage of treatment of the fossil hydrocarbon load in a first treatment section producing a hydrocarbon effluent,

[0026]

[0020] b) a second fractionation step in which the hydrocarbon effluent is fractionated in a second fractionation section into at least one liquid hydrocarbon fraction, and optionally into at least one gaseous fraction.

[0027]

[0021] According to the invention, the first treatment section is chosen from a first desalting section and a first fractionation section, and the hydrocarbon effluent is fractionated in the presence of at least some of the used oil in the second fractionation section.

[0028]

[0022] The process according to the invention thus makes it possible to manufacture hydrocarbon fluids (the liquid hydrocarbon fraction produced in step b) using, in part, recycled feedstocks.

[0023] The incorporation of used oil at the fractionation stage of a refining unit, mixed with a fossil hydrocarbon stream, makes it possible to produce fractions that can then be processed according to their cuts in the refining unit.

[0029]

[0024] Fossil-based hydrocarbon feedstocks typically contain sulfur, nitrogen, metal, or other pollutants that must be removed in subsequent treatments. Used oils and their fractions also contain impurities containing nitrogen, sulfur, metals, as well as phosphorus, chlorine, and silicon. By fractionating them along with a fossil-based hydrocarbon feedstock, it is possible to introduce hydrocarbons from the used oils into each fossil fraction and send them to the usual subsequent treatments of fossil hydrocarbon fluids, where they will be freed of their impurities.

[0030]

[0025] The used oil used in the present invention comes from industrial uses or from engines. It can in particular be chosen from used engine oil, used hydraulic oil, used gear oil, used industrial oil, a cut of one of these oils, and mixtures thereof.

[0031]

[0026] The used oil used in the present invention may be whole or fractionated. Thus, in one embodiment, the used oil may be a cut of used oil, in particular a cut having a boiling range of 400 to 800 °C or 500 to 800 °C, also referred to hereafter as "used oil residue".

[0032]

[0027] The used oil used in the present invention may comprise one or more of the following characteristics:

[0033]

[0028] a phosphorus content 10 to 2000 ppm by mass, a chlorine content of 10 to 6000 ppm by mass, a silicon content of 10 to 2000 ppm by mass, an aromatic content of 0 to 13% by mass, including non-zero, an isoparaffin and naphthene content of 60 to 90% by mass, an ester content of 0.5 to 10% by mass.

[0034]

[0029] In one embodiment, the process may further include a step of fractionating used oil into:

[0035]

[0030] - a cup exhibiting a boiling point range of 400 to 800 °C or of

[0036] 500 to 800 °C,

[0037]

[0031] - a base oil cut having boiling points in the range of

[0038] 350 to 550 °C,

[0039]

[0032] - and optionally in at least one cut chosen from a petrol cut and a diesel cut,

[0040]

[0033] and the hydrocarbon effluent is then fractionated in the second fractionation section in the presence of said cut having a boiling point range of 400 to 800 °C or 500 to 800 °C.

[0041]

[0034] The process may then include:

[0042]

[0035] - a step of producing lubricant from said base oil cut,

[0043]

[0036] - and optionally a fuel production step from said at least one cut selected from a gasoline cut and a diesel cut.

[0037] Depending on the contamination of the used oil, it may be advantageous to introduce the used oil, or a cut thereof, either into the first treatment section, or into the second fractionation section, or into both sections.

[0044]

[0038] Advantageously, at least a portion of the waste oil, or a cut thereof, can be introduced into the first treatment section and / or at least a portion of the waste oil or a cut thereof can be introduced into the second fractionation section.

[0045]

[0039] The used oil, or a cut thereof, can thus be introduced at step a) and / or b). In particular, separate used oils (or separate cuts of oils), for example of different qualities, with more or less impurities, can be introduced at each step.

[0046]

[0040] Advantageously, said fossil hydrocarbon feedstock may be crude oil or a mixture of crude oils. The first treatment section is then selected from a first desalting section of said crude oil or said mixture of crude oils producing a hydrocarbon effluent which is desalted crude oil or a mixture of desalted crude oils, and a first atmospheric distillation fractionation section of said crude oil or said mixture of crude oils, optionally previously desalted, producing a hydrocarbon effluent which is at least a bottom fraction.

[0047]

[0041] Advantageously, according to a first embodiment:

[0048]

[0042] - said fossil hydrocarbon charge is crude oil,

[0049]

[0043] - the first step is a crude oil desalting step in a desalting section producing a desalinated effluent, in particular desalinated crude oil,

[0050]

[0044] - the second step is a fractionation step by atmospheric distillation of desalted crude oil, and

[0051]

[0045] - at least a portion of the used oil, or a cut thereof, is introduced into the first desalting section and / or into the second fractionation section.

