Process for converting fossil-origin hydrocarbons followed by fractionation in the presence of waste oil

Abstract

The invention relates to a method for producing hydrocarbon fluids from a fossil hydrocarbon feedstock and a waste oil, the method comprising: a) a first step of converting the fossil hydrocarbon feedstock in a first conversion section (Cunit) producing a converted hydrocarbon effluent, b) a second fractionation step in which the converted hydrocarbon effluent is fractionated in a second fractionation section (Funit) into at least one liquid hydrocarbon fraction, and optionally into at least one gaseous fraction. The waste oil is fractionated with the converted hydrocarbon effluent in the second fractionation section (Funit).

Description

[0001] DESCRIPTION

[0002] TITLE: PROCESS FOR CONVERSION 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 converting fossil-based 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 method for manufacturing hydrocarbon fluids from a fossil hydrocarbon feedstock and a used oil.

[0025]

[0019] a) a first stage of converting the fossil hydrocarbon feedstock in a first conversion section producing a converted hydrocarbon effluent,

[0026]

[0020] b) a second fractionation step in which the converted 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 used oil is fractionated with the converted hydrocarbon effluent in the second fractionation section. Thus, steps a) and b) follow one another.

[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.

[0029]

[0023] Incorporating used oil at the fractionation stage of a refining unit, mixed with a fossil hydrocarbon feedstock, makes it possible to produce fractions that can then be processed according to their cuts within the refining unit. By incorporating the used oil at the fractionation stage of converted products in an existing refining unit, the process according to the invention results in less dilution of the used oil in the fossil feedstock compared to introduction further upstream in the refinery, for example, at the atmospheric distillation stage of crude oil.

[0030]

[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.

[0031]

[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.

[0032]

[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".

[0033]

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

[0034]

[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.

[0035]

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

[0036]

[0030] a cup exhibiting a boiling point range of 400 to 800 °C or 500 to 800 °C,

[0037]

[0031] a base oil cut having boiling points in the range of 350 to 550 °C,

[0038]

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

[0039]

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

[0040]

[0034] The process may then comprise:

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

[0041]

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

[0042]

[0037] Advantageously, the first conversion step can be chosen from a viscoreduction step and a coking step.

[0043]

[0038] When the first step is a viscoelastic step, said waste oil (a single oil or different oils) or a cut of waste oil can then be introduced into the first conversion section and / or into the second fractionation section.

[0044]

[0039] When the first step is a coking step, said waste oil (a single oil or different oils) or a cut of waste oil can then be introduced only in the second fractionation section.

[0045]

[0040] Advantageously, the waste oil or a waste oil cut can be introduced into the second fractionation section mixed with the converted hydrocarbon effluent or separately, preferably separately.

[0046]

[0041] When introduced into the first conversion section, the waste oil or a cut of waste oil can be introduced mixed with the fossil hydrocarbon feedstock or separately, preferably mixed.

[0047]

[0042] Advantageously, said fossil hydrocarbon feedstock may be crude oil, a mixture of crude oils, a residue or a mixture of residues, preferably a residue or a mixture of residues.

[0048]

[0043] In one embodiment, prior to the first step a) carried out in the conversion section, the fossil hydrocarbon feedstock is fractionated into a heavy fraction and a lighter fraction, and the heavy fraction is sent to the first conversion section of the first step a). This embodiment is particularly suitable for delayed coking units. This fractionation is typically carried out in the same fractionation section as that carrying out the fractionation step b). In this case, the fossil hydrocarbon feedstock is preferably introduced at a point of introduction located lower than a point of introduction of the converted hydrocarbon effluent.

[0049]

[0044] In one embodiment, the first step a) can be carried out in the first conversion section under coking conditions, producing the converted hydrocarbon effluent and a solid residue. The resulting solid residue is then sent to a carbon black production unit for tire manufacturing and / or to an activated carbon production unit for the manufacture of catalyst and / or adsorbent. The process according to the invention may then include a carbon black production step and / or an activated carbon production step from said solid residue, which may optionally be mixed with other residues from the refinery.

[0050]

[0045] Advantageously, the used oil or a used oil cut can be introduced into the second fractionation section mixed with the converted hydrocarbon effluent, or separately at an introduction point higher or lower than an introduction point of the converted hydrocarbon effluent. Separate introduction at a point higher than the converted hydrocarbon effluent can reduce the risk of cracking of the used oil components within the second fractionation section. Separate introduction at a point lower than the converted hydrocarbon effluent can reduce the amount of contaminants, particularly heteroatoms, from the used oil or used oil cut that may end up in the lighter effluents exiting the second fractionation section, since these lighter effluents are not returned to the conversion step.

[0051]

[0046] The ratio of waste oil or waste oil cut / converted hydrocarbon effluent, or the ratio of waste oil or waste oil cut / fossil hydrocarbon feedstock can advantageously be from 0.1 to 50% by mass.

[0052]

[0047] 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, 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.

[0053]

[0048] The treatment in step c) can implement at least one reaction selected from hydrodesulfurization, hydrodeazotation, hydrodemetallation, hydrodearomatization, hydrodehalogenation, catalytic hydrogenation, hydrodeoxygenation, hydrocracking, and fluid catalytic cracking.

[0054]

[0049] In one embodiment, the process according to the invention comprises only steps a) to c).

[0055] Detailed description of the invention

[0056]

[0050] 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.

[0057]

[0051] 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.

[0058]

[0052] Unless otherwise indicated, measurements given in parts per million (ppm) are expressed in mass.

[0059]

[0053] 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 relies on 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.

[0060]

[0054] The term "hydrocarbon" refers to both alkanes (saturated hydrocarbons), cycloalkanes, aromatics and unsaturated hydrocarbons.

[0061]

[0055] By "heteroatom" is meant any element of an organic compound other than carbon and hydrogen.

[0062]

[0056] 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.

[0063]

[0057] The aromatic content can be measured by gas chromatography, for example by a GCxGC method, in particular a high temperature GCxGC method.

[0064]

[0058] The ash content can be determined according to ASTM D7582-2024.

[0065]

[0059] 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.

[0066]

[0060] Fossil hydrocarbon charge

[0067]

[0061] 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.

[0068]

[0062] The fossil hydrocarbon feedstock used in the present invention can be crude oil or a mixture of crude oils, possibly desalted, or a residue or a mixture of residues.

[0069]

[0063] A fossil hydrocarbon feedstock usable in the process may advantageously be selected from crude oil, a residue from the atmospheric distillation of crude oil, also called "RAT," a residue from the vacuum distillation of a residue from the atmospheric distillation of crude oil, also denoted "RSV," and / or any other residue from fractionation sections of other refinery units and possibly treated, such as a heavy hydrocracking residue (commonly called "bleed"), deasphalting pitch, or other, alone or in mixtures.

[0064] A residue, or a mixture of residues, usable in the present invention typically has one or more of the following characteristics:

[0070]

[0065] - a sulfur content of at least 0.1% by mass, for example from 0.1 to 10% by mass, or from 1.5 to 10% by mass,

[0071]

[0066] - a metal content of 1 to 5000 ppm,

[0072]

[0067] - a Conradson carbon content of at least 2% by mass, preferably at least 10% by mass, more preferably at least 15% by mass, and possibly up to 40% by mass,

[0073]

[0068] - an initial boiling point of 300 °C to 550 °C, preferably of at least 325

[0074] °C, preferably more than at least 350 °C, preferably even more than at least 375 °C or at least 525 °C,

[0075]

[0069] - a final boiling point of 700 to 950 °C, preferably 700 to 900 °C, more preferably 700 to 850 °C.

[0076]

[0070] Used oil

[0077]

[0071] Used oil is a mixture of hydrocarbons polluted by various contaminants (metals, oxygen, phosphorus, silicon, chlorine, sulfur, water, sediments).

[0078]

[0072] 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]

[0073] These oils may be of mineral origin and / or be bio-based.

[0080]

[0074] 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]

[0075] 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]

[0076] The phosphorus content can be from 10 to 2000 ppm.