[0052]

[0046] This embodiment allows the used oil to be incorporated at the refinery inlet. The hydrocarbons in the used oil are then diluted throughout the refinery's entire flow. Furthermore, the contaminants present in the used oil can be partially removed during the desalting stage. Advantageously, a first used oil (or a fraction thereof) can be introduced into the first desalting section and a second used oil (or a fraction thereof) into the second fractionation section, the first used oil having a higher impurity level than the second used oil. In particular, a residue of used oil is preferably introduced into the first desalting section.

[0053]

[0047] Advantageously, according to a second embodiment:

[0054]

[0048] - said fossil hydrocarbon feedstock is crude oil, optionally desalted,

[0055]

[0049] - the first step is a fractionation step by atmospheric distillation of crude oil, optionally desalted, carried out in a first fractionation section and producing at least one bottom fraction,

[0050] - the second step is a fractionation step by vacuum distillation of said bottom fraction, and

[0056]

[0051] - at least a portion of the used oil, or a cut thereof, is introduced into the first fractionation section and / or into the second fractionation section.

[0057]

[0052] It may advantageously be possible to introduce a first used oil (or a cut thereof) into the first fractionation section and a second used oil (or a cut thereof) into the second fractionation section, the first used oil or its cut having a higher rate of impurities than the second used oil or its cut.

[0058]

[0053] The ratio of waste oil or waste oil cut / hydrocarbon effluent or the ratio of waste oil or waste oil cut / fossil hydrocarbon feed can advantageously be from 0.1 to 50% by mass.

[0059]

[0054] The process may further include a third step c) of treating at least one liquid hydrocarbon fraction of step b) selected from a hydrotreating step, a hydrocracking step, a thermal cracking step and a fluid catalytic cracking step, and producing an effluent having a reduced content of heteroelements and / or olefins and / or dienes and / or aromatics, and / or more cracked.

[0060]

[0055] The treatment in step c) can implement at least one reaction selected from hydrodesulfurization, hydrodeazotation, hydrodemetallation, hydrodearomatization, hydrodehalogenation, catalytic hydrogenation, hydrodeoxygenation, hydrocracking, thermal cracking and fluid catalytic cracking.

[0061]

[0056] The at least one liquid hydrocarbon fraction separated in step b) can advantageously be subjected to a further fractionation step to produce at least one hydrocarbon fraction which is then sent to the third treatment step c). This further fractionation step is preferably implemented when the first step is a desalting step. The further fractionation step can then be a distillation step under reduced pressure.

[0062]

[0057] In one embodiment, the process according to the invention comprises only steps a) to c).

[0063] Detailed description of the invention

[0064]

[0058] The terms "including" and "includes" as used herein are synonymous with "including", "includes" or "contains", "containing", and are inclusive or boundless and do not exclude additional features, elements or unspecified method steps.

[0065]

[0059] The expressions % by weight and % by mass (also noted %m) have an equivalent meaning and refer to the proportion of the mass of a product relative to 100g of a composition comprising it.

[0066]

[0060] Unless otherwise specified, measurements given in parts per million (ppm) are expressed by mass.

[0061] Boiling points as mentioned herein are measured at atmospheric pressure, unless otherwise specified. An initial boiling point is defined as the temperature at which the first vapor bubble forms. A final boiling point is the highest temperature attainable during distillation. At this temperature, no more vapor can be transported to a condenser. The determination of the initial and final boiling points uses techniques known in the trade, and several methods adapted according to the distillation temperature range are applicable, for example, NF EN 15199-1 (2020 version) or ASTM D2887 for measuring the boiling points of petroleum fractions by gas chromatography, ASTM D7169 for heavy hydrocarbons, and ASTM D7500, D86, or D1160 for distillates.

[0067]

[0062] The term "hydrocarbon" refers to both alkanes (saturated hydrocarbons), cycloalkanes, aromatics and unsaturated hydrocarbons.

[0068]

[0063] By "heteroatom" is meant any element of an organic compound other than carbon and hydrogen.

[0069]

[0064] The concentration of heteroatoms in the hydrocarbon matrix can be determined by any method known in the art. In particular, relevant characterization methods include X-ray fluorescence (XRF), inductively coupled plasma mass spectrometry (ICP-MS), and inductively coupled plasma atomic emission spectrometry (ICP-AES). Analytical scientists are able to identify the most suitable method for measuring each metal and, more generally, each heteroatom, depending on the hydrocarbon matrix considered. The oxygen content can be measured according to ASTM D5622-17 / D2504-88 (2015). The nitrogen content can be measured according to ASTM D4629-17. The sulfur content can be measured according to ISO 20846:2011. The halogen content, including chlorine, bromine, fluorine, can be measured according to the standard: ASTM D7359-18.

[0070]

[0065] The aromatic content can be measured by gas chromatography, for example by a GCxGC method, in particular a high temperature GCxGC method.

[0071]

[0066] The ash content can be determined according to ASTM D7582-2024.

[0072]

[0067] In the following description, the different embodiments described, and in particular the preferred embodiments of each step, can be combined according to the objective sought.