[0083]

[0077] The used oil also typically contains 10 to 6000 ppm of chlorine and 10 to 2000 ppm of silicon.

[0084]

[0078] Sulfur may also be present in a concentration of 500 to 30000 ppm.

[0085]

[0079] 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]

[0080] 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]

[0081] 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]

[0082] 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]

[0083] Oxygen may be present in the form of esters, in the aforementioned amounts.

[0090]

[0084] Used oil also typically contains sediment, generally from 500 to 10,000 ppm. This sediment accumulates during oil use.

[0091]

[0085] Used oil generally also includes ash, in a concentration of 500 to 30000 ppm.

[0092]

[0086] 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]

[0087] 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]

[0088] 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]

[0089] 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]

[0090] 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]

[0091] 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]

[0092] 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]

[0093] Preferably, the used oil has a kinematic viscosity at 40 °C of 40 to 150 mm 2 / s.

[0100]

[0094] In one embodiment, the waste oil used in the present invention is a +400 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 waste oil.

[0101]

[0095] 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]

[0096] 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]

[0097] 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]

[0098] This allows for the best possible recovery of the different parts of a used oil.

[0105]

[0099] Description of steps a) and b) of the process

[0106]

[0100] 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]

[0101] The process thus comprises a first step (a) of converting the fossil hydrocarbon feedstock in a first conversion section producing a converted hydrocarbon effluent, followed by a second step (b) of fractionation in which the converted hydrocarbon effluent is fractionated in a second fractionation section into at least one liquid hydrocarbon fraction, and optionally into at least one gaseous fraction. The used oil used in the present invention can be introduced at step (a), step (b), or both steps.

[0102] Conversion step (a)

[0108]

[0103] Step a) is a conversion step allowing a converted effluent to be obtained, in particular by thermal cracking.

[0109]

[0104] This conversion step can be chosen from a viscoreduction step and a coking step.

[0110]

[0105] This step then makes it possible to obtain an effluent that is at least partially cracked, namely consisting of the feed to be treated that is at least partially cracked.

[0111]

[0106] Viscoreduction and coking are reactions well known to those skilled in the art.

[0112]

[0107] Viscoreduction is a thermal cracking reaction carried out under moderate conditions to achieve partial cracking of the feed to be treated. It reduces the viscosity and the pour point of the treated feed.

[0113]

[0108] The visbreaking process is a treatment of heavy hydrocarbon feedstocks, consisting of bringing these feedstocks (in liquid form) into a furnace at a temperature that cracks the heaviest hydrocarbons and then introducing them into a maturation tank, in which, without further heating, they move at such a speed that, at the given temperature, they have a residence time sufficient to achieve the desired cracking of the heavy molecules into lighter molecules. The cracking results in a reduction of the viscosity of the treated feedstock, hence the terms visbreaking for the process implemented, and viscoreducer for the equipment used.

[0114]

[0109] The feedstock processed may be crude oil, in particular heavy crude oil, atmospheric distillation residue (though this is uncommon, as other types of recovery exist), vacuum distillation residue, bleed, deasphalting pitch, or other, or mixtures of these feedstocks. The products resulting from visbreaking are a vaporized converted effluent and a liquid residue generally called visbreaking vacuum residue.

[0115]

[0110] The vaporized converted effluent can be separated into gaseous hydrocarbons and non-condensable gas, naphtha, diesel and distillate(s), during step b) of fractionation.

[0116]

[0111] The liquid residue, particularly under the implementation conditions of step a), can be used for the production of marine fuel oil type fuel.

[0117]

[0112] Typical visbreaking conditions include a temperature of 350 to 550 °C, preferably 400 to 500 °C, for a duration generally of 1 to 60 minutes, preferably 10 to 45 minutes, and a total pressure generally less than 10 MPa, preferably less than 5 MPa, and more preferably less than 2 MPa. The cracking rate is controlled by adjusting the residence time of the hydrocarbons in the maturation tank. This process can be implemented using the devices described in documents FR2741888A1 or FR2741889A1.

[0118]

[0113] Coking is a thermal cracking reaction carried out under severe conditions capable of reducing the viscosity and pour point of the feedstock being treated.

[0114] In a coking step, the fossil hydrocarbon feedstock is advantageously a residual silica residue (RSV), or any other heavy feedstock from a refinery process, such as a heavy hydrocracking residue, deasphalting pitch, or the like.

[0119]

[0115] Typical coking conditions include a temperature of 400 to 600 °C, a pressure of 0 to 30 bar gauge, preferably 1 to 20 bar gauge, more preferably 1 to 15 bar gauge.

[0120]

[0116] The products resulting from coking are a vaporized converted effluent and a solid residue (coke).

[0121]

[0117] The vaporized converted effluent can be separated into gaseous hydrocarbons and non-condensable gases, naphtha, distillate(s) and residue during step b) of fractionation.

[0122]

[0118] The solid residue, here coke, particularly under the implementation conditions of step a), can be sent to a carbon black production unit for the manufacture of tires, and / or to an activated carbon production unit for the manufacture of catalyst and / or adsorbent, or other.

[0123]

[0119] The coking step can be implemented in a coking unit according to a delayed coking process or a fluid coking process.

[0124]

[0120] The delayed coking process consists of heating the feedstock to the thermal cracking temperature in a furnace before introducing it into coke drums where the cracking reactions take place. In these drums, long-chain hydrocarbon molecules are cracked into an effluent consisting of hydrocarbon vapors containing essentially diesel fuel and lighter components, and solid coke. The solid coke remains in the coke drum, which fills up in 16 to 24 hours. Once the drum is full of solid coke, the process switches to the second drum. While the second drum is filling with solid coke, the top and bottom heads of the first drum are removed, and the solid coke is extracted, for example, using a high-pressure water jet.Before being heated in a furnace and fed into the coke drums, the feedstock is fractionated into a heavy fraction, which is sent to the furnace and then to the coke drums. The remaining gases are recondensed and returned to fractionation along with the incoming feedstock. This fractionation is usually carried out in the same fractionation section as the one to which the effluents from the coke drums are sent.

[0125]

[0121] Step a), when it is a coking step, can thus be preceded by a step of fractionating the feedstock to be treated, namely fossil hydrocarbon feedstock, into a heavy fraction and a lighter fraction, the heavy fraction then being sent to the coking step a) to be cracked. Those skilled in the art will know how to choose the cutting point between the heavy fraction returned to the coking step and the lighter fraction in the usual way under the conditions of implementation of the coking step.

[0126]

[0122] The fluid bed process consists of bringing the feedstock to be treated into contact with a fluidized bed containing hot particles, generally coke particles. This produces an effluent consisting of hydrocarbon vapor and coke that deposits on the particles. These particles can then be regenerated by combustion, and some of the coke particles can then be returned to the coking zone, for example, a fluidized bed reactor. In this case, the entire fossil hydrocarbon feedstock is sent to the coking stage to undergo thermal cracking.

[0127]

[0123] Step b) of splitting

[0128]

[0124] During step b) of fractionation, the converted 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.

[0129]

[0125] This second fractionation section is typically a fractionation column, for example chosen from an atmospheric distillation column and a reduced pressure distillation column.

[0130]

[0126] Step b) of fractionation is preferably carried out on the converted hydrocarbon effluent coming directly from step a), without an intermediate step.

[0131]

[0127] The fractionation of step b) is carried out in the presence of the waste oil or a waste oil cut, the latter being able to be introduced at one of steps a) or b) or at both steps depending on the nature of the conversion step.

[0132]

[0128] Thus, when the first conversion step is a coking step, the waste oil or a waste oil cut is advantageously introduced exclusively inside the second fractionation section.

[0133]

[0129] When the first conversion step is a viscoelastic step, the waste oil or a cut of waste oil is advantageously introduced inside the first viscoelastic section and / or the second fractionation section.

[0134]

[0130] It is 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 oil cut, or used oils of different qualities or different used oil cuts, can then be introduced into each section.

[0135]

[0131] Different cases can thus be considered depending on the quality of the used oil or the available used oil cut, namely its contaminant content.