[0073]

[0068] Fossil hydrocarbon charge

[0074]

[0069] The fossil hydrocarbon feedstock used in the present invention does not include any component of biological origin, for example, from biomass. It consists essentially of hydrocarbons of fossil origin. Metallic or mineral contaminants may also be present.

[0075]

[0070] The fossil hydrocarbon feedstock used in the present invention may be crude oil or a mixture of crude oils, optionally desalted.

[0071] In the following description, the use of the expression "crude oil" is taken to encompass a mixture of crude oils.

[0076]

[0072] Used oil

[0077]

[0073] Used oil is a mixture of hydrocarbons polluted by various contaminants (metals, oxygen, phosphorus, silicon, chlorine, sulfur, water, sediments).

[0078]

[0074] In used oils, chlorine and silicon are present in the form of organic compounds, referred to as organic chlorine or organic silicon. Such organic compounds are not present in crude oil.

[0079]

[0075] These oils may be of mineral origin and / or be bio-based.

[0080]

[0076] They generally comprise 60 to 90% by mass of isoparaffins and naphthenes, and 0 to 13% by mass of aromatics. The isoparaffin and naphthene content can be determined according to ASTM D4124-09(2018). Used oil may also comprise 0.5 to 10% by mass of esters. The ester content can be determined by infrared spectroscopy.

[0081]

[0077] Used oil may contain a total metal (excluding metalloids such as Si) and phosphorus content of 500 ppm to 10,000 ppm, preferably from 1,000 ppm to 8,000 ppm. The metal content in the raw material may be determined using, for example, inductively coupled plasma atomic emission spectrometry based on ASTM D5185. For the purposes of the present invention, the total metal content preferably refers to the total (added) content of Al, Cr, Cu, Fe, Na, Ni, Pb, Sn, V, Ba, Ca, Mg, Mn, and Zn.

[0082]

[0078] The phosphorus content can be from 10 to 2000 ppm.

[0083]

[0079] The used oil also typically contains 10 to 6000 ppm of chlorine and 10 to 2000 ppm of silicon.

[0084]

[0080] Sulfur may also be present in a concentration of 500 to 30000 ppm.

[0085]

[0081] In the present invention, the oxygen content "on a dry basis" means that the oxygen content is determined assuming that all the water is removed before determining the content. The oxygen content on a dry basis can be determined by drying the raw material and determining the oxygen content (for example, by elemental analysis). Alternatively, the oxygen content on a dry basis can be determined from a wet raw material as follows:

[0086]

[0082] Oxygen content (dry basis) = 100% * {(total oxygen content of wet waste oil, for example by elemental analysis) - (oxygen contained in wet waste oil in the form of water)} / {(mass of wet waste oil) - (mass of water in wet waste oil)}.

[0087]

[0083] The water content (mass) contained in the wet used oil can be determined by any suitable means (for example Karl-Fisher titration according to ASTM D6304, or distillation according to ASTM D95).

[0088]

[0084] The used oil preferably has an oxygen content, on a dry basis, in the range of 0.1% by mass to 7.0% by mass, more preferably of at most 5.0% by mass, at most 3.5% by mass or at most 3.0% by mass, and / or of at least 0.2% by mass, at least 0.3% by mass, at least 0.4% by mass or at least 0.5% by mass.

[0089]

[0085] Oxygen may be present in the form of esters, in the aforementioned amounts.

[0090]

[0086] Used oil also typically contains sediment, generally from 500 to 10,000 ppm. This sediment accumulates during oil use.

[0091]

[0087] Used oil generally also includes ash, in a concentration of 500 to 30000 ppm.

[0092]

[0088] The used oil is preferably liquid at 25°C. It can therefore be easily used and does not require excessive heating during storage and / or transport.

[0093]

[0089] Furthermore, it is preferable that the total hydrogen (H) and carbon (C) content in the used oil, on a dry basis, be at least 80% by mass, preferably at least 85% by mass or at least 90% by mass, and up to 95% by mass. It is preferable that the total hydrogen (H) and carbon (C) content in the feedstock, on a dry basis, be at least 90% by mass. The hydrogen and carbon contents in the feedstock can be determined by elemental analysis, for example, using ASTM D5291.

[0094]

[0090] The waste oil of the present invention is preferably predominantly composed of a hydrocarbon material (consisting of C and H) with low levels of heteroatoms which may be contained as inorganic impurities and / or in the form of organic material from additives.

[0095]

[0091] Used oil typically has boiling points in the range of 30 °C to over 750 °C. The lowest boiling points result from hydrocarbons present as impurities.

[0096]

[0092] Used oil may indeed have been contaminated by hydrocarbons from its use in gasoline or diesel engines. These hydrocarbons may be a gasoline fraction, typically exhibiting a boiling point range of 30-35°C to 250°C, or a diesel fraction, typically exhibiting a boiling point range of 200 to 375°C. Since the used oil used in the present invention may be a mixture of oils, both fractions may be present as impurities. Depending on its origin, used oil may thus contain from 0 to 10% by mass of a gasoline fraction and from 0 to 10% by mass of a diesel fraction.

[0097]

[0093] 40 to 95% by mass of the used oil is also made up of a cut having boiling points in the range of 350 to 550 °C and corresponding to the base oil constituting the oil before its use.

[0098]

[0094] Finally, the used oil may include a heavier fraction or residue, in the distillation range of 400 to 800 °C or 500 to 800 °C, which may represent from 0 to 20% by mass of the used oil, most often from 0 to 10% by mass.

[0099]

[0095] Preferably, the used oil has a kinematic viscosity at 40 °C of 40 to 150 mm 2 / s.

[0100]

[0096] In one embodiment, the used oil used in the present invention is a +400 °C or +500 °C or +525 °C cut, with a boiling point range of 400 to 800 °C or 500 to 800 °C. Such a cut is free of water and has a higher sediment and inorganic (metals, alkalis, alkaline earths) content than unfractionated used oil.

[0101]

[0097] The process according to the invention can thus include a step of fractionating a used oil into at least one cut +400 °C or +500 °C or +525 °C, with a range of boiling points from 400 to 800 °C or from 500 to 800 °C, this cut then being fractionated with the converted hydrocarbon effluent in the second fractionation section.

[0102]

[0098] In one embodiment, the waste oil fractionation step separates the waste oil into said +400 °C or +500 °C or +525 °C cut, a base oil cut having boiling points in the range of 350 to 550 °C, and optionally at least one cut selected from a gasoline cut and a diesel cut.

[0103]

[0099] The said base oil cut can then be sent, alone or mixed with other refinery effluents, to a lubricant production unit. Optionally, the said cut, selected from a gasoline cut and a diesel cut, is sent, alone or mixed with other refinery effluents, to a fuel production unit.

[0104]

[0100] This allows for the best possible recovery of the different parts of a used oil.

[0105]

[0101] Description of steps a) and b) of the process

[0106]

[0102] The process according to the invention makes it possible to manufacture hydrocarbon fluids from partially recycled feedstocks. The hydrocarbon fluids produced can, in particular, be fuels and / or lubricants and / or be used in the manufacture of fuels and / or lubricants.

[0107]

[0103] The process thus comprises a first step a) of treating the fossil hydrocarbon feedstock in a first treatment section producing a hydrocarbon effluent, followed by a second step b) of fractionation in which the hydrocarbon effluent is fractionated in a second fractionation section into at least one liquid hydrocarbon fraction, and optionally into at least one gaseous fraction.

[0108]

[0104] The first step a) of treatment, implemented in a first treatment section, allows the fossil hydrocarbon load to be purified or separated before its fractionation.

[0109]

[0105] This can therefore be a desalting step implemented in a desalting section or a fractionation step implemented in a fractionation section.

[0110]

[0106] This first treatment step produces a hydrocarbon effluent which will then be sent to step b) of fractionation.

[0111]

[0107] According to step a) implementation, this hydrocarbon effluent can thus be a mixture of desalted hydrocarbons or a fraction of hydrocarbons.

[0112]

[0108] Step a) of desalting

[0113]

[0109] In one embodiment, step a) is a desalting step. This can be carried out under the usual desalting conditions of a refinery unit. This desalting step is typically used to process crude oil.

[0110] Crude oil often contains water, inorganic salts, suspended solids, and traces of water-soluble metals. The salts present are essentially chlorides, such as magnesium chloride, calcium chloride, and sodium chloride. The first step in refining crude oil typically consists of removing these contaminants by desalting to reduce corrosion, clogging, and fouling of the equipment and to prevent catalyst poisoning in downstream production units.

[0114]

[0111] Chemical desalting, electrostatic separation and filtration are three typical methods of desalting crude oil.

[0115]

[0112] In chemical desalting, water and surfactants (demulsifiers) are added to crude oil, heated to dissolve or fix salts and other impurities to the water, then this mixture is kept in a tank so that the aqueous phase can settle.

[0116]

[0113] In electrostatic desalting, high-voltage electrostatic charges are applied to concentrate the suspended droplets in the lower part of the settling tank. Surfactants are added only when the crude oil contains a large amount of suspended solids.

[0117]

[0114] A third, less common process consists of filtering hot crude oil through diatomaceous earth.

[0118]

[0115] In chemical and electrostatic desalting, the raw material is heated to a temperature between 66 °C and 177 °C, most often between 100 and 150 °C, to reduce viscosity and surface tension and thus facilitate mixing and water separation; the temperature is limited by the vapor pressure of the crude oil. Both desalting methods are carried out continuously. A base or acid is sometimes added to adjust the pH of the wash water. Ammonia may also be added to reduce corrosion. The wastewater and the contaminants it contains are collected at the bottom of a settling tank and conveyed to a wastewater treatment unit. The desalted crude oil is continuously recovered at the top of the settling tank.