[0136]

[0132] In particular, when the contaminant content of the waste oil or waste oil cut is very high, it is preferable to introduce the waste oil or cut into the first conversion section, especially when this is a first viscoelastic section.

[0137]

[0133] A used oil or a cut of used oil having a slightly lower but still high contaminant content may be introduced into the second fractionation section.

[0138]

[0134] It is nevertheless possible, although not preferred, to treat used oil or a used oil 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 of the used oil.

[0135] The used oil or a used oil cut can be introduced into the second fractionation section mixed with the hydrocarbon effluent or separately, preferably separately, at a point higher or lower than the point of introduction of the converted effluent.

[0139]

[0136] Alternatively or in combination, the waste oil or a cut of waste oil can be introduced upstream of the second fractionation section, namely in the first viscoeduction section, mixed or not with the fossil hydrocarbon feed, preferably mixed.

[0140]

[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 / converted 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), then 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.

[0141]

[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.

[0142]

[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.

[0143]

[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, or by lateral withdrawal.

[0144]

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

[0145]

[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.

[0146]

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

[0147]

[0144] The recovered kerosene fraction preferably has a final boiling point below 300 °C, notably 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.

[0148]

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

[0146] In a visbreaking step (a), the fractionation carried out in step (b) typically separates a naphtha, kerosene, and diesel fraction, a vacuum diesel fraction, and a visbreaking residue. The visbreaking residue can then be sent to a partial oxidation (POX) unit or a bitumen pool. The naphtha fraction can be hydrotreated and then optionally steam cracked. The other fractions can be sent to dedicated hydrotreating units and / or hydrocracking and / or sent to a fluid catalytic cracking unit.

[0149]

[0147] In a coking step (a), the fractionation carried out in step (b) typically separates the effluent into naphtha (typically with a final boiling point of approximately 170 °C), light diesel (typically distilling in the range of 170–370 °C), heavy diesel (typically distilling in the range of 370–525 °C), and residue (typically having an initial boiling point of 520 °C to 540 °C). The residue can be returned to the coking step inlet. The naphtha fraction can be hydrotreated and then optionally steam cracked. The diesel fractions can be sent to dedicated hydrotreating units and / or hydrocracking and / or sent to a fluid catalytic cracking unit.

[0150]

[0148] Typically, when step a) is a conversion step, the fractionation in step b) is carried out under the usual fractionation conditions following a coking or visbreaking step. The fractionation step may, in particular, be carried out under atmospheric pressure or under reduced pressure, for example at an absolute pressure of 0.1 mbar to 500 mbar, preferably from 0.1 mbar to 100 mbar, and more preferably from 0.5 to 10 mbar.

[0151]

[0149] During step b), the hydrocarbon effluent converted 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.

[0152]

[0150] This liquid hydrocarbon fraction can then be sent to an optional third processing stage.

[0153]

[0151] Processing step c)

[0154]

[0152] 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.

[0155]

[0153] These heteroatoms can be nitrogen, sulfur, oxygen, silicon, halogens, and / or metals.

[0156]

[0154] 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).

[0157]

[0155] Step c) may carry out one or more of the following reactions: hydrodesulfurization, hydrodeazotation, hydrodemetallation, hydrodearomatization, hydrodehalogenation, catalytic hydrogenation, hydrodeoxygenation, decarboxylation, fluid catalytic cracking.

[0156] Depending on the reactions carried out, step c) may be performed in the presence of dihydrogen and at least one catalyst under suitable, standard conditions.

[0158]

[0157] 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 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]

[0158] Advantageously, step c) of hydrotreating and / or hydrocracking and / or fluid catalytic cracking can thus be implemented in one or more existing hydrotreating units and / or hydrocracking units and / or fluid catalytic cracking units of a refinery, usually used to treat feedstocks of fossil origin, and in particular specific fractions thereof.

[0160]

[0159] The present invention can therefore be implemented in an existing refinery, without having to modify it.

[0161] Detailed description of the figures

[0162]

[0160] 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]

[0161] Figure 1 [Fig.1] schematically represents a manufacturing process according to an embodiment of the invention.