[0119]

[0116] The desalting of crude oil, whether chemical and / or electrostatic, consists of injecting water into the crude oil, emulsifying this mixture to form an aqueous phase dispersed in the hydrocarbon phase as very fine droplets, which then mix with any residual salt water present in the crude oil. By then separating the aqueous phase from the hydrocarbon phase by breaking the emulsion formed, possibly after the addition of a demulsifier, in a suitable device such as an electrostatic desalter, crude oil containing only a small fraction of salt is recovered.

[0120]

[0117] The water / crude oil mass ratio is typically 2 to 12% water by mass, most often 3 to 10% by mass.

[0121]

[0118] The desalted crude oil can then be sent to step b) of fractionation, typically an atmospheric distillation step.

[0122]

[0119] Fractionation step a)

[0120] In another embodiment, step a) is a fractionation step. Preferably, it is a fractionation step by distillation under atmospheric pressure. Typically, this fractionation step is preceded by a desalting step.

[0123]

[0121] The hydrocarbon feedstock of fossil origin treated during this step a) is thus advantageously a crude oil, preferably a desalted crude oil.

[0124]

[0122] During this first fractionation stage, the crude oil, preferably desalted, is fractionated at least into a bottom fraction, or RAT (atmospheric residue). The other fractions usually separated are typically liquid fractions (diesel fuel, middle distillate, kerosene, naphtha) and a gaseous fraction.

[0125]

[0123] It is then the bottom fraction, or RAT, which is sent to the second step b) of fractionation.

[0126]

[0124] Step b) of splitting

[0127]

[0125] During step b) of fractionation, the effluent from step a) is separated into at least one liquid hydrocarbon fraction, and optionally at least one gaseous fraction, in a second fractionation section.

[0128]

[0126] This second fractionation section is typically a fractionation column, for example chosen from an atmospheric distillation column and a reduced pressure distillation column.

[0129]

[0127] The used oil or a fraction thereof used in the present invention can be introduced into the process either in the first treatment section or in the second fractionation section, depending on its contaminant content. It is also possible to introduce part of the oil into the first treatment section and part of the oil into the second fractionation section. The same used oil, or used oils of different qualities, or different fractions of used oils, can then be introduced into each section.

[0130]

[0128] Different cases can thus be considered depending on the quality of the used oil or the available cut, namely its contaminant content.

[0131]

[0129] In particular, when the contaminant content of the waste oil or available cut is very high, it is preferable to introduce the waste oil into the first processing section, especially when this is a first desalting section.

[0132]

[0130] A used oil or a cut with a slightly lower but still high contaminant content may be introduced into the second fractionation section which then advantageously implements vacuum distillation, the first treatment section then preferably being an atmospheric distillation fractionation section.

[0133]

[0131] Used oil or a cut with a lower contaminant content may be introduced into the second fractionation section, which then advantageously employs atmospheric distillation, the first treatment section preferably being a first desalting section.

[0132] It is nevertheless possible, although not preferred, to treat used oil or a cut according to one of the above cases, regardless of its contaminant content. Those skilled in the art will be able to choose the point of introduction of the used oil based on its contaminant content and the desired treatment for the used oil.

[0134]

[0133] Step b) of fractionation is preferably carried out on the hydrocarbon effluent directly from step a), without an intermediate step.

[0135]

[0134] This fractionation is thus implemented in the presence of the used oil, the latter being able to be introduced at one of the steps a) or b) or at both steps.

[0136]

[0135] The used oil can be introduced into the second fractionation section mixed with the hydrocarbon effluent or separately, preferably mixed with the hydrocarbon effluent exiting step a).

[0137]

[0136] Alternatively or in combination, the used oil can be introduced upstream of the second fractionation section, namely in the first treatment section, mixed or not with the fossil hydrocarbon feedstock, preferably mixed.

[0138]

[0137] Step b) of fractionation can be carried out with a waste oil or waste oil cut / fossil hydrocarbon feed ratio, or a waste oil or waste oil cut / hydrocarbon effluent ratio of 0.1 to 50% by mass, preferably 1 to 40% by mass, more preferably 2 to 30% by mass, or even 2 to 15% by mass. It should be noted that when waste oil or a waste oil cut is added in both steps a) and b), the hydrocarbon effluent leaving step a) and entering b) already contains waste oil. The waste oil or waste oil cut / hydrocarbon effluent ratio then does not take into account the waste oil or cut previously introduced in a) and present in the hydrocarbon effluent.

[0139]

[0138] The nature and number of hydrocarbon fractions separated during step b) depends on the nature of the treatment implemented in step a) and the objective sought.

[0140]

[0139] In one embodiment, the effluent from step a) is fractionated into at least one liquid hydrocarbon fraction selected from a naphtha fraction, a kerosene fraction, a diesel fraction, a vacuum diesel fraction, and a residue.

[0141]

[0140] According to the process, this fractionation can be carried out by adding a fractionation column, for example a distillation column, atmospheric or under reduced pressure.

[0142]

[0141] Preferably, the fractionation section is a distillation column, atmospheric or under reduced pressure.

[0143]

[0142] The recovered naphtha fraction preferably has an initial boiling point of 30 °C and a final boiling point of 120 °C to 160 °C. This fraction can be used, after undergoing hydrotreatment, in particular hydrodesulfurization, as feed for a steam cracker, in particular to produce olefins such as ethylene and propylene.

[0144]

[0143] The recovered diesel fraction preferably has an initial boiling point of 230 to 260 °C and a final boiling point of 380 °C or less.

[0144] The recovered kerosene fraction preferably has a final boiling point below 300 °C, particularly as measured according to ASTM D86-12. The initial boiling point according to ASTM D86-12 can be from 120 to 160 °C. The kerosene fraction can be used as jet fuel, generally after hydrotreating.

[0145]

[0145] The gas oil fraction under vacuum typically exhibits a distillation range from 350-400 °C up to 500 °C - 550 °C.

[0146]

[0146] Typically, when step a) is a desalting step, the fractionation of step b) is implemented under the usual conditions for fractionating desalted crude oil.

[0147]

[0147] Typically, when step a) is a fractionation step by distillation under atmospheric pressure, the fractionation of step b) is carried out under the usual fractionation conditions of a RAT, namely under reduced pressure (by vacuum distillation).

[0148]

[0148] During step b), the hydrocarbon effluent from step a) is thus fractionated (separated) into at least one liquid hydrocarbon fraction (forming a hydrocarbon fluid within the meaning of the invention), and optionally into at least one gaseous fraction.

[0149]

[0149] This liquid hydrocarbon fraction can then be sent to an optional third processing step.

[0150]

[0150] Step c) of processing

[0151]

[0151] The at least one liquid hydrocarbon fraction separated in step b) generally contains impurities containing heteroatoms and / or dienes and / or olefins and / or aromatics, and / or relatively long hydrocarbon chains.

[0152]

[0152] These heteroatoms may be nitrogen, sulfur, oxygen, silicon, halogens, and / or metals.

[0153]

[0153] Step c) of treatment makes it possible to reduce the content of heteroatoms and / or dienes and / or olefins and / or aromatics, and / or to further crack at least one liquid hydrocarbon fraction separated in step b).

[0154]

[0154] Step c) may implement one or more of the following reactions: hydrodesulfurization, hydrodeazotation, hydrodemetallation, hydrodearomatization, hydrodehalogenation, catalytic hydrogenation, hydrodeoxygenation, decarboxylation, thermal cracking, fluid catalytic cracking.

[0155]

[0155] Depending on the reactions implemented, step c) can be carried out in the presence of dihydrogen and at least one catalyst under appropriate usual conditions.

[0156]

[0156] Prior to step c) of treatment, the at least one hydrocarbon liquid fraction separated in step b) may be subjected to a further fractionation step (distinct from the previous fractionation step(s)) to produce at least one hydrocarbon fraction which is then sent to the third step c) of treatment.

[0157]

[0157] In particular, in one embodiment, step a) may be a desalting step, step b) a fractionation step by atmospheric distillation, the additional fractionation step then being a fractionation step by vacuum distillation. Each fraction separated in this last fractionation step may then be sent to the treatment step c) to be subjected, separately or in mixture, to one or more of the reactions described above.

[0158]

[0158] Depending on the objective sought, a hydrocarbon liquid fraction separated in step b) may be sent to a hydrotreating unit and / or a hydrocracking unit to remove one or more of the specific impurities, and / or to a thermal cracking unit (e.g. a coking and / or visbreaking unit) or to a dedicated fluid catalytic cracking (FCC) unit for further cracking, alone or mixed with one or more other hydrocarbon liquid fractions separated in step b), or with other refinery effluents.

[0159]

[0159] Advantageously, step c) of hydrotreating and / or hydrocracking and / or thermal cracking and / or fluid catalytic cracking can thus be implemented in one or more existing hydrotreating units and / or hydrocracking units and / or thermal cracking units (e.g. visbreaking and / or coking units) and / or fluid catalytic cracking units of a refinery, usually used to process feedstocks of fossil origin, and in particular specific fractions thereof.

[0160]

[0160] The present invention can therefore be implemented in an existing refinery, without having to modify it.

[0161] Detailed description of the figures

[0162]

[0161] Other features and advantages of the invention will become apparent from the following description of a particular embodiment of the invention, given by way of example but not limitation, with reference to the attached drawing in which:

[0163]

[0162] Figure 1 [Fig.1] schematically represents a manufacturing process according to a first embodiment of the invention.

[0164]

[0163] Figure 2 [Fig.2] schematically represents a manufacturing process according to a second embodiment of the invention.

[0165]

[0164] In the figures, identical elements are designated by the same reference numerals.

[0166]

[0165] In the possible embodiment of Figure 1, a fossil hydrocarbon feedstock (1) is subjected to a first treatment step a), here implemented in a first desalting section D un it.