[0164]

[0162] Figure 2 [Fig. 2] schematically represents a manufacturing process according to another embodiment of the invention.

[0165]

[0163] In the figures, identical elements are designated by the same reference numerals.

[0166]

[0164] Fig. 1 schematically represents one possible embodiment of the invention.

[0167]

[0165] In this possible embodiment of Figure 1, a fossil hydrocarbon feedstock (21), here a residue or a mixture of residues, is subjected to a conversion step a) in a first conversion section C UThe conversion section is capable of implementing a conversion step. To this end, it may include one or more reactors in parallel and / or in series. Any type of reactor commonly used for the type of reaction envisaged may be used, for example, a fixed-bed reactor, a stirred-tank reactor, a bubbling-bed reactor, a slurry reactor, a plug-flow reactor, a batch reactor, etc.

[0168]

[0166] The converted effluent (22) exiting the Cunit conversion section is then fractionated during step b), in particular directly, without an intermediate step, in a Funit fractionation section, capable of carrying out step b), to be fractionated there into at least one liquid hydrocarbon fraction.

[0169]

[0167] According to the invention, waste oil (HU) is introduced into the Funit fractionation section to be fractionated along with the converted effluent (22). This waste oil can be introduced into the fractionation section mixed with the converted effluent, or separately, as shown in Figure 1. In this case, the waste oil (HU) can advantageously be introduced at a point located above the point of introduction of the converted effluent, in other words, in a part of the fractionation section whose temperature is lower than the temperature at the point of introduction of the converted effluent (22). This limits the heating of the waste oil and thus limits secondary cracking-type reactions.However, it can also be introduced at a point below the point of introduction of the converted effluent, particularly when it contains a lot of metallic impurities and / or heteroelements of type S, Cl, Si, P.

[0170]

[0168] When the conversion section is a visbreaking section, the waste oil can be introduced, in whole or in part, into the conversion section. This is particularly advantageous when the waste oil contains a large amount of contaminants.

[0171]

[0169] In the example shown, the converted effluent (22) is fractionated, for example, into a gaseous fraction (23) and several liquid hydrocarbon fractions, for example, a naphtha fraction (24), a kerosene fraction (25), a diesel fraction (26), a VGO fraction (27), and a residue (28). The latter can optionally be recycled upstream of the Cunit reactor for further conversion or sent to a hydrotreating and / or hydrocracking and / or fluid catalytic cracking unit (not shown). 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 implemented and the desired products.Depending on the nature of the conversion reaction, the fractionation section may be integrated into the conversion section (for example, including one or more lateral draw-offs) or be a separate section, in particular a fractionation column.

[0172]

[0170] Depending on the nature of any impurities present, a separated hydrocarbon liquid fraction 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 (24), (25), and (26) separately, respectively, and a hydrocracking unit HCK1 or a fluid catalytic cracking unit FCC1 is provided to treat the VGO (27).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.

[0173]

[0171] The invention is not, however, limited to the number of hydrotreating and / or hydrocracking and / or fluid catalytic cracking units, nor to the nature of the reactions they carry out. 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.

[0172] In the embodiment shown in Figure 1, step a) can in particular be carried out in a visbreaking section or a coking section comprising a fluidized bed reactor.

[0174]

[0173] Figure 2 shows another possible embodiment of the process according to the invention. This embodiment differs from that shown in Figure 1 essentially in that step a) is carried out in a first delayed coking section CRunit.

[0175]

[0174] The hydrocarbon feed treated during a) coking step is here a residue produced during step b) fractionation.

[0176]

[0175] In this embodiment, a fossil hydrocarbon feedstock (31), namely a residue or a mixture of residues, is first sent to the fractionation section of step b) Funit. The feedstock (31) generally enters the lower part of the Funit fractionation section, below the inlet of the converted effluent (32).

[0177]

[0176] The heavier fraction (residue) (28) separated in this fractionation section Funit is sent to the delayed coking section CRunit, typically to one of the two coke drums usually included in this type of unit, where it undergoes thermal cracking. The coking step a) produces a converted effluent (32) that is at least partially cracked and a solid residue (30), namely coke.