[0167]

[0166] At the outlet of step a), the hydrocarbon effluent (2), here the desalted crude oil (2), is sent to step b) of fractionation implemented in a second fractionation section F atm -unit. This fractionation section is here an atmospheric distillation fractionation section.

[0168]

[0167] These desalting and fractionation stages are usually located at the inlet of a refinery and correspond to the first treatments to which crude oil is subjected.

[0168] According to the invention, a used oil (Hll) is treated with the crude oil. The used oil (Hll) can be introduced into the first desalting section D un it to be desalinated there with crude oil (1), and / or in the second fractionation section F atm-unit to be fractionated with desalted crude oil (2). Thus, regardless of its point of introduction, the used oil (Hll) is fractionated with the fossil feedstock in the second fractionation section F a t m -umt.

[0169]

[0169] In the example shown, the hydrocarbon effluent (2) is fractionated, for example, into a gaseous fraction (3) and several liquid hydrocarbon fractions, for example, a naphtha fraction (4), a kerosene fraction (5), a diesel fraction (6), and a residue (7). Of course, the invention is not limited by the number and nature of the fractions separated, which will be chosen by those skilled in the art according to the nature of the conversion reaction carried out and the desired products.

[0170]

[0170] The liquid fractions can be sent to a hydrotreating and / or hydrocracking and / or fluid catalytic cracking unit. The residue can be sent to another fractionation stage F re d-unit, typically a reduced pressure fractionation stage, to be separated into a vacuum diesel fraction VGO (8) and a vacuum residue (RSV) (9) which can be sent respectively to fluid catalytic cracking and / or hydrocracking units, and to visbreaking and / or coking units.

[0171]

[0171] Depending on the nature of any impurities present, a hydrocarbon liquid fraction separated in step b) may be sent to a hydrotreating unit, either alone or mixed with at least one other separated hydrocarbon liquid fraction, or with another refinery effluent. One or more hydrotreating units may thus be provided, each dedicated to one or more separated hydrocarbon liquid fractions. In the embodiment shown in Figure 1, three separate hydrotreating units HDTi, HDT2, and HDT3 are provided, treating fractions (4), (5), and (6) separately, respectively. A hydrocracking unit HCK1 and / or a fluid catalytic cracking unit FCC1 is provided to treat all or part of the VGO (8), and a coking unit Ci and / or a visbreaking unit VR1 is provided to treat all or part of the RSV (9).Each unit can then be operated to remove one or more specific impurities by one or more reactions chosen from hydrodesulfurization, hydrodeazotation, hydrodemetallation, hydrodearomatization, hydrodehalogenation, catalytic hydrogenation, hydrodeoxygenation, hydrocracking, and / or be operated to carry out additional cracking by fluid catalytic cracking and / or hydrocracking, or even thermal cracking.

[0172]

[0172] The invention is not, however, limited to the number of hydrotreating and / or hydrocracking and / or fluid catalytic cracking and / or thermal cracking units, nor to the nature of the reactions they employ. A person skilled in the art will be able to determine which treatment is necessary to remove one or more specific impurities from a given feedstock, or even to carry out other reactions, depending on the objective sought.

[0173] In the embodiment of Figure 1, the used oil (Hll) is introduced into the desalting section D un it, mixed or separately with crude oil (1), and / or used oil (the same or another used oil) is introduced into the fractionation section F a tm-unit separately from the hydrocarbon effluent (2) or mixed with it.

[0173]

[0174] In a particular embodiment, a portion of the waste oil (Hll) (identical or not to the waste oil introduced into the desalting section D) un it and / or the splitting section F a t m -umt) is introduced mixed with RSV (7) or separately into the fractionation section F re d-unit-

[0174]

[0175] Figure 2 shows another possible embodiment of the process according to the invention in which the fossil hydrocarbon feedstock (11), here crude oil, preferably previously desalted, is subjected to a first fractionation step a), carried out in a first fractionation section F at m-unit- This fractionation section is here an atmospheric distillation fractionation section.

[0175]

[0176] At the outlet of step a), the hydrocarbon effluent (12), here the bottom fraction of the fractionation section, namely a RAT, is sent to step b) of fractionation implemented in a second fractionation section F re d-unit. This fractionation section is here a fractionation section by distillation under reduced pressure.

[0176]

[0177] In the example shown, the hydrocarbon effluent (12) is fractionated, for example, into a distillate (13) and a residue (14) (vacuum residue or VRS). Of course, the invention is not limited by the number and nature of the separated fractions, which will be chosen by those skilled in the art according to the nature of the conversion reaction carried out and the desired products. The distillate (13) can then be sent to a fluid catalytic cracking unit (FCCi). The residue (14) can be sent to coking units (Ci) and / or visbreaking units (VRi).

[0177]

[0178] The used oil used in the present invention may be whole or fractionated to recover the base oil fraction, any diesel and / or gasoline fractions, and a residue. The base oil fraction and the diesel and / or gasoline fractions can be used to produce new oils or fuels. The process according to the invention makes it possible to recover the residue that is not currently usable.

[0178]

[0179] The use of whole used oil has the advantage of allowing all of the oil to enter a refinery process, without having to carry out specific prior fractionation.

[0179]

[0180] Using used oil residue has the advantage of limiting the increase in feed volume associated with introducing used oil. This can facilitate the use of existing refinery units.

Claims

DEMANDS 1. A process for manufacturing hydrocarbon fluids from a fossil hydrocarbon feedstock and used oil, the process comprising: a) a first step of treating the fossil hydrocarbon feedstock in a first treatment section producing a hydrocarbon effluent, b) followed by a second fractionation step in which the hydrocarbon effluent is fractionated in a second fractionation section into at least one liquid hydrocarbon fraction, and optionally into at least one gaseous fraction, and in which: said fossil hydrocarbon feedstock being crude oil or a mixture of crude oils, the first treatment section is selected from a first desalting section of said crude oil or said mixture of crude oils producing a hydrocarbon effluent which is desalted crude oil or a mixture of desalted crude oils,and a first fractionation section by atmospheric distillation of said crude oil or said mixture of crude oils, optionally previously desalted, producing a hydrocarbon effluent which is at least a bottom fraction, and the hydrocarbon effluent is fractionated in the presence of at least a portion of the used oil in the second fractionation section.

2. A manufacturing method according to claim 1, wherein said waste oil is selected from waste engine oil, waste hydraulic oil, waste gear oil, waste industrial oil, a cut of one of these oils, and mixtures thereof.

3. A manufacturing process according to claim 1 or 2, wherein said used oil comprises one or more of the following characteristics: a phosphorus content of 10 to 2000 ppm by mass, a chlorine content of 10 to 6000 ppm by mass, a silicon content of 10 to 2000 ppm by mass, an aromatics content of 0 to 13% by mass, in particular non-zero, an isoparaffins and naphthenes content of 60 to 90% by mass, an esters content of 0.5 to 10% by mass.

4. A manufacturing process according to any one of claims 1 to 3, further comprising a step of fractionating a used oil into: a cut having a boiling point range of 400 to 800 °C or 500 to 800 °C, a base oil cut having boiling points in the range of 350 to 550 °C, and optionally in at least one cut chosen from a gasoline cut and a diesel cut, and in which the hydrocarbon effluent is then fractionated in the second fractionation section in the presence of said cut having a boiling point range of 400 to 800 °C or 500 to 800 °C.

5. A manufacturing process according to claim 4, further comprising: a step of producing lubricant from said base oil cut, and optionally a step of producing fuel from said at least one cut selected from a gasoline cut and a diesel cut.

6. A manufacturing process according to any one of claims 1 to 5, wherein: at least a portion of the waste oil, or a cut thereof, is introduced into the first processing section, and / or at least a portion of the waste oil, or a cut thereof, is introduced into the second fractionation section.

7. A manufacturing process according to any one of claims 1 to 6, wherein: said fossil hydrocarbon feedstock is crude oil, the first step is a desalting step of the crude oil in the first desalting section producing a desalted effluent, the second step is a fractionation step by atmospheric distillation of the desalted effluent, and at least a portion of the used oil, or a cut thereof, is introduced into the first desalting section and / or into the second fractionation section.

8. A manufacturing process according to any one of claims 1 to 6, wherein: said fossil hydrocarbon feedstock is crude oil, optionally desalted, the first step is an atmospheric distillation fractionation step of the crude oil, optionally desalted, carried out in a first fractionation section and producing at least one bottom fraction, the second step is a vacuum distillation fractionation step of said bottom fraction, and at least a portion of the spent oil, or a cut thereof, is introduced into the first fractionation section and / or into the second fractionation section.

9. A manufacturing process according to any one of claims 1 to 8, wherein the ratio of waste oil or waste oil cut to hydrocarbon effluent or the ratio of waste oil or waste oil cut to fossil hydrocarbon feedstock is from 0.1 to 50% by mass.

10. A manufacturing process according to any one of claims 1 to 9, further comprising: c) a third treatment step of at least one liquid hydrocarbon fraction from step b), selected from a hydrotreating step, a hydrocracking step, a thermal cracking step, and a fluid catalytic cracking step, and producing an effluent exhibiting a reduced content of heteroelements and / or olefins and / or dienes and / or aromatics, and / or more cracked.

11. A manufacturing process according to claim 10, wherein the third treatment step c) carries out at least one reaction selected from hydrodesulfurization, hydrodeazotation, hydrodemetallation, hydrodearomatization, hydrodehalogenation, catalytic hydrogenation, hydrodeoxygenation, hydrocracking, thermal cracking, and fluid catalytic cracking.

12. A manufacturing process according to claim 10 or 11, wherein the at least one liquid hydrocarbon fraction separated in step b) is subjected to a further fractionation step to produce at least one hydrocarbon fraction which is then sent to the third processing step c).

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