[0178]

[0177] The converted effluent (32) exiting the coke drums is sent to the Funit- fractionation section

[0179]

[0178] In the embodiment shown, the entirety of the heaviest fraction (28) is sent to the delayed coking section CR un it- The invention is not limited to this embodiment, however, and part of the heavier fraction (28) could be sent to the delayed coking section, the remainder being sent to an HCK1 hydrocracking unit and / or an FCC1 fluid catalytic cracking unit (not shown).

[0180]

[0179] According to the invention, a waste oil (HU) is introduced directly into the Funit fractionation section, separately from the converted effluent (32), at a point located above or below the point of introduction of the converted effluent (32). The waste oil could also be introduced mixed with the converted effluent, although this is not preferred.

[0181]

[0180] As explained above, the coke drums operate alternately: the coke from one drum is discharged while thermal cracking is in progress in the other drum. Water is typically used to discharge the coke from the coke drums. The coke can then be used to produce carbon black and / or activated carbon.

[0182]

[0181] The used oil used in the present invention may be whole or have undergone fractionation 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.

[0182] The use of whole used oil has the advantage of allowing all of the oil to be used in a refinery process without having to perform any specific prior fractionation.

[0183]

[0183] The use of a used oil residue has the advantage of limiting the increase in the volume of the feedstock to be treated associated with the introduction of the 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 a waste oil, the process comprising: a) a first conversion step of the fossil hydrocarbon feedstock in a first conversion section producing a converted hydrocarbon effluent, said fossil hydrocarbon feedstock being crude oil or a mixture of crude oils, or a residue or a mixture of residues, said first conversion step being selected from a visbreaking step and a coking step, b) followed by a second fractionation step in which the converted 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 the waste oil is fractionated with the converted hydrocarbon effluent 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 fractionation step of 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 into at least one cut selected from a gasoline cut and a diesel cut, and wherein said cut having a boiling point range of 400 to 800 °C or 500 to 800 °C is fractionated with the hydrocarbon effluent in the second fractionation section.

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

6. A manufacturing process according to any one of claims 1 to 5, wherein: the first step is a viscoelastic step and said waste oil or waste oil cut is introduced into the first conversion section and / or the second fractionation section, or the first step is a coking step and said waste oil or waste oil cut is introduced only into the second fractionation section.

7. A manufacturing process according to any one of claims 1 to 6, wherein the waste oil or a waste oil cut is introduced into the second fractionation section mixed with the converted hydrocarbon effluent or separately.

8. A manufacturing process according to any one of claims 1 to 7, wherein, prior to the first step a) carried out in the first conversion section, said fossil hydrocarbon feedstock is fractionated into a heavy fraction and a fraction lighter than the heavy fraction, and said heavy fraction is sent into the first conversion section of the first step a).

9. A manufacturing process for any one of claims 1 to 8, wherein the first step a) is carried out in the first conversion section under coking conditions producing the converted hydrocarbon effluent and a solid residue, and the solid residue produced is then sent to a carbon black production unit for the manufacture of tires and / or to an activated carbon production unit for the manufacture of catalyst and / or adsorbent.

10. A manufacturing process according to any one of claims 1 to 9, wherein the waste oil or a waste oil cut is introduced into the second fractionation section mixed with the converted hydrocarbon effluent, or separately at an introduction point higher or lower than an introduction point of the hydrocarbon effluent.

11. A manufacturing process according to any one of claims 1 to 10, wherein the ratio of waste oil or waste oil cut / converted hydrocarbon effluent or the ratio of waste oil or waste oil cut / fossil hydrocarbon feedstock is from 0.1 to 50% by mass.

12. A manufacturing process according to any one of claims 1 to 11, further comprising: c) a third treatment step of 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.

13. A manufacturing process according to claim 12, wherein the third treatment step c) carries out at least one reaction selected from hydrodesulfurization, hydrodeazotation, hydrodemetallation, hydrodearomatization, a hydrodehalogenation, catalytic hydrogenation, hydrodeoxygenation, hydrocracking, and fluid catalytic cracking.

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